CN1696094A - Method for preparing 4,4'-dihydroxy benzophenone - Google Patents
Method for preparing 4,4'-dihydroxy benzophenone Download PDFInfo
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- CN1696094A CN1696094A CN 200510018620 CN200510018620A CN1696094A CN 1696094 A CN1696094 A CN 1696094A CN 200510018620 CN200510018620 CN 200510018620 CN 200510018620 A CN200510018620 A CN 200510018620A CN 1696094 A CN1696094 A CN 1696094A
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- phenyl ester
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Abstract
A process for preparing the 4,4'-bihydroxybiphenyl methaneone includes mixing phenyl p-hydroxybenzoate with catalyst in organic solvent, heating while stirring, reaction, separating the resultant and recrystallizing.
Description
Technical field
The invention belongs to meticulous organic chemical industry field, relate to 4,4 '-preparation method of dihydroxy benaophenonel.
Background technology
4,4 '-dihydroxy benaophenonel is chemical industry, pharmaceutical intermediate, its structural formula is:
A lot of about its synthetic report, wherein Japanese Patent JP3123752 report is a raw material with P-hydroxybenzoic acid and phenol, directly utilizes polyphosphoric acid to be solvent catalysis simultaneously, synthesising target compound.At present industrial also synthetic with this method.This method catalyst system therefor type is limited, and waste phosphoric acid is difficult to reclaim, and causes environmental pollution serious, the cost height.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide a kind of new 4,4 '-dihydroxy benaophenonel synthetic route and method.This method technology is more simply fallen, production cost is lower, and product yield is higher, is suitable for industrialized production.
Technical scheme provided by the invention is: 4, the preparation method of 4 '-dihydroxy benaophenonel, in the presence of catalyzer, the P-hydroxybenzoic acid phenyl ester stirred in organic solvent be warming up to 70～170 ℃, kept temperature of reaction 3～20 hours, separate resultant, recrystallization gets 4,4 '-dihydroxy benaophenonel.Its reaction formula is:
Catalyst system therefor is selected from zinc chloride, aluminum chloride, methylsulfonic acid, tosic acid, trifluoromethanesulfonic acid, polyphosphoric acid, perchloric acid, methylsulfonic acid metal-salt, tosic acid metal-salt, metal salts of trifluoromethane sulphonic acid, or the mixture of above-mentioned any two or more acid.
Used organic solvent is benzene, toluene, chlorobenzene, oil of mirbane, dithiocarbonic anhydride, hexanaphthene, C
6～C
10Hydro carbons and/or sherwood oil.
The mol ratio of P-hydroxybenzoic acid phenyl ester and catalyzer is 1: 0.1～1.
The P-hydroxybenzoic acid phenyl ester by to acetoxyl group Benzoyl chloride and phenol in 80～140 ℃ of reactions of chlorobenzene, or generate the acetoxy-benzoic acid phenyl ester at methylene dichloride, trichloromethane or 5～40 ℃ of reactions of tetracol phenixin, the acetoxy-benzoic acid phenyl ester is sloughed acetoxyl group make in solvent ammonia and alcohol.
The above-mentioned used alcohol of acetoxyl group of sloughing is methyl alcohol, ethanol, propyl alcohol or butanols, and alcohol is 100: 5～60 with the consumption volume ratio of ammoniacal liquor.
The above-mentioned acetoxyl group Benzoyl chloride is reacted with P-hydroxybenzoic acid and acetylation reagent generates acetoxy-benzoic acid, and acetoxy-benzoic acid is obtained the acetoxyl group Benzoyl chloride through phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride or sulfur oxychloride chlorination.
The advantage that the present invention has compared with the prior art is: (1) utilizes methyl p-hydroxybenzoate to reset preparation 4,4 '-dihydroxy benaophenonel is widened the kind of useful catalyst, has solved that catalyst levels is big, phosphate discharge liquid is difficult to handle, reduce production costs, simplify technology.(2) the yield height is suitable for industrialized production.
Embodiment
Embodiment 1
(1) to acetoxy-benzoic acid
Add P-hydroxybenzoic acid in the 250ml there-necked flask, aceticanhydride stirs the vitriol oil that the back adds catalytic amount, heats 65 ℃ of reaction 2h, discharging is fallen in frozen water, stirs, and separates out the solid after-filtration, ethyl alcohol recrystallization, get white solid to acetoxy-benzoic acid, yield 93%, mp192～194.
(2) to the acetoxyl group Benzoyl chloride
In the three-necked bottle that stirring, reflux exchanger are housed, add to acetoxy-benzoic acid 28g (0.16mol), sulfur oxychloride 40ml (0.55mol) and pyridine (0.06～0.1ml), be warming up to 70～75 ℃ of stirring reaction 3h to there not being gas evolution.Steam unreacted sulfur oxychloride after being cooled to room temperature, the cut of 140-144 ℃/10.67kPa is collected in the residuum underpressure distillation, gets light yellow proterties oily liquids to acetoxyl group Benzoyl chloride 29g (0.15mol).
(3) to the acetoxy-benzoic acid phenyl ester
Add phenol 15g (0.16mol), pyridine 23g (0.16mol) and methylene dichloride (200ml) in the ice-water bath condition downhill reaction bottle, adding 50mL contains the dichloromethane solution of 29g (0.15mol) to the acetoxyl group Benzoyl chloride after stirring 5min, stirring at room reaction 18h.Add 3mol/L hydrochloric acid 60ml washing, organic phase with 5% sodium hydrogen carbonate solution 50ml and water 50ml washing, is used anhydrous sodium sulfate drying successively.Steaming desolventizes, and the residue yellow solid is through activated carbon decolorizing, ethyl alcohol recrystallization, white crystal to acetoxy-benzoic acid phenyl ester 39g, yield 95%, mp82～83 ℃.FT-IR(KBr，diffuse?reflectance)m
-1ν
max：1767(ν
c＝o)，1736(ν
c＝o)，1597，1493(ν
c＝c)；1269(ν
c-o)，1153(ν
c-o)；H’NMR(CDCl
3，δ，ppm)：8.24(d，2H，J＝11Hz)，7.43(m，2H，J＝12Hz)，7.26(m，5H)，2.43(s，3H)；MS?MS(M/Z，M)256.Element?analysis：C70.28，H5,43.
(4) P-hydroxybenzoic acid phenyl ester
Acetoxy-benzoic acid phenyl ester 30g (0.12mol) is dissolved in methyl alcohol 100ml, and 0～5 ℃ adds 28% ammoniacal liquor 30ml, stirring at room reaction 2.5h.In the reactant impouring 100 gram trash ices, with methylene dichloride (60ml * 3) extraction, organic phase merges the back anhydrous sodium sulfate drying, filter, filtrate decompression is steamed and is removed methylene dichloride, residuum ethyl alcohol recrystallization, white crystal P-hydroxybenzoic acid phenyl ester, yield 92%, mp184～185 ℃.FT-IR(KBr，cm
-1)：3402(ν
c-OH)，1701(ν
c＝O)；1604，1586，1509(ν
c＝C)；1262(ν
c-O)，1158(ν
c-O).H’NMR(DMSO-d，ppm)：10.55(s，1H)，8.0(d，2H，J＝14Hz)，7.46(m，2H)，7.28(t，1H，J＝15Hz)，7.2(d，2H，J＝13Hz)，6.94(d，2H，J＝14Hz)；MS(M/Z，M
+)214.Element?analysis：C?72.45，H4,71.
(5) 4,4 '-the hydroquinol ketone
P-hydroxybenzoic acid phenyl ester 21.5g (0.1mol), methylsulfonic acid 3.8g (0.04mol) are dissolved in the anhydrous dithiocarbonic anhydride of 100ml, are warming up to back flow reaction 8h under stirring.Be as cold as room temperature, add 20ml 5% salt acid elution, filter, filter cake is with 10% sodium hydrogen carbonate solution and water washing, with alcohol-water (1: 4) recrystallization, must white crystal target compound 4,4 '-hydroquinol ketone 20g, yield 93%, mp219～220 ℃.FT-IR(KBr，cm
-1)：3339(ν
c-OH)，1628(ν
c＝O)；1595，1574；1446(ν
c＝C)；1244(ν
c-O)854(1，4benzene)；.H’NMR(acetonr-d
6，ppm)：9.1(s，2H)，7.71(d，4H，J＝6Hz)，6.95(d，4H，J＝6Hz)，；MS(M/Z，M
+)214.Element?analysis：C72.52，H4,68.
Embodiment 2
To acetoxy-benzoic acid, to acetoxyl group Benzoyl chloride, P-hydroxybenzoic acid phenyl ester preparation method with embodiment 1.
Using chlorobenzene instead is solvent, and back flow reaction prepared the acetoxy-benzoic acid phenyl ester in 10 hours, yield 96%.
The P-hydroxybenzoic acid phenyl ester: trifluoromethanesulfonic acid is 1: 0.2 (mol ratio), and sherwood oil is a solvent, intensification stirring and refluxing reaction 10h.10% sodium hydrogen carbonate solution and water washing, methanol-water (1: 3, volume ratio) recrystallization, target compound 4,4 '-the hydroquinol ketone.Yield 98%.mp219～220℃。
Embodiment 3
To acetoxy-benzoic acid, to acetoxyl group Benzoyl chloride, P-hydroxybenzoic acid phenyl ester preparation method with embodiment 1.
Using chlorobenzene instead is solvent, and back flow reaction prepared the acetoxy-benzoic acid phenyl ester in 10 hours, yield 96%.
The P-hydroxybenzoic acid phenyl ester: trifluoromethanesulfonic acid chromium is 1: 0.15 (mol ratio), and hexanaphthene is a solvent, intensification stirring and refluxing reaction 8h.10% sodium hydrogen carbonate solution and water washing, methanol-water (1: 3, volume ratio) recrystallization, target compound 4,4 '-the hydroquinol ketone.Yield 99%.mp219～220℃。
Embodiment 4
To the acetoxy-benzoic acid preparation method with embodiment 1.
Preparation to the acetoxyl group Benzoyl chloride:
In the three-necked bottle that stirring, reflux exchanger are housed, add, be warming up to 70～75 ℃ of stirring reaction 3h acetoxy-benzoic acid 28g (0.16mol), phosphorus trichloride 40ml.Steam the phosphorus oxychloride of unreacted phosphorus trichloride and generation.The cut of 140-144 ℃/10.67kPa is collected in the residuum underpressure distillation, gets light yellow proterties oily liquids to acetoxyl group Benzoyl chloride 28g.
To the preparation of acetoxy-benzoic acid phenyl ester with embodiment 2.
The preparation of P-hydroxybenzoic acid phenyl ester:
Acetoxy-benzoic acid phenyl ester 30g (0.12mol) is dissolved in the mixed solvent (ammoniacal liquor: the weight ratio of propyl carbinol is 25: 100) of 100ml ammoniacal liquor and propyl carbinol, stirring at room reaction 2.5h.In the reactant impouring 100ml water, filter.Use recrystallizing methanol, white crystal P-hydroxybenzoic acid phenyl ester, yield 93%, mp184～185 ℃.
4,4 '-preparation of hydroquinol ketone:
The P-hydroxybenzoic acid phenyl ester: methylsulfonic acid and polyphosphoric acid are 1: 0.3 (mol ratio); The consumption volume ratio of methylsulfonic acid and polyphosphoric acid is 5: 1; Hexanaphthene is a solvent, and intensification stirring and refluxing reaction 10h filters, 10% sodium hydrogen carbonate solution and water washing, methanol-water (1: 3) recrystallization, target compound 4,4 '-the hydroquinol ketone.Yield 95%.mp219～220℃。
Synthesize 4,4 '-hydroquinol ketone purity is more than 99.7%.
Claims (7)
1.4 the preparation method of 4 '-dihydroxy benaophenonel is characterized in that: in the presence of catalyzer, the P-hydroxybenzoic acid phenyl ester stirred in organic solvent be warming up to 70～170 ℃, kept temperature of reaction 3～20 hours, separate resultant, recrystallization gets 4,4 '-dihydroxy benaophenonel.
2. preparation method according to claim 1, it is characterized in that: catalyst system therefor is selected from zinc chloride, aluminum chloride, methylsulfonic acid, tosic acid, trifluoromethanesulfonic acid, polyphosphoric acid, perchloric acid, methylsulfonic acid metal-salt, tosic acid metal-salt, metal salts of trifluoromethane sulphonic acid, or the mixture of above-mentioned any two or more acid.
3. preparation method according to claim 1 and 2 is characterized in that: used organic solvent is benzene, toluene, chlorobenzene, oil of mirbane, dithiocarbonic anhydride, hexanaphthene, C
6～C
10Hydro carbons and/or sherwood oil.
4. preparation method according to claim 1 and 2 is characterized in that: the mol ratio of P-hydroxybenzoic acid phenyl ester and catalyzer is 1: 0.1～1.
5. preparation method according to claim 1 and 2, it is characterized in that: the P-hydroxybenzoic acid phenyl ester by to acetoxyl group Benzoyl chloride and phenol in 80～140 ℃ of reactions of chlorobenzene, or generate the acetoxy-benzoic acid phenyl ester at methylene dichloride, trichloromethane or 5～40 ℃ of reactions of tetracol phenixin, the acetoxy-benzoic acid phenyl ester is sloughed acetoxyl group make in solvent ammonia and alcohol.
6. preparation method according to claim 5 is characterized in that: sloughing the used alcohol of acetoxyl group is methyl alcohol, ethanol, propyl alcohol or butanols, and alcohol is 100: 5～60 with the consumption volume ratio of ammoniacal liquor.
7. preparation method according to claim 5; it is characterized in that: the acetoxyl group Benzoyl chloride is generated acetoxy-benzoic acid with P-hydroxybenzoic acid and acetylation reagent reaction, acetoxy-benzoic acid is obtained the acetoxyl group Benzoyl chloride through phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride or sulfur oxychloride chlorination.
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| CN102153530A (en) * | 2011-02-12 | 2011-08-17 | 北京欧格瑞化学科技有限公司 | Novel method for synthesizing dronedarone key intermediate |
| CN102649721A (en) * | 2011-02-25 | 2012-08-29 | 北京英力科技发展有限公司 | Preparation method for 3,5-dimethoxy-2,6-biacyl phenol |
| CN103497092A (en) * | 2013-10-12 | 2014-01-08 | 武汉怡兴化工有限公司 | Preparation method of 4, 4'-dihydroxy benaophenonel |
| CN107129432A (en) * | 2017-06-06 | 2017-09-05 | 如东金康泰化学有限公司 | A kind of synthetic method of ultra-violet absorber 4,4`- bis- epoxide benzophenone |
| CN107266318A (en) * | 2013-07-01 | 2017-10-20 | Lg化学株式会社 | Polysiloxane compound and preparation method thereof and the copolycarbonate resin comprising it |
| CN108409549A (en) * | 2018-05-10 | 2018-08-17 | 绍兴文理学院 | The preparation method of 2,2 '-dihydroxy benaophenonel class compounds |
| CN113683495A (en) * | 2021-09-16 | 2021-11-23 | 湖北瑞凯兴科技股份有限公司 | Method for preparing 4,4' -dihydroxy benzophenone |
| CN114341227A (en) * | 2019-08-27 | 2022-04-12 | Dic株式会社 | Phenolic resin, curable resin composition, and cured product thereof |
| CN116622218A (en) * | 2023-05-10 | 2023-08-22 | 苏州美福瑞新材料科技有限公司 | Ageing-resistant polyurethane material, preparation method and application thereof on sealing ring |
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| CN102153530A (en) * | 2011-02-12 | 2011-08-17 | 北京欧格瑞化学科技有限公司 | Novel method for synthesizing dronedarone key intermediate |
| CN102649721A (en) * | 2011-02-25 | 2012-08-29 | 北京英力科技发展有限公司 | Preparation method for 3,5-dimethoxy-2,6-biacyl phenol |
| CN102649721B (en) * | 2011-02-25 | 2014-04-16 | 北京英力科技发展有限公司 | Preparation method for 3,5-dimethoxy-2,6-biacyl phenol |
| CN107266318B (en) * | 2013-07-01 | 2020-07-03 | Lg化学株式会社 | Polysiloxane compound, method for preparing the same, and copolycarbonate resin comprising the same |
| CN107266318A (en) * | 2013-07-01 | 2017-10-20 | Lg化学株式会社 | Polysiloxane compound and preparation method thereof and the copolycarbonate resin comprising it |
| CN103497092A (en) * | 2013-10-12 | 2014-01-08 | 武汉怡兴化工有限公司 | Preparation method of 4, 4'-dihydroxy benaophenonel |
| CN107129432B (en) * | 2017-06-06 | 2020-11-03 | 如东金康泰化学有限公司 | Synthesis method of ultraviolet absorbent 4,4' -dihexyl benzophenone |
| CN107129432A (en) * | 2017-06-06 | 2017-09-05 | 如东金康泰化学有限公司 | A kind of synthetic method of ultra-violet absorber 4,4`- bis- epoxide benzophenone |
| CN108409549A (en) * | 2018-05-10 | 2018-08-17 | 绍兴文理学院 | The preparation method of 2,2 '-dihydroxy benaophenonel class compounds |
| CN108409549B (en) * | 2018-05-10 | 2021-05-14 | 绍兴文理学院 | Preparation method of 2, 2' -dihydroxy benzophenone compound |
| CN114341227A (en) * | 2019-08-27 | 2022-04-12 | Dic株式会社 | Phenolic resin, curable resin composition, and cured product thereof |
| CN114341227B (en) * | 2019-08-27 | 2024-04-30 | Dic株式会社 | Phenolic resin, curable resin composition, and cured product thereof |
| CN113683495A (en) * | 2021-09-16 | 2021-11-23 | 湖北瑞凯兴科技股份有限公司 | Method for preparing 4,4' -dihydroxy benzophenone |
| CN113683495B (en) * | 2021-09-16 | 2024-03-29 | 湖北瑞凯兴科技股份有限公司 | Method for preparing 4,4' -dihydroxybenzophenone |
| CN116622218A (en) * | 2023-05-10 | 2023-08-22 | 苏州美福瑞新材料科技有限公司 | Ageing-resistant polyurethane material, preparation method and application thereof on sealing ring |
| CN116622218B (en) * | 2023-05-10 | 2023-12-12 | 苏州美福瑞新材料科技有限公司 | Ageing-resistant polyurethane material, preparation method and application thereof on sealing ring |
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