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CN116396145A - Preparation method of 9-phenanthrene phenol compound - Google Patents

Preparation method of 9-phenanthrene phenol compound Download PDF

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CN116396145A
CN116396145A CN202310343956.0A CN202310343956A CN116396145A CN 116396145 A CN116396145 A CN 116396145A CN 202310343956 A CN202310343956 A CN 202310343956A CN 116396145 A CN116396145 A CN 116396145A
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phenanthrene
dimethylamino
phenol compound
iodobenzene
palladium
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周书光
邹彩常
杨启帆
崔淏南
雷骐尔
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Northwestern Polytechnical University
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    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
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    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
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Abstract

The invention discloses a preparation method of a 9-phenanthrene phenol compound, which comprises the following steps: enaminones and iodobenzene compounds with chemical structural formulas shown as (I) and (II) are used as raw materials, react in an organic solvent under the action of a catalyst and an oxidant to obtain a reaction product, and the obtained reaction product is purified to obtain the 9-phenanthrene phenol compound with the chemical structural formula shown as (III). The invention selects enaminones and iodobenzene compounds which have simple synthesis, high conversion rate and wide substrate application range as raw materials, and the used catalyst has low cost, little pollution and few reaction byproducts; the preparation method has the characteristics of simple and safe operation, high selectivity and high yield. The 9-phenanthrene phenol compounds have wide distribution in biological and pharmaceutical active molecules (such as inhibitors and antitumor drugs), so that the application prospect is wide.

Description

Preparation method of 9-phenanthrene phenol compound
Technical Field
The invention belongs to the technical field of synthesis of organic compounds, and particularly relates to a preparation method of a 9-phenanthrene phenol compound.
Background
9-phenanthrene phenol is an important derivative of phenanthrene, has a polycyclic aromatic hydrocarbon skeleton and a phenolic hydroxyl group, and has been applied to the fields of organic synthesis, material chemistry and pharmaceutical chemistry, such as synthesis of phenanthrene-based alkaloids and complex natural organic substances, organic semiconductors, organic photoelectric materials, superconducting materials, anticancer, antitumor drugs and the like. 9-phenanthrenol has a wide range of characteristics in many bioactive molecules and drugs, often used in traditional medicine, for example 9-aminobenzanthracene converted from 9-phenanthrenol is closely related in structure to morphine, some examples include the most popular drugs such as Adalat and Norvasc known as L-type calcium channel blockers for the treatment of hypertension, and Biktarvy and Tivicay as HIV-1 integrase inhibitors for the treatment of Human Immunodeficiency Virus (HIV) infection. Meanwhile, the research shows that 9-phenanthrene phenol is a TRPM4 inhibitor, and can protect isolated rat hearts from ischemia reperfusion injury. In synthesis, the 9-phenanthrene phenol and the derivative thereof can be used as important intermediates for synthesizing phenanthrene quinone, selenol condensed aromatic compounds, cyclic ethers and other complex aromatic compounds.
The first synthesis of 9-phenanthrene phenol has been reported by oxidizing phenanthrene to phenanthrene ketone, followed by 10,the reduction of 10-dichlorophenanthrene-9 (10H) -one is realized, but the method has the defects of expensive raw materials and PCl serving as a reducing agent 5 The reaction is more intense, and the intermediate products are unstable. Many synthetic methods of 9-phenanthrol have been reported hereafter, such as using metal-catalyzed cyclization, but the method is prone to produce more byproducts, and in some cases, the starting materials are not readily available, and the like; in addition to the complicated steps in the process for the preparation by oxidative radical cyclization of biphenylarylacetylene, the process suffers from productivity due to the hindered rotation on the biaryl axis. In recent years, although transition metal catalyzed synthesis of phenanthrene phenolic compounds has been greatly developed, in most cases, a long reaction time and a cumbersome post-treatment process are always required, and in some cases, starting materials are not readily available.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a preparation method of a 9-phenanthrene phenol compound, which aims to solve the defects of high cost of raw materials and catalysts, expensive ligand, harsh reaction conditions, poor atomic economy and the like existing in the existing synthesis method.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a preparation method of a 9-phenanthrene phenol compound comprises the following steps: enaminones and iodobenzene compounds with chemical structural formulas shown as (I) and (II) are used as raw materials, react for 20-24 hours in an organic solvent under the action of a catalyst and an oxidant to obtain a reaction product, and the obtained reaction product is purified to obtain the 9-phenanthrene phenol compound with the structural formula shown as (III):
Figure BDA0004158960790000021
wherein R is selected from any one of H, C-C3 alkyl, halogen and CN, OMe, COOMe, R is 1 Selected from one of H, C-C3 alkyl, halogen, CHO and COOMe.
Preferably, the temperature of the reaction is 110 to 120 ℃.
Preferably, the molar ratio of the catalyst to the enaminones is 0.01-0.05: 1.
preferably, the molar ratio of the oxidant to the enaminones is 1.0-3.0: 1.
preferably, the molar ratio of the iodobenzene compound to the enaminone compound is 3.0-4.5: 1.0 to 1.5.
Preferably, the catalyst is any one of palladium acetate, palladium chloride, bis (dibenzylideneacetone) palladium, tetrakis (triphenylphosphine) palladium, palladium trifluoroacetate, bis (acetylacetonato) palladium (II) and palladium hydroxide.
Preferably, the enaminones are selected from the group consisting of (E) -3- (dimethylamino) -1-phenylprop-2-en-1-one, (E) -1- (4-fluorophenyl) -3- (dimethylamino) prop-2-en-1-one, methyl 4- [ (2E) -3- (dimethylamino) -1-oxo-2-propen-1-yl ] benzoate, (E) -1- (4-methoxyphenyl) -3- (dimethylamino) prop-2-en-1-one, (E) -3- (dimethylamino) -1- (p-methylphenyl) prop-2-en-1-one, (E) -3- (dimethylamino) -1- (m-methylphenyl) prop-2-en-1-one, (E) -1- (3-fluorophenyl) -3- (dimethylamino) prop-2-en-1-one, (E) -4-3- (dimethylamino) prop-2-enoyl benzonitrile, (E) -any one of 1- (4- (dimethylamino) phenyl) -3- (dimethylamino) prop-2-en-1-one.
Preferably, the iodobenzene compound is selected from any one of iodobenzene, 1-fluoro-4-iodobenzene, 4-iodobenzoic acid ethyl ester, 4-methyl iodobenzene and 2-iodobenzaldehyde.
Preferably, the oxidant is any one of silver oxide, silver trifluoroacetate, silver diethyl dithiocarbamate, silver acetate, silver nitrate, hydrogen peroxide, tert-butyl hydroperoxide and copper acetate.
Preferably, the organic solvent is any one of trifluoroacetic acid, acetic acid, methanesulfonic acid and formic acid.
Preferably, the reaction is carried out in a protective gas atmosphere, the protective gas being nitrogen or argon.
Preferably, the reaction product is purified by thin layer chromatography using a developing solvent system of petroleum ether/ethyl acetate, wherein the volume ratio of petroleum ether to ethyl acetate in the developing solvent system is 100-30: 1.
compared with the prior art, the invention has the following beneficial effects:
the invention selects enaminones and iodobenzene compounds which have simple synthesis, high conversion rate and wide substrate application range as raw materials, and the used catalyst has low cost, little pollution, few reaction byproducts and environmental protection; in addition, the preparation method of the invention has the characteristics of simple and safe operation, high selectivity and high yield. The 9-phenanthrene phenol compounds have wide distribution in biological and pharmaceutical active molecules (such as inhibitors and antitumor drugs), so that the application prospect is wide.
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In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a synthetic route diagram of a 9-phenanthrene phenol compound provided by the invention;
FIG. 2 is a structural formula of a representative example of iodobenzene compounds and enaminones in an embodiment of the present invention;
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of 9-phenanthrene phenol prepared in example 1 of the present invention;
FIG. 4 is a carbon spectrum of 9-phenanthrol prepared in example 1 of the present invention;
Detailed Description
In the following description, for purposes of explanation and not limitation, specific details are set forth such as the particular system architecture, techniques, etc., in order to provide a thorough understanding of the embodiments of the present invention. It will be apparent, however, to one skilled in the art that the present invention may be practiced in other embodiments that depart from these specific details.
Example 1
Referring to FIGS. 1 and 2, the 9-phenanthrene phenol compound III is prepared by a synthetic route of the 9-phenanthrene phenol compound.
To a 10mL Schlenk tube, (E) -3- (dimethylamino) -1-phenylprop-2-en-1-one (1.0 mmol,0.1750 g), silver trifluoroacetate (1.0 mmol,0.2210 g), palladium acetate (5 mol%,0.0112 g), iodobenzene (3.0 mmol,0.612 g) and trifluoroacetic acid (2.0 mL) were sequentially added, and the reaction was stirred at 120℃for 24 hours under nitrogen atmosphere, after completion of the reaction, the product was isolated and purified by thin layer chromatography (developing solvent system petroleum ether/ethyl acetate, volume of both 100:1) as a yellow solid, i.e., compound 3, yield 93%. Referring to fig. 3 and 4: 1 HNMR(400MHz,CDCl 3 ):δ10.79(d,J＝8.1Hz,1H),7.95(d,J＝7.8Hz,1H),7.62(s,1H),7.60(s,1H),7.57(d,J＝7.6Hz,1H),7.48–7.41(m,1H),7.39(d,J＝7.6Hz,1H),7.31–7.23(m,2H),6.77(d,J＝7.9Hz,1H). 13 C NMR(CDCl 3 ,101MHz):δ190.13,151.23,142.68,141.09,138.15,135.51,131.52,131.40,127.96,127.60,122.94,122.31,120.50,120.14.
example 2
To a 10mL Schlenk tube was successively added (E) -1- (4-fluorophenyl) -3- (dimethylamino) prop-2-en-1-one (0.5 mmol,0.0966 g), silver trifluoroacetate (0.5 mmol,0.1105 g), palladium acetate (5 mol%,0.0056 g), iodobenzene (3.0 mmol,0.3060 g) and trifluoroacetic acid (1.0 mL) under nitrogen atmosphere, and after completion of the reaction by TLC monitoring with stirring for 20 hours at 120℃the product was isolated and purified by thin layer chromatography (developing solvent system petroleum ether/ethyl acetate, both volumes 100:1) as an orange solid compound in 88% yield. 1 H NMR(CDCl 3 ,400MHz):δ10.76(dd,J＝29.6,7.8Hz,1H),7.97(dd,J＝28.8,8.0Hz,1H),7.63(dd,J＝19.8,7.6Hz,1H),7.57(d,J＝1.6Hz,1H),7.54(d,J＝8.1Hz,1H),7.49–7.40(m,1H),7.37–7.28(m,1H),7.27–7.22(m,1H),6.78(dd,J＝23.7,7.8Hz,1H). 13 C NMR(CDCl 3 ,101MHz):δ189.85,149.94,144.36,142.59,141.33,139.92,138.59,137.64,136.41,135.79,133.71,131.52,128.66,128.41,127.89,127.67,123.28,122.94,122.39,120.75,120.59.
Example 3
To a 10mL Schlenk tube was added sequentially 4- [ (2E) -3- (dimethylamino) -1-oxoSubstituted-2-propen-1-yl]Methyl benzoate (1.2 mmol,0.2331 g), silver acetate (1.2 mmol,0.2001 g), palladium acetate (2 mol%,0.0054 g), iodobenzene (3.6 mmol,0.7344 g) and trifluoroacetic acid (2.0 ml) were added under nitrogen atmosphere, stirred at 120℃for 22h, and after completion of the reaction, the purified product was isolated by thin layer chromatography (developing solvent system petroleum ether/ethyl acetate, volume of both 30:1) as yellow solid substance in 76% yield. 1 HNMR(CDCl 3 ,400MHz):δ10.81(d,J＝7.8Hz,1H),8.25(dd,J＝7.0,1.5Hz,1H),8.04(dd,J＝15.1,7.9Hz,1H),7.96(dt,J＝8.2,1.7Hz,1H),7.69(dt,J＝11.3,7.2Hz,2H),7.52–7.42(m,1H),7.38–7.29(m,1H),6.86(dd,J＝12.6,7.8Hz,1H),3.97(s,J＝3.9Hz,3H). 13 C NMR(CDCl 3 ,101MHz):δ189.90,166.53,149.84,142.22,141.77,141.13,135.51,132.70,131.72,129.28,128.52,127.63,124.19,121.97,121.13,52.44.
Example 4
To a 10mL Schlenk tube was successively added (E) -1- (4-methoxyphenyl) -3- (dimethylamino) prop-2-en-1-one (1.5 mmol,0.2051 g), silver fluoride (1.5 mmol,0.1903 g), palladium trifluoroacetate (3 mol%,0.0080 g), iodobenzene (4.5 mmol,0.9180 g) and methanesulfonic acid (2.0 mL) under nitrogen atmosphere, and after completion of the reaction by TLC monitoring with stirring at 120℃for 24 hours, the purified product was isolated as an orange solid by thin layer chromatography (developing solvent system petroleum ether/ethyl acetate, both volumes 50:1) in a yield of 52%. 1 HNMR(CDCl 3 ,400MHz):δ10.72(dd,J＝22.8,8.1Hz,1H),7.91(dd,J＝21.2,8.1Hz,1H),7.61–7.54(m,1H),7.51(t,J＝7.5Hz,1H),7.43–7.35(m,1H),7.31–7.21(m,1H),7.07(dd,J＝10.2,2.5Hz,1H),6.75(dt,J＝8.6,2.7Hz,1H),6.68–6.61(m,1H),3.89(s,J＝3.9Hz,3H). 13 C NMR(CDCl 3 ,101MHz):δ281.18,254.38,242.39,234.35,233.39,227.80,222.39,219.38,218.73,215.10,212.93,211.64,204.78,197.10,146.95.
Example 5
To a 10mL Schlenk tube was added successively (E) -3- (dimethylamino) -1- (p-methylphenyl) prop-2-en-1-one (1.0 mmol,0.1891 g), silver oxide (1.0 mmol,0.2317 g), palladium chloride (5 mol%,0.0089 g),iodobenzene (3.0 mmol,0.612 g) and trifluoroacetic acid (2.0 ml) were added under nitrogen atmosphere, stirred at 120 ℃ for reaction for 22h, after completion of the reaction monitored by TLC, the purified product was isolated by thin layer chromatography (developing solvent system petroleum ether/ethyl acetate, 100:1 volumes of both) and was a yellow solid with a yield of 65%. 1 HNMR(CDCl 3 ,400MHz):δ10.63(t,J＝8.1Hz,1H),7.74(dd,J＝50.2,7.8Hz,1H),7.49–7.38(m,1H),7.34(d,J＝7.9Hz,1H),7.30–7.18(m,2H),7.17–7.07(m,1H),6.92(d,J＝7.8Hz,1H),6.58(d,J＝8.1Hz,1H),2.29(s,3H). 13 C NMR(CDCl 3 ,101MHz):δ190.21,151.33,142.92,142.09,141.10,138.61,135.94,135.56,132.91,131.36,128.72,127.82,127.41,122.25,21.83.
Example 6
To a 10mL Schlenk tube was successively added (E) -3- (dimethylamino) -1- (m-methylphenyl) prop-2-en-1-one (1.0 mmol,0.1891 g), silver nitrate (1.0 mmol,0.2317 g), ditriphenylphospholidium dichloride (1 mol%,0.0070 g), iodobenzene (4.0 mmol,0.8160 g) and acetic acid (2.0 mL) under nitrogen atmosphere, and after completion of the reaction by TLC monitoring with stirring for 24 hours at 120℃the purified product was isolated as a yellow solid by thin layer chromatography (developing solvent system petroleum ether/ethyl acetate, both volumes 100:1). 1H NMR (400 MHz, CDCl) 3 )δ10.72(dd,J＝8.1,4.1Hz,1H),7.66(d,J＝3.5Hz,1H),7.49(dd,J＝21.1,7.6Hz,2H),7.41(d,J＝7.7Hz,1H),7.38–7.31(m,1H),7.23–7.11(m,2H),6.67(dd,J＝8.2,1.5Hz,1H),2.36(d,J＝3.1Hz,3H).13C NMR(101MHz,CDCl 3 )δ190.31,137.89,132.35,132.14,131.51,131.39,128.49,127.51,122.81,122.30,120.26,119.96,119.83,21.75.
Example 7
To a 10mL Schlenk tube was successively added (E) -1- (3-fluorophenyl) -3- (dimethylamino) prop-2-en-1-one (1.0 mmol,0.1932 g), copper acetate (1.0 mmol,0.1997 g), palladium acetate (1 mol%,0.0022 g), iodobenzene (3.0 mmol,0.612 g) and trifluoroacetic acid (2.0 mL) under nitrogen atmosphere, and after completion of the reaction, the reaction was stirred at 120℃for 20 hours, and after completion of the reaction, the reaction was separated and purified by TLC using thin layer chromatography (developing solvent system petroleum ether/ethyl acetate, both volumes were 0.01:1)The product was a yellow solid in 10% yield. 1 H NMR(400MHz,CDCl 3 )δ10.68(d,J＝7.6Hz,1H),7.73(d,J＝9.4Hz,2H),7.62(d,J＝7.6Hz,2H),7.58-7.53(m,2H),7.41(s,1H),7.29-7.26(m,1H),7.16-7.09(m,2H),6.81(d,J＝7.6Hz,1H).13C NMR(101MHz,CDCl 3 )δ189.40,163.74,161.30,150.01,149.98,140.39,131.75,127.65,123.38,122.32,121.25,118.17,115.30.
Example 8
To a 10mL Schlenk tube was successively added (E) -4-3- (dimethylamino) prop-2-enoyl benzonitrile (1.2 mmol,0.2631 g), silver trifluoroacetate (1.2 mmol,0.2651 g), palladium hydroxide (2 mol%,0.0043 g), iodobenzene (3.6 mmol,0.7344 g) and methanesulfonic acid (2.0 mL) under nitrogen atmosphere, and after completion of the reaction, the reaction was stirred for 24 hours at 120℃and was separated and purified by TLC using thin layer chromatography (developing solvent system petroleum ether/ethyl acetate, both volumes were 30:1), the product was a yellow solid substance, yield 13%. 1 H NMR(400MHz,CDCl 3 )δδ10.91(t,J＝7.7Hz,1H),8.76(d,J＝8.2Hz,1H),8.66(d,J＝8.0Hz,1H),8.24–8.15(m,1H),8.14–8.02(m,1H),7.93(d,J＝7.6Hz,1H),7.46(dd,J＝13.4,6.2Hz,1H),7.39-7.30(m,1H),6.97-6.88(m,1H). 13 C NMR(101MHz,CDCl 3 )δ189.88,164.04,151.30,148.92,141.22,132.75,127.45,125.78,122.75，122.98,122.55,121.74，120.75，120.36，118.65.
Example 9
E-3- (dimethylamino) -1-phenylprop-2-en-1-one (1.5 mmol,0.2625 g), silver acetate (1.5 mmol,0.2504 g), palladium hydroxide (1 mol%,0.0021 g), ethyl 4-iodobenzoate (4.5 mmol,1.1792 g) and trifluoroacetic acid (2.0 mL) were added sequentially to a 10mL Schlenk tube, and after completion of the reaction, the reaction was stirred at 120℃for 22 hours, and the purified product was isolated as a yellow solid by TLC (developing solvent system petroleum ether/ethyl acetate, both volumes: 30:1) in 53% yield. 1 H NMR(400MHz,CDCl 3 )δ10.81(d,J＝7.9Hz,1H),8.30(d,J＝1.4Hz,1H),8.12(dd,J＝7.8,1.5Hz,1H),8.05(d,J＝7.8Hz,1H),7.68(dd,J＝21.8,7.9Hz,3H),7.49(td,J＝7.5,1.0Hz,1H),7.37(td,J＝7.6,1.2Hz,1H),6.89(d,J＝7.8Hz,1H),4.41(q,J＝7.1Hz,2H),1.43(t,J＝7.1Hz,4H). 13 C NMR(101MHz,CDCl 3 )δ189.82,149.84,144.84,141.52,138.15,136.29,132.93,131.60,130.05,129.03,127.73,123.56,123.35,121.35,119.85,61.32,14.39.
Example 10
To a 10mL Schlenk tube, (E) -3- (dimethylamino) -1-phenylpropan-2-en-1-one (1.0 mmol,0.1750 g) was added sequentially, silver oxide (1.0 mmol,0.2317 g), palladium acetate (5 mol%,0.0112 g) and 1-fluoro-4-iodobenzene (3.0 mmol,0.612 g) and acetic acid (2.0 mL) were added under nitrogen atmosphere, and after completion of the reaction, the reaction was stirred at 120℃for 20 to 24 hours, and after completion of the reaction, the purified product was isolated by thin layer chromatography (developing solvent system petroleum ether/ethyl acetate, both volumes: 100:1) as a yellow solid substance, yield 33%. 1 H NMR(400MHz,CDCl 3 ):δ10.79(dd,J＝7.9,2.7Hz,1H),7.71(dd,J＝9.5,2.7Hz,1H),7.61(td,J＝7.5,2.4Hz,2H),7.49-7.40(m,2H),7.19-7.09(m,2H),6.80(dd,J＝7.7,3.1Hz,1H)； 13 C NMR(101MHz,CDCl 3 )δ189.32,172.03，160.36，131.57，128.28，127.59,123.46，123.32，122.25，121.22，119.87，118.13，114.97，104.83..
Example 11
To a 10mL Schlenk tube, (E) -3- (dimethylamino) -1-phenylprop-2-en-1-one (1.2 mmol,0.2100 g), silver diethyldithiocarbamate (1.2 mmol,0.3074 g), tetrakis (triphenylphosphine) palladium (2 mol%,0.0277 g), 2-iodobenzaldehyde (3.6 mmol,0.8353 g) and trifluoroacetic acid (0.46 mL) were added sequentially, and after completion of the reaction by TLC monitoring, the reaction was stirred for 20 to 24 hours at 120℃and the purified product was isolated as a yellow solid in 63% yield by thin layer chromatography (developing solvent system petroleum ether/ethyl acetate, 50:1 volume). 1 H NMR(400MHz,CDCl 3 ):δ10.43(d,J＝1.9Hz,1H),9.33(d,J＝8.6Hz,1H),8.53–8.44(m,2H),7.97(d,J＝1.6Hz,4H),7.26(s,2H). 13 C NMR(101MHz,CDCl 3 ):δ192.62,141.18,139.95,138.25,137.05,133.58,133.06,131.54,131.12,130.27,129.41,129.04,128.56,128.24.
Example 12
To a 10mL Schlenk tube, (E) -3- (dimethylamino) -1-phenylprop-2-en-1-one (1.0 mmol,0.1750 g), silver nitrate (1.0 mmol,0.1699 g), palladium acetate (5 mol%,0.0112 g) were sequentially added, 4-methyl iodobenzene (3.0 mmol,0.6541 g) and trifluoroacetic acid (1.0 mL) were added under nitrogen atmosphere, and after completion of the reaction by TLC monitoring with stirring at 120℃for 20 to 24 hours, the purified product was isolated as a yellow solid by thin layer chromatography (developing solvent system petroleum ether/ethyl acetate, both volumes: 100:1), yield 73%. 1 H NMR(400MHz,CDCl 3 ):δ10.87-10.75(m,1H),8.00(dd,J＝18.6,7.8Hz,1H),7.61(s,1H),7.52-7.35(m,2H),7.18(m,J＝7.2,5.9Hz,3H),6.82-6.72(m,1H),2.66-2.37(s,3H).； 13 C NMR(101MHz,CDCl 3 ):δ190.32,134.22,132.35,131.39,128.76,127.57,127.21,125.21,123.56,122.73,122.40,121.29,119.83,117.37,20.93.
The present invention is not limited to the above-described specific embodiments, and various modifications may be made by those skilled in the art without inventive effort from the above-described concepts, and are within the scope of the present invention.

Claims (10)

1. A preparation method of a 9-phenanthrene phenol compound comprises the following steps: enaminones and iodobenzene compounds with chemical structural formulas shown as (I) and (II) are used as raw materials, react for 20-24 hours in an organic solvent under the action of a catalyst and an oxidant to obtain a reaction product, and the obtained reaction product is purified to obtain the 9-phenanthrene phenol compound with the structural formula shown as (III):
Figure QLYQS_1
wherein R is selected from any one of H, C-C3 alkyl, halogen and CN, OMe, COOMe, R is 1 Selected from one of H, C-C3 alkyl, halogen, CHO and COOMe.
2. The method for producing a 9-phenanthrene phenol compound according to claim 1, wherein the temperature of the reaction is 110 to 120 ℃.
3. The method for preparing 9-phenanthrene phenol compounds according to claim 1, wherein the molar ratio of the catalyst to enaminones is 0.01-0.05: 1, a step of; the mol ratio of the oxidant to the enaminones is 1.0-3.0: 1.
4. the method for preparing the 9-phenanthrene phenol compound according to claim 1, wherein the molar ratio of the iodobenzene compound to the enaminone compound is 3.0-4.5: 1.0 to 1.5.
5. The method for preparing the 9-phenanthrene phenol compound according to claim 2, wherein the catalyst is any one of palladium acetate, palladium chloride, bis dibenzylideneacetone palladium, tetrakis (triphenylphosphine) palladium, palladium trifluoroacetate, bis (acetylacetonato) palladium (II), bis (triphenylphosphine) palladium dichloride, and palladium hydroxide.
6. The method for producing 9-phenanthrene phenol compounds according to claim 1, wherein the allylketone compound is selected from the group consisting of (E) -3- (dimethylamino) -1-phenylpropan-2-en-1-one, (E) -1- (4-fluorophenyl) -3- (dimethylamino) prop-2-en-1-one, methyl 4- [ (2E) -3- (dimethylamino) -1-oxo-2-propen-1-yl ] benzoate, (E) -1- (4-methoxyphenyl) -3- (dimethylamino) prop-2-en-1-one, (E) -3- (dimethylamino) -1- (p-methylphenyl) prop-2-en-1-one, (E) -3- (dimethylamino) -1- (m-methylphenyl) prop-2-en-1-one, (E) -1- (3-fluorophenyl) -3- (dimethylamino) prop-2-en-1-one, (E) -4-3- (dimethylamino) prop-2-enoyl benzonitrile, (E) -any one of 1- (4- (dimethylamino) phenyl) -3- (dimethylamino) prop-2-en-1-one.
7. The method for producing a 9-phenanthrene phenol compound according to claim 1, wherein the iodobenzene compound is selected from any one of iodobenzene, 1-fluoro-4-iodobenzene, ethyl 4-iodobenzoate, 4-methyl iodobenzene, and 2-iodobenzaldehyde.
8. The method for preparing a 9-phenanthrene phenol compound according to claim 1, wherein the oxidizing agent is any one of silver oxide, silver trifluoroacetate, silver diethyldithiocarbamate, silver acetate, silver nitrate, hydrogen peroxide, tert-butyl hydroperoxide, and copper acetate.
9. The method for producing a 9-phenanthrene phenol compound according to claim 1, wherein the organic solvent is any one of trifluoroacetic acid, acetic acid, methanesulfonic acid, and formic acid.
10. The method for producing a 9-phenanthrene phenol compound according to claim 1, wherein the reaction is performed under a protective gas atmosphere, and the protective gas is nitrogen or argon;
the reaction product is purified by a thin layer chromatography, the used developing agent system is petroleum ether/ethyl acetate, and the volume ratio of petroleum ether to ethyl acetate in the developing agent system is 100-30: 1.
CN202310343956.0A 2023-04-03 2023-04-03 Preparation method of 9-phenanthrene phenol compound Pending CN116396145A (en)

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