CN114149311B - Method for preparing 4-hydroxybenzophenone compound by taking p-methylene quinone as substrate - Google Patents

Method for preparing 4-hydroxybenzophenone compound by taking p-methylene quinone as substrate Download PDF

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CN114149311B
CN114149311B CN202111492099.8A CN202111492099A CN114149311B CN 114149311 B CN114149311 B CN 114149311B CN 202111492099 A CN202111492099 A CN 202111492099A CN 114149311 B CN114149311 B CN 114149311B
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ethyl acetate
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hydroxybenzophenone
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易维银
李静平
王坤鹏
张皓翔
陈妍
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Shanghai Institute of Technology
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Abstract

The invention discloses a method for preparing 4-hydroxybenzophenone and derivatives thereof by taking p-methylene quinone as a substrate, which comprises the following steps: adding a p-methylene quinone compound, an organic solvent, elemental sulfur and alkali into a reaction container, heating the mixture to 100-150 ℃, and stirring for 8-14 hours; after the reaction is finished, adding water into the reaction system, quenching, adding ethyl acetate for dilution, stirring, extracting and separating liquid, drying, concentrating, and then performing column chromatography separation to obtain the 4-hydroxybenzophenone or the derivative thereof. The method has the characteristics of good position selectivity, environmental protection, excellent atom economy, cheap and easily obtained raw materials, mild conditions and the like. In addition, the invention adopts a one-pot method to prepare the 4-hydroxybenzophenone compound, greatly improves the reaction efficiency, has simple post-treatment and has good industrialized application prospect.

Description

Method for preparing 4-hydroxybenzophenone compound by taking p-methylene quinone as substrate
Technical Field
The invention relates to a method for preparing 4-hydroxybenzophenone compounds by taking p-methylene quinone as a substrate, belonging to the technical field of synthesis of organic matters.
Background
Aromatic aldehydes and ketones are very abundant and are an important component of the synthesis of many fine chemicals, including mainly many natural products and bioactive compounds. In addition, the ketone compound has wide functions, has important application in the fields of pharmacy, natural products, organic materials and the like, and can also be used as photosensitizer, spice, aromatic and the like.
At present, typical methods for synthesizing 4-hydroxybenzophenones and derivatives thereof mainly comprise Friedel-Crafts acylation of phenols and Fries rearrangement of aryl benzoates, but the methods generally have the defects of using excessive Lewis acid and alkali, poor functional group position selectivity, unsustainability in environment, poor atom economy, poor functional group tolerance and the like. Therefore, the current novel method for preparing the 4-hydroxybenzophenone compound by taking the p-methylenequinone as a substrate has wide application prospect.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: the existing method for preparing the 4-hydroxy benzophenone compound has the technical problems of complex process, complicated process, troublesome post-treatment, high energy consumption and unfriendly environment.
In order to solve the technical problems, the invention provides a method for preparing 4-hydroxybenzophenone and derivatives thereof by taking p-methylene quinone as a substrate, which comprises the following steps:
step 1): adding a p-methylene quinone compound, an organic solvent, elemental sulfur and alkali into a reaction container, heating the mixture to 100-150 ℃, and stirring for 8-14 hours;
step 2): after the reaction is finished, adding water into the reaction system, quenching, adding ethyl acetate for dilution, stirring, extracting and separating liquid, drying, concentrating, and then performing column chromatography separation to obtain the 4-hydroxybenzophenone or the derivative thereof.
Preferably, the p-methylenequinone compound in the step 1) is 4-benzylidene-2, 6-di-tert-butylcyclohexa-2, 5-dien-1-one, 2, 6-di-tert-butyl-4- (4-methylbenzylidene) cyclohexa-2, 5-dien-1-one, 4- (4-bromobenzylidene) -2, 6-di-tert-butylcyclohexa-2, 5-dien-1-one, 2, 6-di-tert-butyl-4- (3, 4-dimethoxybenzylidene) cyclohexa-2, 5-dien-1-one, 2, 6-di-tert-butyl-4- (2, 4-dichlorobenzylidene) cyclohexa-2, 5-dien-1-one, 2, 6-di-tert-butyl-4- (3, 4, 5-trimethoxybenzylidene) cyclohexa-2, 5-dien-1-one, 2, 6-di-tert-butyl-4-ethylenecyclohexa-2, 5-dien-1-one, 4-di-tert-butyl-1-one, 4-benzylidene-2, 6-di-tert-butyl-4-benzylidene-cyclohexa-1-one, 2, 5-dien-1-one, 2, 6-di-tert-butyl-1-one, at least one of 2, 6-di-tert-butyl-4- (naphthalen-2-ylmethylene) cyclohexa-2, 5-dien-1-one and 4- (4-bromobenzene subunit) -2, 6-dimethylcyclohexa-2, 5-dien-1-one.
Preferably, the organic solvent in the step 1) is at least one of N, N-dimethylformamide, dimethyl sulfoxide, 1, 4-dioxane, toluene and xylene.
Preferably, the base in the step 1) is at least one of potassium carbonate, potassium hydroxide, sodium hydroxide, potassium phosphate, triethylamine, 1, 4-diazabicyclo [2.2.2] octane, sodium acetate and sodium bicarbonate.
Preferably, in the step 1), the molar ratio of elemental sulfur to the methylene quinone compound to the alkali is 3:1:1.
Preferably, the organic phase obtained by the extraction and separation in the step 2) is washed with saturated saline solution, and the aqueous phase is washed with ethyl acetate.
Preferably, the organic phases obtained by the extraction and separation in the step 2) are combined, dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and separated by column chromatography.
More preferably, the eluent used for the column chromatographic separation is a mixture of petroleum ether and ethyl acetate.
Further, the eluent adopted by the column chromatography separation is mixed liquid with the volume ratio of petroleum ether to ethyl acetate being 10:1-50:1.
The reaction equation of the present invention is described as follows:
the invention adopts a p-methylene quinone compound and elemental sulfur-step reaction method to obtain aromatic ketone compounds with different substituents.
The substituents of the invention: r is R 1 And R is R 2 Mainly t-butyl, isopropyl and methyl; r is R 3 Mainly methyl, methoxy, isopropyl, nitro, cyano, fluoro, bromo and the like, and di-substituted and tri-substituted electron withdrawing groups and electron donating groups, and heterocyclic rings such as pyridine, thiophene, naphthalene and the like.
Compared with the prior art, the invention has obvious technical progress. The invention adopts a one-pot method to prepare the 4-hydroxybenzophenone compound, greatly improves the reaction efficiency, has simple post-treatment and has good industrialized application prospect.
Drawings
FIG. 1 is a single crystal spectrum of the product of example 1, (3, 5-di-tert-butyl-4-hydroxyphenyl) (phenyl) methanone;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the product of example 1, (3, 5-di-tert-butyl-4-hydroxyphenyl) (phenyl) methanone;
FIG. 3 shows the nuclear magnetic resonance spectrum of the product (3, 5-di-tert-butyl-4-hydroxyphenyl) (phenyl) methanone of example 1.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments accompanied with figures are described in detail below.
Example 1
1.5mL of dimethyl sulfoxide, 0.5mmol of 4-benzylidene-2, 6-di-tert-butylcyclohexyl-2, 5-dien-1-one, 1.5mmol of elemental sulfur and 0.5mmol of potassium hydroxide are added into a 10mL reaction bottle, the reaction mixture is heated at 120 ℃ for 8 hours, after the reaction is finished, water is added for quenching, ethyl acetate is added for dilution, stirring is carried out for 30 minutes, the extraction and separation liquid is carried out, the water phase is washed by ethyl acetate for 2-3 times, the organic phase is washed by saturated saline, the obtained organic phase is dried by anhydrous magnesium sulfate, then filtration and reduced pressure concentration are carried out, column chromatography separation is carried out, the eluent is 600mL of petroleum ether/ethyl acetate, and the final product (3, 5-di-tert-butyl-4-hydroxyphenyl) (phenyl) methanone is obtained, and the yield is 93%.
The nuclear magnetic resonance and high resolution spectrogram data of the product are as follows: 1 H NMR(400MHz,CDCl 3 )δ7.82(d,J＝7.3Hz,2H),7.77(s,2H),7.59(t,J＝7.4Hz,1H),7.51(t,J＝7.4Hz,2H),5.80(s,1H),1.49(s,18H)； 13 C NMR(101MHz,CDCl 3 )δ196.38,158.21,138.67,135.69,131.74,129.83,128.92,128.26,128.13,34.46,30.24.；HRMS:calcd.for C 21 H 26 O 2 [M+H] + 311.2005；found 311.2006。
FIGS. 1 to 3 show the single crystal spectra, hydrogen nuclear magnetic resonance spectra and carbon nuclear magnetic resonance spectra of the above-mentioned compounds, (3, 5-di-tert-butyl-4-hydroxyphenyl) (phenyl) methanone, respectively.
Example 2
1.5mL of dimethyl sulfoxide, 0.5mmol of 2, 6-di-tert-butyl-4- (2-fluorobenzylidene) cyclohexyl-2, 5-diene-1-ketone, 1.5mmol of elemental sulfur and 0.5mmol of potassium hydroxide are added into a 10mL reaction bottle, the reaction mixture is heated at 120 ℃ for 8 hours, water is added for quenching after the reaction is finished, ethyl acetate is added for dilution, the mixture is stirred for 30 minutes, an extraction liquid is separated, a water phase is washed for 2 to 3 times by ethyl acetate, the obtained organic phase is dried by anhydrous magnesium sulfate, filtered and concentrated under reduced pressure, column chromatography separation is carried out, the eluent is petroleum ether/ethyl acetate 600mL, and the final product (3, 5-di-tert-butyl-4-hydroxyphenyl) (2-fluorophenyl) methanone is obtained, and the yield is 70%.
The nuclear magnetic resonance and high resolution spectrogram data of the product are as follows: 1 H NMR(400MHz,CDCl 3 )δ8.24–8.11(m,1H),7.49–7.38(m,2H),7.39–7.24(m,1H),7.23–7.07(m,1H),6.84(d,J＝8.3Hz,1H),5.51(s,1H),1.57–1.25(m,18H)； 13 C NMR(101MHz,CDCl 3 )δ171.97,155.29,146.57,137.65,133.22,132.26,126.42,124.58,123.75,120.75,34.55,30.31.HRMS:calcd.for C 21 H 25 FO 2 [M+H] + 329.1911；found329.1914。
example 3
1.5mL of dimethyl sulfoxide, 0.5mmol of 2, 6-di-tert-butyl-4- (4-fluorobenzylidene) cyclohexane-2, 5-dien-1-one, 1.5mmol of elemental sulfur and 0.5mmol of potassium hydroxide are added into a reaction bottle with 10mL, the reaction mixture is heated at 100 ℃ for 9 hours, after the reaction is finished, water is added for quenching, ethyl acetate is added for dilution, stirring is carried out for 30 minutes, an extraction liquid is separated, an aqueous phase is washed with ethyl acetate for 2-3 times, an organic phase is washed with saturated saline solution, the obtained organic phase is dried with anhydrous magnesium sulfate, then filtration and reduced pressure concentration are carried out, column chromatography separation is carried out, the eluent is 600mL of petroleum ether/ethyl acetate, and the final product (3, 5-di-tert-butyl-4-hydroxyphenyl) (4-fluorophenyl) methanone is obtained with the yield of 67%.
The nuclear magnetic resonance and high resolution spectrogram data of the product are as follows: 1 H NMR(400MHz,CDCl 3 )δ7.85–7.77(m,2H),7.68(s,2H),7.16(d,J＝8.6Hz,2H),5.76(s,1H),1.45(s,18H)； 13 C NMR(101MHz,CDCl 3 )δ195.04,166.27,163.76,158.26,135.75,134.83,132.40,132.32,128.79,128.11,115.38,115.17,34.46,30.21.HRMS:calcd.for C 21 H 25 FO 2 [M+H] + 329.1911；found 329.1914。
example 4
1.5mL of dimethyl sulfoxide, 0.5mmol of 2, 6-di-tert-butyl-4- (thiophen-2-ylmethylene) cyclohexyl-2, 5-dien-1-one, 1.5mmol of elemental sulfur and 0.5mmol of potassium hydroxide are added into a 10mL reaction bottle, the reaction mixture is heated at 120 ℃ for 12 hours, water is added for quenching after the reaction is finished, ethyl acetate is added for dilution, stirring is carried out for 30 minutes, the extraction and separation liquid is carried out, the water phase is washed with ethyl acetate for 2-3 times, the organic phase is washed with saturated saline, the obtained organic phase is dried with anhydrous magnesium sulfate, then filtered and concentrated under reduced pressure, column chromatography separation is carried out, the eluent is petroleum ether/ethyl acetate 600mL, and the final product (3, 5-di-tert-butyl-4-hydroxyphenyl) (thiophen-2-yl) methanone is obtained, and the yield is 75%.
The nuclear magnetic resonance and high resolution spectrogram data of the product are as follows: 1 H NMR(400MHz,CDCl 3 )δ7.81(d,J＝4.1Hz,2H),7.66(d,J＝3.1Hz,2H),7.21–7.12(m,1H),5.73(s,1H),1.48(s,18H)； 13 C NMR(101MHz,CDCl 3 )δ187.71,158.08,144.20,135.81,133.84,133.26,129.54,127.84,127.28,34.51,30.25.HRMS:calcd.for C 19 H 24 O 2 S[M+H] + 317.1569；found 317.1567。
example 5
1.5mL of dimethyl sulfoxide, 0.5mmol of 2, 6-di-tert-butyl-4- (2-nitrobenzylidene) cyclohexane-2, 5-dien-1-one, 1.5mmol of elemental sulfur and 0.5mmol of potassium hydroxide are added into a reaction bottle with 10mL of the reaction bottle, the reaction mixture is heated at 110 ℃ for 10 hours, water is added for quenching after the reaction is finished, ethyl acetate is added for dilution, stirring is carried out for 30 minutes, the extraction and separation liquid is carried out, the water phase is washed with ethyl acetate for 2-3 times, the organic phase is washed with saturated saline, the obtained organic phase is dried with anhydrous magnesium sulfate, then filtration and reduced pressure concentration are carried out, column chromatography separation is carried out, the eluent is 600mL of petroleum ether/ethyl acetate, and the final product (3, 5-di-tert-butyl-4-hydroxyphenyl) (2-nitrophenyl) methanone is obtained with the yield of 59 percent.
The nuclear magnetic resonance and high resolution spectrogram data of the product are as follows: 1 H NMR(400MHz,CDCl 3 )δ8.19(s,1H),7.48–7.38(m,2H),7.32(d,J＝6.3Hz,1H),7.14(d,J＝6.9Hz,1H),6.87–6.78(m,1H),5.50(s,1H),1.62–1.33(m,18H).； 13 C NMR(101MHz,CDCl 3 )δ172.09,155.31,146.60,137.64,133.27,133.19,132.29,126.39,124.55,123.75,120.67,34.55,30.30.HRMS:calcd.for C 21 H 25 NO 4 [M+H] + 356.1856；found 356.1853。
example 6
1.5mL of dimethyl sulfoxide, 0.5mmol of 2, 6-di-tert-butyl-4- (4-methoxybenzylidene) cyclohexyl-2, 5-diene-1-ketone, 1.5mmol of elemental sulfur and 0.5mmol of potassium hydroxide are added into a reaction bottle with 10mL, the reaction mixture is heated at 120 ℃ for 13 hours, water is added for quenching after the reaction is finished, ethyl acetate is added for dilution, stirring is carried out for 30 minutes, an extraction liquid is separated, an aqueous phase is washed with ethyl acetate for 2-3 times, an organic phase is washed with saturated saline, the obtained organic phase is dried with anhydrous magnesium sulfate, then filtration and reduced pressure concentration are carried out, column chromatography separation is carried out, the eluent is 600mL of petroleum ether/ethyl acetate, and the final product 3, 5-di-tert-butyl-4-hydroxyphenyl) (4-methoxyphenyl) methanone is obtained with the yield of 70 percent.
The nuclear magnetic resonance and high resolution spectrogram data of the product are as follows: 1 H NMR(400MHz,CDCl 3 )δ7.85–7.78(m,2H),7.69(s,2H),7.00–6.93(m,2H),5.77(s,1H),3.86(s,3H),1.45(s,18H)； 13 C NMR(101MHz,CDCl 3 )δ195.37,162.75,157.83,135.61,132.34,131.08,129.46,127.94,113.43,55.47,34.46,30.26.HRMS:calcd.for C 22 H 28 O 3 [M+H] + 341.2111；found 341.2108。
example 7
1.5mL of dimethyl sulfoxide, 0.5mmol of 2, 6-di-tert-butyl-4- (2-methoxybenzylidene) cyclohexyl-2, 5-diene-1-ketone, 1.5mmol of elemental sulfur and 0.5mmol of potassium hydroxide are added into a reaction bottle with 10mL, the reaction mixture is heated at 120 ℃ for 13 hours, water is added for quenching, ethyl acetate is added for dilution, stirring is carried out for 30 minutes, an extraction liquid is separated, an aqueous phase is washed with ethyl acetate for 2-3 times, an organic phase is washed with saturated saline, the obtained organic phase is dried with anhydrous magnesium sulfate, then filtration and reduced pressure concentration are carried out, column chromatography separation is carried out, the eluent is 600mL of petroleum ether/ethyl acetate, and the final product 3, 5-di-tert-butyl-4-hydroxyphenyl) (2-methoxyphenyl) methanone is obtained with the yield of 69%.
The nuclear magnetic resonance and high resolution spectrogram data of the product are as follows: 1 H NMR(400MHz,CDCl 3 )δ7.85–7.78(m,2H),7.69(s,2H),7.00–6.93(m,2H),5.77(s,1H),3.86(s,3H),1.45(s,18H). 13 C NMR(101MHz,CDCl 3 )δ195.37,162.75,157.83,135.61,132.34,131.08,129.46,127.94,113.43,55.47,34.46,30.26.HRMS:calcd.for C 22 H 28 O 3 [M+H] + 341.2111；found 341.2108。
example 8
1.5mL of dimethyl sulfoxide, 0.5mmol of 2, 6-di-tert-butyl-4- (3, 4-dimethoxy-benzylidene) cyclohexyl-2, 5-diene-1-one, 1.5mmol of elemental sulfur and 0.5mmol of potassium hydroxide are added into a 10mL reaction bottle, the reaction mixture is heated at 120 ℃ for 10 hours, water is added after the reaction is finished, ethyl acetate is added for dilution, the mixture is stirred for 30 minutes, the extraction and separation liquid is extracted, the water phase is washed for 2 to 3 times by ethyl acetate, the organic phase is washed by saturated saline, the obtained organic phase is dried by anhydrous magnesium sulfate, then filtered and concentrated under reduced pressure, column chromatography separation is carried out, and the eluent is petroleum ether/ethyl acetate 600mL to obtain the final product (3, 5-di-tert-butyl-4-hydroxyphenyl) (3, 4-dimethoxy phenyl) methanone with the yield of 69 percent.
The nuclear magnetic resonance and high resolution spectrogram data of the product are as follows: 1 H NMR(400MHz,CDCl 3 )δ7.75(s,2H),7.43(t,J＝7.9Hz,1H),7.31(d,J＝7.4Hz,1H),7.06–6.95(m,2H),5.78(s,1H),3.76(s,3H),1.42(s,18H). 13 C NMR(101MHz,CDCl 3 )δ195.72,158.72,156.94,135.54,131.26,129.56,129.26,129.02,128.18,120.41,111.31,55.65,34.38,30.20.HRMS:calcd.for C 23 H 30 O 4 [M+H] + 371.2216；found 371.2211。
example 9
1.5mL of dimethyl sulfoxide, 0.5mmol of 2, 6-di-tert-butyl-4- (3, 4, 5-trimethoxy benzylidene) cyclohexyl-2, 5-diene-1-one, 1.5mmol of elemental sulfur and 0.5mmol of potassium hydroxide are added into a 10mL reaction bottle, the reaction mixture is heated at 120 ℃ for 14 hours, water is added for quenching after the reaction, ethyl acetate is added for dilution, stirring is carried out for 30 minutes, an extraction liquid is separated, an aqueous phase is washed for 2-3 times by ethyl acetate, an organic phase is washed by saturated saline, the obtained organic phase is dried by anhydrous magnesium sulfate, then filtration and decompression concentration are carried out, column chromatography separation is carried out, and an eluent is petroleum ether/ethyl acetate 600mL to obtain a final product (3, 5-di-tert-butyl-4-hydroxyphenyl) (3, 4, 5-trimethoxyphenyl) methanone with the yield of 59 percent.
The nuclear magnetic resonance and high resolution spectrogram data of the product are as follows: 1 H NMR(400MHz,CDCl 3 )δ7.68(s,2H),7.45–7.33(m,2H),6.89(d,J＝8.3Hz,1H),5.73(s,1H),3.91(d,J＝8.3Hz,6H),1.43(s,18H). 13 C NMR(101MHz,CDCl 3 )δ195.32,157.78,152.44,148.74,135.58,131.11,129.39,127.90,124.75,112.55,109.85,60.37,55.99,34.43,30.24.HRMS:calcd.for C 24 H 32 O 5 [M+H] + 401.2322；found 401.2318。
example 10
1.5mL of dimethyl sulfoxide, 0.5mmol of 4- (4-bromobenzene subunit) -2, 6-di-tert-butyl-cyclohexa-2, 5-dien-1-one, 1.5mmol of elemental sulfur and 0.5mmol of potassium hydroxide are added into a reaction bottle with 10mL of the reaction bottle, the reaction mixture is heated at 100 ℃ for 10 hours, water is added for quenching, ethyl acetate is added for dilution, stirring is carried out for 30 minutes, an extraction liquid is separated, an aqueous phase is washed with ethyl acetate for 2-3 times, an organic phase is washed with saturated saline solution, the obtained organic phase is dried with anhydrous magnesium sulfate, then filtration and reduced pressure concentration are carried out, column chromatography separation is carried out, the eluent is petroleum ether/ethyl acetate 600mL, and the final product (4-bromophenyl) (3, 5-di-tert-butyl-4-hydroxyphenyl) methanone is obtained, and the yield is 85%.
The nuclear magnetic resonance and high resolution spectrogram data of the product are as follows: 1 H NMR(400MHz,CDCl 3 )δ7.72–7.58(m,6H),5.78(s,1H),1.45(s,18H). 13 C NMR(101MHz,CDCl 3 )δ190.52,153.69,132.65,131.08,126.69,123.74,123.41,121.95,29.72,25.46.HRMS:calcd.for C 21 H 25 BrO 2 [M+H] + 391.1091；found 391.1088。
example 11
1.5mL of dimethyl sulfoxide, 0.5mmol of 4- (2-bromobenzene subunit) -2, 6-di-tert-butyl-cyclohexa-2, 5-dien-1-one, 1.5mmol of elemental sulfur and 0.5mmol of potassium hydroxide are added into a reaction bottle with 10mL, the reaction mixture is heated at 130 ℃ for 14 hours, water is added for quenching, ethyl acetate is added for dilution, stirring is carried out for 30 minutes, an extraction liquid is separated, an aqueous phase is washed with ethyl acetate for 2-3 times, an organic phase is washed with saturated saline solution, the obtained organic phase is dried with anhydrous magnesium sulfate, then filtration and reduced pressure concentration are carried out, column chromatography separation is carried out, the eluent is petroleum ether/ethyl acetate 600mL, and the final product (2-bromophenyl) (3, 5-di-tert-butyl-4-hydroxyphenyl) methanone is obtained, and the yield is 55%.
The nuclear magnetic resonance and high resolution spectrogram data of the product are as follows: 1 H NMR(400MHz,CDCl 3 )δ7.70(s,2H),7.65(s,1H),7.40(s,1H),7.31(s,2H),5.82(s,1H),1.41(s,18H). 13 C NMR(101MHz,CDCl 3 )δ195.18,159.24,141.39,135.98,133.08,130.71,128.91,128.47,127.66,127.04,119.56,34.39,30.13.HRMS:calcd.for C 21 H 25 BrO 2 [M+H] + 391.1091；found 391.1088。
example 12
1.5mL of dimethyl sulfoxide, 0.5mmol of 4- (3-bromobenzene subunit) -2, 6-di-tert-butyl-cyclohexa-2, 5-dien-1-one, 1.5mmol of elemental sulfur and 0.5mmol of potassium hydroxide are added into a reaction bottle with 10mL, the reaction mixture is heated at 140 ℃ for 8 hours, water is added for quenching after the reaction is finished, ethyl acetate is added for dilution, stirring is carried out for 30 minutes, an extraction liquid is separated, an aqueous phase is washed with ethyl acetate for 2-3 times, an organic phase is washed with saturated saline solution, the obtained organic phase is dried with anhydrous magnesium sulfate, then filtration and reduced pressure concentration are carried out, column chromatography separation is carried out, the eluent is petroleum ether/ethyl acetate 600mL, and the final product (3-bromophenyl) (3, 5-di-tert-butyl-4-hydroxyphenyl) methanone is obtained with the yield of 85%.
The nuclear magnetic resonance and high resolution spectrogram data of the product are as follows: 1 H NMR(400MHz,CDCl3)δ7.92(s,1H),7.71(s,4H),7.35(t,J＝7.8Hz,1H),5.80(s,1H),1.46(s,18H). 13 C NMR(101MHz,CDCl3)δ194.79,158.58,140.55,135.90,134.60,132.77,129.70,128.29,122.45,34.48,30.22.HRMS:calcd.for C 21 H 25 BrO 2 [M+H] + 391.1091；found391.1088。
example 13
1.5mL of dimethyl sulfoxide, 0.5mmol of 2, 6-diisopropyl-4- (4-methylbenzylidene) cyclohexane-2, 5-dien-1-one, 1.5mmol of elemental sulfur and 0.5mmol of potassium hydroxide are added into a reaction bottle with 10mL of the mixture, the reaction mixture is heated at 100 ℃ for 10 hours, water is added for quenching, ethyl acetate is added for dilution, stirring is carried out for 30 minutes, an extraction liquid is separated, an aqueous phase is washed with ethyl acetate for 2-3 times, an organic phase is washed with saturated saline, the obtained organic phase is dried with anhydrous magnesium sulfate, then filtration and reduced pressure concentration are carried out, column chromatography separation is carried out, the eluent is 600mL of petroleum ether/ethyl acetate, and the final product 4-hydroxy- (3, 5-diisopropylphenyl) (p-tolyl) methanone is obtained with the yield of 91 percent.
The nuclear magnetic resonance and high resolution spectrogram data of the product are as follows: 1 H NMR(400MHz,CDCl 3 )δ7.75(d,J＝7.8Hz,2H),7.64(s,2H),7.32(d,J＝7.7Hz,2H),5.91(s,1H),3.27(p,J＝6.7Hz,2H),2.49(s,3H),1.31(d,J＝6.8Hz,12H)； 13 C NMR(101MHz,CDCl 3 )δ196.40,154.50,142.57,135.81,133.68,130.21,130.07,128.88,126.79,27.19,22.71,21.67.HRMS:calcd.for C 20 H 24 O 2 [M+H] + 297.1849；found 297.1848。
example 14
1.5mL of dimethyl sulfoxide, 0.5mmol of 4- ((3, 5-di-tert-butyl-4-oxo-cyclohexane-2, 5-diene-1-ylidene) methyl) benzonitrile, 1.5mmol of elemental sulfur and 0.5mmol of potassium hydroxide are added into a 10mL reaction bottle, the reaction mixture is heated at 110 ℃ for 14 hours, water is added to quench the reaction, ethyl acetate is added for dilution, stirring is carried out for 30 minutes, the extraction and separation liquid is extracted, the water phase is washed for 2-3 times by ethyl acetate, the organic phase is washed by saturated saline, the obtained organic phase is dried by anhydrous magnesium sulfate, then filtered and concentrated under reduced pressure, column chromatography separation is carried out, the eluent is petroleum ether/ethyl acetate 600mL, and the final product 4- (3, 5-di-tert-butyl-4-hydroxybenzoyl) benzonitrile is obtained with the yield of 40%.
The nuclear magnetic resonance and high resolution spectrogram data of the product are as follows: 1 H NMR(400MHz,CDCl 3 )δ7.83(d,J＝8.3Hz,2H),7.78(d,J＝8.3Hz,2H),7.68(s,2H),5.85(s,1H),1.44(s,18H). 13 C NMR(101MHz,CDCl 3 )δ194.58,158.98,142.59,136.11,132.06,130.00,128.30,127.76,118.28,115.01,34.48,30.15.HRMS:calcd.for C 22 H 25 NO 2 [M+H] + 336.1958；found 336.1965。
example 15
1.5mL of dimethyl sulfoxide, 0.5mmol of 2, 6-di-tert-butyl-4- (4-isopropylbenzylidene) cyclohexyl-2, 5-diene-1-one, 1.5mmol of elemental sulfur and 0.5mmol of potassium hydroxide are added into a reaction bottle with 10mL, the reaction mixture is heated at 120 ℃ for 14 hours, water is added for quenching after the reaction is finished, ethyl acetate is added for dilution, stirring is carried out for 30 minutes, the extraction and separation liquid is carried out, the water phase is washed with ethyl acetate for 2-3 times, the organic phase is washed with saturated saline, the obtained organic phase is dried with anhydrous magnesium sulfate, then filtered and concentrated under reduced pressure, column chromatography separation is carried out, the eluent is petroleum ether/ethyl acetate 600mL, and the final product (3, 5-di-tert-butyl-4-hydroxyphenyl) (4-isopropylphenyl) methanone is obtained, and the yield is 75%.
The nuclear magnetic resonance and high resolution spectrogram data of the product are as follows: 1 H NMR(400MHz,CDCl 3 )δ7.75(d,J＝8.2Hz,4H),7.33(d,J＝7.9Hz,2H),5.76(s,1H),3.00(p,J＝6.8Hz,1H),1.47(s,18H),1.31(d,J＝6.9Hz,6H). 13 C NMR(101MHz,CDCl 3 )δ196.12,158.01,153.21,136.16,135.60,130.28,129.22,128.14,126.27,34.48,34.29,30.28,23.85.HRMS:calcd.for C 24 H 32 O 2 [M+H] + 353.2475；found 353.2470。
example 16
1.5mL of dimethyl sulfoxide, 0.5mmol of 2, 6-di-tert-butyl-4- (3-methylbenzylidene) cyclohexane-2, 5-dien-1-one, 1.5mmol of elemental sulfur and 0.5mmol of potassium hydroxide are added into a reaction bottle with 10mL, the reaction mixture is heated at 120 ℃ for 14 hours, water is added for quenching after the reaction is finished, ethyl acetate is added for dilution, stirring is carried out for 30 minutes, an extraction liquid is separated, an aqueous phase is washed with ethyl acetate for 2-3 times, an organic phase is washed with saturated saline, the obtained organic phase is dried with anhydrous magnesium sulfate, then filtration and reduced pressure concentration are carried out, column chromatography separation is carried out, the eluent is 600mL of petroleum ether/ethyl acetate, and the final product (3, 5-di-tert-butyl-4-hydroxyphenyl) (m-tolyl) methanone is obtained with the yield of 80 percent.
The nuclear magnetic resonance and high resolution spectrogram data of the product are as follows: 1 H NMR(400MHz,CDCl 3 )δ7.75(s,2H),7.63(s,1H),7.56(d,J＝6.3Hz,1H),7.36(d,J＝6.5Hz,2H),5.77(s,1H),2.43(s,3H),1.46(s,18H). 13 C NMR(101MHz,CDCl 3 )δ196.57,158.19,138.62,137.99,135.63,132.54,130.42,129.00,128.31,127.91,127.14,34.47,30.26,21.45.HRMS:calcd.for C 22 H 28 O 2 [M+H] + 325.2162；found 325.2156。
example 17
1.5mL of dimethyl sulfoxide, 0.5mmol of 2, 6-di-tert-butyl-4- (4-methylbenzylidene) cyclohexane-2, 5-dien-1-one, 1.5mmol of elemental sulfur and 0.5mmol of potassium hydroxide are added into a reaction bottle with 10mL, the reaction mixture is heated at 120 ℃ for 14 hours, water is added for quenching after the reaction is finished, ethyl acetate is added for dilution, stirring is carried out for 30 minutes, an extraction liquid is separated, an aqueous phase is washed with ethyl acetate for 2-3 times, an organic phase is washed with saturated saline, the obtained organic phase is dried with anhydrous magnesium sulfate, then filtration and reduced pressure concentration are carried out, column chromatography separation is carried out, the eluent is 600mL of petroleum ether/ethyl acetate, and the final product (3, 5-di-tert-butyl-4-hydroxyphenyl) (p-tolyl) methanone is obtained, and the yield is 82%.
The nuclear magnetic resonance and high resolution spectrogram data of the product are as follows: 1 H NMR(400MHz,CDCl 3 )δ7.75(d,J＝10.6Hz,4H),7.31(d,J＝7.9Hz,2H),5.78(s,1H),2.48(s,3H),1.50(s,18H). 13 C NMR(101MHz,CDCl 3 )δ196.22,158.01,142.43,135.83,135.58,130.15,129.20,128.85,128.15,34.46,30.26,21.69.HRMS:calcd.for C 22 H 28 O 2 [M+H] + 325.2162；found 325.2156。
example 18
1.5mL of dimethyl sulfoxide, 0.5mmol of 2, 6-di-tert-butyl-4- (pyridin-2-ylmethylene) cyclohexane-2, 5-dien-1-one, 1.5mmol of elemental sulfur and 0.5mmol of potassium hydroxide are added into a 10mL reaction bottle, the reaction mixture is heated at 120 ℃ for 12 hours, after the reaction is finished, water is added for quenching, ethyl acetate is added for dilution, stirring is carried out for 30 minutes, the extraction and separation liquid is carried out, the aqueous phase is washed with ethyl acetate for 2-3 times, the organic phase is washed with saturated saline, the obtained organic phase is dried with anhydrous magnesium sulfate, then filtered and concentrated under reduced pressure, column chromatography separation is carried out, the eluent is petroleum ether/ethyl acetate 600mL, and the final product (3, 5-di-tert-butyl-4-hydroxyphenyl) (pyridin-2-yl) methanone is obtained, and the yield is 49%.
The nuclear magnetic resonance and high resolution spectrogram data of the product are as follows: 1 H NMR(400MHz,CDCl 3 )δ8.74(d,J＝3.3Hz,1H),8.02(s,3H),7.93(s,1H),7.55–7.40(m,1H),5.81(s,1H),1.49(d,J＝2.4Hz,18H). 13 C NMR(101MHz,CDCl 3 )δ193.40,158.78,156.25,148.29,137.00,135.51,129.22,127.76,125.67,124.54,34.44,30.19.HRMS:calcd.for C 20 H 25 NO 2 [M+H] + 312.1958；found 312.1957。
example 19
1.5mL of dimethyl sulfoxide, 0.5mmol of 4- (4-bromobenzene subunit) -2, 6-diisopropylcyclohexyl-2, 5-dien-1-one, 1.5mmol of elemental sulfur and 0.5mmol of potassium hydroxide are added into a reaction bottle with 10mL of the mixture, the reaction mixture is heated at 120 ℃ for 12 hours, water is added for quenching after the reaction is finished, ethyl acetate is added for dilution, stirring is carried out for 30 minutes, an extraction liquid is separated, an aqueous phase is washed with ethyl acetate for 2-3 times, an organic phase is washed with saturated saline solution, the obtained organic phase is dried with anhydrous magnesium sulfate, then filtration and reduced pressure concentration are carried out, column chromatography separation is carried out, the eluent is petroleum ether/ethyl acetate 600mL, and the final product (4-bromophenyl) (4-hydroxy-3, 5-diisopropylphenyl) methanone is obtained, and the yield is 79%.
The nuclear magnetic resonance and high resolution spectrogram data of the product are as follows: 1 H NMR(400MHz,CDCl 3 )δ7.63(s,4H),7.56(s,2H),5.54(s,1H),3.19(p,J＝6.6Hz,2H),1.27(d,J＝7.8Hz,12H)； 13 C NMR(101MHz,CDCl 3 )δ195.23,154.67,137.36,133.73,131.43,129.52,126.76,27.24,22.64.HRMS:calcd.for C 19 H 21 BrO 2 [M+H] + 361.0797；found361.0794。
example 20
1.5mL of dimethyl sulfoxide, 0.5mmol of 2, 6-di-tert-butyl-4- (naphthalen-2-ylmethylene) cyclohexane-2, 5-dien-1-one, 1.5mmol of elemental sulfur and 0.5mmol of potassium hydroxide are added into a 10mL reaction bottle, the reaction mixture is heated at 120 ℃ for 12 hours, water is added after the reaction is finished, ethyl acetate is added for dilution, stirring is carried out for 30 minutes, the extraction and separation liquid is carried out, the aqueous phase is washed with ethyl acetate for 2-3 times, the organic phase is washed with saturated saline, the obtained organic phase is dried with anhydrous magnesium sulfate, then the filtration and the decompression concentration are carried out, the column chromatography separation is carried out, the eluent is 600mL of petroleum ether/ethyl acetate, and the final product (3, 5-di-tert-butyl-4-hydroxyphenyl) (naphthalen-2-yl) methanone is obtained, and the yield is 79%.
The nuclear magnetic resonance and high resolution spectrogram data of the product are as follows: 1 H NMR(400MHz,CDCl 3 )δ8.34(s,1H),8.04–7.81(m,6H),7.58(dt,J＝16.1,6.9Hz,2H),5.88(s,1H),1.50(s,18H)； 13 C NMR(101MHz,CDCl 3 )δ196.38,158.34,135.90,135.84,135.08,132.52,131.30,129.34,129.16,128.44,128.11,128.06,127.92,126.81,126.26,34.55,30.32.HRMS:calcd.for C 25 H 28 O 2 [M+H] + 361.2162；found 361.2158。
example 21
1.5mL of dimethyl sulfoxide, 0.5mmol of 4-benzylidene-2, 6-diisopropylcyclohexyl-2, 5-dien-1-one, 1.5mmol of elemental sulfur and 0.5mmol of potassium hydroxide are added into a 10mL reaction bottle, the reaction mixture is heated for 14 hours at 120 ℃, after the reaction is finished, water is added for quenching, ethyl acetate is added for dilution, stirring is carried out for 30 minutes, the extraction and separation liquid is carried out, the water phase is washed for 2-3 times by ethyl acetate, the organic phase is washed by saturated saline, the obtained organic phase is dried by anhydrous magnesium sulfate, then filtration and reduced pressure concentration are carried out, column chromatography separation is carried out, the eluent is 600mL of petroleum ether/ethyl acetate, and the final product (4-hydroxy-3, 5-diisopropylphenyl) methanone is obtained, and the yield is 65%.
The nuclear magnetic resonance and high resolution spectrogram data of the product are as follows: 1 H NMR(400MHz,CDCl 3 )δ7.84(d,J＝7.5Hz,2H),7.68(s,2H),7.61(t,J＝7.2Hz,1H),7.52(t,J＝7.4Hz,2H),6.42(s,1H),3.34(d,J＝6.5Hz,2H),1.30(d,J＝6.9Hz,12H)； 13 C NMR(101MHz,CDCl 3 )δ196.91,155.08,138.59,134.03,131.96,129.99,129.59,128.20,126.99,27.13,22.74.HRMS:calcd.for C 19 H 22 O 2 [M+H] + 283.1692；found 283.1691。
example 22
1.5mL of dimethyl sulfoxide, 0.5mmol of 4- (4-bromobenzene subunit) -2, 6-dimethylcyclohex-2, 5-dien-1-one, 1.5mmol of elemental sulfur and 0.5mmol of potassium hydroxide are added into a reaction bottle with 10mL, the reaction mixture is heated at 120 ℃ for 12 hours, water is added for quenching, ethyl acetate is added for dilution, the mixture is stirred for 30 minutes, an extraction liquid is separated, a water phase is washed with ethyl acetate for 2-3 times, an organic phase is washed with saturated saline solution, the obtained organic phase is dried with anhydrous magnesium sulfate, then the filtration and the reduced pressure concentration are carried out, the column chromatography separation is carried out, and the eluent is petroleum ether/ethyl acetate 600mL, so that a final product (4-bromophenyl) (4-hydroxy-3, 5-dimethylphenyl) methanone is obtained.
The nuclear magnetic resonance and high resolution spectrogram data of the product are as follows: 1 H NMR(400MHz,CDCl 3 )δ7.62(s,4H),7.48(s,2H),5.33(s,1H),2.29(s,6H). 13 C NMR(101MHz,CDCl 3 )δ195.19,156.98,137.22,131.51,131.37,129.15,126.79,123.21,16.04.HRMS:calcd.for C 15 H 13 BrO 2 [M+Na] + 326.9991；found 326.9988.
example 23
1.5mL of dimethyl sulfoxide, 0.5mmol of 2, 6-di-tert-butyl-4- (4-nitrobenzylidene) cyclohexane-2, 5-diene-1-one, 1.5mmol of elemental sulfur and 0.5mmol of potassium hydroxide are added into a reaction bottle with 10mL, the reaction mixture is heated at 120 ℃ for 12 hours, water is added for quenching after the reaction is finished, ethyl acetate is added for dilution, stirring is carried out for 30 minutes, the extraction and separation liquid is carried out, the water phase is washed with ethyl acetate for 2-3 times, the organic phase is washed with saturated saline, the obtained organic phase is dried with anhydrous magnesium sulfate, then filtered and concentrated under reduced pressure, column chromatography separation is carried out, the eluent is petroleum ether/ethyl acetate 600mL, and the final product (3, 5-di-tert-butyl-4-hydroxyphenyl) (4-nitrophenyl) methanone is obtained with the yield of 70 percent.
The nuclear magnetic resonance and high resolution spectrogram data of the product are as follows: 1 H NMR(400MHz,CDCl 3 )δ8.34(dd,J＝13.5,8.7Hz,2H),7.90(dd,J＝13.5,8.7Hz,2H),7.71(d,J＝13.5Hz,2H),5.90(d,J＝13.5Hz,1H),1.46(d,J＝13.6Hz,18H)； 13 C NMR(101MHz,CDCl 3 )δ194.34,159.11,149.46,144.33,136.17,130.39,128.34,127.74,123.44,34.48,30.15.HRMS:calcd.for C 21 H 25 NO 4 [M+H] + 356.1856；found 356.1853。

Claims (5)

1. a method for preparing 4-hydroxybenzophenone and derivatives thereof by using p-methylene quinone as a substrate, which is characterized by comprising the following steps:
step 1): adding a p-methylene quinone compound, an organic solvent, elemental sulfur and alkali into a reaction container, heating the mixture to 100-150 ℃, and stirring for 8-14 hours; the p-methylene quinone compound is at least one of 4-benzylidene-2, 6-di-tert-butylcyclohexa-2, 5-dien-1-one, 2, 6-di-tert-butyl-4- (4-methylbenzylidene) cyclohexa-2, 5-dien-1-one, 4- (4-bromobenzylidene) -2, 6-di-tert-butylcyclohexa-2, 5-dien-1-one, 2, 6-di-tert-butyl-4- (3, 4-dimethoxybenzylidene) cyclohexa-2, 5-dien-1-one, 2, 6-di-tert-butyl-4- (2, 4-dichlorobenzylidene) cyclohexa-2, 5-dien-1-one, 2, 6-di-tert-butyl-4- (3, 4, 5-trimethoxybenzylidene) cyclohexa-2, 5-dien-1-one, 4-benzylidene-2, 6-di-tert-butyl-4-ethylenecyclohexa-2, 5-dien-1-one, 4-benzylidene-2, 6-di-isopropylidene-2, 5-dien-1-one, 2, 6-di-tert-butyl-4- (2, 4-dichlorobenzylidene) cyclohexa-2, 5-dien-1-one, 2, 5-dien-one and 2, 6-di-tert-butyl-4- (4-methylbenzylidene) cyclohexa-4-2, 5-benzylidene) -1-one; the organic solvent is at least one of N, N-dimethylformamide, dimethyl sulfoxide, 1, 4-dioxane, toluene and xylene; the alkali is at least one of potassium carbonate, potassium hydroxide, sodium hydroxide, potassium phosphate, triethylamine, 1, 4-diazabicyclo [2.2.2] octane, sodium acetate and sodium bicarbonate; the molar ratio of the elemental sulfur to the p-methylene quinone compound to the alkali is 3:1:1;
step 2): after the reaction is finished, adding water into the reaction system, quenching, adding ethyl acetate for dilution, stirring, extracting and separating liquid, drying, concentrating, and then performing column chromatography separation to obtain the 4-hydroxybenzophenone or the derivative thereof.
2. The method for preparing 4-hydroxybenzophenone and its derivatives using p-methylenequinone as substrate as claimed in claim 1, wherein the organic phase obtained by the extraction and separation in the step 2) is washed with saturated saline solution, and the aqueous phase is washed with ethyl acetate.
3. The method for preparing 4-hydroxybenzophenone and its derivatives using p-methylenequinone as substrate as claimed in claim 1 or 2, wherein the organic phases obtained by the separation of the extract in step 2) are combined and dried over anhydrous magnesium sulfate, then filtered, concentrated under reduced pressure, and then separated by column chromatography.
4. The method for preparing 4-hydroxybenzophenone and its derivatives with p-methylenequinone as substrate as claimed in claim 3, wherein the eluent used in the column chromatographic separation is a mixture of petroleum ether and ethyl acetate.
5. The method for preparing 4-hydroxybenzophenone and derivatives thereof with p-methylenequinone as substrate as claimed in claim 4, wherein the eluent used in the column chromatography separation is a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 10:1-50:1.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB810570A (en) * 1955-07-18 1959-03-18 American Cyanamid Co Hydroxylated benzophenone ethers
CN108467382A (en) * 2018-03-29 2018-08-31 青岛科技大学 A kind of preparation method of 4H- chromene derivatives

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Publication number Priority date Publication date Assignee Title
GB810570A (en) * 1955-07-18 1959-03-18 American Cyanamid Co Hydroxylated benzophenone ethers
CN108467382A (en) * 2018-03-29 2018-08-31 青岛科技大学 A kind of preparation method of 4H- chromene derivatives

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