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CN112079859A - Polycyclic aromatic compound and application thereof in electroluminescent device - Google Patents

Polycyclic aromatic compound and application thereof in electroluminescent device Download PDF

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CN112079859A
CN112079859A CN202011019238.0A CN202011019238A CN112079859A CN 112079859 A CN112079859 A CN 112079859A CN 202011019238 A CN202011019238 A CN 202011019238A CN 112079859 A CN112079859 A CN 112079859A
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乔娟
薛杰
徐靖一
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Tsinghua University
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Abstract

The invention relates to a polycyclic aromatic compound and application thereof. The compound has a structure shown in formula I. When the compound is used as a luminescent layer material in an organic electroluminescent device, the luminous efficiency of the device can be effectively improved, the spectral color purity of the device can be improved, and the optimal technical effect of narrow luminous half-peak width of the device can be obtained.
Figure DDA0002700091580000011

Description

Polycyclic aromatic compound and application thereof in electroluminescent device
Technical Field
The invention relates to a novel organic compound, in particular to a triarylamine series derivative with a bridging structure, and simultaneously relates to application of the compound in an electroluminescent device.
Background
Over the last several decades, the field of Organic Light-Emitting Diodes (OLEDs) has made rapid progress, and has become one of the most promising technologies for full-color display and lighting applications. Compared with the traditional inorganic luminescent material, the organic luminescent material is more flexible in molecular design, various performance indexes such as thermal stability, luminescent property, electric conductivity and the like of molecules can be regulated and controlled by modifying and modifying a molecular structure, and meanwhile, many organic materials also have high luminescent quantum efficiency. In the aspect of display, OLEDs have the advantages of self-luminescence, wide color gamut, wide viewing angle, low response time, high blackness, flexible display realization and the like, and are known as a star flat display product in the 21 st century.
Unlike photoexcitation, only 25% of total excitons generated by electrons and holes injected from both the anode and the cathode under electrical excitation are singlet excitons, and the remaining 75% are triplet excitons. The most primitive OLEDs, which use conventional fluorescent materials, cannot utilize triplet excitons, which account for 75% of the total number of excitons, and thus their external quantum efficiency is often difficult to break through by 5%. In order to solve the triplet exciton utilization problem, second generation OLED materials have been developed since 1998, which are structurally characterized by transition metal complexes based on noble metals (e.g., iridium, platinum, osmium, etc.). Due to the heavy atom effect of the central noble metal, the material can effectively utilize triplet excitons, emit phosphorescence and realize 100% of exciton utilization rate. However, the cost of the noble metal used in the efficient phosphorescent material is high, the resource amount is small, and the long-term application is limited. Since 2011, professor Adachi at kyusha university of japan reported OLEDs based on purely organic Thermally Activated Delayed Fluorescence (TADF) materials. TADF materials can convert triplet excitons into singlet excitons by means of room temperature, thereby emitting delayed fluorescence, and thus achieving 100% exciton utilization. Therefore, the TADF material has a series of advantages of low cost and abundant sources, and is a third generation OLED material.
Meanwhile, the organic TADF material still faces many problems to be solved when it is practically applied to the display field. One of the most important is color purity. Recently, both gallium nitride based micro LEDs and CdS/ZnS based quantum dot LEDs achieve a-20 nm half-peak width (FWHM) in the blue region. In the case of organic light-emitting diodes, the half-width of their electroluminescence spectra is mostly above 40 nm. For TADF materials, the intrinsic strong charge transfer excited state property makes the half-peak width of the luminescence spectrum reach more than 60nm, which is very disadvantageous for commercial application. Even if commercial OLED display materials are recently realized, color filters or optical micro-cavities are added in practical use to improve the luminescent color purity under electroluminescence. However, at the same time, these methods inevitably bring about a loss of energy and an increase in cost. Therefore, there is an urgent need to design organic electroluminescent materials with high color purity and high efficiency to realize true high-quality full-color OLEDs. On the other hand, the stability of the material is crucial to the life of the corresponding OLED, and the use of a high-stability light-emitting material or the improvement of the stability of the light-emitting material is beneficial to the realization of a long-life OLED.
Disclosure of Invention
The invention aims to solve the problem that in the prior art, the number of high-color-purity and high-efficiency luminescent materials is small, and provides a novel triarylamine derivative with a bridging structure, which has high luminescent color purity and high efficiency when applied to an electroluminescent device. Meanwhile, the triarylamine derivative with the bridging structure provided by the invention is a rigid parallel ring structure, and is favorable for realizing high stability.
The invention provides a polycyclic aromatic compound, the structure of which is shown as the following formula I:
Figure BDA0002700091560000011
in the formula I, Ar1 ring, Ar2 ring and Ar3 ring respectively and independently represent one of substituted or unsubstituted C6-C60 aromatic ring and substituted or unsubstituted C4-C60 heteroaromatic ring, Ar4 represents one of substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C4-C60 heteroaromatic ring;
in formula I, X is selected from any one of the structures shown below:
Figure BDA0002700091560000021
"+" represents the position of the access bond of the group;
when the Ar1 ring, the Ar2 ring, the Ar3 ring and the Ar4 have substituents, the substituents are respectively and independently selected from one or a combination of at least two of deuterium, halogen, cyano, chain alkyl of C1-C36, chain alkenyl of C1-C36, chain alkynyl of C1-C36, cycloalkyl of C3-C36, cycloalkenyl of C4-C36, ring alkynyl of C4-C36, alkoxy of C1-C30, thioalkoxy of C1-C30, carbonyl, carboxyl, nitro, amino, arylamino of C6-C30, heteroarylamino of C3-C30, monocyclic aryl of C6-C60, fused ring aryl of C6-C60, aryloxy of C4-C60, monocyclic 60 of C2-C heteroaryl, and fused ring heteroaryl of C2-C60.
Further, the polycyclic aromatic compound of the present invention has a structure represented by any one of the following formulae I-1, I-2 or I-3:
Figure BDA0002700091560000022
in formula I-1, formula I-2 and formula I-3, the definitions of the Ar1 ring, Ar2 ring, Ar3 ring and Ar4 ring are the same as those in formula I.
Preferably, in formula I, formula I-1, formula I-2 or formula I-3, the Ar1 ring, Ar2 ring, Ar3 ring are each independently selected from one of the following substituted or unsubstituted groups: benzene ring, biphenyl ring, terphenyl ring, naphthalene ring, anthracene ring, phenanthrene ring, indene ring, fluorene ring, fluoranthene ring, triphenylene ring, pyrene ring, perylene ring,
Figure BDA0002700091560000024
A ring, a tetracene ring, a furan ring, a thiophene ring, a pyrrole ring, a benzofuran ring, a benzothiophene ring, an isobenzofuran ring, an indole ring, a dibenzofuran ring, a dibenzothiophene ring or a carbazole ring, Ar4 is selected from one of the following substituted or unsubstituted groups: phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, indenyl, fluorenyl, fluoranthenyl, triphenylenyl, pyrenyl, perylenyl, perylene, and the like,
Figure BDA0002700091560000025
Aryl, tetracenylFuryl, thienyl, pyrrolyl, benzofuryl, benzothienyl, isobenzofuryl, indolyl, dibenzofuryl, dibenzothienyl or carbazolyl.
Further preferably, in formula I, formula I-1, formula I-2 or formula I-3, the Ar1 ring is selected from a substituted or unsubstituted benzene ring, and the Ar2 ring, Ar3 ring are each independently selected from one of the following substituted or unsubstituted groups: benzene ring, biphenyl ring, terphenyl ring, naphthalene ring, anthracene ring, phenanthrene ring, indene ring, fluorene ring, fluoranthene ring, triphenylene ring, perylene,
Figure BDA0002700091560000026
A ring, a tetracene ring, a furan ring, a thiophene ring, a pyrrole ring, a benzofuran ring, a benzothiophene ring, an isobenzofuran ring, an indole ring, a dibenzofuran ring, a dibenzothiophene ring, or a carbazole ring; ar4 is selected from one of substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl.
When the Ar1 ring, the Ar2 ring, the Ar3 ring and the Ar4 have substituents, the substituents are respectively and independently selected from one or a combination of at least two of deuterium, halogen, cyano, chain alkyl of C1-C36, chain alkenyl of C1-C36, chain alkynyl of C1-C36, cycloalkyl of C3-C36, cycloalkenyl of C4-C36, ring alkynyl of C4-C36, alkoxy of C1-C30, thioalkoxy of C1-C30, carbonyl, carboxyl, nitro, amino, arylamino of C6-C30, heteroarylamino of C3-C30, monocyclic aryl of C6-C60, fused ring aryl of C6-C60, aryloxy of C4-C60, monocyclic 60 of C2-C heteroaryl, and fused ring heteroaryl of C2-C60.
In formula I, formula I-1, formula I-2, or formula I-3, the Ar1 ring is selected from any one of the structures represented by formulae D1 to D298:
Figure BDA0002700091560000023
Figure BDA0002700091560000031
Figure BDA0002700091560000041
Figure BDA0002700091560000051
Figure BDA0002700091560000061
wherein,
Figure BDA0002700091560000072
represents a site of attachment to a nitrogen atom in the structure of formula I, formula I-1, formula I-2 or formula I-3, · · · · · · · · · · · · · represents a site of attachment to a boron atom in the structure of formula I, formula I-1, formula I-2 or formula I-3, · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·;
when formulae D1 to D298 contain only one substituent group in varying positions and numbers, n represents from 1 to the maximum number of substituents permitted; when two substituent groups with variable positions and numbers are contained in the structural formulas D1-D298, m and n respectively and independently represent 0 to the maximum allowable number of the substituent groups and are not simultaneously 0; when three substituent groups with variable positions and numbers are contained in the structural formulas D1 to D298, m, l and n respectively and independently represent 0 to the maximum allowable number of the substituent groups and are not simultaneously 0.
In formula I, formula I-1, formula I-2 or formula I-3, the Ar2 ring and Ar3 ring are each independently selected from any one of the structures shown in formulas E1 to E612:
Figure BDA0002700091560000071
Figure BDA0002700091560000081
Figure BDA0002700091560000091
Figure BDA0002700091560000101
Figure BDA0002700091560000111
Figure BDA0002700091560000121
Figure BDA0002700091560000131
Figure BDA0002700091560000141
Figure BDA0002700091560000151
wherein,
Figure BDA0002700091560000153
represents a site of attachment to a nitrogen atom in the structure of formula I, formula I-1, formula I-2 or formula I-3, · represents a site of attachment to another bridging group other than a nitrogen atom in the structure of formula I, formula I-1, formula I-2 or formula I-3;
when the structural formulas E1 to E612 only contain one substituent group with variable positions and quantities, n represents 1 to the maximum allowable number of the substituent groups, and when the structural formulas contain two substituent groups with variable positions and quantities, m and n independently represent 0 to the maximum allowable number of the substituent groups and are not 0 simultaneously; when three substituent groups with variable positions and numbers are contained in structural formulas E1-E612, m, l and n respectively and independently represent 0 to the maximum allowable number of substituent groups and are not simultaneously 0.
In the formula I, the formula I-1, the formula I-2 or the formula I-3, Ar4 is selected from any one of structures shown in the following formulas F1 to F186:
Figure BDA0002700091560000152
Figure BDA0002700091560000161
Figure BDA0002700091560000171
wherein, represents a bonding site with a boron atom in the structure of formula I, formula I-1, formula I-2 or formula I-3.
Further preferably, in formula I, formula I-1, formula I-2, or formula I-3, the Ar1 ring is selected from any one of the structures shown below:
Figure BDA0002700091560000172
wherein,
Figure BDA0002700091560000174
represents a site of attachment to a nitrogen atom in the structure of formula I, formula I-1, formula I-2 or formula I-3, · · · · · · · · · · · · · represents a site of attachment to a boron atom in the structure of formula I, formula I-1, formula I-2 or formula I-3, · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·;
in formula I, formula I-1, formula I-2, or formula I-3, the Ar2 and Ar3 rings are each independently selected from any one of the structures shown below:
Figure BDA0002700091560000173
Figure BDA0002700091560000181
wherein,
Figure BDA0002700091560000183
represents a site of attachment to a nitrogen atom in the structure of formula I, formula I-1, formula I-2 or formula I-3, · represents a site of attachment to another bridging group other than a nitrogen atom in the structure of formula I, formula I-1, formula I-2 or formula I-3;
in formula I, formula I-1, formula I-2 or formula I-3, Ar4 is selected from any one of the structures shown below:
Figure BDA0002700091560000182
wherein, represents a bonding site with a boron atom in the structure of formula I, formula I-1, formula I-2 or formula I-3.
Further preferably, when a substituent is present on the Ar1 ring, the Ar2 ring, the Ar3 ring, the Ar4 ring in formula I, formula I-1, formula I-2 or formula I-3, said substituent is independently selected from deuterium or one of the following substituents: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2, 2-trifluoroethyl, 2, 2-dicyanovinyl, phenyl, naphthyl, anthracenyl, benzanthryl, phenanthryl, benzophenanthryl, pyrenyl, bornyl, perylenyl, fluoranthenyl, tetracenyl, pentacenyl, benzopyrenyl, biphenyl, terphenyl, tetrabenzyl, spirobifluorenyl, dihydrophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis-or trans-indenofluorenyl, trimeric indenyl, isotridecylinyl, spirotrimeric indenyl, spiroisotridecylindenyl, spiroisotridecylinyl, Furyl, benzofuryl, isobenzofuryl, dibenzofuryl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, isoindolyl, carbazolyl, indenocarbazolyl, pyridyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5, 6-quinolyl, benzo-6, 7-quinolyl, benzo-7, 8-quinolyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalimidazolyl, kanilino, benzoxazolyl, naphthoxazolyl, anthraoxazolyl, phenanthroizolyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinyl, benzpyridazinyl, pyrimidinyl, benzopyrimidinyl, etc, Quinoxalinyl, 1, 5-diazahthranyl, 2, 7-diazpyrenyl, 2, 3-diazpyrenyl, 1, 6-diazpyrenyl, 1, 8-diazpyrenyl, 4,5,9, 10-tetraazaperylenyl, pyrazinyl, phenazinyl, phenothiazinyl, naphthyridinyl, azacarbazolyl, benzocarbazinyl, phenanthrolinyl, 1,2, 3-triazolyl, 1,2, 4-triazolyl, benzotriazolyl, 1,2, 3-oxadiazolyl, 1,2, 4-oxadiazolyl, 1,2, 5-oxadiazolyl, 1,2, 3-thiadiazolyl, 1,2, 4-thiadiazolyl, 1,2, 5-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,3, 5-triazinyl, 1,2, 4-triazinyl, 1,2, 3-triazinyl, tetrazolyl, 1,2,4, 5-tetrazinyl, 1,2,3, 4-tetrazinyl, 1,2,3, 5-tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, 9-dimethylanilino, triarylamine, adamantane, fluorophenyl, methylphenyl, trimethylphenyl, cyanophenyl, tetrahydropyrrole, piperidine, methoxy, silyl, cyano, fluoro, chloro.
In the present specification, the expression of Ca to Cb represents that the group has carbon atoms a to b, and the carbon atoms do not generally include the carbon atoms of the substituents unless otherwise specified. In the structural formulae disclosed in the present specification, the expression of the "-" underlined loop structure indicates that the linking site is located at an arbitrary position on the loop structure where the linking site can form a bond.
The heteroatom in the present specification is generally referred to as being selected from N, O, S, P, Si and Se, preferably from N, O, S.
In the present specification, examples of the halogen include: fluorine, chlorine, bromine, iodine, and the like.
In the present specification, the "substituted or unsubstituted" group may be substituted with one substituent, or may be substituted with a plurality of substituents, and when a plurality of substituents are present, different substituents may be selected from the group.
Further, based on the general structures of formula I-1, formula I-2 and formula I-3, tables 1 to 3 respectively list representative compounds M1-M5058 of the present invention as specific preferred structural compounds of the general compounds of the present invention. It should be noted that the preferred compounds of the present invention are not limited to the structural schemes of the compounds listed in the following tables.
Table 1: partially preferred structural compounds based on the general formula I-1
Figure BDA0002700091560000191
Figure BDA0002700091560000201
Figure BDA0002700091560000211
Figure BDA0002700091560000221
Figure BDA0002700091560000231
Figure BDA0002700091560000241
Figure BDA0002700091560000251
Figure BDA0002700091560000261
Figure BDA0002700091560000271
Figure BDA0002700091560000281
Figure BDA0002700091560000291
Figure BDA0002700091560000301
Figure BDA0002700091560000311
Figure BDA0002700091560000321
Table 2: partially preferred structural compounds based on the general formula I-2
Figure BDA0002700091560000322
Figure BDA0002700091560000331
Figure BDA0002700091560000341
Figure BDA0002700091560000351
Figure BDA0002700091560000361
Figure BDA0002700091560000371
Figure BDA0002700091560000381
Figure BDA0002700091560000391
Figure BDA0002700091560000401
Figure BDA0002700091560000411
Figure BDA0002700091560000421
Figure BDA0002700091560000431
Figure BDA0002700091560000441
Figure BDA0002700091560000451
Figure BDA0002700091560000461
Table 3: partially preferred structural compounds based on the general formula I-3
Figure BDA0002700091560000462
Figure BDA0002700091560000471
Figure BDA0002700091560000481
Figure BDA0002700091560000491
Figure BDA0002700091560000501
Figure BDA0002700091560000511
Figure BDA0002700091560000521
Figure BDA0002700091560000531
Figure BDA0002700091560000541
Figure BDA0002700091560000551
Figure BDA0002700091560000561
Figure BDA0002700091560000571
Figure BDA0002700091560000581
Figure BDA0002700091560000591
Further, the polycyclic aromatic compound of the present invention may preferably be a compound having a specific structure shown by C1 to C293 below, and these compounds are merely representative and do not limit the scope of the present invention.
Figure BDA0002700091560000592
Figure BDA0002700091560000601
Figure BDA0002700091560000611
Figure BDA0002700091560000621
Figure BDA0002700091560000631
Figure BDA0002700091560000641
Figure BDA0002700091560000651
Figure BDA0002700091560000661
Figure BDA0002700091560000671
The use of the above-mentioned compounds of the invention as functional materials in organic electronic devices comprising: an organic electroluminescent device, an optical sensor, a solar cell, a lighting element, an organic thin film transistor, an organic field effect transistor, an organic thin film solar cell, an information label, an electronic artificial skin sheet, a sheet type scanner, or electronic paper, preferably an organic electroluminescent device.
The invention also provides an organic electroluminescent device, which comprises a substrate, a first electrode, a second electrode and one or more organic layers which are inserted between the first electrode and the second electrode, wherein the organic layers comprise compounds shown in any one of the general formula I, the general formula I-1, the general formula I-2 and the general formula I-3, and further preferably comprise specific compounds listed in any one of the table 1, the table 2 or the table 3.
Specifically, embodiments of the present invention provide an organic electroluminescent device including a substrate, and an anode layer, a plurality of light emitting functional layers, and a cathode layer sequentially formed on the substrate; the light-emitting functional layer comprises a hole injection layer, a hole transport layer, a light-emitting layer and an electron transport layer, wherein the hole injection layer is formed on the anode layer, the hole transport layer is formed on the hole injection layer, the cathode layer is formed on the electron transport layer, and the light-emitting layer is arranged between the hole transport layer and the electron transport layer; among them, it is preferable that the light-emitting layer contains the compound represented by the general formula of the present invention represented by any one of the general formula I, the general formula I-1, the general formula I-2 and the general formula I-3. More preferably, the light-emitting layer contains a specific compound listed in any one of table 1, table 2 and table 3.
The specific reasons why the compounds of the structures represented by the general formulae I, I-1, I-2 and I-3 of the present invention can further achieve excellent technical effects are not clear, and the specific reasons why the compounds are excellent in the performance as a light-emitting layer material in an organic electroluminescent device are not clear, and the inventors presume that these presumptions do not limit the scope of the present invention.
The triarylamine series derivatives with bridging structures designed by the invention have excellent bipolar transmission performance because of the nitrogen atoms for electron donor and the bridging groups for electron withdrawing. Meanwhile, the rigidity of the molecular structure of the compound can effectively inhibit the vibration and rotation of molecules, and the recombination energy is reduced, so that the compound shows narrower full width at half maximum (FWHM) and lower nonradiative transition rate. The triarylamine series derivative with the bridging structure is applied to an organic electroluminescent device, and high-efficiency luminescence with high color purity can be obtained.
The organic electroluminescent device adopting the triarylamine series derivatives with the bridging structure as the luminescent layer material has the excellent technical effects of high luminescent efficiency, high spectral color purity and narrow half-peak width.
Drawings
FIG. 1 is a UV-VIS absorption spectrum and a fluorescence spectrum of Compound C1 prepared in Synthesis example 1 according to the present invention;
FIG. 2 is a graph showing an electroluminescence spectrum of an organic electroluminescent device OLED1 prepared in device example 1 of the present invention;
fig. 3 is an external quantum efficiency-current density curve of an organic electroluminescent device OLED1 device prepared according to device example 1 of the present invention.
Detailed Description
In order that those skilled in the art will better understand the present invention, the following detailed description of the invention is provided in conjunction with the accompanying drawings and the detailed description of the invention.
Compound synthesis embodiments:
the specific production method of the above-mentioned novel compound of the present invention will be described in detail below by taking a plurality of synthesis examples as examples, but the production method of the present invention is not limited to these synthesis examples.
Compounds of synthetic methods not mentioned in the examples of the present invention are all starting products obtained commercially. The solvents and reagents used in the present invention, such as ethyl acetate, toluene, sodium carbonate and other chemical reagents, can be purchased from domestic chemical product markets, such as from national drug group reagent company, TCI company, shanghai Bide medicine company, Bailingwei reagent company, and the like. In addition, they can be synthesized by a known method by those skilled in the art.
Examples of Synthesis of Compounds
Representative synthetic route 1:
this representative synthetic route can be used for the synthesis of compounds M1-M1686, C1-C44, and C285-C287.
Figure BDA0002700091560000681
Synthesis example 1: synthesis of Compound C1
Figure BDA0002700091560000682
In this synthesis example, compound C1 was synthesized according to the following scheme.
4.34g (12mmol) of 1, 3-dibromo-2-iodobenzene, 1.72g (10mmol) of 2-bromoaniline, 2.08g (15mmol) of potassium carbonate, and 0.32g (5mmol) of activated copper powder were sequentially charged into a 250mL three-necked flask, followed by 120mL of o-dichlorobenzene. The atmosphere in the three-necked flask was replaced with nitrogen, and the mixture was refluxed at 180 ℃ under a closed condition for 48 hours. After the reaction is completed, when the reaction system is cooled to room temperature, the reaction liquid is subjected to vacuum filtration, and a filter cake is washed by a dichloromethane solvent. The solution obtained after filtration was collected and spin-evaporated to remove the solvent. And then carrying out column chromatography separation on the product after spin drying, wherein the used eluent and the mixture ratio are dichloromethane: petroleum ether was 1:4 (volume ratio). Column chromatography gave 3.41g of a pale yellowish white solid in 84% yield.
3.25g (8mmol) of the intermediate obtained in the previous step and 200mL of ultra-dry THF were charged into a 500mL three-necked flask, and stirred while maintaining the temperature of the system at-78 ℃. 10.3mL of n-butyllithium (16mmol) were added dropwise to the solution, and after the addition was complete the reaction was allowed to proceed at-78 ℃ for about 3 h. Then, 3.13g (10mmol) of bis (phenylsulfonyl) sulfide was added to the system, and the mixture was reacted for 24 hours with stirring at room temperature. Subsequently, 0.5mL of 30% hydrogen peroxide solution was added dropwise to the reaction system, and the reaction was carried out for 32 hours with stirring at room temperature. After the reaction was completed, the reaction solution was poured into water and extracted with a dichloromethane solvent. The organic phase was collected with a separatory funnel, dried over anhydrous magnesium sulfate, filtered to remove solid particles, and then rotary evaporated to remove the organic solvent. And (3) carrying out column chromatography separation on the obtained crude product, wherein the used eluent and the mixture ratio are dichloromethane: n-hexane was 1:3 (volume ratio). The column chromatography separation and recrystallization processes are carried out to obtain 1.31g of near-white powdery solid with the yield of 53 percent.
1.30g (4.2mmol) of the intermediate obtained in the previous step, 1.42g (5mmol) of 2-bromo-1-iodobenzene, 1.04g (7.5mmol) of potassium carbonate, and 0.16g (2.5mmol) of activated copper powder were successively charged into a 100mL three-necked flask, followed by 50mL of o-dichlorobenzene. The gas in the three-necked flask was replaced with nitrogen, followed by reflux stirring at 150 ℃ for 24 hours under a closed condition. After the reaction is completed, when the reaction system is cooled to room temperature, the reaction liquid is subjected to vacuum filtration, and a filter cake is washed by a dichloromethane solvent. The solution obtained after filtration was collected and spin-evaporated to remove the solvent. And then carrying out column chromatography separation on the product after spin drying, wherein the used eluent and the mixture ratio are dichloromethane: petroleum ether is 1:1 (volume ratio). Column chromatography gave 1.58g of a pale yellowish white solid in 81% yield.
1.58g (3.4mmol) of the intermediate obtained in the previous step and 0.51g (3.4mmol) of dimethyl phenylboronate were successively charged into a 250mL three-necked flask, followed by addition of 100mL of tetrahydrofuran, and the reaction system was cooled to-78 ℃. 0.35g (5.4mmol) of tert-butyllithium was slowly added to the reaction solution, and the reaction was continued at-78 ℃ for 10min with stirring, then the temperature was raised to-21 ℃ and the reaction was continued for 3h with stirring, finally the temperature was raised to room temperature and the reaction was continued for 12h with stirring. After the reaction reached a predetermined time, 20mL of a saturated ammonium chloride solution was poured into the reaction system to quench the reaction, and the organic phase was collected with a separatory funnel. The separated aqueous phase was extracted three more times with 20mL of diethyl ether, and the organic phases obtained by separation were combined, followed by drying over anhydrous magnesium sulfate, filtration to remove solid particles, and rotary evaporation to remove the organic solvent. And (3) carrying out column chromatography separation on the obtained crude product, wherein the used eluent and the mixture ratio are that ethyl acetate: n-hexane was 1:100 (volume ratio). The white powdery solid 0.80g was obtained by column chromatography separation and recrystallization, with a yield of 60%. MALDI-TOF-MS results: molecular ion peaks: 393.10. elemental analysis results: theoretical value: c, 73.30; h, 4.10; b, 2.75; n, 3.56; o, 8.14; and S, 8.15. Experimental values: c, 73.32; h, 4.11; b, 2.74; n, 3.55; o, 8.13; and S, 8.14.
Synthesis example 2: synthesis of Compound C2
This example is substantially the same as synthetic example 1 except that: in this case, the 2-bromo-1-iodobenzene in the third reaction step is converted to 3-bromo-4-iodotrifluorotoluene in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 461.09. elemental analysis results: theoretical value: c, 65.10; h, 3.28; b, 2.34; f, 12.36; n, 3.04; o, 6.94; and S, 6.95. Experimental values: c, 65.12; h, 3.27; b, 2.35; f, 12.35; n, 3.03; o, 6.94; and S, 6.94.
Synthetic example 3: synthesis of Compound C3
This example is substantially the same as synthetic example 1 except that: in this case, the 2-bromoaniline in the first reaction step is replaced by 4-amino-3-bromotrifluorotoluene in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 461.09. elemental analysis results: theoretical value: c, 65.10; h, 3.28; b, 2.34; f, 12.36; n, 3.04; o, 6.94; and S, 6.95. Experimental values: c, 65.09; h, 3.27; b, 2.35; f, 12.36; n, 3.05; o, 6.95; and S, 6.94.
Synthetic example 4: synthesis of Compound C4
This example is substantially the same as synthetic example 1 except that: in this example, 2-bromoaniline in the first reaction step and 2-bromo-1-iodobenzene in the third reaction step were exchanged to 4-amino-3-bromotrifluorotoluene and 3-bromo-4-iodotrifluorotoluene, respectively, in equal amounts. MALDI-TOF-MS results: molecular ion peaks: 529.07. elemental analysis results: theoretical value: c, 59.00; h, 2.67; b, 2.04; f, 21.54; n, 2.65; o, 6.05; and S, 6.06. Experimental values: c, 59.02; h, 2.68; b, 2.02; f, 21.55; n, 2.64; o, 6.06; and S, 6.06.
Synthesis example 5: synthesis of Compound C5
This example is substantially the same as synthetic example 1 except that: in this example, the amount of 2-amino-3-bromonaphthalene in the first reaction step is changed to an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 443.12. elemental analysis results: theoretical value: c, 75.86; h, 4.09; b, 2.44; n, 3.16; o, 7.22; and S, 7.23. Experimental values: c, 75.88; h, 4.08; b, 2.45; n, 3.14; o, 7.23; and S, 7.23.
Synthetic example 6: synthesis of Compound C6
This example is substantially the same as synthetic example 1 except that: in this example, 2-amino-3-bromonaphthalene and 3-bromo-4-iodotrifluorotoluene were used in equal amounts as 2-bromoaniline in the first reaction and 2-bromo-1-iodobenzene in the third reaction. MALDI-TOF-MS results: molecular ion peaks: 511.10. elemental analysis results: theoretical value: c, 68.12; h, 3.35; b, 2.11; f, 11.15; n, 2.74; o, 6.26; and S, 6.27. Experimental values: c, 68.13; h, 3.36; b, 2.10; f, 11.16; n, 2.73; o, 6.26; and S, 6.26.
Synthetic example 7: synthesis of Compound C7
This example is substantially the same as synthetic example 1 except that: in this example, the amount of 2-bromoaniline in the first reaction step is changed to 1-amino-2-bromonaphthalene in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 443.12. elemental analysis results: theoretical value: c, 75.86; h, 4.09; b, 2.44; n, 3.16; o, 7.22; and S, 7.23. Experimental values: c, 75.85; h, 4.10; b, 2.43; n, 3.17; o, 7.23; and S, 7.23.
Synthesis example 8: synthesis of Compound C8
This example is substantially the same as synthetic example 1 except that: in this case, the amounts of 2-bromoaniline in the first reaction step and 2-bromo-1-iodobenzene in the third reaction step are equal to the amounts of 1-amino-2-bromonaphthalene and 3-bromo-4-iodotrifluorotoluene. MALDI-TOF-MS results: molecular ion peaks: 511.10. elemental analysis results: theoretical value: c, 68.12; h, 3.35; b, 2.11; f, 11.15; n, 2.74; o, 6.26; and S, 6.27. Experimental values: c, 68.11; h, 3.37; b, 2.10; f, 11.16; n, 2.74; o, 6.25; and S, 6.26.
Synthetic example 9: synthesis of Compound C9
This example is substantially the same as synthetic example 1 except that: in this case, the 2-bromo-1-iodobenzene in the third reaction step is converted to 2-bromo-3-iodonaphthalene in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 443.12. elemental analysis results: theoretical value: c, 75.86; h, 4.09; b, 2.44; n, 3.16; o, 7.22; and S, 7.23. Experimental values: c, 75.85; h, 4.10; b, 2.45; n, 3.17; o, 7.22; and S, 7.22.
Synthetic example 10: synthesis of Compound C10
This example is substantially the same as synthetic example 1 except that: in this example, the amounts of 2-bromoaniline in the first reaction step and 2-bromo-1-iodobenzene in the third reaction step were changed to the same amounts of 4-amino-3-bromotrifluorotoluene and 2-bromo-3-iodonaphthalene. MALDI-TOF-MS results: molecular ion peaks: 511.10. elemental analysis results: theoretical value: c, 68.12; h, 3.35; b, 2.11; f, 11.15; n, 2.74; o, 6.26; and S, 6.27. Experimental values: c, 68.14; h, 3.34; b, 2.10; f, 11.16; n, 2.74; o, 6.27; and S, 6.26.
Synthetic example 11: synthesis of Compound C11
This example is substantially the same as synthetic example 1 except that: in this example, the amount of 2-bromoaniline in the first reaction step and the amount of 2-bromo-1-iodobenzene in the third reaction step are equal to the amount of 1-amino-2-bromonaphthalene and 2-bromo-3-iodonaphthalene. MALDI-TOF-MS results: molecular ion peaks: 493.13. elemental analysis results: theoretical value: c, 77.90; h, 4.09; b, 2.19; n, 2.84; o, 6.49; and S, 6.50. Experimental values: c, 77.92; h, 4.08; b, 2.20; n, 2.83; o, 6.49; s, 6.49.
Synthetic example 12: synthesis of Compound C12
This example is substantially the same as synthetic example 1 except that: in this case, dimethyl phenylboronate in the fourth reaction stage is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 435.15. elemental analysis results: theoretical value: c, 74.49; h, 5.09; b, 2.48; n, 3.22; o, 7.35; and S, 7.36. Experimental values: c, 74.48; h, 5.10; b, 2.49; n, 3.22; o, 7.36; and S, 7.35.
Synthetic example 13: synthesis of Compound C13
This example is essentially the same as synthetic example 2, except that: in this case, dimethyl phenylboronate in the fourth reaction stage is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 503.13. elemental analysis results: theoretical value: c, 66.81; h, 4.21; b, 2.15; f, 11.32; n, 2.78; o, 6.36; s, 6.37. Experimental values: c, 66.82; h, 4.20; b, 2.14; f, 11.33; n, 2.76; o, 6.37; s, 6.37.
Synthesis example 14: synthesis of Compound C14
This example is essentially the same as synthetic example 3, except that: in this case, dimethyl phenylboronate in the fourth reaction stage is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 503.13. elemental analysis results: theoretical value: c, 66.81; h, 4.21; b, 2.15; f, 11.32; n, 2.78; o, 6.36; s, 6.37. Experimental values: c, 66.80; h, 4.20; b, 2.16; f, 11.32; n, 2.79; o, 6.37; s, 6.37.
Synthetic example 15: synthesis of Compound C15
This example is essentially the same as synthetic example 4, except that: in this case, dimethyl phenylboronate in the fourth reaction stage is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 571.12. elemental analysis results: theoretical value: c, 60.96; h, 3.53; b, 1.89; f, 19.95; n, 2.45; o, 5.60; and S, 5.61. Experimental values: c, 60.97; h, 3.52; b, 1.90; f, 19.96; n, 2.44; o, 5.60; and S, 5.60.
Synthetic example 16: synthesis of Compound C16
This example is substantially the same as synthetic example 5 except that: in this case, dimethyl phenylboronate in the fourth reaction stage is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 485.16. elemental analysis results: theoretical value: c, 76.71; h, 4.98; b, 2.23; n, 2.89; o, 6.59; and S, 6.60. Experimental values: c, 76.70; h, 4.99; b, 2.22; n, 2.89; o, 6.60; and S, 6.60.
Synthetic example 17: synthesis of Compound C17
This example is substantially the same as synthetic example 6, except that: in this case, dimethyl phenylboronate in the fourth reaction stage is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 553.15. elemental analysis results: theoretical value: c, 69.45; h, 4.19; b, 1.95; f, 10.30; n, 2.53; o, 5.78; s, 5.79. Experimental values: c, 69.47; h, 4.18; b, 1.94; f, 10.31; n, 2.52; o, 5.79; s, 5.79.
Synthetic example 18: synthesis of Compound C18
This example is substantially the same as synthetic example 7, except that: in this case, dimethyl phenylboronate in the fourth reaction stage is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 485.16. elemental analysis results: theoretical value: c, 76.71; h, 4.98; b, 2.23; n, 2.89; o, 6.59; and S, 6.60. Experimental values: c, 76.73; h, 4.97; b, 2.24; n, 2.88; o, 6.59; and S, 6.59.
Synthetic example 19: synthesis of Compound C19
This example is substantially the same as synthetic example 8 except that: in this case, dimethyl phenylboronate in the fourth reaction stage is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 553.15. elemental analysis results: theoretical value: c, 69.45; h, 4.19; b, 1.95; f, 10.30; n, 2.53; o, 5.78; s, 5.79. Experimental values: c, 69.47; h, 4.18; b, 1.96; f, 10.29; n, 2.53; o, 5.78; and S, 5.78.
Synthesis example 20: synthesis of Compound C20
This example is substantially the same as synthetic example 9 except that: in this case, dimethyl phenylboronate in the fourth reaction stage is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 485.16. elemental analysis results: theoretical value: c, 76.71; h, 4.98; b, 2.23; n, 2.89; o, 6.59; and S, 6.60. Experimental values: c, 76.70; h, 4.99; b, 2.25; n, 2.88; o, 6.59; and S, 6.59.
Synthetic example 21: synthesis of Compound C21
This example is substantially the same as synthetic example 10 except that: in this case, dimethyl phenylboronate in the fourth reaction stage is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 553.15. elemental analysis results: theoretical value: c, 69.45; h, 4.19; b, 1.95; f, 10.30; n, 2.53; o, 5.78; s, 5.79. Experimental values: c, 69.44; h, 4.20; b, 1.96; f, 10.30; n, 2.51; o, 5.79; s, 5.79.
Synthetic example 22: synthesis of Compound C22
This example is substantially the same as synthetic example 11 except that: in this case, dimethyl phenylboronate in the fourth reaction stage is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 535.18. elemental analysis results: theoretical value: c, 78.51; h, 4.89; b, 2.02; n, 2.62; o, 5.98; and S, 5.99. Experimental values: c, 78.50; h, 4.91; b, 2.03; n, 2.61; o, 5.98; and S, 5.98.
Synthetic example 23: synthesis of Compound C23
This example is substantially the same as synthetic example 1 except that: in this case, the dimethyl phenylboronate in the fourth reaction stage is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 519.24. elemental analysis results: theoretical value: c, 76.30; h, 6.60; b, 2.08; n, 2.70; o, 6.16; and S, 6.17. Experimental values: c, 76.28; h, 6.61; b, 2.09; n, 2.69; o, 6.16; and S, 6.16.
Synthetic example 24: synthesis of Compound C24
This example is essentially the same as synthetic example 2, except that: in this case, the dimethyl phenylboronate in the fourth reaction stage is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 587.23. elemental analysis results: theoretical value: c, 69.51; h, 5.66; b, 1.84; f, 9.70; n, 2.38; o, 5.45; and S, 5.46. Experimental values: c, 69.50; h, 5.67; b, 1.83; f, 9.69; n, 2.39; o, 5.46; and S, 5.46.
Synthetic example 25: synthesis of Compound C25
This example is essentially the same as synthetic example 3, except that: in this case, the dimethyl phenylboronate in the fourth reaction stage is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 587.23. elemental analysis results: theoretical value: c, 69.51; h, 5.66; b, 1.84; f, 9.70; n, 2.38; o, 5.45; and S, 5.46. Experimental values: c, 69.52; h, 5.65; b, 1.85; f, 9.71; n, 2.39; o, 5.45; and S, 5.45.
Synthetic example 26: synthesis of Compound C26
This example is essentially the same as synthetic example 4, except that: in this case, the dimethyl phenylboronate in the fourth reaction stage is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 655.22. elemental analysis results: theoretical value: c, 64.13; h, 4.92; b, 1.65; f, 17.39; n, 2.14; o, 4.88; and S, 4.89. Experimental values: c, 64.14; h, 4.90; b, 1.66; f, 17.40; n, 2.13; o, 4.87; and S, 4.88.
Synthetic example 27: synthesis of Compound C27
This example is substantially the same as synthetic example 5 except that: in this case, the dimethyl phenylboronate in the fourth reaction stage is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 569.26. elemental analysis results: theoretical value: c, 78.03; h, 6.37; b, 1.90; n, 2.46; o, 5.62; and S, 5.63. Experimental values: c, 78.04; h, 6.38; b, 1.89; n, 2.47; o, 5.62; and S, 5.62.
Synthetic example 28: synthesis of Compound C28
This example is substantially the same as synthetic example 6, except that: in this case, the dimethyl phenylboronate in the fourth reaction stage is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 637.24. elemental analysis results: theoretical value: c, 71.59; h, 5.53; b, 1.70; f, 8.94; n, 2.20; o, 5.02; and S, 5.03. Experimental values: c, 71.60; h, 5.54; b, 1.69; f,8.93N, 2.19; o, 5.03; and S, 5.03.
Synthetic example 29: synthesis of Compound C29
This example is substantially the same as synthetic example 7, except that: in this case, the dimethyl phenylboronate in the fourth reaction stage is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 569.26. elemental analysis results: theoretical value: c, 78.03; h, 6.37; b, 1.90; n, 2.46; o, 5.62; and S, 5.63. Experimental values: c, 78.04; h, 6.36; b, 1.92; n, 2.45; o, 5.62; and S, 5.62.
Synthetic example 30: synthesis of Compound C30
This example is substantially the same as synthetic example 8 except that: in this case, the dimethyl phenylboronate in the fourth reaction stage is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 637.24. elemental analysis results: theoretical value: c, 71.59; h, 5.53; b, 1.70; f, 8.94; n, 2.20; o, 5.02; and S, 5.03. Experimental values: c, 71.57; h, 5.54; b, 1.71; f, 8.93; n, 2.19; o, 5.03; and S, 5.03.
Synthetic example 31: synthesis of Compound C31
This example is substantially the same as synthetic example 9 except that: in this case, the dimethyl phenylboronate in the fourth reaction stage is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 569.26. elemental analysis results: theoretical value: c, 78.03; h, 6.37; b, 1.90; n, 2.46; o, 5.62; and S, 5.63. Experimental values: c, 78.05; h, 6.36; b, 1.89; n, 2.45; o, 5.63; and S, 5.62.
Synthetic example 32: synthesis of Compound C32
This example is substantially the same as synthetic example 10 except that: in this case, the dimethyl phenylboronate in the fourth reaction stage is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 637.24. elemental analysis results: theoretical value: c, 71.59; h, 5.53; b, 1.70; f, 8.94; n, 2.20; o, 5.02; and S, 5.03. Experimental values: c, 71.61; h, 5.54; b, 1.71; f, 8.93; n, 2.22; o, 5.01; and S, 5.02.
Synthetic example 33: synthesis of Compound C33
This example is substantially the same as synthetic example 11 except that: in this case, the dimethyl phenylboronate in the fourth reaction stage is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 619.27. elemental analysis results: theoretical value: c, 79.48; h, 6.18; b, 1.74; n, 2.26; o, 5.16; and S, 5.17. Experimental values: c, 79.49; h, 6.19; b, 1.73; n, 2.25; o, 5.15; and S, 5.16.
Synthesis example 34: synthesis of Compound C34
This example is substantially the same as synthetic example 1 except that: in this case, the dimethyl phenylboronate in the fourth reaction stage is replaced by an equivalent amount of dimethyl 1,3, 5-tri-trifluoromethyl phenylboronate. MALDI-TOF-MS results: molecular ion peaks: 597.06. elemental analysis results: theoretical value: c, 54.30; h, 2.19; b, 1.81; f, 28.63; n, 2.35; o, 5.36; s, 5.37. Experimental values: c, 54.31; h, 2.18; b, 1.82; f, 28.64; n, 2.34; o, 5.36; and S, 5.36.
Synthetic example 35: synthesis of Compound C35
This example is essentially the same as synthetic example 2, except that: in this case, the dimethyl phenylboronate in the fourth reaction stage is replaced by an equivalent amount of dimethyl 1,3, 5-tri-trifluoromethyl phenylboronate. MALDI-TOF-MS results: molecular ion peaks: 665.05. elemental analysis results: theoretical value: c, 50.55; h, 1.82; b, 1.62; f, 34.27; n, 2.11; o, 4.81; and S, 4.82. Experimental values: c, 50.54; h, 1.83; b, 1.63; f, 34.25; n, 2.12; o, 4.82; and S, 4.82.
Synthetic example 36: synthesis of Compound C36
This example is essentially the same as synthetic example 3, except that: in this case, the dimethyl phenylboronate in the fourth reaction stage is replaced by an equivalent amount of dimethyl 1,3, 5-tri-trifluoromethyl phenylboronate. MALDI-TOF-MS results: molecular ion peaks: 665.05. elemental analysis results: theoretical value: c, 50.55; h, 1.82; b, 1.62; f, 34.27; n, 2.11; o, 4.81; and S, 4.82. Experimental values: c, 50.54; h, 1.83; b, 1.63; f, 34.25; n, 2.12; o, 4.82; and S, 4.81.
Synthetic example 37: synthesis of Compound C37
This example is essentially the same as synthetic example 4, except that: in this case, the dimethyl phenylboronate in the fourth reaction stage is replaced by an equivalent amount of dimethyl 1,3, 5-tri-trifluoromethyl phenylboronate. MALDI-TOF-MS results: molecular ion peaks: 733.04. elemental analysis results: theoretical value: c, 47.50; h, 1.51; b, 1.47; f, 38.86; n, 1.91; o, 4.36; s, 4.37. Experimental values: c, 47.52; h, 1.50; b, 1.45; f, 38.87; n, 1.90; o, 4.37; s, 4.37.
Synthetic example 38: synthesis of Compound C38
This example is substantially the same as synthetic example 5 except that: in this case, the dimethyl phenylboronate in the fourth reaction stage is replaced by an equivalent amount of dimethyl 1,3, 5-tri-trifluoromethyl phenylboronate. MALDI-TOF-MS results: molecular ion peaks: 647.08. elemental analysis results: theoretical value: c, 57.52; h, 2.34; b, 1.67; f, 26.41; n, 2.16; o, 4.94; and S, 4.95. Experimental values: c, 57.53; h, 2.35; b, 1.66; f, 26.39; n, 2.17; o, 4.95; and S, 4.95.
Synthetic example 39: synthesis of Compound C39
This example is substantially the same as synthetic example 6, except that: in this case, the dimethyl phenylboronate in the fourth reaction stage is replaced by an equivalent amount of dimethyl 1,3, 5-tri-trifluoromethyl phenylboronate. MALDI-TOF-MS results: molecular ion peaks: 715.06. elemental analysis results: theoretical value: c, 53.73; h, 1.97; b, 1.51; f, 31.87; n, 1.96; o, 4.47; and S, 4.48. Experimental values: c, 53.75; h, 1.98; b, 1.49; f, 31.86; n, 1.95; o, 4.47; and S, 4.47.
Synthetic example 40: synthesis of Compound C40
This example is substantially the same as synthetic example 7, except that: in this case, the dimethyl phenylboronate in the fourth reaction stage is replaced by an equivalent amount of dimethyl 1,3, 5-tri-trifluoromethyl phenylboronate. MALDI-TOF-MS results: molecular ion peaks: 647.08. elemental analysis results: theoretical value: c, 57.52; h, 2.34; b, 1.67; f, 26.41; n, 2.16; o, 4.94; and S, 4.95. Experimental values: c, 57.51; h, 2.33; b, 1.68; f, 26.43; n, 2.15; o, 4.95; and S, 4.94.
Synthesis example 41: synthesis of Compound C41
This example is substantially the same as synthetic example 8 except that: in this case, the dimethyl phenylboronate in the fourth reaction stage is replaced by an equivalent amount of dimethyl 1,3, 5-tri-trifluoromethyl phenylboronate. MALDI-TOF-MS results: molecular ion peaks: 715.06. elemental analysis results: theoretical value: c, 53.73; h, 1.97; b, 1.51; f, 31.87; n, 1.96; o, 4.47; and S, 4.48. Experimental values: c, 53.75; h, 1.96; b, 1.53; f, 31.86; n, 1.95; o, 4.48; and S, 4.48.
Synthesis example 42: synthesis of Compound C42
This example is substantially the same as synthetic example 9 except that: in this case, the dimethyl phenylboronate in the fourth reaction stage is replaced by an equivalent amount of dimethyl 1,3, 5-tri-trifluoromethyl phenylboronate. MALDI-TOF-MS results: molecular ion peaks: 647.08. elemental analysis results: theoretical value: c, 57.52; h, 2.34; b, 1.67; f, 26.41; n, 2.16; o, 4.94; and S, 4.95. Experimental values: c, 57.53; h, 2.35; b, 1.66; f, 26.40; n, 2.15; o, 4.95; and S, 4.95.
Synthetic example 43: synthesis of Compound C43
This example is substantially the same as synthetic example 10 except that: in this case, the dimethyl phenylboronate in the fourth reaction stage is replaced by an equivalent amount of dimethyl 1,3, 5-tri-trifluoromethyl phenylboronate. MALDI-TOF-MS results: molecular ion peaks: 715.06. elemental analysis results: theoretical value: c, 53.73; h, 1.97; b, 1.51; f, 31.87; n, 1.96; o, 4.47; and S, 4.48. Experimental values: c, 53.75; h, 1.96; b, 1.50; f, 31.88; n, 1.95; o, 4.47; and S, 4.47.
Synthetic example 44: synthesis of Compound C44
This example is substantially the same as synthetic example 11 except that: in this case, the dimethyl phenylboronate in the fourth reaction stage is replaced by an equivalent amount of dimethyl 1,3, 5-tri-trifluoromethyl phenylboronate. MALDI-TOF-MS results: molecular ion peaks: 697.09. elemental analysis results: theoretical value: c, 60.28; h, 2.46; b, 1.55; f, 24.52; n, 2.01; o, 4.59; and S, 4.60. Experimental values: c, 60.29; h, 2.47; b, 1.54; f, 24.53; n, 2.00; o, 4.59; and S, 4.59.
Representative synthetic route 2:
the following two schemes can be used for the synthesis of compounds M1687-M3372, C45-C164 and C288-C290.
The first scheme is as follows:
Figure BDA0002700091560000741
scheme II:
Figure BDA0002700091560000742
synthetic example 45: synthesis of Compound C45
Figure BDA0002700091560000743
In this synthesis example, compound C45 was synthesized according to the first scheme above.
Methyl 2-aminobenzoate 2.42g (16mmol), 1-bromo-2-iodobenzene 4.53g (16mmol), potassium carbonate 2.50g (18mmol), and activated copper powder 0.38g (6mmol) were charged in this order to a 250mL three-necked flask, followed by addition of 100mL o-dichlorobenzene. The atmosphere in the three-necked flask was replaced with nitrogen, and then the mixture was refluxed and stirred under a closed condition for 48 hours. After the reaction is completed, when the reaction system is cooled to room temperature, the reaction liquid is subjected to vacuum filtration, and a filter cake is washed by a dichloromethane solvent. The solution obtained after filtration was collected and spin-evaporated to remove the solvent. And then carrying out column chromatography separation on the product after spin drying, wherein the used eluent and the mixture ratio are dichloromethane: petroleum ether was 1:5 (volume ratio). Column chromatography gave 4.16g of a white powdery solid in 85% yield.
4.16g (13.6mmol) of the intermediate obtained in the previous step and 2.72g (68mmol) of sodium hydroxide were charged into a 250mL three-necked flask, followed by 120mL of an aqueous ethanol solution having a volume fraction of 50%. The gas in the three-necked flask was replaced with nitrogen, and then the mixture was heated under reflux and stirred under a closed condition for 24 hours. After the hydrolysis reaction is completed, the solvent amount of the reaction system is concentrated to about half, and then concentrated hydrochloric acid is used for acidification, so that a light yellow white solid is separated out. The precipitated solid was suction filtered under reduced pressure and the filter cake was washed with a large amount of deionized water. After washing, the filter cake was recovered and placed in a vacuum oven to dry overnight at 80 ℃. After drying, 3.62g of a white powder was obtained, representing a yield of 91%.
3.62g (12.4mmol) of intermediate obtained in the previous step was dissolved in 150mL of ultra-dry dichloromethane and charged into a 250mL three-necked flask, followed by 1.3mL (14.9mmol) of oxalyl chloride and one drop of ultra-dry DMF. And (3) carrying out nitrogen replacement on the gas in the three-neck flask, and heating the reaction system to reflux under the conditions of a closed environment and stirring. After refluxing for 0.5h, 1.7mL (14.9mmol) of stannic chloride was added and the reaction was continued under reflux for 4 h. After the reaction is completed, when the reaction system is cooled to room temperature, 1M sodium hydroxide aqueous solution is dropwise added into the reaction solution, and the pH value of the system is adjusted to be neutral. The reaction solution was extracted three times with dichloromethane, and the resulting organic phase was dried over anhydrous sodium sulfate, filtered to remove solid particles, and then subjected to rotary evaporation to remove the organic solvent. And (3) carrying out column chromatography separation on the obtained crude product, wherein the used eluent and the mixture ratio are dichloromethane: petroleum ether was 1:4 (volume ratio). Column chromatography gave 2.52g of a white solid in 74% yield.
2.52g (9.2mmol) of the intermediate obtained in the previous step, 2.83g (10mmol) of 1-bromo-2-iodobenzene, 2.08g (15mmol) of potassium carbonate and 0.32g (5mmol) of activated copper powder were successively charged into a 250mL three-necked flask, followed by 100mL of o-dichlorobenzene. The atmosphere in the three-necked flask was replaced with nitrogen, and then the mixture was refluxed and stirred under a closed condition for 48 hours. After the reaction is completed, when the reaction system is cooled to room temperature, the reaction liquid is subjected to vacuum filtration, and a filter cake is washed by a dichloromethane solvent. The solution obtained after filtration was collected and spin-evaporated to remove the solvent. And then carrying out column chromatography separation on the product after spin drying, wherein the used eluent and the mixture ratio are dichloromethane: petroleum ether is 1:2 (volume ratio). Column chromatography separation gave 3.12g of a pale yellowish white powdery solid with a yield of 79%.
3.12g (7.3mmol) of the intermediate obtained in the previous step, 0.67g (10.8mmol) of ethylene glycol and 0.62g of activated polyaniline sulfate (intermediate 20% in weight) were respectively charged into a 100mL round-bottomed flask, followed by addition of 25mL of toluene. The reaction was refluxed with stirring for 45min, and water produced in the reaction was removed by azeotropy. The progress of the reaction was monitored by TLC method until the starting material disappeared. After the reaction is completed, the catalyst is removed by filtration when the reaction system is cooled to room temperature. The obtained filtrate is washed by deionized water, an organic phase is collected by separating liquid, and after being dried by anhydrous sodium sulfate, solid particles are removed by filtration, and then the organic solvent is removed by rotary evaporation. And (3) carrying out column chromatography separation on the obtained crude product, wherein the used eluent and the mixture ratio are dichloromethane: petroleum ether was 1:4 (volume ratio). Column chromatography gave 3.13g of a pale yellowish white solid in 92% yield.
3.13g (6.6mmol) of the intermediate obtained in the previous step and 0.99g (6.6mmol) of dimethyl phenylboronate were successively charged into a 250mL three-necked flask, followed by addition of 150mL of tetrahydrofuran, and the reaction system was cooled to-78 ℃. 0.53g (9.9mmol) of tert-butyllithium was slowly added to the reaction mixture, and the reaction was continued at-78 ℃ for 10min with stirring, then the temperature was raised to-21 ℃ and the reaction was continued for 4h with stirring, finally the temperature was raised to room temperature and the reaction was continued for 18h with stirring. After the reaction reached a predetermined time, 20mL of a saturated ammonium chloride solution was poured into the reaction system to quench the reaction, and the organic phase was collected with a separatory funnel. The separated aqueous phase was extracted three more times with 20mL of diethyl ether, and the organic phases obtained by separation were combined, followed by drying over anhydrous magnesium sulfate, filtration to remove solid particles, and rotary evaporation to remove the organic solvent. And (3) carrying out column chromatography separation on the obtained crude product, wherein the used eluent and the mixture ratio are that ethyl acetate: n-hexane was 1:100 (volume ratio). Column chromatography gave 1.64g of a white powdery solid in 62% yield.
1.64g (4.1mmol) of the intermediate obtained in the previous step was charged into a 100mL round-bottom flask, followed by 20mL of anhydrous hexane. While stirring, 2.03g (12.3mmol) of chloral hydrate was added to the system, followed by reaction for 2 hours. After the reaction is completed, when the reaction system is cooled to room temperature, 20mL of deionized water is added into the system, and the organic phase is collected by liquid separation. Washing the obtained organic phase with brine, drying with anhydrous magnesium sulfate, filtering to remove solid particles, performing rotary evaporation to remove an organic solvent, and performing column chromatography separation on the obtained crude product, wherein the eluent and the mixture ratio are that ethyl acetate: n-hexane was 1:100 (volume ratio). The white powdery solid obtained by column chromatography separation and recrystallization was 1.32g, the yield was 90%. MALDI-TOF-MS results: molecular ion peaks: 357.13. elemental analysis results: theoretical value: c, 84.06; h, 4.51; b, 3.03; n, 3.92; and O, 4.48. Experimental values: c, 84.05; h, 4.52; b, 3.05; n, 3.91; and O, 4.47.
Synthesis example 46: synthesis of Compound C46
This example is substantially the same as synthetic example 45, except that: in this case, 1-bromo-2-iodobenzene in the first step is exchanged for 3-bromo-4-iodo-N, N-diphenylaniline in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 524.21. elemental analysis results: theoretical value: c, 84.74; h, 4.81; b, 2.06; n, 5.34; and O, 3.05. Experimental values: c, 84.76; h, 4.80; b, 2.06; n, 5.35; and O, 3.04.
Synthetic example 47: synthesis of Compound C47
This example is substantially the same as synthetic example 45, except that: in this case, the 1-bromo-2-iodobenzene in the first step is exchanged for an equivalent amount of 3 ' -bromo-4 ' -iodo-N, N-diphenyl- [1,1 ' -biphenyl ] -4-amine. MALDI-TOF-MS results: molecular ion peaks: 600.24. elemental analysis results: theoretical value: c, 86.00; h, 4.87; b, 1.80; n, 4.66; o, 2.66. Experimental values: c, 86.02; h, 4.85; b, 1.81; n, 4.67; o, 2.66.
Synthetic example 48: synthesis of Compound C48
This example is substantially the same as synthetic example 45, except that: in this example, 1-bromo-2-iodobenzene in the first step is exchanged for an equivalent amount of 10- (3 ' -bromo-4 ' -iodo- [1,1 ' -biphenyl ] -4-yl) -9, 9-dimethyl-9, 10-dihydroacridine. MALDI-TOF-MS results: molecular ion peaks: 640.27. elemental analysis results: theoretical value: c, 86.25; h, 5.19; b, 1.69; n, 4.37; o, 2.50. Experimental values: c, 86.24; h, 5.18; b, 1.69; n, 4.38; o, 2.51.
Synthetic example 49: synthesis of Compound C49
This example is substantially the same as synthetic example 45, except that: in this case, the 1-bromo-2-iodobenzene in the first step is exchanged for an equivalent amount of 10- (3 ' -bromo-4 ' -iodo- [1,1 ' -biphenyl ] -4-yl) -10H-phenoxazine. MALDI-TOF-MS results: molecular ion peaks: 614.22. elemental analysis results: theoretical value: c, 84.05; h, 4.43; b, 1.76; n, 4.56; and O, 5.21. Experimental values: c, 84.07; h, 4.42; b, 1.75; n, 4.58; and O, 5.20.
Synthetic example 50: synthesis of Compound C50
This example is substantially the same as synthetic example 45, except that: in this case, the 1-bromo-2-iodobenzene in the fourth step is converted to 3-bromo-4-iodotrifluorotoluene in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 425.12. elemental analysis results: theoretical value: c, 73.44; h, 3.56; b, 2.54; f, 13.40; n, 3.29; and O, 3.76. Experimental values: c, 73.45; h, 3.55; b, 2.55; f, 13.39; n, 3.29; o, 3.77.
Synthetic example 51: synthesis of Compound C51
This example is substantially the same as synthetic example 45, except that: in this case, 1-bromo-2-iodobenzene in the first step is converted to 3-bromo-4-iodotrifluorotoluene in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 425.12. elemental analysis results: theoretical value: c, 73.44; h, 3.56; b, 2.54; f, 13.40; n, 3.29; and O, 3.76. Experimental values: c, 73.42; h, 3.57; b, 2.55; f, 13.41; n, 3.28; and O, 3.76.
Synthesis example 52: synthesis of Compound C52
This example is substantially the same as synthetic example 45, except that: in this case, methyl 2-aminobenzoate in the first step was changed to methyl 2-amino-5-trifluoromethylbenzoate in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 425.12. elemental analysis results: theoretical value: c, 73.44; h, 3.56; b, 2.54; f, 13.40; n, 3.29; and O, 3.76. Experimental values: c, 73.43; h, 3.57; b, 2.52; f, 13.41; n, 3.29; o, 3.77.
Synthetic example 53: synthesis of Compound C53
This example is substantially the same as synthetic example 45, except that: in this case, methyl 2-aminobenzoate in the first step and 1-bromo-2-iodobenzene in the fourth step were exchanged for methyl 2-amino-5-trifluoromethylbenzoate and 3-bromo-4-iodotrifluorotoluene in the same amounts, respectively. MALDI-TOF-MS results: molecular ion peaks: 493.11. elemental analysis results: theoretical value: c, 65.75; h, 2.86; b, 2.19; f, 23.11; n, 2.84; and O, 3.24. Experimental values: c, 65.77; h, 2.85; b, 2.20; f, 23.10; n, 2.84; and O, 3.23.
Synthetic example 54: synthesis of Compound C54
This example is substantially the same as synthetic example 45, except that: in this example, 1-bromo-2-iodobenzene, methyl 2-aminobenzoate in the first step and 1-bromo-2-iodobenzene in the fourth step were exchanged for 3-bromo-4-iodotrifluorotoluene, methyl 2-amino-5-trifluoromethylbenzoate and 3-bromo-4-iodotrifluorotoluene in the same amounts, respectively. MALDI-TOF-MS results: molecular ion peaks: 561.09. elemental analysis results: theoretical value: c, 59.93; h, 2.33; b, 1.93; f, 30.47; n, 2.50; o, 2.85. Experimental values: c, 59.95; h, 2.34; b, 1.92; f, 30.45; n, 2.51; o, 2.84.
Synthetic example 55: synthesis of Compound C55
This example is substantially the same as synthetic example 45, except that: in this case, the 1-bromo-2-iodobenzene in the fourth step is converted to 2-bromo-3-iodonaphthalene in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 407.15. elemental analysis results: theoretical value: c, 85.52; h, 4.45; b, 2.65; n, 3.44; and O, 3.93. Experimental values: c, 85.53; h, 4.46; b, 2.64; n, 3.44; and O, 3.92.
Synthetic example 56: synthesis of Compound C56
This example is substantially the same as synthetic example 45, except that: in this case, methyl 2-aminobenzoate in the first step and 1-bromo-2-iodobenzene in the fourth step were exchanged for methyl 2-amino-5-trifluoromethylbenzoate and 2-bromo-3-iodonaphthalene, respectively, in equal amounts. MALDI-TOF-MS results: molecular ion peaks: 475.14. elemental analysis results: theoretical value: c, 75.81; h, 3.61; b, 2.27; f, 11.99; n, 2.95; o, 3.37. Experimental values: c, 75.80; h, 3.60; b, 2.28; f, 12.00; n, 2.96; and O, 3.36.
Synthetic example 57: synthesis of Compound C57
This example is substantially the same as synthetic example 45, except that: in this example, 1-bromo-2-iodobenzene, methyl 2-aminobenzoate in the first step and 1-bromo-2-iodobenzene in the fourth step were exchanged for 3-bromo-4-iodotrifluorotoluene, methyl 2-amino-5-trifluoromethylbenzoate and 2-bromo-3-iodonaphthalene, respectively, in equal amounts. MALDI-TOF-MS results: molecular ion peaks: 543.12. elemental analysis results: theoretical value: c, 68.54; h, 2.97; b, 1.99; f, 20.98; n, 2.58; o, 2.94. Experimental values: c, 68.55; h, 2.96; b, 1.97; f, 20.99; n, 2.58; o, 2.95.
Synthetic example 58: synthesis of Compound C58
This example is substantially the same as synthetic example 45, except that: in this case, methyl 2-aminobenzoate in the first step was changed to methyl 3-amino-2-naphthoate in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 407.15. elemental analysis results: theoretical value: c, 85.52; h, 4.45; b, 2.65; n, 3.44; and O, 3.93. Experimental values: c, 85.53; h, 4.45; b, 2.64; n, 3.43; and O, 3.94.
Synthetic example 59: synthesis of Compound C59
This example is substantially the same as synthetic example 45, except that: in this example, methyl 2-aminobenzoate in the first step and 1-bromo-2-iodobenzene in the fourth step were exchanged for methyl 3-amino-2-naphthoate and 3-bromo-4-iodobenzotrifluoride in the same amounts, respectively. MALDI-TOF-MS results: molecular ion peaks: 475.14. elemental analysis results: theoretical value: c, 75.81; h, 3.61; b, 2.27; f, 11.99; n, 2.95; o, 3.37. Experimental values: c, 75.82; h, 3.62; b, 2.26; f, 11.98; n, 2.94; o, 3.37.
Synthesis example 60: synthesis of Compound C60
This example is substantially the same as synthetic example 45, except that: in this example, 1-bromo-2-iodobenzene, methyl 2-aminobenzoate in the first step and 1-bromo-2-iodobenzene in the fourth step were exchanged for 3-bromo-4-iodotrifluorotoluene, methyl 3-amino-2-naphthoate and 3-bromo-4-iodotrifluorotoluene in the same amounts, respectively. MALDI-TOF-MS results: molecular ion peaks: 543.12. elemental analysis results: theoretical value: c, 68.54; h, 2.97; b, 1.99; f, 20.98; n, 2.58; o, 2.94. Experimental values: c, 68.55; h, 2.98; b, 1.98; f, 20.97; n, 2.58; o, 2.93.
Synthetic example 61: synthesis of Compound C61
This example is substantially the same as synthetic example 45, except that: in this example, methyl 2-aminobenzoate in the first step and 1-bromo-2-iodobenzene in the fourth step were exchanged for methyl 3-amino-2-naphthoate and 2-bromo-3-iodonaphthalene, respectively, in equal amounts. MALDI-TOF-MS results: molecular ion peaks: 457.16. elemental analysis results: theoretical value: c, 86.67; h, 4.41; b, 2.36; n, 3.06; and O, 3.50. Experimental values: c, 86.66; h, 4.42; b, 2.35; n, 3.05; and O, 3.51.
Synthesis example 62: synthesis of Compound C62
This example is substantially the same as synthetic example 45, except that: in this example, 1-bromo-2-iodobenzene, methyl 2-aminobenzoate in the first step and 1-bromo-2-iodobenzene in the fourth step were exchanged for 3-bromo-4-iodotrifluorotoluene, methyl 3-amino-2-naphthoate and 2-bromo-3-iodonaphthalene, respectively, in equal amounts. MALDI-TOF-MS results: molecular ion peaks: 525.15. elemental analysis results: theoretical value: c, 77.74; h, 3.65; b, 2.06; f, 10.85; n, 2.67; and O, 3.05. Experimental values: c, 77.75; h, 3.66; b, 2.05; f, 10.84; n, 2.68; and O, 3.05.
Synthetic example 63: synthesis of Compound C63
Figure BDA0002700091560000771
In this synthesis example, compound C63 was synthesized according to scheme two above.
3.68g (16mmol) of methyl 2-amino-3-bromobenzoate, 4.07g (16mmol) of 1-iodonaphthalene, 2.50g (18mmol) of potassium carbonate and 0.38g (6mmol) of activated copper powder were successively charged into a 250mL three-necked flask followed by 100mL of o-dichlorobenzene. The atmosphere in the three-necked flask was replaced with nitrogen, and then the mixture was refluxed and stirred under a closed condition for 48 hours. After the reaction is completed, when the reaction system is cooled to room temperature, the reaction liquid is subjected to vacuum filtration, and a filter cake is washed by a dichloromethane solvent. The solution obtained after filtration was collected and spin-evaporated to remove the solvent. And then carrying out column chromatography separation on the product after spin drying, wherein the used eluent and the mixture ratio are dichloromethane: petroleum ether was 1:4 (volume ratio). Column chromatography gave 4.62g of a white powdery solid in 81% yield.
4.62g (13.0mmol) of the intermediate obtained in the previous step and 2.63g (65mmol) of sodium hydroxide were charged into a 250mL three-necked flask, followed by 120mL of an aqueous ethanol solution having a volume fraction of 50%. The gas in the three-necked flask was replaced with nitrogen, and then the mixture was heated under reflux and stirred under a closed condition for 24 hours. After the hydrolysis reaction is completed, the solvent amount of the reaction system is concentrated to about half, and then concentrated hydrochloric acid is used for acidification, so that a light yellow white solid is separated out. The precipitated solid was suction filtered under reduced pressure and the filter cake was washed with a large amount of deionized water. After washing, the filter cake was recovered and placed in a vacuum oven to dry overnight at 80 ℃. After drying, 3.91g of white powder were obtained, yield 88%.
3.91g (11.4mmol) of the intermediate obtained in the previous step was dissolved in 150mL of ultra-dry dichloromethane and added to a 250mL three-necked flask, followed by 1.2mL (13.7mmol) of oxalyl chloride and one drop of ultra-dry DMF. And (3) carrying out nitrogen replacement on the gas in the three-neck flask, and heating the reaction system to reflux under the conditions of a closed environment and stirring. After refluxing for 0.5h, 1.6mL (13.7mmol) of stannic chloride was added and the reaction was continued under reflux for 4 h. After the reaction is completed, when the reaction system is cooled to room temperature, 1M sodium hydroxide aqueous solution is dropwise added into the reaction solution, and the pH value of the system is adjusted to be neutral. The reaction solution was extracted three times with dichloromethane, and the resulting organic phase was dried over anhydrous sodium sulfate, filtered to remove solid particles, and then subjected to rotary evaporation to remove the organic solvent. And (3) carrying out column chromatography separation on the obtained crude product, wherein the used eluent and the mixture ratio are dichloromethane: petroleum ether is 1:3 (volume ratio). Column chromatography gave 2.62g of a white solid in 71% yield.
2.62g (8.1mmol) of the intermediate obtained in the previous step, 2.55g (9mmol) of 1-bromo-2-iodobenzene, 1.67g (12mmol) of potassium carbonate, and 0.26g (4mmol) of activated copper powder were successively charged into a 250mL three-necked flask, followed by 100mL of o-dichlorobenzene. The atmosphere in the three-necked flask was replaced with nitrogen, and then the mixture was refluxed and stirred under a closed condition for 48 hours. After the reaction is completed, when the reaction system is cooled to room temperature, the reaction liquid is subjected to vacuum filtration, and a filter cake is washed by a dichloromethane solvent. The solution obtained after filtration was collected and spin-evaporated to remove the solvent. And then carrying out column chromatography separation on the product after spin drying, wherein the used eluent and the mixture ratio are dichloromethane: petroleum ether is 1:1 (volume ratio). Column chromatography gave 3.18g of a pale yellowish white powdery solid in 82% yield.
3.18g (6.6mmol) of the intermediate obtained in the previous step, 0.67g (10.8mmol) of ethylene glycol and 0.64g of activated polyaniline sulfate (intermediate 20% in weight) were respectively charged into a 100mL round-bottomed flask, followed by addition of 25mL of toluene. The reaction was refluxed with stirring for 50min, and water produced in the reaction was removed by azeotropy. The progress of the reaction was monitored by TLC method until the starting material disappeared. After the reaction is completed, the catalyst is removed by filtration when the reaction system is cooled to room temperature. The obtained filtrate is washed by deionized water, an organic phase is collected by separating liquid, and after being dried by anhydrous sodium sulfate, solid particles are removed by filtration, and then the organic solvent is removed by rotary evaporation. And (3) carrying out column chromatography separation on the obtained crude product, wherein the used eluent and the mixture ratio are dichloromethane: petroleum ether is 1:3 (volume ratio). Column chromatography gave 3.11g of a pale yellowish white solid in 90% yield.
3.11g (5.9mmol) of the intermediate obtained in the previous step and 0.89g (5.9mmol) of dimethyl phenylboronate were successively charged into a 250mL three-necked flask, followed by addition of 150mL of tetrahydrofuran, and the reaction system was cooled to-78 ℃. 0.48g (8.9mmol) of tert-butyllithium was slowly added to the reaction solution, and the reaction was continued at-78 ℃ for 10min with stirring, then the temperature was raised to-21 ℃ and the reaction was continued for 4h with stirring, finally the temperature was raised to room temperature and the reaction was continued for 18h with stirring. After the reaction reached a predetermined time, 20mL of a saturated ammonium chloride solution was poured into the reaction system to quench the reaction, and the organic phase was collected with a separatory funnel. The separated aqueous phase was extracted three more times with 20mL of diethyl ether, and the organic phases obtained by separation were combined, followed by drying over anhydrous magnesium sulfate, filtration to remove solid particles, and rotary evaporation to remove the organic solvent. And (3) carrying out column chromatography separation on the obtained crude product, wherein the used eluent and the mixture ratio are that ethyl acetate: n-hexane was 1:100 (volume ratio). Column chromatography gave 1.70g of a white powdery solid in 64% yield.
1.70g (3.8mmol) of the intermediate obtained in the previous step was charged into a 100mL round-bottom flask, followed by 20mL of anhydrous hexane. Under stirring, 1.88g (11.4mmol) of chloral hydrate was added to the system, followed by reaction for 2 h. After the reaction is completed, when the reaction system is cooled to room temperature, 20mL of deionized water is added into the system, and the organic phase is collected by liquid separation. Washing the obtained organic phase with brine, drying with anhydrous magnesium sulfate, filtering to remove solid particles, performing rotary evaporation to remove an organic solvent, and performing column chromatography separation on the obtained crude product, wherein the eluent and the mixture ratio are that ethyl acetate: n-hexane was 1:100 (volume ratio). The white powdery solid obtained by column chromatography separation and recrystallization was 1.36g, with a yield of 88%. MALDI-TOF-MS results: molecular ion peaks: 407.15. elemental analysis results: theoretical value: c, 85.52; h, 4.45; b, 2.65; n, 3.44; and O, 3.93. Experimental values: c, 85.50; h, 4.44; b, 2.67; n, 3.43; and O, 3.95.
Synthetic example 64: synthesis of Compound C64
This example is substantially the same as synthetic example 63 except that: in this case, the 1-bromo-2-iodobenzene in the fourth step is converted to 3-bromo-4-iodotrifluorotoluene in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 475.14. elemental analysis results: theoretical value: c, 75.81; h, 3.61; b, 2.27; f, 11.99; n, 2.95; o, 3.37. Experimental values: c, 75.80; h, 3.62; b, 2.26; f, 11.98; n, 2.96; and O, 3.38.
Synthetic example 65: synthesis of Compound C65
This example is substantially the same as synthetic example 63 except that: in this case, the 1-bromo-2-iodobenzene in the first step and the 1-bromo-2-iodobenzene in the fourth step were exchanged to 3-bromo-4-iodotrifluorotoluene and 3-bromo-4-iodotrifluorotoluene, respectively, in equal amounts. MALDI-TOF-MS results: molecular ion peaks: 543.12. elemental analysis results: theoretical value: c, 68.54; h, 2.97; b, 1.99; f, 20.98; n, 2.58; o, 2.94. Experimental values: c, 68.53; h, 2.96; b, 2.00; f, 20.99; n, 2.57; o, 2.94.
Synthetic example 66: synthesis of Compound C66
This example is substantially the same as synthetic example 45, except that: in this case, methyl 2-aminobenzoate in the first step was exchanged for an equivalent amount of methyl 3-amino-2-phenanthrenecarboxylate. MALDI-TOF-MS results: molecular ion peaks: 457.16. elemental analysis results: theoretical value: c, 86.67; h, 4.41; b, 2.36; n, 3.06; and O, 3.50. Experimental values: c, 86.68; h, 4.42; b, 2.35; n, 3.06; and O, 3.49.
Synthetic example 67: synthesis of Compound C67
This example is substantially the same as synthetic example 45, except that: in this case, methyl 2-aminobenzoate in the first step and 1-bromo-2-iodobenzene in the fourth step were exchanged for methyl 3-amino-2-phenanthrenecarboxylate and 3-bromo-4-iodobenzotrifluoride in equal amounts, respectively. MALDI-TOF-MS results: molecular ion peaks: 475.14. elemental analysis results: theoretical value: c, 75.81; h, 3.61; b, 2.27; f, 11.99; n, 2.95; o, 3.37. Experimental values: c, 75.82; h, 3.62; b, 2.26; f, 11.98; n, 2.94; o, 3.37.
Synthetic example 68: synthesis of Compound C68
This example is substantially the same as synthetic example 45, except that: in this example, 1-bromo-2-iodobenzene, methyl 2-aminobenzoate in the first step and 1-bromo-2-iodobenzene in the fourth step were exchanged for 3-bromo-4-iodotrifluorotoluene, methyl 3-amino-2-phenanthrenecarboxylate and 3-bromo-4-iodotrifluorotoluene, respectively, in equal amounts. MALDI-TOF-MS results: molecular ion peaks: 593.14. elemental analysis results: theoretical value: c, 70.85; h, 3.06; b, 1.82; f, 19.21; n, 2.36; o, 2.70. Experimental values: c, 70.83; h, 3.05; b, 1.83; f, 19.22; n, 2.36; o, 2.71.
Synthetic example 69: synthesis of Compound C69
This example is substantially the same as synthetic example 45, except that: in this case, methyl 2-aminobenzoate in the first step was changed to methyl 3-amino-2-triphenylbenzoate in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 507.18. elemental analysis results: theoretical value: c, 87.59; h, 4.37; b, 2.13; n, 2.76; and O, 3.15. Experimental values: c, 87.58; h, 4.39; b, 2.12; n, 2.75; and O, 3.16.
Synthesis example 70: synthesis of Compound C70
This example is substantially the same as synthetic example 45, except that: in this example, methyl 2-aminobenzoate in the first step and 1-bromo-2-iodobenzene in the fourth step were exchanged for methyl 3-amino-2-triphenylbenzoate and 3-bromo-4-iodotrifluorotoluene in the same amounts, respectively. MALDI-TOF-MS results: molecular ion peaks: 575.17. elemental analysis results: theoretical value: c, 79.32; h, 3.68; b, 1.88; f, 9.91; n, 2.43; o, 2.78. Experimental values: c, 79.31; h, 3.67; b, 1.89; f, 9.92; n, 2.43; o, 2.77.
Synthesis example 71: synthesis of Compound C71
This example is substantially the same as synthetic example 45, except that: in this example, 1-bromo-2-iodobenzene, methyl 2-aminobenzoate in the first step and 1-bromo-2-iodobenzene in the fourth step were exchanged for 3-bromo-4-iodotrifluorotoluene, methyl 3-amino-2-triphenylate and 3-bromo-4-iodotrifluorotoluene in the same amounts, respectively. MALDI-TOF-MS results: molecular ion peaks: 643.15. elemental analysis results: theoretical value: c, 72.81; h, 3.13; b, 1.68; f, 17.72; n, 2.18; o, 2.49. Experimental values: c, 72.80; h, 3.12; b, 1.69; f, 17.73; n, 2.19; o, 2.49.
Synthetic example 72: synthesis of Compound C72
This example is substantially the same as synthetic example 63 except that: in this example, 1-iodonaphthalene in the first step is changed to 1-iodopyrene in an amount equivalent to that of the substance. MALDI-TOF-MS results: molecular ion peaks: 483.18. elemental analysis results: theoretical value: c, 86.97; h, 4.59; b, 2.24; n, 2.90; and O, 3.31. Experimental values: c, 86.96; h, 4.60; b, 2.22; n, 2.91; and O, 3.32.
Synthetic example 73: synthesis of Compound C73
This example is substantially the same as synthetic example 63 except that: in this example, 1-iodonaphthalene in the first step and 1-bromo-2-iodobenzene in the fourth step were exchanged for 1-iodopyrene and 3-bromo-4-iodobenzotrifluoride in equal amounts, respectively. MALDI-TOF-MS results: molecular ion peaks: 551.17. elemental analysis results: theoretical value: c, 78.42; h, 3.84; b, 1.96; f, 10.34; n, 2.54; o, 2.90. Experimental values: c, 78.44; h, 3.83; b, 1.95; f, 10.35; n, 2.54; and O, 2.89.
Synthetic example 74: synthesis of Compound C74
This example is substantially the same as synthetic example 63 except that: in this example, the 1-bromo-2-iodobenzene, 1-iodonaphthalene in the first step and the 1-bromo-2-iodobenzene in the fourth step were exchanged to 3-bromo-4-iodotrifluorotoluene, 1-iodopyrene and 3-bromo-4-iodotrifluorotoluene in equal amounts, respectively. MALDI-TOF-MS results: molecular ion peaks: 619.15. elemental analysis results: theoretical value: c, 71.75; h, 3.25; b, 1.75; f, 18.40; n, 2.26; o, 2.58. Experimental values: c, 71.73; h, 3.26; b, 1.74; f, 18.41; n, 2.26; o, 2.59.
Synthetic example 75: synthesis of Compound C75
This example is substantially the same as synthetic example 45, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 399.18. elemental analysis results: theoretical value: c, 84.22; h, 5.55; b, 2.71; n, 3.51; and O, 4.01. Experimental values: c, 84.23; h, 5.56; b, 2.70; n, 3.51; and O, 4.00.
Synthetic example 76: synthesis of Compound C76
This example is substantially the same as synthetic example 46 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 566.25. elemental analysis results: theoretical value: c, 84.81; h, 5.52; b, 1.91; n, 4.95; o, 2.82. Experimental values: c, 84.80; h, 5.53; b, 1.90; n, 4.94; o, 2.84.
Synthetic example 77: synthesis of Compound C77
This example is substantially the same as synthetic example 47 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 642.28. elemental analysis results: theoretical value: c, 85.98; h, 5.49; b, 1.68; n, 4.36; o, 2.49. Experimental values: c, 85.99; h, 5.48; b, 1.67; n, 4.36; o, 2.50.
Synthesis example 78: synthesis of Compound C78
This example is substantially the same as synthetic example 48, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 682.32. elemental analysis results: theoretical value: c, 86.21; h, 5.76; b, 1.58; n, 4.10; o, 2.34. Experimental values: c, 86.20; h, 5.77; b, 1.57; n, 4.12; o, 2.34.
Synthetic example 79: synthesis of Compound C79
This example is substantially the same as synthetic example 49 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 656.26. elemental analysis results: theoretical value: c, 84.15; h, 5.07; b, 1.65; n, 4.27; and O, 4.87. Experimental values: c, 84.17; h, 5.06; b, 1.64; n, 4.26; and O, 4.87.
Synthetic example 80: synthesis of Compound C80
This example is substantially the same as synthetic example 50, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 467.17. elemental analysis results: theoretical value: c, 74.54; h, 4.53; b, 2.31; f, 12.20; n, 3.00; and O, 3.42. Experimental values: c, 74.53; h, 4.52; b, 2.33; f, 12.21; n, 3.00; o, 3.41.
Synthetic example 81: synthesis of Compound C81
This example is substantially the same as synthetic example 51, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 467.17. elemental analysis results: theoretical value: c, 74.54; h, 4.53; b, 2.31; f, 12.20; n, 3.00; and O, 3.42. Experimental values: c, 74.55; h, 4.54; b, 2.30; f, 12.19; n, 2.99; and O, 3.42.
Synthetic example 82: synthesis of Compound C82
This example is substantially the same as synthetic example 52 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 467.17. elemental analysis results: theoretical value: c, 74.54; h, 4.53; b, 2.31; f, 12.20; n, 3.00; and O, 3.42. Experimental values: c, 74.54; h, 4.55; b, 2.30; f, 12.21; n, 3.00; o, 3.41.
Synthetic example 83: synthesis of Compound C83
This example is substantially the same as synthetic example 53 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 535.15. elemental analysis results: theoretical value: c, 67.31; h, 3.77; b, 2.02; f, 21.29; n, 2.62; and O, 2.99. Experimental values: c, 67.30; h, 3.76; b, 2.04; f, 21.30; n, 2.61; and O, 2.99.
Synthesis example 84: synthesis of Compound C84
This example is substantially the same as synthetic example 54 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 603.14. elemental analysis results: theoretical value: c, 61.72; h, 3.17; b, 1.79; f, 28.34; n, 2.32; o, 2.65. Experimental values: c, 61.74; h, 3.16; b, 1.79; f, 28.33; n, 2.33; o, 2.64.
Synthetic example 85: synthesis of Compound C85
This example is substantially the same as synthesis example 55, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 449.20. elemental analysis results: theoretical value: c, 85.53; h, 5.38; b, 2.41; n, 3.12; and O, 3.56. Experimental values: c, 85.52; h, 5.39; b, 2.40; n, 3.13; and O, 3.55.
Synthetic example 86: synthesis of Compound C86
This example is substantially the same as synthetic example 56 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 517.18. elemental analysis results: theoretical value: c, 76.61; h, 4.48; b, 2.09; f, 11.02; n, 2.71; and O, 3.09. Experimental values: c, 76.60; h, 4.49; b, 2.10; f, 11.03; n, 2.70; and O, 3.09.
Synthesis example 87: synthesis of Compound C87
This example is substantially the same as synthetic example 57 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 585.17. elemental analysis results: theoretical value: c, 69.77; h, 3.79; b, 1.85; f, 19.47; n, 2.39; o, 2.73. Experimental values: c, 69.76; h, 3.78; b, 1.87; f, 19.48; n, 2.38; o, 2.73.
Synthetic example 88: synthesis of Compound C88
This example is substantially the same as synthetic example 58, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 449.20. elemental analysis results: theoretical value: c, 85.53; h, 5.38; b, 2.41; n, 3.12; and O, 3.56. Experimental values: c, 85.52; h, 5.39; b, 2.40; n, 3.12; and O, 3.55.
Synthetic example 89: synthesis of Compound C89
This example is substantially the same as synthetic example 59, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 517.18. elemental analysis results: theoretical value: c, 76.61; h, 4.48; b, 2.09; f, 11.02; n, 2.71; and O, 3.09. Experimental values: c, 76.62; h, 4.49; b, 2.08; f, 11.02; n, 2.70; and O, 3.10.
Synthetic example 90: synthesis of Compound C90
This example is substantially the same as synthetic example 60 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 585.17. elemental analysis results: theoretical value: c, 69.77; h, 3.79; b, 1.85; f, 19.47; n, 2.39; o, 2.73. Experimental values: c, 69.78; h, 3.77; b, 1.86; f, 19.46; n, 2.39; o, 2.74.
Synthetic example 91: synthesis of Compound C91
This example is substantially the same as synthetic example 61 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 499.21. elemental analysis results: theoretical value: c, 86.58; h, 5.25; b, 2.16; n, 2.80; and O, 3.20. Experimental values: c, 86.59; h, 5.26; b, 2.15; n, 2.79; and O, 3.21.
Synthetic example 92: synthesis of Compound C92
This example is substantially the same as synthetic example 62 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 567.20. elemental analysis results: theoretical value: c, 78.32; h, 4.44; b, 1.91; f, 10.04; n, 2.47; o, 2.82. Experimental values: c, 78.34; h, 4.43; b, 1.90; f, 10.05; n, 2.47; o, 2.83.
Synthetic example 93: synthesis of Compound C93
This example is substantially the same as synthetic example 63 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 449.20. elemental analysis results: theoretical value: c, 85.53; h, 5.38; b, 2.41; n, 3.12; and O, 3.56. Experimental values: c, 85.55; h, 5.37; b, 2.42; n, 3.11; and O, 3.55.
Synthetic example 94: synthesis of Compound C94
This example is substantially the same as synthetic example 64, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 517.18. elemental analysis results: theoretical value: c, 76.61; h, 4.48; b, 2.09; f, 11.02; n, 2.71; and O, 3.09. Experimental values: c, 76.62; h, 4.49; b, 2.08; f, 11.02; n, 2.70; and O, 3.10.
Synthetic example 95: synthesis of Compound C95
This example is substantially the same as synthetic example 65 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 585.17. elemental analysis results: theoretical value: c, 69.77; h, 3.79; b, 1.85; f, 19.47; n, 2.39; o, 2.73. Experimental values: c, 69.78; h, 3.80; b, 1.84; f, 19.46; n, 2.40; o, 2.72.
Synthetic example 96: synthesis of Compound C96
This example is substantially the same as synthetic example 66, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 499.21. elemental analysis results: theoretical value: c, 86.58; h, 5.25; b, 2.16; n, 2.80; and O, 3.20. Experimental values: c, 86.59; h, 5.24; b, 2.15; n, 2.79; and O, 3.21.
Synthetic example 97: synthesis of Compound C97
This example is substantially the same as synthetic example 67, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 567.20. elemental analysis results: theoretical value: c, 78.32; h, 4.44; b, 1.91; f, 10.04; n, 2.47; o, 2.82. Experimental values: c, 78.33; h, 4.45; b, 1.90; f, 10.03; n, 2.47; o, 2.81.
Synthetic example 98: synthesis of Compound C98
This example is substantially the same as synthetic example 68 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 635.19. elemental analysis results: theoretical value: c, 71.83; h, 3.81; b, 1.70; f, 17.94; n, 2.20; o, 2.52. Experimental values: c, 71.85; h, 3.80; b, 1.71; f, 17.93; n, 2.20; o, 2.51.
Synthetic example 99: synthesis of Compound C99
This example is substantially the same as synthetic example 69 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 549.23. elemental analysis results: theoretical value: c, 87.44; h, 5.14; b, 1.97; n, 2.55; o, 2.91. Experimental values: c, 87.42; h, 5.15; b, 1.97; n, 2.56; o, 2.92.
Synthesis example 100: synthesis of Compound C100
This example is substantially the same as synthetic example 70, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 617.21. elemental analysis results: theoretical value: c, 79.75; h, 4.41; b, 1.75; f, 9.23; n, 2.27; o, 2.59. Experimental values: c, 79.74; h, 4.40; b, 1.76; f, 9.23; n, 2.28; o, 2.60.
Synthetic example 101: synthesis of Compound C101
This example is substantially the same as Synthesis example 71 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 685.20. elemental analysis results: theoretical value: c, 73.59; h, 3.82; b, 1.58; f, 16.63; n, 2.04; o, 2.33. Experimental values: c, 73.58; h, 3.81; b, 1.59; f, 16.63; n, 2.05; o, 2.33.
Synthesis example 102: synthesis of Compound C102
This example is substantially the same as synthetic example 72 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 525.23. elemental analysis results: theoretical value: c, 86.86; h, 5.37; b, 2.06; n, 2.67; and O, 3.04. Experimental values: c, 86.87; h, 5.38; b, 2.05; n, 2.67; and O, 3.03.
Synthetic example 103: synthesis of Compound C103
This example is substantially the same as synthetic example 73 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 593.21. elemental analysis results: theoretical value: c, 78.93; h, 4.59; b, 1.82; f, 9.60; n, 2.36; o, 2.70. Experimental values: c, 78.91; h, 4.60; b, 1.81; f, 9.61; n, 2.36; o, 2.71.
Synthesis example 104: synthesis of Compound C104
This example is substantially the same as Synthesis example 74, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 661.20. elemental analysis results: theoretical value: c, 72.63; h, 3.96; b, 1.63; f, 17.23; n, 2.12; o, 2.42. Experimental values: c, 72.62; h, 3.98; b, 1.64; f, 17.22; n, 2.12; o, 2.41.
Synthetic example 105: synthesis of Compound C105
This example is substantially the same as synthetic example 45, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 483.27. elemental analysis results: theoretical value: c, 84.47; h, 7.09; b, 2.24; n, 2.90; and O, 3.31. Experimental values: c, 84.49; h, 7.08; b, 2.24; n, 2.89; and O, 3.32.
Synthesis example 106: synthesis of Compound C106
This example is substantially the same as synthetic example 46 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 650.35. elemental analysis results: theoretical value: c, 84.91; h, 6.66; b, 1.66; n, 4.31; o, 2.46. Experimental values: c, 84.92; h, 6.67; b, 1.65; n, 4.31; o, 2.45.
Synthetic example 107: synthesis of Compound C107
This example is substantially the same as synthetic example 47 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 726.38. elemental analysis results: theoretical value: c, 85.94; h, 6.52; b, 1.49; n, 3.85; o, 2.20. Experimental values: c, 85.95; h, 6.51; b, 1.48; n, 3.84; o, 2.22.
Synthetic example 108: synthesis of Compound C108
This example is substantially the same as synthetic example 48, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 766.41. elemental analysis results: theoretical value: c, 86.15; h, 6.70; b, 1.41; n, 3.65; and O, 2.09. Experimental values: c, 86.14; h, 6.71; b, 1.42; n, 3.66; and O, 2.08.
Synthetic example 109: synthesis of Compound C109
This example is substantially the same as synthetic example 49 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 740.36. elemental analysis results: theoretical value: c, 84.32; h, 6.12; b, 1.46; n, 3.78; and O, 4.32. Experimental values: c, 84.33; h, 6.13; b, 1.46; n, 3.77; o, 4.31.
Synthesis example 110: synthesis of Compound C110
This example is substantially the same as synthetic example 50, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 551.26. elemental analysis results: theoretical value: c, 76.23; h, 6.03; b, 1.96; f, 10.34; n, 2.54; o, 2.90. Experimental values: c, 76.24; h, 6.04; b, 1.95; f, 10.34; n, 2.55; and O, 2.89.
Synthetic example 111: synthesis of Compound C111
This example is substantially the same as synthetic example 51, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 551.26. elemental analysis results: theoretical value: c, 76.23; h, 6.03; b, 1.96; f, 10.34; n, 2.54; o, 2.90. Experimental values: c, 76.25; h, 6.02; b, 1.95; f, 10.35; n, 2.53; o, 2.90.
Synthesis example 112: synthesis of Compound C112
This example is substantially the same as synthetic example 52 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 551.26. elemental analysis results: theoretical value: c, 76.23; h, 6.03; b, 1.96; f, 10.34; n, 2.54; o, 2.90. Experimental values: c, 76.23; h, 6.05; b, 1.97; f, 10.34; n, 2.53; and O, 2.89.
Synthetic example 113: synthesis of Compound C113
This example is substantially the same as synthetic example 53 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 619.25. elemental analysis results: theoretical value: c, 69.80; h, 5.21; b, 1.75; f, 18.40; n, 2.26; o, 2.58. Experimental values: c, 69.81; h, 5.22; b, 1.74; f, 18.40; n, 2.25; o, 2.59.
Synthesis example 114: synthesis of Compound C114
This example is substantially the same as synthetic example 54 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 687.24. elemental analysis results: theoretical value: c, 64.65; h, 4.55; b, 1.57; f, 24.87; n, 2.04; o, 2.33. Experimental values: c, 64.66; h, 4.56; b, 1.55; f, 24.88; n, 2.04; o, 2.32.
Synthetic example 115: synthesis of Compound C115
This example is substantially the same as synthesis example 55, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 533.29. elemental analysis results: theoretical value: c, 85.55; h, 6.80; b, 2.03; n, 2.63; and O, 3.00. Experimental values: c, 85.57; h, 6.79; b, 2.04; n, 2.61; and O, 3.00.
Synthetic example 116: synthesis of Compound C116
This example is substantially the same as synthetic example 56 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 601.28. elemental analysis results: theoretical value: c, 77.87; h, 5.87; b, 1.80; f, 9.48; n, 2.33; o, 2.66. Experimental values: c, 77.86; h, 5.86; b, 1.81; f, 9.49; n, 2.35; o, 2.65.
Synthesis example 117: synthesis of Compound C117
This example is substantially the same as synthetic example 57 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 669.26. elemental analysis results: theoretical value: c, 71.76; h, 5.12; b, 1.61; f, 17.03; n, 2.09; o, 2.39. Experimental values: c, 71.75; h, 5.11; b, 1.62; f, 17.02; n, 2.10; o, 2.40.
Synthetic example 118: synthesis of Compound C118
This example is substantially the same as synthetic example 58, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 533.29. elemental analysis results: theoretical value: c, 85.55; h, 6.80; b, 2.03; n, 2.63; and O, 3.00. Experimental values: c, 85.54; h, 6.79; b, 2.05; n, 2.62; and O, 3.01.
Synthetic example 119: synthesis of Compound C119
This example is substantially the same as synthetic example 59, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 601.28. elemental analysis results: theoretical value: c, 77.87; h, 5.87; b, 1.80; f, 9.48; n, 2.33; o, 2.66. Experimental values: c, 77.85; h, 5.88; b, 1.80; f, 9.49; n, 2.32; o, 2.65.
Synthetic example 120: synthesis of Compound C120
This example is substantially the same as synthetic example 60 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 669.26. elemental analysis results: theoretical value: c, 71.76; h, 5.12; b, 1.61; f, 17.03; n, 2.09; o, 2.39. Experimental values: c, 71.75; h, 5.13; b, 1.60; f, 17.04; n, 2.08; o, 2.39.
Synthesis example 121: synthesis of Compound C121
This example is substantially the same as synthetic example 61 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 583.30. elemental analysis results: theoretical value: c, 86.44; h, 6.56; b, 1.85; n, 2.40; o, 2.74. Experimental values: c, 86.45; h, 6.54; b, 1.85; n, 2.41; o, 2.73.
Synthesis example 122: synthesis of Compound C122
This example is substantially the same as synthetic example 62 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 651.29. elemental analysis results: theoretical value: c, 79.26; h, 5.72; b, 1.66; f, 8.75; n, 2.15; o, 2.46. Experimental values: c, 79.25; h, 5.71; b, 1.68; f, 8.76; n, 2.15; o, 2.45.
Synthetic example 123: synthesis of Compound C123
This example is substantially the same as synthetic example 63 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 533.29. elemental analysis results: theoretical value: c, 85.55; h, 6.80; b, 2.03; n, 2.63; and O, 3.00. Experimental values: c, 85.56; h, 6.81; b, 2.02; n, 2.63; and O, 2.99.
Synthetic example 124: synthesis of Compound C124
This example is substantially the same as synthetic example 64, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 601.28. elemental analysis results: theoretical value: c, 77.87; h, 5.87; b, 1.80; f, 9.48; n, 2.33; o, 2.66. Experimental values: c, 77.85; h, 5.86; b, 1.82; f, 9.49; n, 2.33; o, 2.65.
Synthetic example 125: synthesis of Compound C125
This example is substantially the same as synthetic example 65 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 669.26. elemental analysis results: theoretical value: c, 71.76; h, 5.12; b, 1.61; f, 17.03; n, 2.09; o, 2.39. Experimental values: c, 71.78; h, 5.11; b, 1.62; f, 17.02; n, 2.10; o, 2.40.
Synthetic example 126: synthesis of Compound C126
This example is substantially the same as synthetic example 66, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 583.30. elemental analysis results: theoretical value: c, 86.44; h, 6.56; b, 1.85; n, 2.40; o, 2.74. Experimental values: c, 86.46; h, 6.55; b, 1.86; n, 2.39; o, 2.73.
Synthetic example 127: synthesis of Compound C127
This example is substantially the same as synthetic example 67, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 651.29. elemental analysis results: theoretical value: c, 79.26; h, 5.72; b, 1.66; f, 8.75; n, 2.15; o, 2.46. Experimental values: c, 79.28; h, 5.71; b, 1.67; f, 8.74; n, 2.15; o, 2.45.
Synthetic example 128: synthesis of Compound C128
This example is substantially the same as synthetic example 68 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 719.28. elemental analysis results: theoretical value: c, 73.44; h, 5.04; b, 1.50; f, 15.84; n, 1.95; o, 2.22. Experimental values: c, 73.45; h, 5.03; b, 1.51; f, 15.84; n, 1.96; o, 2.23.
Synthesis example 129: synthesis of Compound C129
This example is substantially the same as synthetic example 69 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 633.32. elemental analysis results: theoretical value: c, 87.20; h, 6.36; b, 1.71; n, 2.21; o, 2.52. Experimental values: c, 87.22; h, 6.35; b, 1.72; n, 2.20; o, 2.51.
Synthesis example 130: synthesis of Compound C130
This example is substantially the same as synthetic example 70, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 701.31. elemental analysis results: theoretical value: c, 80.46; h, 5.60; b, 1.54; f, 8.12; n, 2.00; o, 2.28. Experimental values: c, 80.47; h, 5.61; b, 1.53; f, 8.13; n, 2.00; o, 2.26.
Synthesis example 131: synthesis of Compound C131
This example is substantially the same as Synthesis example 71 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 769.30. elemental analysis results: theoretical value: c, 74.91; h, 4.98; b, 1.40; f, 14.81; n, 1.82; and O, 2.08. Experimental values: c, 74.92; h, 4.99; b, 1.39; f, 14.81; n, 1.81; and O, 2.09.
Synthetic example 132: synthesis of Compound C132
This example is substantially the same as synthetic example 72 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 609.32. elemental analysis results: theoretical value: c, 86.69; h, 6.61; b, 1.77; n, 2.30; o, 2.62. Experimental values: c, 86.68; h, 6.60; b, 1.78; n, 2.30; o, 2.63.
Synthetic example 133: synthesis of Compound C133
This example is substantially the same as synthetic example 73 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 677.31. elemental analysis results: theoretical value: c, 79.76; h, 5.80; b, 1.60; f, 8.41; n, 2.07; o, 2.36. Experimental values: c, 79.78; h, 5.79; b, 1.60; f, 8.40; n, 2.06; o, 2.35.
Synthetic example 134: synthesis of Compound C134
This example is substantially the same as Synthesis example 74, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 745.30. elemental analysis results: theoretical value: c, 74.10; h, 5.14; b, 1.45; f, 15.29; n, 1.88; o, 2.15. Experimental values: c, 74.12; h, 5.13; b, 1.46; f, 15.28; n, 1.87; o, 2.15.
Synthesis example 135: synthesis of Compound C135
This example is substantially the same as synthetic example 45, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 561.09. elemental analysis results: theoretical value: c, 59.93; h, 2.33; b, 1.93; f, 30.47; n, 2.50; o, 2.85. Experimental values: c, 59.92; h, 2.32; b, 1.94; f, 30.47; n, 2.51; o, 2.86.
Synthetic example 136: synthesis of Compound C136
This example is substantially the same as synthetic example 46 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 728.17. elemental analysis results: theoretical value: c, 65.96; h, 3.04; b, 1.48; f, 23.47; n, 3.85; o, 2.20. Experimental values: c, 65.98; h, 3.03; b, 1.49; f, 23.46; n, 3.85; o, 2.19.
Synthesis example 137: synthesis of Compound C137
This example is substantially the same as synthetic example 47 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 804.20. elemental analysis results: theoretical value: c, 68.68; h, 3.26; b, 1.34; f, 21.25; n, 3.48; o, 1.99. Experimental values: c, 68.69; h, 3.25; b, 1.35; f, 21.24; n, 3.49; o, 1.99.
Synthetic example 138: synthesis of Compound C138
This example is substantially the same as synthetic example 48, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 561.09. elemental analysis results: theoretical value: c, 59.93; h, 2.33; b, 1.93; f, 30.47; n, 2.50; o, 2.85. Experimental values: c, 59.92; h, 2.32; b, 1.94; f, 30.47; n, 2.51; o, 2.86.
Synthetic example 139: synthesis of Compound C139
This example is substantially the same as synthetic example 49 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 844.23. elemental analysis results: theoretical value: c, 69.68; h, 3.58; b, 1.28; f, 20.24; n, 3.32; o, 1.89. Experimental values: c, 69.66; h, 3.59; b, 1.28; f, 20.25; n, 3.33; o, 1.88.
Synthesis example 140: synthesis of Compound C140
This example is substantially the same as synthetic example 50, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 629.08. elemental analysis results: theoretical value: c, 55.36; h, 1.92; b, 1.72; f, 36.23; n, 2.23; o, 2.54. Experimental values: c, 55.35; h, 1.93; b, 1.73; f, 36.22; n, 2.25; o, 2.55.
Synthesis example 141: synthesis of Compound C141
This example is substantially the same as synthetic example 51, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 629.08. elemental analysis results: theoretical value: c, 55.36; h, 1.92; b, 1.72; f, 36.23; n, 2.23; o, 2.54. Experimental values: c, 55.37; h, 1.93; b, 1.71; f, 36.23; n, 2.24; o, 2.53.
Synthesis example 142: synthesis of Compound C142
This example is substantially the same as synthetic example 52 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 629.08. elemental analysis results: theoretical value: c, 55.36; h, 1.92; b, 1.72; f, 36.23; n, 2.23; o, 2.54. Experimental values: c, 55.36; h, 1.91; b, 1.71; f, 36.23; n, 2.24; o, 2.55.
Synthesis example 143: synthesis of Compound C143
This example is substantially the same as synthetic example 53 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 697.07. elemental analysis results: theoretical value: c, 51.68; h, 1.59; b, 1.55; f, 40.87; n, 2.01; o, 2.29. Experimental values: c, 51.69; h, 1.58; b, 1.56; f, 40.88; n, 2.01; o, 2.30.
Synthesis example 144: synthesis of Compound C144
This example is substantially the same as synthetic example 54 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 765.06. elemental analysis results: theoretical value: c, 48.66; h, 1.32; b, 1.41; f, 44.69; n, 1.83; and O, 2.09. Experimental values: c, 48.68; h, 1.33; b, 1.40; f, 44.68; n, 1.82; and O, 2.09.
Synthetic example 145: synthesis of Compound C145
This example is substantially the same as synthesis example 55, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 611.11. elemental analysis results: theoretical value: c, 62.88; h, 2.47; b, 1.77; f, 27.97; n, 2.29; o, 2.62. Experimental values: c, 62.89; h, 2.46; b, 1.78; f, 27.98; n, 2.28; o, 2.62.
Synthetic example 146: synthesis of Compound C146
This example is substantially the same as synthetic example 56 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 679.10. elemental analysis results: theoretical value: c, 58.35; h, 2.08; b, 1.59; f, 33.56; n, 2.06; o, 2.36. Experimental values: c, 58.36; h, 2.07; b, 1.58; f, 33.57; n, 2.05; o, 2.37.
Synthetic example 147: synthesis of Compound C147
This example is substantially the same as synthetic example 57 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 747.09. elemental analysis results: theoretical value: c, 54.65; h, 1.75; b, 1.45; f, 38.14; n, 1.87; o, 2.14. Experimental values: c, 54.65; h, 1.76; b, 1.45; f, 38.15; n, 1.86; o, 2.13.
Synthetic example 148: synthesis of Compound C148
This example is substantially the same as synthetic example 58, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 611.11. elemental analysis results: theoretical value: c, 62.88; h, 2.47; b, 1.77; f, 27.97; n, 2.29; o, 2.62. Experimental values: c, 62.86; h, 2.46; b, 1.77; f, 27.98; n, 2.30; o, 2.63.
Synthetic example 149: synthesis of Compound C149
This example is substantially the same as synthetic example 59, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 679.10. elemental analysis results: theoretical value: c, 58.35; h, 2.08; b, 1.59; f, 33.56; n, 2.06; o, 2.36. Experimental values: c, 58.36; h, 2.06; b, 1.58; f, 33.57; n, 2.06; o, 2.37.
Synthesis example 150: synthesis of Compound C150
This example is substantially the same as synthetic example 60 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 747.09. elemental analysis results: theoretical value: c, 54.65; h, 1.75; b, 1.45; f, 38.14; n, 1.87; o, 2.14. Experimental values: c, 54.64; h, 1.74; b, 1.46; f, 38.14; n, 1.88; o, 2.15.
Synthesis example 151: synthesis of Compound C151
This example is substantially the same as synthetic example 61 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 661.13. elemental analysis results: theoretical value: c, 65.38; h, 2.59; b, 1.63; f, 25.85; n, 2.12; o, 2.42. Experimental values: c, 65.36; h, 2.60; b, 1.62; f, 25.86; n, 2.13; o, 2.43.
Synthesis example 152: synthesis of Compound C152
This example is substantially the same as synthetic example 62 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 729.11. elemental analysis results: theoretical value: c, 60.93; h, 2.21; b, 1.48; f, 31.26; n, 1.92; o, 2.19. Experimental values: c, 60.92; h, 2.23; b, 1.48; f, 31.27; n, 1.91; o, 2.18.
Synthesis example 153: synthesis of Compound C153
This example is substantially the same as synthetic example 63 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 611.11. elemental analysis results: theoretical value: c, 62.88; h, 2.47; b, 1.77; f, 27.97; n, 2.29; o, 2.62. Experimental values: c, 62.89; h, 2.45; b, 1.78; f, 27.96; n, 2.28; o, 2.63.
Synthesis example 154: synthesis of Compound C154
This example is substantially the same as synthetic example 64, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 679.10. elemental analysis results: theoretical value: c, 58.35; h, 2.08; b, 1.59; f, 33.56; n, 2.06; o, 2.36. Experimental values: c, 58.36; h, 2.09; b, 1.58; f, 33.56; n, 2.07; o, 2.35.
Synthetic example 155: synthesis of Compound C155
This example is substantially the same as synthetic example 65 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 747.09. elemental analysis results: theoretical value: c, 54.65; h, 1.75; b, 1.45; f, 38.14; n, 1.87; o, 2.14. Experimental values: c, 54.64; h, 1.74; b, 1.46; f, 38.14; n, 1.88; o, 2.15.
Synthetic example 156: synthesis of Compound C156
This example is substantially the same as synthetic example 66, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 661.13. elemental analysis results: theoretical value: c, 65.38; h, 2.59; b, 1.63; f, 25.85; n, 2.12; o, 2.42. Experimental values: c, 65.37; h, 2.60; b, 1.62; f, 25.84; n, 2.12; o, 2.43.
Synthetic example 157: synthesis of Compound C157
This example is substantially the same as synthetic example 67, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 729.11. elemental analysis results: theoretical value: c, 60.93; h, 2.21; b, 1.48; f, 31.26; n, 1.92; o, 2.19. Experimental values: c, 60.95; h, 2.20; b, 1.49; f, 31.26; n, 1.91; o, 2.18.
Synthetic example 158: synthesis of Compound C158
This example is substantially the same as synthetic example 68 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 797.10. elemental analysis results: theoretical value: c, 57.24; h, 1.90; b, 1.36; f, 35.74; n, 1.76; and O, 2.01. Experimental values: c, 57.25; h, 1.91; b, 1.35; f, 35.74; n, 1.75; and O, 2.01.
Synthetic example 159: synthesis of Compound C159
This example is substantially the same as synthetic example 69 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 711.14. elemental analysis results: theoretical value: c, 67.54; h, 2.69; b, 1.52; f, 24.04; n, 1.97; o, 2.25. Experimental values: c, 67.55; h, 2.68; b, 1.54; f, 24.03; n, 1.97; o, 2.26.
Synthetic example 160: synthesis of Compound C160
This example is substantially the same as synthetic example 70, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 779.13. elemental analysis results: theoretical value: c, 63.18; h, 2.33; b, 1.39; f, 29.25; n, 1.80; o, 2.05. Experimental values: c, 63.20; h, 2.32; b, 1.38; f, 29.27; n, 1.79; and O, 2.04.
Synthetic example 161: synthesis of Compound C161
This example is substantially the same as Synthesis example 71 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 847.12. elemental analysis results: theoretical value: c, 59.53; h, 2.02; b, 1.28; f, 33.63; n, 1.65; o, 1.89. Experimental values: c, 59.52; h, 2.01; b, 1.29; f, 33.62; n, 1.66; o, 1.90.
Synthetic example 162: synthesis of Compound C162
This example is substantially the same as synthetic example 72 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 685.13. elemental analysis results: theoretical value: c, 66.60; h, 2.50; b, 1.58; f, 24.95; n, 2.04; o, 2.33. Experimental values: c, 66.62; h, 2.49; b, 1.58; f, 24.94; n, 2.03; o, 2.34.
Synthesis example 163: synthesis of Compound C163
This example is substantially the same as synthetic example 73 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 753.11. elemental analysis results: theoretical value: c, 62.18; h, 2.14; b, 1.43; f, 30.26; n, 1.86; o, 2.12. Experimental values: c, 62.19; h, 2.15; b, 1.42; f, 30.26; n, 1.85; o, 2.13.
Synthetic example 164: synthesis of Compound C164
This example is substantially the same as Synthesis example 74, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 821.10. elemental analysis results: theoretical value: c, 58.49; h, 1.84; b, 1.32; f, 34.70; n, 1.71; o, 1.95. Experimental values: c, 58.48; h, 1.83; b, 1.33; f, 34.71; n, 1.72; o, 1.94.
Representative synthetic route 3:
the following two schemes can be used for the synthesis of compounds M3373-M5058, C165-C284 and C291-C293.
The first scheme is as follows:
Figure BDA0002700091560000891
scheme II:
Figure BDA0002700091560000892
Figure BDA0002700091560000901
synthetic example 165: synthesis of Compound C165
Figure BDA0002700091560000902
In this synthesis example, compound C165 was synthesized according to the first scheme above.
Methyl 2-aminobenzoate 2.42g (16mmol), 1-bromo-2-iodobenzene 4.53g (16mmol), potassium carbonate 2.50g (18mmol), and activated copper powder 0.38g (6mmol) were charged in this order to a 250mL three-necked flask, followed by addition of 100mL o-dichlorobenzene. The atmosphere in the three-necked flask was replaced with nitrogen, and then the mixture was refluxed and stirred under a closed condition for 48 hours. After the reaction is completed, when the reaction system is cooled to room temperature, the reaction liquid is subjected to vacuum filtration, and a filter cake is washed by a dichloromethane solvent. The solution obtained after filtration was collected and spin-evaporated to remove the solvent. And then carrying out column chromatography separation on the product after spin drying, wherein the used eluent and the mixture ratio are dichloromethane: petroleum ether was 1:5 (volume ratio). Column chromatography gave 4.16g of a white powdery solid in 85% yield.
4.16g (13.6mmol) of the intermediate obtained in the previous step and 2.72g (68mmol) of sodium hydroxide were charged into a 250mL three-necked flask, followed by 120mL of an aqueous ethanol solution having a volume fraction of 50%. The gas in the three-necked flask was replaced with nitrogen, and then the mixture was heated under reflux and stirred under a closed condition for 24 hours. After the hydrolysis reaction is completed, the solvent amount of the reaction system is concentrated to about half, and then concentrated hydrochloric acid is used for acidification, so that a light yellow white solid is separated out. The precipitated solid was suction filtered under reduced pressure and the filter cake was washed with a large amount of deionized water. After washing, the filter cake was recovered and placed in a vacuum oven to dry overnight at 80 ℃. After drying, 3.62g of a white powder was obtained, representing a yield of 91%.
3.62g (12.4mmol) of intermediate obtained in the previous step was dissolved in 150mL of ultra-dry dichloromethane and charged into a 250mL three-necked flask, followed by 1.3mL (14.9mmol) of oxalyl chloride and one drop of ultra-dry DMF. And (3) carrying out nitrogen replacement on the gas in the three-neck flask, and heating the reaction system to reflux under the conditions of a closed environment and stirring. After refluxing for 0.5h, 1.7mL (14.9mmol) of stannic chloride was added and the reaction was continued under reflux for 4 h. After the reaction is completed, when the reaction system is cooled to room temperature, 1M sodium hydroxide aqueous solution is dropwise added into the reaction solution, and the pH value of the system is adjusted to be neutral. The reaction solution was extracted three times with dichloromethane, and the resulting organic phase was dried over anhydrous sodium sulfate, filtered to remove solid particles, and then subjected to rotary evaporation to remove the organic solvent. And (3) carrying out column chromatography separation on the obtained crude product, wherein the used eluent and the mixture ratio are dichloromethane: petroleum ether was 1:4 (volume ratio). Column chromatography gave 2.52g of a white solid in 74% yield.
2.52g (9.2mmol) of the intermediate obtained in the previous step, 2.83g (10mmol) of 1-bromo-2-iodobenzene, 2.08g (15mmol) of potassium carbonate and 0.32g (5mmol) of activated copper powder were successively charged into a 250mL three-necked flask, followed by 100mL of o-dichlorobenzene. The atmosphere in the three-necked flask was replaced with nitrogen, and then the mixture was refluxed and stirred under a closed condition for 48 hours. After the reaction is completed, when the reaction system is cooled to room temperature, the reaction liquid is subjected to vacuum filtration, and a filter cake is washed by a dichloromethane solvent. The solution obtained after filtration was collected and spin-evaporated to remove the solvent. And then carrying out column chromatography separation on the product after spin drying, wherein the used eluent and the mixture ratio are dichloromethane: petroleum ether is 1:2 (volume ratio). Column chromatography separation gave 3.12g of a pale yellowish white powdery solid with a yield of 79%.
3.12g (7.3mmol) of the intermediate obtained in the previous step, 0.67g (10.8mmol) of ethylene glycol and 0.62g of activated polyaniline sulfate (intermediate 20% in weight) were respectively charged into a 100mL round-bottomed flask, followed by addition of 25mL of toluene. The reaction was refluxed with stirring for 45min, and water produced in the reaction was removed by azeotropy. The progress of the reaction was monitored by TLC method until the starting material disappeared. After the reaction is completed, the catalyst is removed by filtration when the reaction system is cooled to room temperature. The obtained filtrate is washed by deionized water, an organic phase is collected by separating liquid, and after being dried by anhydrous sodium sulfate, solid particles are removed by filtration, and then the organic solvent is removed by rotary evaporation. And (3) carrying out column chromatography separation on the obtained crude product, wherein the used eluent and the mixture ratio are dichloromethane: petroleum ether was 1:4 (volume ratio). Column chromatography gave 3.13g of a pale yellowish white solid in 92% yield.
3.13g (6.6mmol) of the intermediate obtained in the previous step and 0.99g (6.6mmol) of dimethyl phenylboronate were successively charged into a 250mL three-necked flask, followed by addition of 150mL of tetrahydrofuran, and the reaction system was cooled to-78 ℃. 0.53g (9.9mmol) of tert-butyllithium was slowly added to the reaction mixture, and the reaction was continued at-78 ℃ for 10min with stirring, then the temperature was raised to-21 ℃ and the reaction was continued for 4h with stirring, finally the temperature was raised to room temperature and the reaction was continued for 18h with stirring. After the reaction reached a predetermined time, 20mL of a saturated ammonium chloride solution was poured into the reaction system to quench the reaction, and the organic phase was collected with a separatory funnel. The separated aqueous phase was extracted three more times with 20mL of diethyl ether, and the organic phases obtained by separation were combined, followed by drying over anhydrous magnesium sulfate, filtration to remove solid particles, and rotary evaporation to remove the organic solvent. And (3) carrying out column chromatography separation on the obtained crude product, wherein the used eluent and the mixture ratio are that ethyl acetate: n-hexane was 1:100 (volume ratio). Column chromatography gave 1.64g of a white powdery solid in 62% yield.
1.64g (4.1mmol) of the intermediate obtained in the previous step was charged into a 100mL round-bottom flask, followed by 20mL of anhydrous hexane. While stirring, 2.03g (12.3mmol) of chloral hydrate was added to the system, followed by reaction for 2 hours. After the reaction is completed, when the reaction system is cooled to room temperature, 20mL of deionized water is added into the system, and the organic phase is collected by liquid separation. Washing the obtained organic phase with brine, drying with anhydrous magnesium sulfate, filtering to remove solid particles, performing rotary evaporation to remove an organic solvent, and performing column chromatography separation on the obtained crude product, wherein the eluent and the mixture ratio are that ethyl acetate: n-hexane was 1:100 (volume ratio). The white powdery solid obtained by column chromatography separation and recrystallization was 1.32g, the yield was 90%.
1.32g (3.7mmol) of the intermediate obtained in the previous step and 2.44g of malononitrile (37mmol) were added to a 250mL round-bottom flask, followed by 100mL of acetic anhydride. The atmosphere in the three-necked flask was replaced with nitrogen, and then the mixture was stirred under reflux for 24 hours under a closed condition. After the reaction is completed, carrying out reduced pressure suction filtration when the reaction system is cooled to room temperature, and washing a filter cake by using a small amount of acetic anhydride to remove the excessive reactant malononitrile. After washing, the filter cake was recovered and placed in a vacuum oven to dry overnight at 80 ℃. After drying, 1.36g of a yellow-white powdery solid was obtained with a yield of 91%. MALDI-TOF-MS results: molecular ion peaks: 405.14. elemental analysis results: theoretical value: c, 82.98; h, 3.98; b, 2.67; n, 10.37. Experimental values: c, 82.97; h, 3.97; b, 2.68; n, 10.38.
Synthesis example 166: synthesis of Compound C166
This example is substantially the same as synthetic example 165, except that: in this case, 1-bromo-2-iodobenzene in the first step is exchanged for 3-bromo-4-iodo-N, N-diphenylaniline in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 572.22. elemental analysis results: theoretical value: c, 83.92; h, 4.40; b, 1.89; n, 9.79. Experimental values: c, 83.94; h, 4.41; b, 1.88; n, 9.78.
Synthesis example 167: synthesis of Compound C167
This example is substantially the same as synthetic example 165, except that: in this case, the 1-bromo-2-iodobenzene in the first step is exchanged for an equivalent amount of 3 ' -bromo-4 ' -iodo-N, N-diphenyl- [1,1 ' -biphenyl ] -4-amine. MALDI-TOF-MS results: molecular ion peaks: 648.25. elemental analysis results: theoretical value: c, 85.19; h, 4.51; b, 1.67; and N, 8.64. Experimental values: c, 85.19; h, 4.51; b, 1.67; and N, 8.64.
Synthetic example 168: synthesis of Compound C168
This example is substantially the same as synthetic example 165, except that: in this example, 1-bromo-2-iodobenzene in the first step is exchanged for an equivalent amount of 10- (3 ' -bromo-4 ' -iodo- [1,1 ' -biphenyl ] -4-yl) -9, 9-dimethyl-9, 10-dihydroacridine. MALDI-TOF-MS results: molecular ion peaks: 688.28. elemental analysis results: theoretical value: c, 85.46; h, 4.83; b, 1.57; and N, 8.14. Experimental values: c, 85.47; h, 4.84; b, 1.56; and N, 8.13.
Synthetic example 169: synthesis of Compound C169
This example is substantially the same as synthetic example 45, except that: in this case, the 1-bromo-2-iodobenzene in the first step is exchanged for an equivalent amount of 10- (3 ' -bromo-4 ' -iodo- [1,1 ' -biphenyl ] -4-yl) -10H-phenoxazine. MALDI-TOF-MS results: molecular ion peaks: 662.23. elemental analysis results: theoretical value: c, 83.39; h, 4.11; b, 1.63; n, 8.46; o, 2.41. Experimental values: c, 83.40; h, 4.10; b, 1.63; n, 8.47; o, 2.40.
Synthesis example 170: synthesis of Compound C170
This example is substantially the same as synthetic example 165, except that: in this case, the 1-bromo-2-iodobenzene in the fourth step is converted to 3-bromo-4-iodotrifluorotoluene in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 473.13. elemental analysis results: theoretical value: c, 73.60; h, 3.19; b, 2.28; f, 12.04; and N, 8.88. Experimental values: c, 73.62; h, 3.18; b, 2.28; f, 12.05; and N, 8.86.
Synthetic example 171: synthesis of Compound C171
This example is substantially the same as synthetic example 165, except that: in this case, 1-bromo-2-iodobenzene in the first step is converted to 3-bromo-4-iodotrifluorotoluene in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 473.13. elemental analysis results: theoretical value: c, 73.60; h, 3.19; b, 2.28; f, 12.04; and N, 8.88. Experimental values: c, 73.61; h, 3.19; b, 2.29; f, 12.03; and N, 8.87.
Synthesis example 172: synthesis of Compound C172
This example is substantially the same as synthetic example 165, except that: in this case, methyl 2-aminobenzoate in the first step was changed to methyl 2-amino-5-trifluoromethylbenzoate in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 473.13. elemental analysis results: theoretical value: c, 73.60; h, 3.19; b, 2.28; f, 12.04; and N, 8.88. Experimental values: c, 73.58; h, 3.18; b, 2.29; f, 12.04; and N, 8.89.
Synthetic example 173: synthesis of Compound C173
This example is substantially the same as synthetic example 165, except that: in this case, methyl 2-aminobenzoate in the first step and 1-bromo-2-iodobenzene in the fourth step were exchanged for methyl 2-amino-5-trifluoromethylbenzoate and 3-bromo-4-iodotrifluorotoluene in the same amounts, respectively. MALDI-TOF-MS results: molecular ion peaks: 541.12. elemental analysis results: theoretical value: c, 66.57; h, 2.61; b, 2.00; f, 21.06; and N, 7.76. Experimental values: c, 66.58; h, 2.60; b, 2.01; f, 21.07; and N, 7.76.
Synthesis example 174: synthesis of Compound C174
This example is substantially the same as synthetic example 165, except that: in this example, 1-bromo-2-iodobenzene, methyl 2-aminobenzoate in the first step and 1-bromo-2-iodobenzene in the fourth step were exchanged for 3-bromo-4-iodotrifluorotoluene, methyl 2-amino-5-trifluoromethylbenzoate and 3-bromo-4-iodotrifluorotoluene in the same amounts, respectively. MALDI-TOF-MS results: molecular ion peaks: 609.11. elemental analysis results: theoretical value: c, 61.11; h, 2.15; b, 1.77; f, 28.06; and N, 6.90. Experimental values: c, 61.12; h, 2.14; b, 1.77; f, 28.05; n, 6.92.
Synthetic example 175: synthesis of Compound C175
This example is substantially the same as synthetic example 165, except that: in this case, the 1-bromo-2-iodobenzene in the fourth step is converted to 2-bromo-3-iodonaphthalene in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 455.16. elemental analysis results: theoretical value: c, 84.41; h, 3.98; b, 2.37; and N, 9.23. Experimental values: c, 84.42; h, 3.99; b, 2.36; and N, 9.22.
Synthesis example 176: synthesis of Compound C176
This example is substantially the same as synthetic example 165, except that: in this case, methyl 2-aminobenzoate in the first step and 1-bromo-2-iodobenzene in the fourth step were exchanged for methyl 2-amino-5-trifluoromethylbenzoate and 2-bromo-3-iodonaphthalene, respectively, in equal amounts. MALDI-TOF-MS results: molecular ion peaks: 523.15. elemental analysis results: theoretical value: c, 75.74; h, 3.27; b, 2.07; f, 10.89; and N, 8.03. Experimental values: c, 75.75; h, 3.26; b, 2.07; f, 10.88; and N, 8.05.
Synthesis example 177: synthesis of Compound C177
This example is substantially the same as synthetic example 165, except that: in this example, 1-bromo-2-iodobenzene, methyl 2-aminobenzoate in the first step and 1-bromo-2-iodobenzene in the fourth step were exchanged for 3-bromo-4-iodotrifluorotoluene, methyl 2-amino-5-trifluoromethylbenzoate and 2-bromo-3-iodonaphthalene, respectively, in equal amounts. MALDI-TOF-MS results: molecular ion peaks: 591.13. elemental analysis results: theoretical value: c, 69.06; h, 2.73; b, 1.83; f, 19.28; and N, 7.11. Experimental values: c, 69.07; h, 2.74; b, 1.82; f, 19.28; and N, 7.10.
Synthesis example 178: synthesis of Compound C178
This example is substantially the same as synthetic example 165, except that: in this case, methyl 2-aminobenzoate in the first step was changed to methyl 3-amino-2-naphthoate in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 455.16. elemental analysis results: theoretical value: c, 84.41; h, 3.98; b, 2.37; and N, 9.23. Experimental values: c, 84.43; h, 3.97; b, 2.36; and N, 9.23.
Synthetic example 179: synthesis of Compound C179
This example is substantially the same as synthetic example 165, except that: in this example, methyl 2-aminobenzoate in the first step and 1-bromo-2-iodobenzene in the fourth step were exchanged for methyl 3-amino-2-naphthoate and 3-bromo-4-iodobenzotrifluoride in the same amounts, respectively. MALDI-TOF-MS results: molecular ion peaks: 523.15. elemental analysis results: theoretical value: c, 75.74; h, 3.27; b, 2.07; f, 10.89; and N, 8.03. Experimental values: c, 75.73; h, 3.26; b, 2.08; f, 10.89; and N, 8.04.
Synthetic example 180: synthesis of Compound C180
This example is substantially the same as synthetic example 165, except that: in this example, 1-bromo-2-iodobenzene, methyl 2-aminobenzoate in the first step and 1-bromo-2-iodobenzene in the fourth step were exchanged for 3-bromo-4-iodotrifluorotoluene, methyl 3-amino-2-naphthoate and 3-bromo-4-iodotrifluorotoluene in the same amounts, respectively. MALDI-TOF-MS results: molecular ion peaks: 591.13. elemental analysis results: theoretical value: c, 69.06; h, 2.73; b, 1.83; f, 19.28; and N, 7.11. Experimental values: c, 69.08; h, 2.72; b, 1.82; f, 19.28; and N, 7.12.
Synthetic example 181: synthesis of Compound C181
This example is substantially the same as synthetic example 165, except that: in this example, methyl 2-aminobenzoate in the first step and 1-bromo-2-iodobenzene in the fourth step were exchanged for methyl 3-amino-2-naphthoate and 2-bromo-3-iodonaphthalene, respectively, in equal amounts. MALDI-TOF-MS results: molecular ion peaks: 505.18. elemental analysis results: theoretical value: c, 85.56; h, 3.99; b, 2.14; n, 8.31. Experimental values: c, 85.55; h, 3.98; b, 2.15; n, 8.32.
Synthetic example 182: synthesis of Compound C182
This example is substantially the same as synthetic example 165, except that: in this example, 1-bromo-2-iodobenzene, methyl 2-aminobenzoate in the first step and 1-bromo-2-iodobenzene in the fourth step were exchanged for 3-bromo-4-iodotrifluorotoluene, methyl 3-amino-2-naphthoate and 2-bromo-3-iodonaphthalene, respectively, in equal amounts. MALDI-TOF-MS results: molecular ion peaks: 573.16. elemental analysis results: theoretical value: c, 77.51; h, 3.34; b, 1.89; f, 9.94; n, 7.33. Experimental values: c, 77.52; h, 3.35; b, 1.88; f, 9.94; and N, 7.32.
Synthesis example 183: synthesis of Compound C183
Figure BDA0002700091560000931
In this synthesis example, compound C183 was synthesized according to the second scheme above.
3.68g (16mmol) of methyl 2-amino-3-bromobenzoate, 4.07g (16mmol) of 1-iodonaphthalene, 2.50g (18mmol) of potassium carbonate and 0.38g (6mmol) of activated copper powder were successively charged into a 250mL three-necked flask followed by 100mL of o-dichlorobenzene. The atmosphere in the three-necked flask was replaced with nitrogen, and then the mixture was refluxed and stirred under a closed condition for 48 hours. After the reaction is completed, when the reaction system is cooled to room temperature, the reaction liquid is subjected to vacuum filtration, and a filter cake is washed by a dichloromethane solvent. The solution obtained after filtration was collected and spin-evaporated to remove the solvent. And then carrying out column chromatography separation on the product after spin drying, wherein the used eluent and the mixture ratio are dichloromethane: petroleum ether was 1:4 (volume ratio). Column chromatography gave 4.62g of a white powdery solid in 81% yield.
4.62g (13.0mmol) of the intermediate obtained in the previous step and 2.63g (65mmol) of sodium hydroxide were charged into a 250mL three-necked flask, followed by 120mL of an aqueous ethanol solution having a volume fraction of 50%. The gas in the three-necked flask was replaced with nitrogen, and then the mixture was heated under reflux and stirred under a closed condition for 24 hours. After the hydrolysis reaction is completed, the solvent amount of the reaction system is concentrated to about half, and then concentrated hydrochloric acid is used for acidification, so that a light yellow white solid is separated out. The precipitated solid was suction filtered under reduced pressure and the filter cake was washed with a large amount of deionized water. After washing, the filter cake was recovered and placed in a vacuum oven to dry overnight at 80 ℃. After drying, 3.91g of white powder were obtained, yield 88%.
3.91g (11.4mmol) of the intermediate obtained in the previous step was dissolved in 150mL of ultra-dry dichloromethane and added to a 250mL three-necked flask, followed by 1.2mL (13.7mmol) of oxalyl chloride and one drop of ultra-dry DMF. And (3) carrying out nitrogen replacement on the gas in the three-neck flask, and heating the reaction system to reflux under the conditions of a closed environment and stirring. After refluxing for 0.5h, 1.6mL (13.7mmol) of stannic chloride was added and the reaction was continued under reflux for 4 h. After the reaction is completed, when the reaction system is cooled to room temperature, 1M sodium hydroxide aqueous solution is dropwise added into the reaction solution, and the pH value of the system is adjusted to be neutral. The reaction solution was extracted three times with dichloromethane, and the resulting organic phase was dried over anhydrous sodium sulfate, filtered to remove solid particles, and then subjected to rotary evaporation to remove the organic solvent. And (3) carrying out column chromatography separation on the obtained crude product, wherein the used eluent and the mixture ratio are dichloromethane: petroleum ether is 1:3 (volume ratio). Column chromatography gave 2.62g of a white solid in 71% yield.
2.62g (8.1mmol) of the intermediate obtained in the previous step, 2.55g (9mmol) of 1-bromo-2-iodobenzene, 1.67g (12mmol) of potassium carbonate, and 0.26g (4mmol) of activated copper powder were successively charged into a 250mL three-necked flask, followed by 100mL of o-dichlorobenzene. The atmosphere in the three-necked flask was replaced with nitrogen, and then the mixture was refluxed and stirred under a closed condition for 48 hours. After the reaction is completed, when the reaction system is cooled to room temperature, the reaction liquid is subjected to vacuum filtration, and a filter cake is washed by a dichloromethane solvent. The solution obtained after filtration was collected and spin-evaporated to remove the solvent. And then carrying out column chromatography separation on the product after spin drying, wherein the used eluent and the mixture ratio are dichloromethane: petroleum ether is 1:1 (volume ratio). Column chromatography gave 3.18g of a pale yellowish white powdery solid in 82% yield.
3.18g (6.6mmol) of the intermediate obtained in the previous step, 0.67g (10.8mmol) of ethylene glycol and 0.64g of activated polyaniline sulfate (intermediate 20% in weight) were respectively charged into a 100mL round-bottomed flask, followed by addition of 25mL of toluene. The reaction was refluxed with stirring for 50min, and water produced in the reaction was removed by azeotropy. The progress of the reaction was monitored by TLC method until the starting material disappeared. After the reaction is completed, the catalyst is removed by filtration when the reaction system is cooled to room temperature. The obtained filtrate is washed by deionized water, an organic phase is collected by separating liquid, and after being dried by anhydrous sodium sulfate, solid particles are removed by filtration, and then the organic solvent is removed by rotary evaporation. And (3) carrying out column chromatography separation on the obtained crude product, wherein the used eluent and the mixture ratio are dichloromethane: petroleum ether is 1:3 (volume ratio). Column chromatography gave 3.11g of a pale yellowish white solid in 90% yield.
3.11g (5.9mmol) of the intermediate obtained in the previous step and 0.89g (5.9mmol) of dimethyl phenylboronate were successively charged into a 250mL three-necked flask, followed by addition of 150mL of tetrahydrofuran, and the reaction system was cooled to-78 ℃. 0.48g (8.9mmol) of tert-butyllithium was slowly added to the reaction solution, and the reaction was continued at-78 ℃ for 10min with stirring, then the temperature was raised to-21 ℃ and the reaction was continued for 4h with stirring, finally the temperature was raised to room temperature and the reaction was continued for 18h with stirring. After the reaction reached a predetermined time, 20mL of a saturated ammonium chloride solution was poured into the reaction system to quench the reaction, and the organic phase was collected with a separatory funnel. The separated aqueous phase was extracted three more times with 20mL of diethyl ether, and the organic phases obtained by separation were combined, followed by drying over anhydrous magnesium sulfate, filtration to remove solid particles, and rotary evaporation to remove the organic solvent. And (3) carrying out column chromatography separation on the obtained crude product, wherein the used eluent and the mixture ratio are that ethyl acetate: n-hexane was 1:100 (volume ratio). Column chromatography gave 1.70g of a white powdery solid in 64% yield.
1.70g (3.8mmol) of the intermediate obtained in the previous step was charged into a 100mL round-bottom flask, followed by 20mL of anhydrous hexane. Under stirring, 1.88g (11.4mmol) of chloral hydrate was added to the system, followed by reaction for 2 h. After the reaction is completed, when the reaction system is cooled to room temperature, 20mL of deionized water is added into the system, and the organic phase is collected by liquid separation. Washing the obtained organic phase with brine, drying with anhydrous magnesium sulfate, filtering to remove solid particles, performing rotary evaporation to remove an organic solvent, and performing column chromatography separation on the obtained crude product, wherein the eluent and the mixture ratio are that ethyl acetate: n-hexane was 1:100 (volume ratio). The white powdery solid obtained by column chromatography separation and recrystallization was 1.36g, with a yield of 88%.
1.36g (3.3mmol) of the intermediate obtained in the previous step and 2.18g of malononitrile (33mmol) were added to a 250mL round-bottom flask, followed by 100mL of acetic anhydride. The atmosphere in the three-necked flask was replaced with nitrogen, and then the mixture was stirred under reflux for 24 hours under a closed condition. After the reaction is completed, carrying out reduced pressure suction filtration when the reaction system is cooled to room temperature, and washing a filter cake by using a small amount of acetic anhydride to remove the excessive reactant malononitrile. After washing, the filter cake was recovered and placed in a vacuum oven to dry overnight at 80 ℃. After drying, 1.35g of a yellow solid was obtained in 89% yield. MALDI-TOF-MS results: molecular ion peaks: 455.16. elemental analysis results: theoretical value: c, 84.41; h, 3.98; b, 2.37; and N, 9.23. Experimental values: c, 84.41; h, 3.97; b, 2.36; and N, 9.25.
Synthesis example 184: synthesis of Compound C184
This example is substantially the same as synthesis example 183 except that: in this case, the 1-bromo-2-iodobenzene in the fourth step is converted to 3-bromo-4-iodotrifluorotoluene in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 523.15. elemental analysis results: theoretical value: c, 75.74; h, 3.27; b, 2.07; f, 10.89; and N, 8.03. Experimental values: c, 75.75; h, 3.28; b, 2.06; f, 10.89; and N, 8.02.
Synthesis example 185: synthesis of Compound C185
This example is substantially the same as synthesis example 183 except that: in this case, the 1-bromo-2-iodobenzene in the first step and the 1-bromo-2-iodobenzene in the fourth step were exchanged to 3-bromo-4-iodotrifluorotoluene and 3-bromo-4-iodotrifluorotoluene, respectively, in equal amounts. MALDI-TOF-MS results: molecular ion peaks: 591.13. elemental analysis results: theoretical value: c, 69.06; h, 2.73; b, 1.83; f, 19.28; and N, 7.11. Experimental values: c, 69.05; h, 2.74; b, 1.83; f, 19.27; and N, 7.12.
Synthetic example 186: synthesis of Compound C186
This example is substantially the same as synthetic example 165, except that: in this case, methyl 2-aminobenzoate in the first step was exchanged for an equivalent amount of methyl 3-amino-2-phenanthrenecarboxylate. MALDI-TOF-MS results: molecular ion peaks: 505.18. elemental analysis results: theoretical value: c, 85.56; h, 3.99; b, 2.14; n, 8.31. Experimental values: c, 85.57; h, 3.98; b, 2.13; n, 8.32.
Synthesis example 187: synthesis of Compound C187
This example is substantially the same as synthetic example 165, except that: in this case, methyl 2-aminobenzoate in the first step and 1-bromo-2-iodobenzene in the fourth step were exchanged for methyl 3-amino-2-phenanthrenecarboxylate and 3-bromo-4-iodobenzotrifluoride in equal amounts, respectively. MALDI-TOF-MS results: molecular ion peaks: 573.16. elemental analysis results: theoretical value: c, 77.51; h, 3.34; b, 1.89; f, 9.94; n, 7.33. Experimental values: c, 77.53; h, 3.33; b, 1.88; f, 9.95; and N, 7.32.
Synthetic example 188: synthesis of Compound C188
This example is substantially the same as synthetic example 165, except that: in this example, 1-bromo-2-iodobenzene, methyl 2-aminobenzoate in the first step and 1-bromo-2-iodobenzene in the fourth step were exchanged for 3-bromo-4-iodotrifluorotoluene, methyl 3-amino-2-phenanthrenecarboxylate and 3-bromo-4-iodotrifluorotoluene, respectively, in equal amounts. MALDI-TOF-MS results: molecular ion peaks: 641.15. elemental analysis results: theoretical value: c, 71.16; h, 2.83; b, 1.69; f, 17.77; and N, 6.55. Experimental values: c, 71.15; h, 2.84; b, 1.68; f, 17.77; n, 6.56.
Synthetic example 189: synthesis of Compound C189
This example is substantially the same as synthetic example 165, except that: in this case, methyl 2-aminobenzoate in the first step was changed to methyl 3-amino-2-triphenylbenzoate in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 555.19. elemental analysis results: theoretical value: c, 86.50; h, 3.99; b, 1.95; and N, 7.57. Experimental values: c, 86.50; h, 3.98; b, 1.96; and N, 7.58.
Synthetic example 190: synthesis of Compound C190
This example is substantially the same as synthetic example 165, except that: in this example, methyl 2-aminobenzoate in the first step and 1-bromo-2-iodobenzene in the fourth step were exchanged for methyl 3-amino-2-triphenylbenzoate and 3-bromo-4-iodotrifluorotoluene in the same amounts, respectively. MALDI-TOF-MS results: molecular ion peaks: 623.18. elemental analysis results: theoretical value: c, 78.99; h, 3.40; b, 1.73; f, 9.14; n, 6.74. Experimental values: c, 78.97; h, 3.41; b, 1.73; f, 9.15; and N, 6.75.
Synthetic example 191: synthesis of Compound C191
This example is substantially the same as synthetic example 165, except that: in this example, 1-bromo-2-iodobenzene, methyl 2-aminobenzoate in the first step and 1-bromo-2-iodobenzene in the fourth step were exchanged for 3-bromo-4-iodotrifluorotoluene, methyl 3-amino-2-triphenylate and 3-bromo-4-iodotrifluorotoluene in the same amounts, respectively. MALDI-TOF-MS results: molecular ion peaks: 691.17. elemental analysis results: theoretical value: c, 72.96; h, 2.92; b, 1.56; f, 16.49; and N, 6.08. Experimental values: c, 72.95; h, 2.93; b, 1.56; f, 16.48; and N, 6.09.
Synthetic example 192: synthesis of Compound C192
This example is substantially the same as synthesis example 183 except that: in this example, 1-iodonaphthalene in the first step is changed to 1-iodopyrene in an amount equivalent to that of the substance. MALDI-TOF-MS results: molecular ion peaks: 531.19. elemental analysis results: theoretical value: c, 85.89; h, 4.17; b, 2.03; and N, 7.91. Experimental values: c, 85.88; h, 4.17; b, 2.04; and N, 7.92.
Synthetic example 193: synthesis of Compound C193
This example is substantially the same as synthesis example 183 except that: in this example, 1-iodonaphthalene in the first step and 1-bromo-2-iodobenzene in the fourth step were exchanged for 1-iodopyrene and 3-bromo-4-iodobenzotrifluoride in equal amounts, respectively. MALDI-TOF-MS results: molecular ion peaks: 599.18. elemental analysis results: theoretical value: c, 78.15; h, 3.53; b, 1.80; f, 9.51; and N, 7.01. Experimental values: c, 78.14; h, 3.55; b, 1.80; f, 9.50; and N, 7.02.
Synthesis example 194: synthesis of Compound C194
This example is substantially the same as synthesis example 183 except that: in this example, the 1-bromo-2-iodobenzene, 1-iodonaphthalene in the first step and the 1-bromo-2-iodobenzene in the fourth step were exchanged to 3-bromo-4-iodotrifluorotoluene, 1-iodopyrene and 3-bromo-4-iodotrifluorotoluene in equal amounts, respectively. MALDI-TOF-MS results: molecular ion peaks: 667.17. elemental analysis results: theoretical value: c, 71.98; h, 3.02; b, 1.62; f, 17.08; and N, 6.30. Experimental values: c, 71.99; h, 3.01; b, 1.62; f, 17.07; and N, 6.32.
Synthetic example 195: synthesis of Compound C195
This example is substantially the same as synthetic example 165, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 447.19. elemental analysis results: theoretical value: c, 83.23; h, 4.96; b, 2.42; and N, 9.39. Experimental values: c, 83.24; h, 4.95; b, 2.41; and N, 9.38.
Synthetic example 196: synthesis of Compound C196
This example is substantially the same as synthetic example 166, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 614.26. elemental analysis results: theoretical value: c, 84.04; h, 5.08; b, 1.76; and N, 9.12. Experimental values: c, 84.03; h, 5.07; b, 1.77; and N, 9.13.
Synthetic example 197: synthesis of Compound C197
This example is substantially the same as synthesis example 167 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 690.30. elemental analysis results: theoretical value: c, 85.21; h, 5.11; b, 1.57; n, 8.11. Experimental values: c, 85.20; h, 5.10; b, 1.58; and N, 8.12.
Synthetic example 198: synthesis of Compound C198
This example is substantially the same as synthetic example 168, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 730.33. elemental analysis results: theoretical value: c, 85.47; h, 5.38; b, 1.48; and N, 7.67. Experimental values: c, 85.48; h, 5.37; b, 1.49; and N, 7.67.
Synthetic example 199: synthesis of Compound C199
This example is substantially the same as synthetic example 169 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 704.27. elemental analysis results: theoretical value: c, 83.52; h, 4.72; b, 1.53; n, 7.95; o, 2.27. Experimental values: c, 83.52; h, 4.71; b, 1.52; n, 7.96; o, 2.28.
Synthesis example 200: synthesis of Compound C200
This example is substantially the same as synthesis example 170, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 515.18. elemental analysis results: theoretical value: c, 74.58; h, 4.11; b, 2.10; f, 11.06; and N, 8.15. Experimental values: c, 74.59; h, 4.12; b, 2.11; f, 11.05; and N, 8.14.
Synthesis example 201: synthesis of Compound C201
This example is substantially the same as synthetic example 171, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 515.18. elemental analysis results: theoretical value: c, 74.58; h, 4.11; b, 2.10; f, 11.06; and N, 8.15. Experimental values: c, 74.57; h, 4.11; b, 2.10; f, 11.05; and N, 8.17.
Synthesis example 202: synthesis of Compound C202
This example is substantially the same as synthetic example 172 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 515.18. elemental analysis results: theoretical value: c, 74.58; h, 4.11; b, 2.10; f, 11.06; and N, 8.15. Experimental values: c, 74.58; h, 4.13; b, 2.11; f, 11.04; and N, 8.14.
Synthesis example 203: synthesis of Compound C203
This example is substantially the same as synthesis example 173 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 583.17. elemental analysis results: theoretical value: c, 67.95; h, 3.46; b, 1.85; f, 19.54; and N, 7.20. Experimental values: c, 67.94; h, 3.45; b, 1.86; f, 19.54; and N, 7.21.
Synthesis example 204: synthesis of Compound C204
This example is substantially the same as synthetic example 174, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 651.15. elemental analysis results: theoretical value: c, 62.70; h, 2.94; b, 1.66; f, 26.25; and N, 6.45. Experimental values: c, 62.71; h, 2.93; b, 1.67; f, 26.25; n, 6.44.
Synthesis example 205: synthesis of Compound C205
This example is substantially the same as Synthesis example 175 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 497.21. elemental analysis results: theoretical value: c, 84.52; h, 4.86; b, 2.17; and N, 8.45. Experimental values: c, 84.54; h, 4.85; b, 2.17; n, 8.44.
Synthesis example 206: synthesis of Compound C206
This example is substantially the same as synthetic example 176, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 565.19. elemental analysis results: theoretical value: c, 76.48; h, 4.10; b, 1.91; f, 10.08; and N, 7.43. Experimental values: c, 76.47; h, 4.11; b, 1.92; f, 10.08; and N, 7.42.
Synthetic example 207: synthesis of Compound C207
This example is substantially the same as synthetic example 177 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 633.18. elemental analysis results: theoretical value: c, 70.16; h, 3.50; b, 1.71; f, 18.00; and N, 6.63. Experimental values: c, 70.15; h, 3.51; b, 1.72; f, 18.00; and N, 6.62.
Synthetic example 208: synthesis of Compound C208
This example is substantially the same as synthesis example 178 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 497.21. elemental analysis results: theoretical value: c, 84.52; h, 4.86; b, 2.17; and N, 8.45. Experimental values: c, 84.51; h, 4.85; b, 2.16; n, 8.44.
Synthetic example 209: synthesis of Compound C209
This example is substantially the same as synthesis example 179 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 565.19. elemental analysis results: theoretical value: c, 76.48; h, 4.10; b, 1.91; f, 10.08; and N, 7.43. Experimental values: c, 76.49; h, 4.11; b, 1.90; f, 10.08; and N, 7.42.
Synthesis example 210: synthesis of Compound C210
This example is substantially the same as synthetic example 180 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 633.18. elemental analysis results: theoretical value: c, 70.16; h, 3.50; b, 1.71; f, 18.00; and N, 6.63. Experimental values: c, 70.15; h, 3.50; b, 1.70; f, 18.01; and N, 6.64.
Synthesis example 211: synthesis of Compound C211
This example is substantially the same as synthetic example 181, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 547.22. elemental analysis results: theoretical value: c, 85.56; h, 4.79; b, 1.97; and N, 7.68. Experimental values: c, 85.57; h, 4.78; b, 1.98; and N, 7.67.
Synthetic example 212: synthesis of Compound C212
This example is substantially the same as synthesis example 182, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 615.21. elemental analysis results: theoretical value: c, 78.06; h, 4.09; b, 1.76; f, 9.26; and N, 6.83. Experimental values: c, 78.07; h, 4.10; b, 1.76; f, 9.25; and N, 6.82.
Synthetic example 213: synthesis of Compound C213
This example is substantially the same as synthesis example 183 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 497.21. elemental analysis results: theoretical value: c, 84.52; h, 4.86; b, 2.17; and N, 8.45. Experimental values: c, 84.53; h, 4.85; b, 2.18; n, 8.44.
Synthesis example 214: synthesis of Compound C214
This example is substantially the same as synthetic example 184, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 565.19. elemental analysis results: theoretical value: c, 76.48; h, 4.10; b, 1.91; f, 10.08; and N, 7.43. Experimental values: c, 76.49; h, 4.11; b, 1.91; f, 10.07; and N, 7.42.
Synthetic example 215: synthesis of Compound C215
This example is substantially the same as synthesis example 185, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 633.18. elemental analysis results: theoretical value: c, 70.16; h, 3.50; b, 1.71; f, 18.00; and N, 6.63. Experimental values: c, 70.15; h, 3.51; b, 1.71; f, 18.01; and N, 6.62.
Synthetic example 216: synthesis of Compound C216
This example is substantially the same as synthetic example 186, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 547.22. elemental analysis results: theoretical value: c, 85.56; h, 4.79; b, 1.97; and N, 7.68. Experimental values: c, 85.58; h, 4.79; b, 1.96; and N, 7.67.
Synthesis example 217: synthesis of Compound C217
This example is substantially the same as synthetic example 187 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 615.21. elemental analysis results: theoretical value: c, 78.06; h, 4.09; b, 1.76; f, 9.26; and N, 6.83. Experimental values: c, 78.08; h, 4.09; b, 1.75; f, 9.24; and N, 6.84.
Synthetic example 218: synthesis of Compound C218
This example is substantially the same as Synthesis example 188, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 683.20. elemental analysis results: theoretical value: c, 72.05; h, 3.54; b, 1.58; f, 16.68; and N, 6.15. Experimental values: c, 72.06; h, 3.55; b, 1.57; f, 16.68; and N, 6.14.
Synthesis example 219: synthesis of Compound C219
This example is substantially the same as synthetic example 189, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 597.24. elemental analysis results: theoretical value: c, 86.43; h, 4.72; b, 1.81; and N, 7.03. Experimental values: c, 86.42; h, 4.71; b, 1.82; and N, 7.04.
Synthetic example 220: synthesis of Compound C220
This example is substantially the same as synthetic example 190 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 665.23. elemental analysis results: theoretical value: c, 79.41; h, 4.09; b, 1.62; f, 8.56; and N, 6.31. Experimental values: c, 79.42; h, 4.08; b, 1.62; f, 8.55; and N, 6.32.
Synthesis example 221: synthesis of Compound C221
This example is substantially the same as synthetic example 191 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 733.21. elemental analysis results: theoretical value: c, 73.68; h, 3.57; b, 1.47; f, 15.54; n, 5.73. Experimental values: c, 73.69; h, 3.57; b, 1.48; f, 15.53; and N, 5.72.
Synthetic example 222: synthesis of Compound C222
This example is substantially the same as synthetic example 192 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 573.24. elemental analysis results: theoretical value: c, 85.87; h, 4.92; b, 1.88; n, 7.33. Experimental values: c, 85.86; h, 4.91; b, 1.89; and N, 7.34.
Synthesis example 223: synthesis of Compound C223
This example is substantially the same as synthetic example 193 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 641.23. elemental analysis results: theoretical value: c, 78.64; h, 4.24; b, 1.69; f, 8.88; and N, 6.55. Experimental values: c, 78.65; h, 4.24; b, 1.68; f, 8.89; n, 6.54.
Synthesis example 224: synthesis of Compound C224
This example is substantially the same as synthetic example 194, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trimethylphenylborate. MALDI-TOF-MS results: molecular ion peaks: 709.21. elemental analysis results: theoretical value: c, 72.79; h, 3.69; b, 1.52; f, 16.07; n, 5.92. Experimental values: c, 72.79; h, 3.70; b, 1.53; f, 16.06; and N, 5.91.
Synthesis example 225: synthesis of Compound C225
This example is substantially the same as synthetic example 165, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 531.28. elemental analysis results: theoretical value: c, 83.61; h, 6.45; b, 2.03; and N, 7.91. Experimental values: c, 83.60; h, 6.44; b, 2.04; and N, 7.92.
Synthesis example 226: synthesis of Compound C226
This example is substantially the same as synthetic example 166, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 698.36. elemental analysis results: theoretical value: c, 84.23; h, 6.20; b, 1.55; and N, 8.02. Experimental values: c, 84.21; h, 6.20; b, 1.56; and N, 8.03.
Synthetic example 227: synthesis of Compound C227
This example is substantially the same as synthesis example 167 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 774.39. elemental analysis results: theoretical value: c, 85.26; h, 6.11; b, 1.40; and N, 7.23. Experimental values: c, 85.25; h, 6.10; b, 1.41; and N, 7.24.
Synthetic example 228: synthesis of Compound C228
This example is substantially the same as synthetic example 168, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 814.42. elemental analysis results: theoretical value: c, 85.49; h, 6.31; b, 1.33; and N, 6.88. Experimental values: c, 85.48; h, 6.32; b, 1.32; and N, 6.89.
Synthetic example 229: synthesis of Compound C229
This example is substantially the same as synthetic example 169 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 788.37. elemental analysis results: theoretical value: c, 83.75; h, 5.75; b, 1.37; n, 7.10; and O, 2.03. Experimental values: c, 83.74; h, 5.75; b, 1.38; n, 7.11; and O, 2.02.
Synthesis example 230: synthesis of Compound C230
This example is substantially the same as synthesis example 170, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 599.27. elemental analysis results: theoretical value: c, 76.13; h, 5.55; b, 1.80; f, 9.51; and N, 7.01. Experimental values: c, 76.14; h, 5.53; b, 1.80; f, 9.50; and N, 7.03.
Synthesis example 231: synthesis of Compound C231
This example is substantially the same as synthetic example 171, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 599.27. elemental analysis results: theoretical value: c, 76.13; h, 5.55; b, 1.80; f, 9.51; and N, 7.01. Experimental values: c, 76.13; h, 5.54; b, 1.81; f, 9.53; and N, 7.00.
Synthetic example 232: synthesis of Compound C232
This example is substantially the same as synthetic example 172 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 599.27. elemental analysis results: theoretical value: c, 76.13; h, 5.55; b, 1.80; f, 9.51; and N, 7.01. Experimental values: c, 76.14; h, 5.56; b, 1.79; f, 9.49; and N, 7.01.
Synthetic example 233: synthesis of Compound C233
This example is substantially the same as synthesis example 173 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 667.26. elemental analysis results: theoretical value: c, 70.18; h, 4.83; b, 1.62; f, 17.08; and N, 6.30. Experimental values: c, 70.19; h, 4.82; b, 1.61; f, 17.08; and N, 6.31.
Synthesis example 234: synthesis of Compound C234
This example is substantially the same as synthetic example 174, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 735.25. elemental analysis results: theoretical value: c, 65.32; h, 4.25; b, 1.47; f, 23.25; n, 5.71. Experimental values: c, 65.33; h, 4.26; b, 1.47; f, 23.24; and N, 5.70.
Synthesis example 235: synthesis of Compound C235
This example is substantially the same as Synthesis example 175 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 581.30. elemental analysis results: theoretical value: c, 84.68; h, 6.24; b, 1.86; and N, 7.23. Experimental values: c, 84.69; h, 6.25; b, 1.85; and N, 7.22.
Synthetic example 236: synthesis of Compound C236
This example is substantially the same as synthetic example 176, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 649.29. elemental analysis results: theoretical value: c, 77.66; h, 5.43; b, 1.66; f, 8.77; and N, 6.47. Experimental values: c, 77.67; h, 5.44; b, 1.65; f, 8.77; and N, 6.46.
Synthesis example 237: synthesis of Compound C237
This example is substantially the same as synthetic example 177 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 717.27. elemental analysis results: theoretical value: c, 71.98; h, 4.78; b, 1.51; f, 15.89; and N, 5.86. Experimental values: c, 71.99; h, 4.79; b, 1.50; f, 15.89; and N, 5.85.
Synthetic example 238: synthesis of Compound C23
This example is substantially the same as synthesis example 178 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 581.30. elemental analysis results: theoretical value: c, 84.68; h, 6.24; b, 1.86; and N, 7.23. Experimental values: c, 84.69; h, 6.24; b, 1.87; and N, 7.21.
Synthetic example 239: synthesis of Compound C239
This example is substantially the same as synthesis example 179 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 649.29. elemental analysis results: theoretical value: c, 77.66; h, 5.43; b, 1.66; f, 8.77; and N, 6.47. Experimental values: c, 77.65; h, 5.44; b, 1.66; f, 8.78; and N, 6.45.
Synthetic example 240: synthesis of Compound C240
This example is substantially the same as synthetic example 180 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 717.27. elemental analysis results: theoretical value: c, 71.98; h, 4.78; b, 1.51; f, 15.89; and N, 5.86. Experimental values: c, 71.99; h, 4.78; b, 1.52; f, 15.88; and N, 5.85.
Synthetic example 241: synthesis of Compound C241
This example is substantially the same as synthetic example 181, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 631.32. elemental analysis results: theoretical value: c, 85.57; h, 6.06; b, 1.71; and N, 6.65. Experimental values: c, 85.56; h, 6.05; b, 1.72; and N, 6.66.
Synthetic example 242: synthesis of Compound C242
This example is substantially the same as synthesis example 182, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 699.30. elemental analysis results: theoretical value: c, 78.97; h, 5.33; b, 1.55; f, 8.15; and N, 6.01. Experimental values: c, 78.97; h, 5.35; b, 1.54; f, 8.14; and N, 6.02.
Synthetic example 243: synthesis of Compound C243
This example is substantially the same as synthesis example 183 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 581.30. elemental analysis results: theoretical value: c, 84.68; h, 6.24; b, 1.86; and N, 7.23. Experimental values: c, 84.69; h, 6.25; b, 1.85; and N, 7.22.
Synthetic example 244: synthesis of Compound C244
This example is substantially the same as synthetic example 184, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 649.29. elemental analysis results: theoretical value: c, 77.66; h, 5.43; b, 1.66; f, 8.77; and N, 6.47. Experimental values: c, 77.65; h, 5.43; b, 1.67; f, 8.76; and N, 6.48.
Synthetic example 245: synthesis of Compound C245
This example is substantially the same as synthesis example 185, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 717.27. elemental analysis results: theoretical value: c, 71.98; h, 4.78; b, 1.51; f, 15.89; and N, 5.86. Experimental values: c, 71.97; h, 4.79; b, 1.51; f, 15.88; and N, 5.87.
Synthetic example 246: synthesis of Compound C246
This example is substantially the same as synthetic example 186, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 631.32. elemental analysis results: theoretical value: c, 85.57; h, 6.06; b, 1.71; and N, 6.65. Experimental values: c, 85.56; h, 6.05; b, 1.70; and N, 6.66.
Synthetic example 247: synthesis of Compound C247
This example is substantially the same as synthetic example 187 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 699.30. elemental analysis results: theoretical value: c, 78.97; h, 5.33; b, 1.55; f, 8.15; and N, 6.01. Experimental values: c, 78.96; h, 5.33; b, 1.56; f, 8.16; and N, 6.00.
Synthesis example 248: synthesis of Compound C248
This example is substantially the same as Synthesis example 188, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 767.29. elemental analysis results: theoretical value: c, 73.54; h, 4.73; b, 1.41; f, 14.85; and N, 5.47. Experimental values: c, 73.53; h, 4.73; b, 1.40; f, 14.86; and N, 5.48.
Synthesis example 249: synthesis of Compound C249
This example is substantially the same as synthetic example 189, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 681.33. elemental analysis results: theoretical value: c, 86.34; h, 5.91; b, 1.59; and N, 6.16. Experimental values: c, 86.33; h, 5.92; b, 1.58; and N, 6.17.
Synthetic example 250: synthesis of Compound C250
This example is substantially the same as synthetic example 190 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 749.32. elemental analysis results: theoretical value: c, 80.11; h, 5.24; b, 1.44; f, 7.60; and N, 5.61. Experimental values: c, 80.10; h, 5.24; b, 1.43; f, 7.61; n, 5.62.
Synthesis example 251: synthesis of Compound C251
This example is substantially the same as synthetic example 191 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 817.31. elemental analysis results: theoretical value: c, 74.91; h, 4.68; b, 1.32; f, 13.94; and N, 5.14. Experimental values: c, 74.92; h, 4.69; b, 1.32; f, 13.93; and N, 5.13.
Synthetic example 252: synthesis of Compound C252
This example is substantially the same as synthetic example 192 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 657.33. elemental analysis results: theoretical value: c, 85.84; h, 6.13; b, 1.64; and N, 6.39. Experimental values: c, 85.85; h, 6.14; b, 1.63; and N, 6.38.
Synthetic example 253: synthesis of Compound C253
This example is substantially the same as synthetic example 193 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 725.32. elemental analysis results: theoretical value: c, 79.45; h, 5.42; b, 1.49; f, 7.85; n, 5.79. Experimental values: c, 79.46; h, 5.43; b, 1.49; f, 7.84; n, 5.78.
Synthetic example 254: synthesis of Compound C254
This example is substantially the same as synthetic example 194, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-triisopropylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 793.31. elemental analysis results: theoretical value: c, 74.15; h, 4.83; b, 1.36; f, 14.36; and N, 5.29. Experimental values: c, 74.16; h, 4.83; b, 1.35; f, 14.35; and N, 5.30.
Synthesis example 255: synthesis of Compound C255
This example is substantially the same as synthetic example 165, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 609.11. elemental analysis results: theoretical value: c, 61.11; h, 2.15; b, 1.77; f, 28.06; and N, 6.90. Experimental values: c, 61.10; h, 2.14; b, 1.77; f, 28.07; and N, 6.91.
Synthetic example 256: synthesis of Compound C256
This example is substantially the same as synthetic example 166, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 776.18. elemental analysis results: theoretical value: c, 66.52; h, 2.86; b, 1.39; f, 22.02; and N, 7.22. Experimental values: c, 66.51; h, 2.85; b, 1.38; f, 22.03; and N, 7.21.
Synthetic example 257: synthesis of Compound C257
This example is substantially the same as synthesis example 167 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 852.21. elemental analysis results: theoretical value: c, 69.03; h, 3.07; b, 1.27; f, 20.06; and N, 6.57. Experimental values: c, 69.02; h, 3.08; b, 1.27; f, 20.05; and N, 6.58.
Synthetic example 258: synthesis of Compound C258
This example is substantially the same as synthetic example 168, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 892.24. elemental analysis results: theoretical value: c, 69.97; h, 3.39; b, 1.21; f, 19.16; and N, 6.28. Experimental values: c, 69.98; h, 3.39; b, 1.22; f, 19.15; and N, 6.27.
Synthesis example 259: synthesis of Compound C259
This example is substantially the same as synthetic example 169 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 866.19. elemental analysis results: theoretical value: c, 67.92; h, 2.79; b, 1.25; f, 19.73; n, 6.47; o, 1.85. Experimental values: c, 67.91; h, 2.78; b, 1.26; f, 19.72; n, 6.48; o, 1.86.
Synthesis example 260: synthesis of Compound C260
This example is substantially the same as synthesis example 170, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 677.09. elemental analysis results: theoretical value: c, 56.75; h, 1.79; b, 1.60; f, 33.66; and N, 6.20. Experimental values: c, 56.76; h, 1.78; b, 1.62; f, 33.65; and N, 6.20.
Synthetic example 261: synthesis of Compound C261
This example is substantially the same as synthetic example 171, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 677.09. elemental analysis results: theoretical value: c, 56.75; h, 1.79; b, 1.60; f, 33.66; and N, 6.20. Experimental values: c, 56.74; h, 1.80; b, 1.60; f, 33.67; and N, 6.19.
Synthesis example 262: synthesis of Compound C262
This example is substantially the same as synthetic example 172 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 677.09. elemental analysis results: theoretical value: c, 56.75; h, 1.79; b, 1.60; f, 33.66; and N, 6.20. Experimental values: c, 56.75; h, 1.79; b, 1.62; f, 33.65; and N, 6.19.
Synthetic example 263: synthesis of Compound C263
This example is substantially the same as synthesis example 173 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 745.08. elemental analysis results: theoretical value: c, 53.18; h, 1.49; b, 1.45; f, 38.24; and N, 5.64. Experimental values: c, 53.19; h, 1.48; b, 1.45; f, 38.23; and N, 5.65.
Synthesis example 264: synthesis of Compound C264
This example is substantially the same as synthetic example 174, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 813.07. elemental analysis results: theoretical value: c, 50.21; h, 1.24; b, 1.33; f, 42.05; and N, 5.17. Experimental values: c, 50.20; h, 1.24; b, 1.35; f, 42.06; and N, 5.18.
Synthesis example 265: synthesis of Compound C265
This example is substantially the same as Synthesis example 175 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 659.12. elemental analysis results: theoretical value: c, 63.76; h, 2.29; b, 1.64; f, 25.93; n, 6.37. Experimental values: c, 63.77; h, 2.30; b, 1.64; f, 25.92; and N, 6.36.
Synthetic example 266: synthesis of Compound C266
This example is substantially the same as synthetic example 176, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 727.11. elemental analysis results: theoretical value: c, 59.45; h, 1.94; b, 1.49; f, 31.35; n, 5.78. Experimental values: c, 59.46; h, 1.94; b, 1.50; f, 31.34; n, 5.77.
Synthetic example 267: synthesis of Compound C267
This example is substantially the same as synthetic example 177 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 795.10. elemental analysis results: theoretical value: c, 55.88; h, 1.65; b, 1.36; f, 35.83; and N, 5.28. Experimental values: c, 55.87; h, 1.64; b, 1.36; f, 35.84; and N, 5.29.
Synthesis example 268: synthesis of Compound C268
This example is substantially the same as synthesis example 178 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 659.12. elemental analysis results: theoretical value: c, 63.76; h, 2.29; b, 1.64; f, 25.93; n, 6.37. Experimental values: c, 63.75; h, 2.29; b, 1.65; f, 25.92; and N, 6.38.
Synthetic example 269: synthesis of Compound C269
This example is substantially the same as synthesis example 179 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 727.11. elemental analysis results: theoretical value: c, 59.45; h, 1.94; b, 1.49; f, 31.35; n, 5.78. Experimental values: c, 59.44; h, 1.95; b, 1.49; f, 31.34; n, 5.79.
Synthesis example 270: synthesis of Compound C270
This example is substantially the same as synthetic example 180 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 795.10. elemental analysis results: theoretical value: c, 55.88; h, 1.65; b, 1.36; f, 35.83; and N, 5.28. Experimental values: c, 55.87; h, 1.66; b, 1.36; f, 35.82; and N, 5.29.
Synthesis example 271: synthesis of Compound C271
This example is substantially the same as synthetic example 181, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 709.14. elemental analysis results: theoretical value: c, 66.03; h, 2.42; b, 1.52; f, 24.10; n, 5.92. Experimental values: c, 66.02; h, 2.41; b, 1.52; f, 24.11; and N, 5.93.
Synthesis of example 272: synthesis of Compound C272
This example is substantially the same as synthesis example 182, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 777.12. elemental analysis results: theoretical value: c, 61.80; h, 2.07; b, 1.39; f, 29.33; n, 5.41. Experimental values: c, 61.79; h, 2.07; b, 1.38; f, 29.34; n, 5.42.
Synthetic example 273: synthesis of Compound C273
This example is substantially the same as synthesis example 183 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 659.12. elemental analysis results: theoretical value: c, 63.76; h, 2.29; b, 1.64; f, 25.93; n, 6.37. Experimental values: c, 63.75; h, 2.28; b, 1.64; f, 25.94; and N, 6.38.
Synthetic example 274: synthesis of Compound C274
This example is substantially the same as synthetic example 184, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 727.11. elemental analysis results: theoretical value: c, 59.45; h, 1.94; b, 1.49; f, 31.35; n, 5.78. Experimental values: c, 59.45; h, 1.95; b, 1.50; f, 31.34; n, 5.77.
Synthetic example 275: synthesis of Compound C275
This example is substantially the same as synthesis example 185, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 795.10. elemental analysis results: theoretical value: c, 55.88; h, 1.65; b, 1.36; f, 35.83; and N, 5.28. Experimental values: c, 55.89; h, 1.64; b, 1.36; f, 35.82; and N, 5.29.
Synthetic example 276: synthesis of Compound C276
This example is substantially the same as synthetic example 186, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 709.14. elemental analysis results: theoretical value: c, 66.03; h, 2.42; b, 1.52; f, 24.10; n, 5.92. Experimental values: c, 66.02; h, 2.42; b, 1.51; f, 24.11; and N, 5.93.
Synthetic example 277: synthesis of Compound C277
This example is substantially the same as synthetic example 187 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 777.12. elemental analysis results: theoretical value: c, 61.80; h, 2.07; b, 1.39; f, 29.33; n, 5.41. Experimental values: c, 61.81; h, 2.06; b, 1.40; f, 29.32; n, 5.42.
Synthetic example 278: synthesis of Compound C278
This example is substantially the same as Synthesis example 188, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 845.11. elemental analysis results: theoretical value: c, 58.25; h, 1.79; b, 1.28; f, 33.71; and N, 4.97. Experimental values: c, 58.26; h, 1.78; b, 1.28; f, 33.70; and N, 4.98.
Synthetic example 279: synthesis of Compound C279
This example is substantially the same as synthetic example 189, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 759.15. elemental analysis results: theoretical value: c, 68.01; h, 2.52; b, 1.42; f, 22.51; n, 5.53. Experimental values: c, 68.02; h, 2.51; b, 1.41; f, 22.50; and N, 5.55.
Synthetic example 280: synthesis of Compound C280
This example is substantially the same as synthetic example 190 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 827.14. elemental analysis results: theoretical value: c, 63.87; h, 2.19; b, 1.31; f, 27.55; and N, 5.08. Experimental values: c, 63.86; h, 2.19; b, 1.30; f, 27.56; and N, 5.09.
Synthetic example 281: synthesis of Compound C281
This example is substantially the same as synthetic example 191 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 895.13. elemental analysis results: theoretical value: c, 60.36; h, 1.91; b, 1.21; f, 31.83; and N, 4.69. Experimental values: c, 60.37; h, 1.91; b, 1.22; f, 31.82; and N, 4.68.
Synthesis example 282: synthesis of Compound C282
This example is substantially the same as synthetic example 192 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 733.14. elemental analysis results: theoretical value: c, 67.15; h, 2.34; b, 1.47; f, 23.31; n, 5.73. Experimental values: c, 67.14; h, 2.34; b, 1.48; f, 23.30; n, 5.74.
Synthesis example 283: synthesis of Compound C283
This example is substantially the same as synthetic example 193 except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 801.12. elemental analysis results: theoretical value: c, 62.95; h, 2.01; b, 1.35; f, 28.45; and N, 5.24. Experimental values: c, 62.96; h, 2.01; b, 1.34; f, 28.46; and N, 5.23.
Synthetic example 284: synthesis of Compound C284
This example is substantially the same as synthetic example 194, except that: in this case, the dimethyl phenylboronate in the sixth step is replaced by an equivalent amount of dimethyl 1,3, 5-trifluoromethyphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 869.11. elemental analysis results: theoretical value: c, 59.41; h, 1.74; b, 1.24; f, 32.78; and N, 4.83. Experimental values: c, 59.40; h, 1.75; b, 1.23; f, 32.79; n, 4.84.
Synthesis example 285: synthesis of Compound C285
This example is substantially the same as synthetic example 1 except that: in this case, the dimethyl phenylboronate in the fourth reaction stage is replaced by an equivalent amount of dimethyl 2-methyl-6-trifluoromethylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 475.10. elemental analysis results: theoretical value: c, 65.70; h, 3.61; b, 2.27; f, 11.99; n, 2.95; o, 6.73; and S, 6.75. Experimental values: c, 65.71; h, 3.60; b, 2.28; f, 12.00; n, 2.93; o, 6.74; and S, 6.74.
Synthetic example 286: synthesis of Compound C286
This example is substantially the same as synthetic example 1 except that: in this case, the dimethyl phenylboronate in the fourth reaction stage is replaced by an equivalent amount of dimethyl 2-tert-butyl-6-trifluoromethylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 517.15. elemental analysis results: theoretical value: c, 67.32; h, 4.48; b, 2.09; f, 11.02; n, 2.71; o, 6.18; and S, 6.20. Experimental values: c, 67.34; h, 4.48; b, 2.08; f, 11.01; n, 2.70; o, 6.19; and S, 6.18.
Synthesis example 287: synthesis of Compound C287
This example is substantially the same as synthetic example 1 except that: in this case, the dimethyl phenylboronate in the fourth reaction stage is replaced by an equivalent amount of dimethyl 2, 4-dimethyl-6-trifluoromethylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 489.12. elemental analysis results: theoretical value: c, 66.28; h, 3.91; b, 2.21; f, 11.65; n, 2.86; o, 6.54; s, 6.55. Experimental values: c, 66.26; h, 3.92; b, 2.21; f, 11.64; n, 2.87; o, 6.54; and S, 6.56.
Synthetic example 288: synthesis of Compound C288
This example is substantially the same as synthetic example 45, except that: in this case, dimethyl phenylboronate in the sixth reaction stage is replaced by an equivalent amount of dimethyl 2-methyl-6-trifluoromethylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 439.14. elemental analysis results: theoretical value: c, 73.83; h, 3.90; b, 2.46; f, 12.98; n, 3.19; and O, 3.64. Experimental values: c, 73.82; h, 3.92; b, 2.45; f, 12.97; n, 3.18; and O, 3.65.
Synthetic example 289: synthesis of Compound C289
This example is substantially the same as synthetic example 45, except that: in this case, dimethyl phenylboronate in the sixth reaction stage is replaced by an equivalent amount of dimethyl 2-tert-butyl-6-trifluoromethylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 481.18. elemental analysis results: theoretical value: c, 74.86; h, 4.82; b, 2.25; f, 11.84; n, 2.91; and O, 3.32. Experimental values: c, 74.85; h, 4.81; b, 2.25; f, 11.83; n, 2.92; and O, 3.34.
Synthetic example 290: synthesis of Compound C290
This example is substantially the same as synthetic example 45, except that: in this case, dimethyl phenylboronate in the sixth reaction stage is replaced by an equivalent amount of dimethyl 2, 4-dimethyl-6-trifluoromethylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 453.15. elemental analysis results: theoretical value: c, 74.20; h, 4.23; b, 2.38; f, 12.57; n, 3.09; o, 3.53. Experimental values: c, 74.22; h, 4.22; b, 2.39; f, 12.57; n, 3.08; and O, 3.52.
Synthetic example 291: synthesis of Compound C291
This example is substantially the same as synthetic example 165, except that: in this case, dimethyl phenylboronate in the sixth reaction stage is replaced by an equivalent amount of dimethyl 2-methyl-6-trifluoromethylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 487.15. elemental analysis results: theoretical value: c, 73.95; h, 3.52; b, 2.22; f, 11.70; n, 8.62. Experimental values: c, 73.94; h, 3.52; b, 2.21; f, 11.71; and N, 8.63.
Synthesis example 292: synthesis of Compound C292
This example is substantially the same as synthetic example 165, except that: in this case, dimethyl phenylboronate in the sixth reaction stage is replaced by an equivalent amount of dimethyl 2-tert-butyl-6-trifluoromethylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 529.19. elemental analysis results: theoretical value: c, 74.87; h, 4.38; b, 2.04; f, 10.77; and N, 7.94. Experimental values: c, 74.88; h, 4.38; b, 2.03; f, 10.76; and N, 7.95.
Synthetic example 293: synthesis of Compound C293
This example is substantially the same as synthetic example 165, except that: in this case, dimethyl phenylboronate in the sixth reaction stage is replaced by an equivalent amount of dimethyl 2, 4-dimethyl-6-trifluoromethylphenylboronate. MALDI-TOF-MS results: molecular ion peaks: 501.16. elemental analysis results: theoretical value: c, 74.27; h, 3.82; b, 2.16; f, 11.37; and N, 8.38. Experimental values: c, 74.28; h, 3.81; b, 2.15; f, 11.36; n, 8.39.
Application embodiments of the compounds prepared according to the invention:
the compound of the invention can be applied to an organic electroluminescent device, namely an OLED device, and is most preferably used as a material in a light-emitting layer.
The OLED includes first and second electrodes, and an organic material layer between the electrodes. The organic material may in turn be divided into a plurality of regions. For example, the organic material layer may include a hole transport region, a light emitting layer, and an electron transport region.
In a specific embodiment, a substrate may be used below the first electrode or above the second electrode. The substrate is a glass or polymer material having excellent mechanical strength, thermal stability, water resistance, and transparency. In addition, a Thin Film Transistor (TFT) may be provided on a substrate for a display.
The first electrode may be formed by sputtering or depositing a material used as the first electrode on the substrate. When the first electrode is used as an anode, an oxide transparent conductive material such as Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO), or any combination thereof may be used. When the first electrode is used as a cathode, a metal or an alloy such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), or any combination thereof can be used.
The organic material layer may be formed on the electrode by vacuum thermal evaporation, spin coating, inkjet printing, or the like. The compound used as the organic material layer may be an organic small molecule, an organic large molecule, and a polymer, and a combination thereof.
The hole transport region is located between the anode and the light emitting layer. The hole transport region may be a Hole Transport Layer (HTL) of a single layer structure including a single layer containing only one compound and a single layer containing a plurality of compounds. The hole transport region may also be a multilayer structure including at least one of a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), and an Electron Blocking Layer (EBL).
The material of the hole transport region may be selected from, but is not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylenevinylenes, polyaniline/dodecylbenzenesulfonic acid (Pani/DBSA), poly (3, 4-ethylenedioxythiophene)/poly (4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphorsulfonic acid (Pani/CSA), polyaniline/poly (4-styrenesulfonate) (Pani/PSS), aromatic amine derivatives.
The hole injection layer is positioned between the anode and the hole transport layer, and the hole injection layer can be a single compound material or a combination of a plurality of compounds.
The material of the light-emitting layer employed in the organic electroluminescent device of the present invention is selected from one of the preferred compounds M1-M5058 of the present invention.
The OLED organic material layer may further include an electron transport region between the light emitting layer and the cathode. The electron transport region may be an Electron Transport Layer (ETL) of a single-layer structure including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing a plurality of compounds. The electron transport region may also be a multilayer structure including at least one of an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), and a Hole Blocking Layer (HBL).
An electron injection layer may also be included in the device between the electron transport layer and the cathode, the electron injection layer material including, but not limited to, combinations of one or more of the following: liq, LiF, NaCl, CsF, Li2O,Cs2CO3,BaO,Na,Li,Ca。
The technical effects and advantages of the present invention are demonstrated and verified by testing the practical use properties of the compounds of the present invention, particularly by applying the compounds of the present invention to organic electroluminescent devices.
The preparation process of the organic electroluminescent device comprises the following steps:
the glass plate coated with the ITO transparent conductive layer was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an isopropanol mixed solvent, baking in a clean environment until water is completely removed, cleaning by using ultraviolet light and ozone, and bombarding the surface by using a low-energy cationic beam;
placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 1 × 10-5～9×10-3Pa, vacuum evaporating a hole injection layer on the anode layer film, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 5-10 nm; vacuum evaporating a hole transport layer on the hole injection layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 60-80 nm; the luminescent layer of the device is vacuum evaporated on the hole transport layer, the luminescent layer comprises a host material and a dye material, the dye material is selected from one of the compounds C1, C11, C45, C47, C61, C72, C165, C167, C181 and C192, the evaporation rate of the host material is adjusted to be 0.1nm/s, the evaporation rate of the dye in the luminescent layer is adjusted to be 3%, and the total thickness of the luminescent layer is 30 nm. Vacuum evaporating an electron transport layer material of the device on the luminescent layer, wherein the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 30-60 nm; LiF with the thickness of 1nm is vacuum-evaporated on the Electron Transport Layer (ETL) to be used as an electron injection layer, and an Al layer with the thickness of 150nm is used as a cathode of the device.
The OLED device is tested in an integrating sphere under room temperature and atmospheric conditions, and parameters such as voltage, external quantum efficiency, current density, brightness and the like of the device can be measured through an absolute external quantum efficiency measuring system C9920-12 of Hamamatsu company, Japan, and a prepared Hamamatsu C10027-02 type PMA-12 photon multi-channel spectrometer (the detection range is 350-.
The following devices OLED1 to OLED10 using the compounds C1, C11, C45, C47, C61, C72, C165, C167, C181 and C192 of the present invention were prepared according to the above-described step method.
The structure of each OLED device and the thickness of each layer are respectively as follows:
device embodiment 1 of the invention:
when the compound C1 is used as a luminescent material, the device structure is as follows: ITO/HATCN (10nm)/TAPC (50nm)/TCTA (10nm)/3 wt% C1 mCP (30nm)/B4PyMPM (45nm)/LiF (1nm)/Al (150nm), and device performance tests were performed according to the organic electroluminescent device test method described above.
Device embodiment 2 of the invention:
when the compound C11 is used as a luminescent material, the device structure is as follows: ITO/HATCN (10nm)/TAPC (50nm)/TCTA (10nm)/3 wt% C11 mCP (30nm)/B4PyMPM (45nm)/LiF (1nm)/Al (150nm), and device performance tests were performed according to the organic electroluminescent device test method described above.
Device example 3 of the invention:
when the compound C45 is used as a luminescent material, the device structure is as follows: ITO/HATCN (10nm)/TAPC (50nm)/TCTA (10nm)/3 wt% C45 mCP (30nm)/B4PyMPM (45nm)/LiF (1nm)/Al (150nm), and device performance tests were performed according to the organic electroluminescent device test method described above.
Device example 4 of the invention:
when the compound C47 is used as a luminescent material, the device structure is as follows: ITO/HATCN (10nm)/TAPC (50nm)/TCTA (10nm)/3 wt% C47 mCP (30nm)/B4PyMPM (45nm)/LiF (1nm)/Al (150nm), and device performance tests were performed according to the organic electroluminescent device test method described above.
Device example 5 of the invention:
when the compound C61 is used as a luminescent material, the device structure is as follows: ITO/HATCN (10nm)/NPB (70nm)/TCTA (10nm)/3 wt% C61 TBPi (30nm)/TPBi (60nm)/LiF (1nm)/Al (150nm), device performance tests were performed according to the organic electroluminescent device test method described above.
Device example 6 of the present invention:
when the compound C72 is used as a luminescent material, the device structure is as follows: ITO/HATCN (10nm)/NPB (70nm)/TCTA (10nm)/3 wt% C72 TBPi (30nm)/TPBi (60nm)/LiF (1nm)/Al (150nm), device performance tests were performed according to the organic electroluminescent device test method described above.
Device example 7 of the present invention:
the compound C165 of the invention is used as a luminescent material, and the device structure is as follows: ITO/HATCN (10nm)/NPB (70nm)/TCTA (10nm)/3 wt% C165: TBPi (30nm)/TPBi (60nm)/LiF (1nm)/Al (150nm), device performance tests were performed according to the organic electroluminescent device test method described above.
Device example 8 of the present invention:
the compound C167 of the invention is used as a luminescent material, and the structure of the device is as follows: ITO/HATCN (10nm)/NPB (70nm)/TCTA (10nm)/3 wt% C167: TBPi (30nm)/TPBi (60nm)/LiF (1nm)/Al (150nm), and device performance tests were performed according to the organic electroluminescent device test method described above.
Device example 9 of the present invention:
when the compound C181 of the invention is used as a luminescent material, the device structure is as follows: ITO/HATCN (10nm)/NPB (70nm)/TCTA (10nm)/3 wt% C181: TBPi (30nm)/TPBi (60nm)/LiF (1nm)/Al (150nm), and device performance tests were carried out according to the organic electroluminescent device test method described above.
Device example 10 of the present invention:
when the compound C192 provided by the invention is used as a luminescent material, the device structure is as follows: ITO/HATCN (10nm)/NPB (70nm)/TCTA (10nm)/3 wt% C192: TBPi (30nm)/TPBi (60nm)/LiF (1nm)/Al (150nm), and device performance tests were carried out according to the organic electroluminescent device test method described above.
Comparative device example 1:
the compound DABNA-1 in the prior art is used as a luminescent material, and the device structure is as follows: ITO/NPD (40nm)/TCTA (15nm)/1 wt% DABNA-1: mCBP (20nm)/TSPO1(40nm)/LiF (1nm)/Al (100nm), device performance tests were performed according to the above organic electroluminescent device test method.
Figure BDA0002700091560001061
Specific data on the performance of each of the organic electroluminescent devices prepared as described above are listed in table 4 below.
Table 4:
Figure BDA0002700091560001062
Figure BDA0002700091560001071
the details of the performance of the organic electroluminescent device prepared in example 1 are specifically shown in fig. 2 and fig. 3, where fig. 2 is the electroluminescent spectrum of the device OLED1, and fig. 3 is the external quantum efficiency-current density curve of the device OLED 1.
As can be seen from the performance comparison results of the device embodiments prepared by the invention, the organic electroluminescent device prepared by adopting the preferable compound has the advantages of high luminous efficiency, high spectral color purity, narrow half-peak width and the like. The analysis of the specific reasons is as follows: due to the existence of the bridging group for electron withdrawing and the nitrogen atom for electron donating in the molecule of the compound and the rigid structure of the molecule, the compound has bipolar transmission performance, higher luminescent color purity and higher efficiency in electroluminescent devices.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (11)

1. A polycyclic aromatic compound represented by the following formula I:
Figure FDA0002700091550000011
in the formula I, Ar1 ring, Ar2 ring and Ar3 ring respectively and independently represent one of substituted or unsubstituted C6-C60 aromatic ring and substituted or unsubstituted C4-C60 heteroaromatic ring, Ar4 represents one of substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C4-C60 heteroaromatic ring;
in formula I, X is selected from any one of the structures shown below:
Figure FDA0002700091550000012
"+" represents the position of the access bond of the group;
when the Ar1 ring, the Ar2 ring, the Ar3 ring and the Ar4 have substituents, the substituents are respectively and independently selected from one or a combination of at least two of deuterium, halogen, cyano, chain alkyl of C1-C36, chain alkenyl of C1-C36, chain alkynyl of C1-C36, cycloalkyl of C3-C36, cycloalkenyl of C4-C36, ring alkynyl of C4-C36, alkoxy of C1-C30, thioalkoxy of C1-C30, carbonyl, carboxyl, nitro, amino, arylamino of C6-C30, heteroarylamino of C3-C30, monocyclic aryl of C6-C60, fused ring aryl of C6-C60, aryloxy of C4-C60, monocyclic 60 of C2-C heteroaryl, and fused ring heteroaryl of C2-C60.
2. The polycyclic aromatic compound of claim 1, having a structure represented by the following formula I-1, formula I-2 or formula I-3:
Figure FDA0002700091550000013
in formula I-1, formula I-2 and formula I-3, the definitions of the Ar1 ring, Ar2 ring, Ar3 ring and Ar4 ring are the same as those in formula I.
3. The polycyclic aromatic compound of claim 1 or 2, formula I-1, formula I-2 or formula I-3, wherein the Ar1, Ar2, Ar3 rings are each independently selected from one of the following substituted or unsubstituted groups: benzene ring, biphenyl ring, naphthalene ring, anthracene ring, phenanthrene ring, indene ring, fluorene ring, fluorantheneA ring, a triphenylene ring, a pyrene ring, a perylene ring,
Figure FDA0002700091550000014
The compound is characterized by comprising a ring, a tetracene ring, a furan ring, a thiophene ring, a pyrrole ring, a benzofuran ring, a benzothiophene ring, an isobenzofuran ring, an indole ring, a dibenzofuran ring, a dibenzothiophene ring or a carbazole ring, wherein Ar4 is selected from one of the following substituted or unsubstituted groups: phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, indenyl, fluorenyl, fluoranthenyl, triphenylenyl, pyrenyl, perylenyl, perylene, and the like,
Figure FDA0002700091550000015
A phenyl, tetracenyl, furyl, thienyl, pyrrolyl, benzofuryl, benzothienyl, isobenzofuryl, indolyl, dibenzofuryl, dibenzothienyl or carbazolyl group;
preferably, the Ar1 ring is selected from a substituted or unsubstituted benzene ring, and the Ar2 ring and the Ar3 ring are each independently selected from one of the following substituted or unsubstituted groups: benzene ring, biphenyl ring, terphenyl ring, naphthalene ring, anthracene ring, phenanthrene ring, indene ring, fluorene ring, fluoranthene ring, triphenylene ring, perylene,
Figure FDA0002700091550000016
The compound is characterized by comprising a ring, a tetracene ring, a furan ring, a thiophene ring, a pyrrole ring, a benzofuran ring, a benzothiophene ring, an isobenzofuran ring, an indole ring, a dibenzofuran ring, a dibenzothiophene ring or a carbazole ring, wherein Ar4 is selected from one of substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl;
when the Ar1 ring, the Ar2 ring, the Ar3 ring and the Ar4 have substituents, the substituents are respectively and independently selected from one or a combination of at least two of deuterium, halogen, cyano, chain alkyl of C1-C36, chain alkenyl of C1-C36, chain alkynyl of C1-C36, cycloalkyl of C3-C36, cycloalkenyl of C4-C36, ring alkynyl of C4-C36, alkoxy of C1-C30, thioalkoxy of C1-C30, carbonyl, carboxyl, nitro, amino, arylamino of C6-C30, heteroarylamino of C3-C30, monocyclic aryl of C6-C60, fused ring aryl of C6-C60, aryloxy of C4-C60, monocyclic 60 of C2-C heteroaryl, and fused ring heteroaryl of C2-C60.
4. The polycyclic aromatic compound of any one of claims 1 to 3, wherein when a substituent is present on Ar1 ring, Ar2 ring, Ar3 ring, Ar4 in formula I, formula I-1, formula I-2, or formula I-3, said substituent is independently selected from deuterium or from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2, 2-trifluoroethyl, 2, 2-dicyanovinyl, phenyl, naphthyl, anthracenyl, benzanthracenyl, phenanthrenyl, benzophenanthrenyl, pyrenyl, bornyl, fluoranthenyl, tetracenyl, perylene, tetracenyl, perylene, Pentacenyl, benzopyrenyl, biphenyl, biphenylyl, terphenyl, quaterphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis-or trans-indenofluorenyl, trimeric indenyl, isotridecyl, spirotrimeric indenyl, spiroisotridecyl, furyl, benzofuryl, isobenzofuryl, dibenzofuryl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, isoindolyl, carbazolyl, indenocarbazolyl, pyridyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5, 6-quinolyl, benzo-6, 7-quinolyl, benzo-7, 8-quinolyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, etc, Pyrazinoimidazolyl, quinoxalinylazolyl, oxazolyl, benzoxazolyl, naphthooxazolyl, anthracenyloxazolyl, phenanthrenyloxazolyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyrazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1, 5-diazanthronyl, 2, 7-diazpyreneyl, 2, 3-diazyrenyl, 1, 6-diazyrenyl, 1, 8-diazyrenyl, 4,5,9, 10-tetraazaperyl, pyrazinyl, phenazinyl, phenothiazinyl, naphthyridinyl, azacarbazolyl, benzocainenyl, phenanthrolinyl, 1,2, 3-triazolyl, 1,2, 4-triazolyl, benzotriazolyl, 1,2, 3-oxadiazolyl, 1,2, 4-oxadiazolyl, 1,2, 5-oxadiazolyl, 1,2, 3-thiadiazolyl, 1,2, 4-thiadiazolyl, 1,2, 5-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,3, 5-triazinyl, 1,2, 4-triazinyl, 1,2, 3-triazinyl, tetrazolyl, 1,2,4, 5-tetrazinyl, 1,2,3, 4-tetrazinyl, 1,2,3, 5-tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, 9-dimethylazinyl, triarylamine, adamantane, fluorophenyl, methylphenyl, trimethylphenyl, cyanophenyl, tetrahydropyrrole, piperidine, methoxy, silyl, cyano, fluorine, chlorine, or a combination of at least two thereof.
5. The polycyclic aromatic compound of claim 1 or 2, formula I-1, formula I-2 or formula I-3, wherein the Ar1 ring is selected from any one of the structures represented by formulae D1 to D298 below:
Figure FDA0002700091550000021
Figure FDA0002700091550000031
Figure FDA0002700091550000041
Figure FDA0002700091550000051
Figure FDA0002700091550000061
wherein,
Figure FDA0002700091550000062
represents a linking site with a nitrogen atom in the structure of formula I, formula I-1, formula I-2 or formula I-3,
Figure FDA0002700091550000063
represents a linking site to a boron atom in the structure of formula I, formula I-1, formula I-2 or formula I-3,
Figure FDA0002700091550000064
represents the connecting site with X group in the structure of formula I, sulfone group in the structure of formula I-1, carbonyl group in the structure of formula I-2 and dicyanovinyl group in the structure of formula I-3;
when formulae D1 to D298 contain only one substituent group in varying positions and numbers, n represents from 1 to the maximum number of substituents permitted; when two substituent groups with variable positions and numbers are contained in the structural formulas D1-D298, m and n respectively and independently represent 0 to the maximum allowable number of the substituent groups and are not simultaneously 0; when three substituent groups with variable positions and numbers are contained in the structural formulas D1 to D298, m, l and n respectively and independently represent 0 to the maximum allowable number of the substituent groups and are not simultaneously 0.
6. The polycyclic aromatic compound of claim 1 or 2, formula I-1, formula I-2 or formula I-3, wherein the Ar2 ring and Ar3 ring are each independently selected from any one of the structures represented by formulae E1 to E612 below:
Figure FDA0002700091550000071
Figure FDA0002700091550000081
Figure FDA0002700091550000091
Figure FDA0002700091550000101
Figure FDA0002700091550000111
Figure FDA0002700091550000121
Figure FDA0002700091550000131
Figure FDA0002700091550000141
wherein,
Figure FDA0002700091550000152
represents a linking site with a nitrogen atom in the structure of formula I, formula I-1, formula I-2 or formula I-3,
Figure FDA0002700091550000153
represents a site of attachment to another bridging group other than a nitrogen atom in the structure of formula I, formula I-1, formula I-2 or formula I-3;
when formulae E1 to E612 above contain only one substituent group in varying positions and numbers, n represents from 1 to the maximum number of substituents permitted; when two substituent groups with variable positions and numbers are contained in structural formulas E1-E612, m and n respectively and independently represent 0 to the maximum allowable number of substituent groups and are not 0 at the same time; when three substituent groups with variable positions and numbers are contained in structural formulas E1-E612, m, l and n respectively and independently represent 0 to the maximum allowable number of substituent groups and are not simultaneously 0.
7. The polycyclic aromatic compound of claim 1 or 2, formula I-1, formula I-2 or formula I-3, wherein Ar4 is selected from any one of the structures represented by formulae F1 to F186:
Figure FDA0002700091550000151
Figure FDA0002700091550000161
Figure FDA0002700091550000171
wherein,
Figure FDA0002700091550000172
represents a site of attachment to a boron atom in the structure of formula I, formula I-1, formula I-2 or formula I-3.
8. The polycyclic aromatic compound of claim 1 or 2, formula I-1, formula I-2 or formula I-3, wherein the Ar1 ring is selected from any one of the structures shown below:
Figure FDA0002700091550000173
wherein,
Figure FDA0002700091550000177
represents a linking site with a nitrogen atom in the structure of formula I, formula I-1, formula I-2 or formula I-3,
Figure FDA0002700091550000174
represents a compound of formula I, formula I-1, formula I-2 or formula I-3The attachment site of the boron atom in the structure,
Figure FDA0002700091550000175
represents the connecting site with X group in the structure of formula I, sulfone group in the structure of formula I-1, carbonyl group in the structure of formula I-2 and dicyanovinyl group in the structure of formula I-3;
in formula I, formula I-1, formula I-2, or formula I-3, the Ar2 and Ar3 rings are each independently selected from any one of the structures shown below:
Figure FDA0002700091550000176
Figure FDA0002700091550000181
wherein,
Figure FDA0002700091550000182
represents a linking site with a nitrogen atom in the structure of formula I, formula I-1, formula I-2 or formula I-3,
Figure FDA0002700091550000183
represents a site of attachment to another bridging group other than a nitrogen atom in the structure of formula I, formula I-1, formula I-2 or formula I-3;
in formula I, formula I-1, formula I-2 or formula I-3, Ar4 is selected from any one of the structures shown below:
Figure FDA0002700091550000184
wherein,
Figure FDA0002700091550000185
represents a site of attachment to a boron atom in the structure of formula I, formula I-1, formula I-2 or formula I-3.
9. The polycyclic aromatic compound of claim 1 or 2, the compound of formula I, formula I-1, formula I-2, or formula I-3 having the structure shown below:
Figure FDA0002700091550000186
Figure FDA0002700091550000191
Figure FDA0002700091550000201
Figure FDA0002700091550000211
Figure FDA0002700091550000221
Figure FDA0002700091550000231
Figure FDA0002700091550000241
Figure FDA0002700091550000251
Figure FDA0002700091550000261
10. use of the polycyclic aromatic compound of any one of claims 1 to 9 as a functional material in an organic electronic device comprising: an organic electroluminescent device, an optical sensor, a solar cell, a lighting element, an organic thin film transistor, an organic field effect transistor, an organic thin film solar cell, an information label, an electronic artificial skin sheet, a sheet type scanner, or electronic paper.
11. An organic electroluminescent device comprising a first electrode, a second electrode and one or more organic layers interposed between said first and second electrodes, characterized in that said organic layers comprise at least one compound according to any one of claims 1 to 9.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA3016778A1 (en) * 2017-09-14 2019-03-14 Cynora Gmbh Organic molecules, in particular for use in optoelectronic devices
CN110790782A (en) * 2019-11-11 2020-02-14 北京大学深圳研究生院 Dark blue organic luminescent material and preparation method and application thereof
WO2020138964A1 (en) * 2018-12-26 2020-07-02 주식회사 엘지화학 Compound and organic light-emitting element comprising same
CN111574544A (en) * 2019-02-18 2020-08-25 江苏三月科技股份有限公司 Organic compound containing boron and application thereof in organic electroluminescent device
CN111606935A (en) * 2019-02-25 2020-09-01 三星显示有限公司 Heterocyclic compound and organic light-emitting device including the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA3016778A1 (en) * 2017-09-14 2019-03-14 Cynora Gmbh Organic molecules, in particular for use in optoelectronic devices
WO2020138964A1 (en) * 2018-12-26 2020-07-02 주식회사 엘지화학 Compound and organic light-emitting element comprising same
CN111574544A (en) * 2019-02-18 2020-08-25 江苏三月科技股份有限公司 Organic compound containing boron and application thereof in organic electroluminescent device
CN111606935A (en) * 2019-02-25 2020-09-01 三星显示有限公司 Heterocyclic compound and organic light-emitting device including the same
CN110790782A (en) * 2019-11-11 2020-02-14 北京大学深圳研究生院 Dark blue organic luminescent material and preparation method and application thereof

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