CN107641085B - Synthesis method of diphenylenone and derivatives thereof - Google Patents
Synthesis method of diphenylenone and derivatives thereof Download PDFInfo
- Publication number
- CN107641085B CN107641085B CN201610616926.2A CN201610616926A CN107641085B CN 107641085 B CN107641085 B CN 107641085B CN 201610616926 A CN201610616926 A CN 201610616926A CN 107641085 B CN107641085 B CN 107641085B
- Authority
- CN
- China
- Prior art keywords
- phenylacetylene
- reaction
- formula
- column chromatography
- source
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Hydrogenated Pyridines (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for synthesizing diphenylenone or derivatives thereof, which comprises the following steps: adding phenylacetylene shown in formula a intoIn an organic solvent containing a nitro source, a chlorine source and tetramethylpiperidine, completely reacting at 25-70 ℃, and separating and purifying reaction liquid after the reaction to obtain the diphenylenone and derivatives thereof shown in the formula b, wherein the dosage ratio of the nitro source to phenylacetylene is 1-3: 1, the mass ratio of the chlorine source to the phenylacetylene feeding substance is 1-3: 1. r in the formula a and the formula b is hydrogen simultaneously, or hydrogen is mono-substituted or multi-substituted by methyl, methoxy, chlorine, bromine or fluorine, and the number of the substituent groups is n. Compared with the prior art, the method has the advantages of simple reaction, one-step synthesis of the target product, no use of acid and alkali in the reaction, less environmental pollution, mild reaction conditions, energy consumption saving, high yield and strong substrate universality.
Description
Technical Field
The invention relates to a synthetic method of an organic compound, in particular to a synthetic method of diphenylketene and derivatives thereof.
Background
The dibenzoenone and the derivatives thereof are important intermediates for synthesizing compounds with physiological and pharmacological activities, and also make the fluorescent probe and the fluorescent detection technology present exponential progress. The dibenzoenone and the derivatives thereof show good antitumor functions in medicine, and can be used as edible dye curcumin, and most curcumin has wide biological activities such as antioxidation, anti-inflammation, anti-swelling, antivirus and the like. At present, a plurality of relevant documents about a synthetic route of the diphenylenone and derivatives thereof are reported, and the following methods are mainly adopted: a synthesis method of substituted aldehyde and ketone under the catalysis condition of organic base such as sodium alkoxide or potassium alkoxide (see Rec. Trav. Chim. Pays-Bas.,1964,83, 379); synthesis methods using substituted aldehydes and ketones under catalytic conditions of weak acids (see j.med.chem.,1998,41, 3948). However, in any method, acid and alkali are used, so that waste acid and waste alkali are generated after reaction, and environmental pollution is caused; and the reaction steps of the two methods are relatively complicated. Compared with the two synthesis methods, the invention has the following specific advantages: the direct use of phenylacetylene for one-step synthesis of benzophenone compounds has the advantages of mild conditions, no environmental pollution, easily obtained raw materials and the like.
Disclosure of Invention
Aiming at the defects of the traditional method and the technical difficulty, the invention provides a method for synthesizing the diphenylenone and the derivatives thereof.
The synthetic route of the invention is as follows:
the technical scheme adopted by the invention is as follows:
a chemical synthesis method of a diphenylenone and derivatives thereof shown in a formula b comprises the following steps:
adding phenylacetylene shown in the formula into an organic solvent containing a nitro source, a chlorine source and tetramethylpiperidine, completely reacting at 25-70 ℃, and separating and purifying reaction liquid after the reaction to obtain the diphenylenone shown in the formula and derivatives thereof, wherein the dosage ratio of the nitro source to the phenylacetylene is 1-3: 1, the mass ratio of the chlorine source to the phenylacetylene feeding substance is 1-3: 1; the nitro source is silver nitrite, sodium nitrite, potassium nitrite or tert-butyl nitrite; the chlorine source is N-chlorobutyl diamide, N-chlorophthalimide or trichlorotriazinetrione;
r in the formula a and the formula b is the same, R is H, or H is mono-substituted or multi-substituted by methyl, methoxy, chlorine, bromine or fluorine, the number of the substituents is n, and n is 1 or 2.
The mass ratio of the nitro source to the phenylacetylene feeding substance is 2: 1.
further, the chlorine source is preferably N-chlorobutyl diamide, and the dosage ratio of the chlorine source to the phenylacetylene is 2: 1.
still further, the organic solvent of the present invention is acetonitrile, 1, 2-dichloroethane or tetrahydrofuran, preferably acetonitrile, and the amount of the organic solvent is an amount that dissolves the solute. The volume of the organic solvent is generally recommended to be 5-15 mL/mmol, most preferably 10mL/mmol, based on the amount of phenylacetylene.
Furthermore, the reaction time of the reaction is 3-12 h, and the reaction is particularly recommended to be carried out for 8h at 25 ℃.
Specifically, the reaction solution separation and purification method of the invention comprises the following steps: and after the reaction is finished, adding column chromatography silica gel into the reaction liquid, distilling under reduced pressure to remove the solvent, performing column chromatography separation and elution by using a mixed solution of ethyl acetate and petroleum ether in a ratio of 1:30 as an eluent, collecting eluent containing a target product, and removing the solvent to obtain the diphenylketene and the derivative thereof. The column chromatography silica gel is 100-200 meshes, and the mass ratio of the column chromatography silica gel to the diphenylketene and the derivatives thereof is about 10: 1, the vacuum degree of the reduced pressure distillation is-0.08 MPa, and the ratio of the volume of the eluent to the molar mass of the raw material is about 0.8-1L/mmol.
Compared with the prior art, the invention has the beneficial effects that:
(1) the reaction is simple, and the target product is synthesized in one step;
(2) acid and alkali are not used in the reaction, so that the environmental pollution is less;
(3) the reaction condition is mild, and the energy consumption is saved;
(4) high yield and strong substrate universality.
Detailed description of the invention
The invention will be further illustrated by the following examples, without limiting the scope of the invention:
example 1
0.5mmol of phenylacetylene, 1.0mmol of silver nitrite, 1.0mmol of N-chlorosuccinamide and 0.75mmol of tetramethylpiperidine were put into a 25mL pressure-resistant tube, and 5mL of acetonitrile was added as a solvent. Then, the mixture was magnetically stirred at 25 ℃ for 8 hours. Then, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product (petroleum ether/ethyl acetate: 30:1 as eluent). The chemical name of the substance is 2, 2-dichloro-4-nitro-1, 3-diphenyl butan-3-en-1-one, and the yield is 86%.
Characterization data: white solid; m.p.80 ℃; ir (kbr): nu 3056(-C ═ C-H),1654(-C ═ O),1590(-C ═ C-NO)2),770(-C-Cl)cm-1；1H NMR(500MHz,CDCl3)δ8.37(dd,J1＝8.5Hz,J2＝1.5Hz,2H),7.87(dd,J1＝7.5Hz,J2＝1.5Hz,1H),7.68(t,J＝7.5Hz,1H),7.58–7.51(m,5H),7.07(s,1H).13C NMR(125MHz,CDCl3)δ185.8,170.8,162.5,135.8,134.1,130.7,130.7,129.2,128.6,126.8,126.0,100.3.
Example 2
0.5mmol of phenylacetylene, 0.5mmol of sodium nitrite, 0.5mmol of N-chlorophthalimide and 0.75mmol of tetramethylpiperidine are added into a 25mL pressure-resistant tube, and 5mL of 1, 2-dichloroethane is added as a solvent. Then, the mixture was magnetically stirred at 70 ℃ for 3 hours. Then, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product (petroleum ether/ethyl acetate: 30:1 as eluent). The chemical name of the substance is 2, 2-dichloro-4-nitro-1, 3-diphenyl butan-3-en-1-one, and the yield is 36%.
Characterization data: white solid; m.p.80 ℃; ir (kbr): nu 3056(-C ═ C-H),1654(-C ═ O),1590(-C ═ C-NO)2),770(-C-Cl)cm-1；1H NMR(500MHz,CDCl3)δ8.37(dd,J1＝8.5Hz,J2＝1.5Hz,2H),7.87(dd,J1＝7.5Hz,J2＝1.5Hz,1H),7.68(t,J＝7.5Hz,1H),7.58–7.51(m,5H),7.07(s,1H).13C NMR(125MHz,CDCl3)δ185.8,170.8,162.5,135.8,134.1,130.7,130.7,129.2,128.6,126.8,126.0,100.3.
Example 3
0.5mmol of phenylacetylene, 1.5mmol of potassium nitrite, 1.5mmol of trichlorotriazinetrione and 0.75mmol of tetramethylpiperidine were introduced into a 25mL pressure-resistant tube, and 2.5mL of tetrahydrofuran was added as a solvent. Then, the mixture was magnetically stirred at 25 ℃ for 12 hours. Then, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product (petroleum ether/ethyl acetate: 30:1 as eluent). The chemical name of the substance is 2, 2-dichloro-4-nitro-1, 3-diphenyl butan-3-en-1-one, and the yield is 56%.
Characterization data: white solid; m.p.80 ℃; ir (kbr): nu 3056(-C ═ C-H),1654(-C ═ O),1590(-C ═ C-NO)2),770(-C-Cl)cm-1；1H NMR(500MHz,CDCl3)δ8.37(dd,J1＝8.5Hz,J2＝1.5Hz,2H),7.87(dd,J1＝7.5Hz,J2＝1.5Hz,1H),7.68(t,J＝7.5Hz,1H),7.58–7.51(m,5H),7.07(s,1H).13C NMR(125MHz,CDCl3)δ185.8,170.8,162.5,135.8,134.1,130.7,130.7, 129.2,128.6,126.8,126.0,100.3.
Example 4
0.5mmol of phenylacetylene, 1.0mmol of tert-butyl nitrite, 1.0mmol of N-chlorobutadiene diamide and 0.75mmol of tetramethylpiperidine are added into a 25mL pressure-resistant tube, and then 7.5mL of acetonitrile is added as a solvent. Then, the mixture was magnetically stirred at 25 ℃ for 8 hours. Then, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product (petroleum ether/ethyl acetate: 30:1 as eluent). The chemical name of the substance is 2, 2-dichloro-4-nitro-1, 3-diphenyl butan-3-en-1-one, and the yield is 86%.
Characterization data: white solid; m.p.80 ℃; ir (kbr): nu 3056(-C ═ C-H),1654(-C ═ O),1590(-C ═ C-NO)2),770(-C-Cl)cm-1；1H NMR(500MHz,CDCl3)δ8.37(dd,J1＝8.5Hz,J2＝1.5Hz,2H),7.87(dd,J1＝7.5Hz,J2＝1.5Hz,1H),7.68(t,J＝7.5Hz,1H),7.58–7.51(m,5H),7.07(s,1H).13C NMR(125MHz,CDCl3)δ185.8,170.8,162.5,135.8,134.1,130.7,130.7,129.2,128.6,126.8,126.0,100.3.
Example 5
0.5mmol of o-tolylacetylene, 1.5mmol of silver nitrite, 1.5mmol of N-chlorobutadiene diamide and 0.75mmol of tetramethylpiperidine are added into a 25mL pressure-resistant tube, and 5mL of acetonitrile is added as a solvent. Then, the mixture was magnetically stirred at 25 ℃ for 3 hours. Then, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product (petroleum ether/ethyl acetate: 30:1 as eluent). The chemical name of the substance is 2, 2-dichloro-4-nitro-1, 3-di-o-tolylbut-3-en-1-one, and the yield is 55%.
Characterization data: white solid; m.p.82 ℃; ir (kbr): ν 1652(-C ═ O),1597(-C ═ C-NO)2),792(-C-Cl)cm-1；1H NMR(500MHz,CDCl3)δ7.92–7.90(m,1H),7.80–7.79(m,1H),7.51–7.48(m,1H),7.43–7.40(m,1H),7.37–7.34(m,1H),6.98(s,1H),2.58(s,3H),2.55(s,3H).13C NMR(125MHz,CDCl3)δ189.1,171.2,162.9,138.9,136.5,136.1,132.1,131.6,131.5,131.1,130.5,128.6,126.4,126.3,125.4,102.7,21.5,20.7.
Example 6
0.5mmol of m-methylphenylacetylene, 0.5mmol of silver nitrite, 0.5mmol of N-chlorobutanediamide and 0.75mmol of tetramethylpiperidine were put into a 25mL pressure-resistant tube, and 5mL of acetonitrile was added as a solvent. Then, the mixture was magnetically stirred at 70 ℃ for 12 hours. Then, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product (petroleum ether/ethyl acetate: 30:1 as eluent). The chemical name of the substance is 2, 2-dichloro-4-nitro-1, 3-di-m-tolylbut-3-en-1-one, and the yield is 69%.
Characterization data: white solid; m.p.92 ℃; ir (kbr): nu 3056(-C ═ C-H),1654(-C ═ O),1590(-C ═ C-NO)2),770(-C-Cl)cm-1；1H NMR(500MHz,CDCl3)δ8.16(d,J＝7.5Hz,1H),8.14(s,1H),7.68–7.66(m,2H),7.49(d,J＝7.5Hz,1H),7.46–7.39(m,2H),7.31(d,J＝7.5Hz,1H),7.03(s,1H),2.48(s,3H),2.46(s,3H).13C NMR(125MHz,CDCl3)δ186.1,170.9,162.5,139.0,138.4,135.9,134.9,131.5,131.0,129.1,128.5,128.0,126.7,126.6,123.2,100.2,21.4,21.4.
Example 7
0.5mmol of p-methylphenylacetylene, 1.0mmol of silver nitrite, 1.0mmol of N-chlorobutanediamide and 0.75mmol of tetramethylpiperidine are added into a 25mL pressure-resistant tube, and then 5mL of acetonitrile is added as a solvent. Then, the mixture was magnetically stirred at 25 ℃ for 8 hours. Then, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product (petroleum ether/ethyl acetate: 30:1 as eluent). The chemical name of the substance is 2, 2-dichloro-4-nitro-1, 3-di-p-tolylbut-3-en-1-one, and the yield is 69%.
Characterization data: white solid; m.p.82 ℃; ir (kbr): nu 1649(-C ═ O),1566(-C ═ C-NO)2),758(-C-Cl)cm-1；1H NMR(500MHz,CDCl3)δ8.27(d,J＝8.5Hz,2H),7.75(d,J＝8.0Hz,2H),7.36–7.32(m,4H),6.99(s,1H),2.47(s,3H),2.44(s,3H).13C NMR(125MHz,CDCl3)δ185.5,170.9,162.6,145.1,141.1,133.4,130.9,129.8,129.3,126.0,124.2,99.7,21.8,21.5.
Example 8
0.5mmol of o-chlorobenzeneacetylene, 1.0mmol of silver nitrite, 1.0mmol of N-chlorobutanediamide and 0.75mmol of tetramethylpiperidine are added into a 25mL pressure-resistant tube, and then 5mL of acetonitrile is added as a solvent. Then, the mixture was magnetically stirred at 25 ℃ for 8 hours. Then, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product (petroleum ether/ethyl acetate: 30:1 as eluent). The chemical name of the substance is 2, 2-dichloro-4-nitro-1, 3-di-o-chlorophenyl but-3-en-1-one, and the yield is 78%.
Characterization data: white solid; m.p.93 ℃; ir (kbr): ν ═ 1689(-C ═ O),1591(-C ═ C-NO)2),774(-C-Cl)cm-1；1H NMR(500MHz,CDCl3)δ7.99(dd,J1＝6.0Hz,J2＝3.5Hz,1H),7.72–7.70(m,1H),7.56(dd,J1＝6.0Hz,J2＝3.0Hz,1H),7.52–7.50(m,2H),7.50(s,1H),7.45–7.41(m, 3H).13C NMR(125MHz,CDCl3)δ186.9,168.0,162.4,136.7,132.5,132.3,132.1,131.5,131.0,130.6,130.4,129.4,127.3,126.6,125.4,103.8.
Example 9
0.5mmol of p-chlorophenylacetylene, 1.0mmol of silver nitrite, 1.0mmol of N-chlorobutanediamide and 0.75mmol of tetramethylpiperidine were put into a 25mL pressure-resistant tube, and 5mL of acetonitrile was added as a solvent. Then, the mixture was magnetically stirred at 25 ℃ for 8 hours. Then, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product (petroleum ether/ethyl acetate: 30:1 as eluent). The chemical name of the substance is 2, 2-dichloro-4-nitro-1, 3-di-p-chlorophenyl but-3-en-1-one, and the yield is 73 percent.
Characterization data: white solid; m.p.214 ℃; ir (kbr): ν ═ C-H, 1661(-C ═ O),1588(-C ═ C-NO)2),764(-C-Cl)cm-1；1H NMR(500MHz,CDCl3)δ8.36–8.32(m,2H),7.80(d,J＝9.0Hz,2H),7.54–7.49(m,4H),7.06(s,1H).13C NMR(125MHz,CDCl3)δ184.2,169.8,162.4,140.9,137.0,133.9,132.1,129.6,129.0,127.3,125.1,100.6,
Example 10
0.5mmol of p-bromophenylacetylene, 1.0mmol of silver nitrite, 1.0mmol of N-chlorobutanediamide and 0.75mmol of tetramethylpiperidine are added into a 25mL pressure-resistant tube, and then 5mL of acetonitrile is added as a solvent. Then, the mixture was magnetically stirred at 25 ℃ for 8 hours. Then, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product (petroleum ether/ethyl acetate: 30:1 as eluent). The chemical name of the substance is 2, 2-dichloro-4-nitro-1, 3-di-p-bromophenylbut-3-en-1-one, and the yield is 69%.
Characterization data: white solid; m.p.205 ℃; ir (kbr): ν 1659(-C ═ O),1563(-C ═ C-NO)2),760(-C-Cl)cm-1；1H NMR(500MHz,CDCl3)δ8.26(d,J＝8.5Hz,2H),7.77–7.64(m,6H),7.07(s,1H).13C NMR(125MHz,CDCl3)δ184.4,169.9,162.4,134.3,132.5,132.2,132.0,129.7,127.5,125.5,125.4,100.6.
Example 11
0.5mmol of p-methoxyphenylacetylene, 1.0mmol of silver nitrite, 1.0mmol of N-chlorobutanediamide and 0.75mmol of tetramethylpiperidine were put into a 25mL pressure-resistant tube, and 5mL of acetonitrile was added as a solvent. Then, the mixture was magnetically stirred at 25 ℃ for 8 hours. Then, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product (petroleum ether/ethyl acetate: 30:1 as eluent). The chemical name of the substance is 2, 2-dichloro-4-nitro-1, 3-di-p-methoxyphenyl butan-3-en-1-one, and the yield is 78%.
Characterization data: white solid; m.p.101 ℃; ir (kbr): ν 3015(-C ═ C-H),1655(-C ═ O),1597(-C ═ C-NO)2),792(-C-Cl)cm-1；1H NMR(500MHz,CDCl3)δ8.39(d,J＝9.0Hz,2H),7.80(d,J＝8.5Hz,2H),7.02(dd,J1＝9.0Hz,J2＝2.5Hz,1H),6.91(s,1H),3.92(s,3H),3.89(s,3H).13C NMR(125MHz,CDCl3)δ184.2,170.6,164.5,162.7,161.5,133.2,128.8,127.6,119.7,114.6,113.9,99.0,55.5,55.4.
Example 12
0.5mmol of 2-bromo-5-chlorophenylacetylene, 1.0mmol of silver nitrite, 1.0mmol of N-chlorobutyldiamide and 0.75mmol of tetramethylpiperidine were put into a 25mL pressure-resistant tube, and 5mL of acetonitrile was added as a solvent. Then, the mixture was magnetically stirred at 25 ℃ for 8 hours. Then, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product (petroleum ether/ethyl acetate: 30:1 as eluent). The chemical name of the substance is 2, 2-dichloro-4-nitro-1, 3-di-2-bromo-5-chlorophenyl but-3-en-1-one, and the yield is 80%.
Characterization data: white solid; m.p.128 ℃; ir (kbr): ν 3096(-C ═ C-H),1690(-C ═ O),1597(-C ═ C-NO)2),768(-C-Cl)cm-1；1H NMR(500MHz,CDCl3)δ7.91(d,J＝2.5Hz,1H),7.70(d,J＝9.0Hz,1H),7.65–7.63(m,2H),7.57(s,1H),7.41(dd,J1＝7.5Hz,J2＝2.5Hz,2H),7.34(dd,J1＝7.5Hz,J2＝2.0Hz,2H).13C NMR(125MHz,CDCl3)δ186.1,168.4,161.6,139.7,135.5,135.0,134.2,133.7,132.6,131.7,130.2,129.9,128.7,119.2,118.2,104.2.
Example 13
0.5mmol of 2-bromo-5-methoxyphenylacetylene, 1.0mmol of silver nitrite, 1.0mmol of N-chlorobutyldiamide and 0.75mmol of tetramethylpiperidine were put into a 25mL pressure-resistant tube, and 5mL of acetonitrile was added as a solvent. Then, the mixture was magnetically stirred at 25 ℃ for 8 hours. Then, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product (petroleum ether/ethyl acetate: 30:1 as eluent). The chemical name of the substance is 2, 2-dichloro-4-nitro-1, 3-di-2-bromo-5-methoxyphenyl butan-3-en-1-one, and the yield is 79%.
Characterization data: white solid; m.p.201 ℃; ir (kbr): ν 3084(-C ═ C-H),1686(-C ═ O),1572(-C ═ C-NO)2),771(-C-Cl)cm-1；1H NMR(500MHz,CDCl3)δ7.62(d,J＝9.0Hz,1H),7.57(d,J＝9.0Hz,1H),7.54(s,1H),7.44(d, J＝3.0Hz,1H),7.18(d,J＝3.0Hz,1H),6.97(dd,J1＝9.0Hz,J2＝3.0Hz,1H),6.91(dd,J1＝9.0Hz,J2＝3.0Hz,1H),3.86(s,1H),3.85(s,1H).13C NMR(125MHz,CDCl3)δ187.4,169.3,161.9,159.0,158.6,139.2,135.1,134.5,128.0,118.7,118.2,115.6,114.9,111.7,110.5,103.8,55.7.
Example 14
0.5mmol of 2-fluoro-3-chlorophenylacetylene, 1.0mmol of silver nitrite, 1.0mmol of N-chlorobutyldiamide and 0.75mmol of tetramethylpiperidine were put into a 25mL pressure-resistant tube, and 5mL of acetonitrile was added as a solvent. Then, the mixture was magnetically stirred at 25 ℃ for 8 hours. Then, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product (petroleum ether/ethyl acetate: 30:1 as eluent). The chemical name of the substance is 2, 2-dichloro-4-nitro-1, 3-di-2-fluoro-3-chlorophenyl but-3-en-1-one, and the yield is 75 percent.
Characterization data: white solid; m.p.129 ℃; ir (kbr): ν 3180(-C ═ C-H),1673(-C ═ O),1570(-C ═ C-NO)2),788(-C-Cl)cm-1；1H NMR(500MHz,CDCl3)δ7.92–7.89(m,1H),7.79–7.76(m,1H),7.68–7.65(m,1H),7.58–7.52(m,1H),7.29–7.25(m,3H).13C NMR(125MHz,CDCl3)δ183.4,164.6(d,J＝2.5Hz),162.5,156.7(d,J＝240.0Hz),154.8(d,J＝255.0Hz),135.0,132.8,129.6,126.8(d,J＝11.3Hz),125.9,125.3(d,J＝5.0 Hz),124.7(d,J＝3.8 Hz),122.6,122.5,116.5(d,J＝12.5 Hz),103.6(d,J＝11.3 Hz)。
Claims (10)
1. A method for synthesizing diphenylenone and derivatives thereof shown in a formula b is characterized in that the preparation method comprises the following steps:
adding phenylacetylene shown in a formula a into an organic solvent containing a nitro source, a chlorine source and tetramethyl piperidine, completely reacting at 25-70 ℃, separating and purifying reaction liquid after the reaction is finished to obtain the diphenylenone shown in a formula b and derivatives thereof, wherein the dosage ratio of the nitro source to the phenylacetylene is 1-3: 1, the mass ratio of the chlorine source to the phenylacetylene feeding substance is 1-3: 1; the nitro source is silver nitrite, sodium nitrite, potassium nitrite or tert-butyl nitrite; the chlorine source is N-chlorobutyl diamide, N-chlorophthalimide or trichlorotriazinetrione;
r in the formula a and the formula b is the same, R is H, or H is mono-substituted or multi-substituted by methyl, methoxy, chlorine, bromine or fluorine, the number of the substituents is n, n is 1 or 2,
2. the synthesis process according to claim 1, wherein the ratio of the amount of nitro source to the amount of phenylacetylene fed is 2: 1.
3. the method of synthesis according to claim 1, wherein the ratio of the amount of chlorine source to the amount of phenylacetylene charged is 2: 1.
4. the method of claim 1, wherein the organic solvent is acetonitrile, 1, 2-dichloroethane, or tetrahydrofuran.
5. The synthetic method according to claim 1, wherein the volume usage amount of the organic solvent is 5 to 15mL/mmol based on the amount of phenylacetylene.
6. The synthesis method according to claim 1, wherein the reaction time is 3-12 h.
7. The synthesis process according to claim 1, characterized in that the reaction is carried out at 25 ℃ for 8 h.
8. The synthesis method according to claim 1, wherein the reaction solution is separated and purified by: and after the reaction is finished, adding column chromatography silica gel into the reaction liquid, distilling under reduced pressure to remove the solvent, performing column chromatography separation and elution by using a mixed solution of ethyl acetate and petroleum ether in a ratio of 1:30 as an eluent, collecting eluent containing the target product, and removing the solvent to obtain the diphenylenone and the derivatives thereof.
9. The method as claimed in claim 8, wherein the column chromatography silica gel is 100-200 mesh.
10. The method of claim 8, wherein the mass ratio of the column chromatography silica gel to the mass of the dibenzoenone and its derivatives is about 10: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610616926.2A CN107641085B (en) | 2016-07-29 | 2016-07-29 | Synthesis method of diphenylenone and derivatives thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610616926.2A CN107641085B (en) | 2016-07-29 | 2016-07-29 | Synthesis method of diphenylenone and derivatives thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107641085A CN107641085A (en) | 2018-01-30 |
| CN107641085B true CN107641085B (en) | 2019-12-24 |
Family
ID=61110075
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610616926.2A Active CN107641085B (en) | 2016-07-29 | 2016-07-29 | Synthesis method of diphenylenone and derivatives thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107641085B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103274917A (en) * | 2013-06-17 | 2013-09-04 | 浙江工业大学 | Method for catalyzing and synthesizing benzil derivatives from alkali type copper fluoride |
| CN104262122A (en) * | 2014-08-29 | 2015-01-07 | 浙江工业大学 | Method for synthesizing 1,4-butene diketone compound |
| CN104262295A (en) * | 2014-08-29 | 2015-01-07 | 浙江工业大学 | Synthesis method of epoxy chalcone and derivatives thereof |
-
2016
- 2016-07-29 CN CN201610616926.2A patent/CN107641085B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103274917A (en) * | 2013-06-17 | 2013-09-04 | 浙江工业大学 | Method for catalyzing and synthesizing benzil derivatives from alkali type copper fluoride |
| CN104262122A (en) * | 2014-08-29 | 2015-01-07 | 浙江工业大学 | Method for synthesizing 1,4-butene diketone compound |
| CN104262295A (en) * | 2014-08-29 | 2015-01-07 | 浙江工业大学 | Synthesis method of epoxy chalcone and derivatives thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107641085A (en) | 2018-01-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103992225B (en) | A kind of salicylaldehyde derivatives and preparation method thereof | |
| CN109879733B (en) | Synthetic method of monofluoro bromoacetone derivative | |
| Howard et al. | Mechanochemical electrophilic fluorination of liquid beta-ketoesters | |
| CN107641100B (en) | Method for synthesizing 6-cyanophenanthridine compound | |
| CN113620891B (en) | Method for preparing quinoxaline-2-ketone derivative by controllable catalysis | |
| CN107513050A (en) | The preparation method that a kind of olefin(e) acid bromine lactonizes | |
| CN107892654B (en) | Isolongifolane-based fluorescent acid-base indicator and synthetic method and application thereof | |
| CN107641085B (en) | Synthesis method of diphenylenone and derivatives thereof | |
| CN109942459B (en) | Method for synthesizing 3-difluoromethyl-3-acrylonitrile compounds | |
| CN111362795B (en) | Preparation method of substituted butyrate derivatives | |
| CN112778317B (en) | Synthetic method of [1,2,4] triazolo [1,5-a ] pyrimidine compound | |
| CN104447336A (en) | Triptycene derivative and preparation method thereof | |
| CN112299981B (en) | Preparation method of alpha, alpha-difluoroketone derivative | |
| CN110317170B (en) | Green synthesis method of 3-phenanthridinyl propyl formate compound | |
| CN110028409B (en) | Polysubstituted naphthalene derivative and preparation method thereof | |
| CN108191736B (en) | 2, 3-disubstituted indole derivatives and preparation method thereof | |
| CN112441935B (en) | Synthesis method of beta-aminoketone compound | |
| CN107963976A (en) | A kind of preparation method of phenyl ethyl amine compounds intermediate | |
| CN110577456A (en) | synthesis method of beta-trifluoromethyl-2-methylene cyclopentanone compound | |
| CN111499600A (en) | Synthesis method of polysubstituted 2, 3-dihydrofuran compound | |
| CN109422631B (en) | Synthetic method of indanone compound | |
| CN110734443A (en) | Preparation method of tadalafil-related substances I | |
| CN112321398B (en) | Method for synthesizing alpha-fluorinated ketone by hydrazonating aliphatic chain monoketone | |
| CN112441961B (en) | Synthetic method of 3-pyrroline-2-ketone compound | |
| CN115260192B (en) | Nitrogen-containing condensed ring compound and synthesis method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |