CN107011124B - Production method of trisphenol compound - Google Patents
Production method of trisphenol compound Download PDFInfo
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- CN107011124B CN107011124B CN201710153709.9A CN201710153709A CN107011124B CN 107011124 B CN107011124 B CN 107011124B CN 201710153709 A CN201710153709 A CN 201710153709A CN 107011124 B CN107011124 B CN 107011124B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
- C07C37/16—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 by condensation involving hydroxy groups of phenols or alcohols or the ether or mineral ester group derived therefrom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
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Abstract
The invention discloses a production method of a trisphenol compound, which comprises the following steps: carrying out acylation reaction on the compound of the formula 1 and the compound of the formula 2 to obtain a compound of a formula 3; reacting the compound of the formula 3 with the compound of the formula 4 to obtain a compound of a formula 5; reacting the compound of the formula 5 with the compound of the formula 6 to obtain a trisphenol compound of the formula 7; wherein R is1、R6、R7Each independently is hydrogen, alkyl or alkoxy, R2、R3、R4、R5、R8、R9、R10、R11、R12、R13、R14、R15Independently represents hydrogen, alkyl, alkoxy, aromatic hydrocarbon, acyloxy or hydroxyl, X represents halogen, and Y represents halogen or acetoxy. The compound of formula 1 is used as a raw material, and a target product can be obtained through 3 steps of reactions such as acylation, bisphenol, alkylation and the like.
Description
Technical Field
The invention belongs to the field of chemical product preparation, and particularly relates to a production process of a trisphenol compound.
Background
The trisphenol compound is mainly used as the raw material of high molecular compounds such as epoxy resin, polycarbonate resin and the like, and can also be used as photoresist or additive of the high molecular compounds. The structure is as follows:
in the patent of nojirimine hydrochloride, etc. (CN 102428061 and US 20120108853A 1), the compound shown in the following general formula 8 (R1 '-R4' is H, alkyl, alkoxy, aromatic hydrocarbon radical, halogen atom, acyloxy or hydroxyl, R5 ', R6' is H or alkyl) is used as raw material, and the target product is obtained by multi-step reaction, and the typical compound of the compound shown in the formula 8 is the compound shown in the formula 9, and the cost is high, and the two-step reaction of acylation protection of phenolic hydroxyl and deprotection is needed, and the process is not simple.
Formula 8 formula 9.
Disclosure of Invention
The invention aims to provide a production process of a trisphenol compound on the basis of the prior art. The compound of formula 1 is used as a raw material, and a target product is obtained through 3 steps of reactions such as acylation, bisphenol, alkylation and the like, and the compound has the advantages of easily obtained raw material, simple process and high product yield.
The object of the invention can be achieved by the following measures:
a production method of trisphenol compounds comprises the following steps:
I. carrying out acylation reaction on the compound of the formula 1 and the compound of the formula 2 to obtain a compound of a formula 3;
II. Reacting the compound of the formula 3 with the compound of the formula 4 to obtain a compound of a formula 5;
III, reacting the compound of the formula 5 with the compound of the formula 6 to obtain a trisphenol compound of the formula 7;
wherein R is1、R6、R7Each independently is hydrogen, alkyl or alkoxy, R2、R3、R4、R5、R8、R9、R10、R11、R12、R13、R14、R15Independently represents hydrogen, alkyl, alkoxy, aromatic hydrocarbon, acyloxy or hydroxyl, X represents halogen, and Y represents halogen or acetoxy.
In a preferred embodiment, R1、R6、R7Are each independently hydrogen, C1～3Alkyl or C1～3Alkoxy radical, R2、R3、R4、R5、R8、R9、R10、R11、R12、R13、R14、R15Are each independently hydrogen, C1～3Alkyl radical, C1～3Alkoxy, phenyl substituted C1～3Alkyl, acyloxy or hydroxy, X is halogen, YIs halogen or acetoxy.
In a more preferred embodiment, R1、R2、R3、R4、R5、R8、R9、R10、R11、R12、R13、R14Each independently is hydrogen, methyl, ethyl, methoxybenzene or ethoxy, R6、R7、R15Each independently hydrogen, methyl or ethyl, and X or Y each independently chlorine.
In a more preferred embodiment, R1、R2、R3、R4、R5、R8、R9、R10、R11、R12、R13、R14Are each independently hydrogen, R6、R7、R15Each independently is methyl or ethyl, and X or Y each independently is chloro.
In the reaction of step I, the compound of formula 1 and the compound of formula 2 are subjected to acylation reaction under the action of Lewis acid catalyst.
The Lewis acid catalyst in the step I reaction may be AlCl3、ZnCl2、FeCl3、TiCl4、SnCl4Or BF3·OEt2Etc., preferably AlCl3。
The molar ratio of the Lewis acid catalyst to the compound shown in the formula 2 in the step I reaction is 1.1-1.5: 1.
The molar ratio of the compound shown in the formula 1 to the compound shown in the formula 2 in the step I is 1: 0.9-1.3, and the compound shown in the formula 2 can be added dropwise or added at one time for reaction.
The solvent used in the step I reaction can be polar organic solvent, such as dichloromethane, chloroform, toluene, dichloroethane, nitrobenzene, carbon disulfide, etc.
The reaction temperature in the step I is 0-70 ℃, preferably 20-60 ℃, more preferably 30-50 ℃, and the reaction time is 0.5-10 hours, preferably 1-5 hours.
A specific reaction process of the step I reaction is as follows: in a four-necked flask equipped with an electric stirring device, a constant pressure dropping funnel, a reflux condenser (drying tube) and a thermometer, 0.2mol of the raw material 1 (i.e., the compound of formula 1), 100mL of methylene chloride and 0.24mol of AlCl were charged3The mixture was heated to 40 ℃ and then 0.22mol of Compound 2 (i.e., the compound of formula 2) was slowly added dropwise while maintaining the temperature stable, and the temperature was maintained for 5 hours after dropping. The reaction mixture was poured into 100mL of dilute hydrochloric acid to which crushed ice was added, stirred, the organic layer was separated, the aqueous layer was washed with 30 mL of dichloromethane, and the organic layers were combined. Then 5g of activated carbon is added and stirred. Filtered and the charcoal washed with 20 mL of dichloromethane. The organic phase was dried over anhydrous sodium sulfate and distilled to give intermediate 3 (i.e., a compound of formula 3).
In the reaction of step II, the compound of formula 3 is reacted with the compound of formula 4 under the action of a strong acid catalyst and a mercapto compound-containing cocatalyst to obtain the compound of formula 5.
The strong acid catalyst in the step II reaction is selected from sulfuric acid, hydrochloric acid, methanesulfonic acid or p-toluenesulfonic acid, preferably concentrated sulfuric acid or concentrated hydrochloric acid. The mass concentration of concentrated sulfuric acid in the invention is more than 70%, and the mass concentration of concentrated salt in the invention is more than 37%.
The mercapto compound promoter in the step II reaction is selected from thioglycolic acid, ethanethiol or dodecyl mercaptan, etc.
The reaction solvent in the step II reaction is a weak polar organic solvent, such as toluene, xylene or carbon tetrachloride.
In the step II, the molar ratio of the compound of formula 4 to the compound of formula 3 is 1.9-2.2: 1.
The reaction temperature in the step II is 20-70 ℃, preferably 30-50 ℃, and more preferably 35-40 ℃; the reaction time is 1 to 10 hours, preferably 2 to 5 hours.
A step ofThe specific reaction process of the reaction II is as follows: in a four-necked flask equipped with an electric stirring device, a constant pressure dropping funnel and a thermometer, 0.2mol of starting material 4 (i.e., the compound of formula 4) and 100mL of toluene were charged, and 10mL of 80% H was further charged2SO4And 0.5g of thioglycolic acid. The temperature of the system is controlled between 35 ℃ and 40 ℃, and a 50mL toluene solution of 0.1mol of intermediate product 3 (namely the compound of formula 3) is added dropwise and is kept for 4 hours. The aqueous phase was separated and washed 3 times with 100mL of hot water. The organic phase was cooled to room temperature to precipitate intermediate 5 (i.e., the compound of formula 5).
In the reaction of step III, the compound of formula 5 is reacted with the compound of formula 6 under the action of a Lewis acid catalyst to obtain the trisphenol compound of formula 7.
The Lewis acid catalyst in the step III reaction is selected from AlCl3、ZnCl2、FeCl3、TiCl4、SnCl4Or BF3·OEt2Etc., preferably ZnCl2。
The molar ratio of the Lewis acid catalyst to the compound shown in the formula 5 in the reaction in the step III is 0.05-0.20: 1; preferably 0.08-0.12: 1, preferably 0.09-0.11: 1.
The molar ratio of the compound shown in the formula 6 to the compound shown in the formula 5 in the step III reaction is 0.95-1.1: 1.
The solvent used in the step III reaction is a polar solvent, such as dichloromethane, chloroform, etc.
The reaction temperature in the step III reaction is 0-70 ℃, preferably 20-60 ℃, and more preferably 30-40 ℃; the reaction time is 0.5 to 7 hours, preferably 1 to 5 hours.
A specific reaction process of the step III reaction is as follows: into a four-necked flask equipped with an electric stirring device, a reflux condenser (drying tube) and a thermometer, 0.2mol of the starting material 6 (i.e., the compound of formula 6) and 0 mol of the compound of formula 6 were charged2mol of intermediate 5 (i.e. the compound of formula 5), 200mL of dichloromethane, 0.02mol of ZnCl is added with stirring2Then, the mixture was heated to reflux and reacted for 3 hours. The mixture was poured into 100mL of ice-water mixture, and a suitable amount of concentrated hydrochloric acid was added and stirred. The aqueous phase was separated and the organic phase was washed 3 times. The organic phase was transferred to a distillation flask, part of the dichloromethane was distilled off, the residue was transferred to a beaker and cooled to room temperature, and the product 7 (i.e., the compound of formula 7) was precipitated and purified by recrystallization.
The compound of formula 1 is used as a raw material, and a target product can be obtained through 3 steps of reactions such as acylation, bisphenol, alkylation and the like.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to the following examples.
Example 1: preparation of 1- (4- (alpha-chloro isopropyl) phenyl) ethanone
0.2mol of 2-phenyl-2-chloropropane, 100mL of dichloromethane and 0.24mol of AlCl were placed in a four-neck flask equipped with an electric stirrer, a constant-pressure dropping funnel, a reflux condenser (drying tube) and a thermometer3The mixture was heated to 40 ℃ and then 0.22mol of acetyl chloride was slowly added dropwise while maintaining the temperature stable, and the temperature was maintained for 3 hours after the addition. The mixture was poured into cold 100mL of dilute hydrochloric acid, stirred, the organic layer was separated, the aqueous layer was washed with 30 mL of dichloromethane, and the organic layers were combined. Then 5g of activated carbon is added and stirred. Filtered and the charcoal washed with 20 mL of dichloromethane. The organic phase was dried over 3g of anhydrous sodium sulfate and distilled to obtain 35.2g of 1- (4- (. alpha. -chloroisopropyl) phenyl) ethanone in a yield of 89.5%.
Example 2: preparation of 1- (4- (alpha-bromoisopropyl) phenyl) ethanone
In a four-necked flask equipped with an electric stirring device, a constant pressure dropping funnel, a reflux condenser (drying tube) and a thermometer, 0.2mol of 2-phenyl-2-bromopropane, 100mL of methylene chloride and 0.24mol of AlCl were charged3Heating the mixture to 45 ℃, then slowly dripping 0.22mol of acetyl chloride and keeping the temperature stable, and preserving the temperature by 2 ℃ after drippingAnd (4) hours. The mixture was poured into cold 100mL of dilute hydrochloric acid, stirred, the organic layer was separated, the aqueous layer was washed with 40 mL of dichloromethane, and the organic layers were combined. Then 5g of activated carbon is added and stirred. Filtered and the charcoal washed with 20 mL of dichloromethane. The organic phase was dried over 5g of anhydrous sodium sulfate and distilled to obtain 44.0g of 1- (4- (. alpha. -bromoisopropyl) phenyl) ethanone in a yield of 91.2%.
Example 3: preparation of 1, 1-bis (4-hydroxyphenyl) -1- [4/- (alpha-chloroisopropylphenyl) ] ethane
In a four-necked flask equipped with an electric stirring device, a constant pressure dropping funnel and a thermometer, 0.2mol of phenol and 100mL of toluene were charged, and 10mL of 80% H was further charged2SO4And 0.5g of thioglycolic acid. Controlling the temperature of the system between 35 and 40 ℃, dropwise adding a solution of 1- (4- (alpha-chloro isopropyl) phenyl) ethanone of 0.1mol in 50mL of toluene, and preserving the temperature for 4 hours. The aqueous phase was separated and washed 3 times with 100mL of hot water. The organic phase is cooled to room temperature, and 1, 1-bis (4-hydroxyphenyl) -1- [4/- (alpha-chloroisopropylphenyl) is precipitated]Ethane 34.5g, yield 94.0%.
Example 4: preparation of 1, 1-bis (4-hydroxyphenyl) -1- [4/- (alpha-bromoisopropylphenyl) ] ethane
In a four-necked flask equipped with an electric stirring device, a constant pressure dropping funnel and a thermometer, 0.2mol of phenol and 100mL of toluene were charged, and 10mL of 80% H was further charged2SO4And 1g of thioglycolic acid. Controlling the temperature of the system between 30 and 40 ℃, dropwise adding a solution of 1- (4- (alpha-bromoisopropyl) phenyl) ethanone of 0.1mol in 70mL of toluene, and preserving the temperature for 5 hours. The aqueous phase was separated and washed 3 times with 100mL of hot water. The organic phase is cooled to room temperature, and 1, 1-bis (4-hydroxyphenyl) -1- [4/- (alpha-bromoisopropylphenyl) is precipitated]Ethane 37.6g, yield 91.5%.
Example 5: 1- [ alpha, alpha-bis (4-hydroxyphenyl) ethyl]-4-[α/-methyl-alpha/-(4/-hydroxyphenyl) ethyl]Preparation of benzene 1
Is provided with an electric stirring device0.1mol of phenol and 0.1mol of 1, 1-bis (4-hydroxyphenyl) -1- [4/- (alpha-chloroisopropylphenyl) were charged in a four-necked flask equipped with a reflux condenser (drying tube) and a thermometer]Ethane, 200mL of methylene chloride, and 1.5g of ZnCl were added with stirring2Slowly heating to boil, and reacting for 3 hours. The mixture was poured into 100mL of ice-water mixture, and 1.5mL of concentrated hydrochloric acid was added thereto and stirred. The aqueous phase was separated and the organic phase was washed 3 times with hot water. The hot organic phase is transferred to a distillation flask, a portion of the dichloromethane is removed by distillation under reduced pressure, the residue is transferred to a beaker and cooled to room temperature, and 1- [ alpha, alpha-bis (4-hydroxyphenyl) ethyl is precipitated]-4-[α/-methyl-alpha/-(4/-hydroxyphenyl) ethyl]Benzene was recrystallized once from methylene chloride to give 38.3g (m/z: 424.20) of a product, yield 90.2%.
Example 6: 1- [ alpha, alpha-bis (4-hydroxyphenyl) ethyl]-4-[α/-methyl-alpha/-(4/-hydroxyphenyl) ethyl]Preparation of benzene 2
In a four-necked flask equipped with an electric stirring device, a reflux condenser (drying tube) and a thermometer, 0.1mol of phenol, 0.1mol of 1, 1-bis (4-hydroxyphenyl) -1- [4/- (alpha-bromoisopropylphenyl)]Ethane, 200mL of methylene chloride, 2g of ZnCl were added with stirring2The temperature was slowly raised to 40 ℃ and the reaction was carried out for 3 hours. The mixture was poured into 100mL of ice-water mixture, and 2mL of concentrated hydrochloric acid was added thereto and stirred. The aqueous phase was separated and the organic phase was washed 3 times with hot water. The hot organic phase is transferred to a distillation flask, a portion of the dichloromethane is removed by distillation under reduced pressure, the residue is transferred to a beaker and cooled to room temperature, and 1- [ alpha, alpha-bis (4-hydroxyphenyl) ethyl is precipitated]-4-[α/-methyl-alpha/-(4/-hydroxyphenyl) ethyl]Benzene was recrystallized once from methylene chloride to give 39.3g (m/z: 424.20) of a product in 92.6% yield.
Claims (6)
1. A production method of a trisphenol compound is characterized by comprising the following steps:
step I: carrying out acylation reaction on the compound of the formula 1 and the compound of the formula 2 to obtain a compound of a formula 3;
step II: reacting the compound of the formula 3 with the compound of the formula 4 to obtain a compound of a formula 5;
step III: reacting the compound of the formula 5 with the compound of the formula 6 to obtain a trisphenol compound of the formula 7;
wherein, R1, R2, R3, R4, R5, R8, R9, R10, R11, R12, R13 and R14 are respectively and independently hydrogen, R6, R7 and R15 are respectively and independently methyl or ethyl, X is halogen, Y is halogen or acetoxy;
in the step III, the compound shown in the formula 5 and the compound shown in the formula 6 react under the action of a Lewis acid catalyst to obtain a trisphenol compound shown in the formula 7;
in step III, the lewis acid catalyst is selected from AlCl3, ZnCl2, FeCl3, TiCl4, SnCl4 or BF3 · OEt 2; the molar ratio of the Lewis acid catalyst to the compound shown in the formula 5 is 0.05-0.20: 1; the molar ratio of the compound shown in the formula 6 to the compound shown in the formula 5 is 0.95-1.1: 1; in the step III, a reaction solvent is dichloromethane or chloroform, the reaction temperature is 0-70 ℃, and the reaction time is 0.5-7 hours;
in step II, the compound of formula 3 is reacted with the compound of formula 4 under the action of a strong acid catalyst and a mercapto compound-containing cocatalyst to obtain the compound of formula 5.
2. The method according to claim 1, wherein in step I, the compound of formula 1 and the compound of formula 2 are subjected to acylation reaction under the action of Lewis acid catalyst.
3. The process according to claim 2, characterized in that in step I, the lewis acid catalyst is AlCl3, ZnCl2, FeCl3, TiCl4, SnCl4 or BF 3-OEt 2; the molar ratio of the Lewis acid catalyst to the compound of formula 2 is 1.1-1.5: 1.
4. The process according to claim 1, wherein in step I, the solvent is dichloromethane, chloroform, toluene, dichloroethane, nitrobenzene or carbon disulfide; the reaction temperature is 0-70 ℃, and the reaction time is 0.5-10 hours.
5. The process according to claim 1, characterized in that in step II, the strong acid catalyst is selected from sulfuric acid, hydrochloric acid, methanesulfonic acid or p-toluenesulfonic acid; the mercapto compound promoter is selected from thioglycolic acid, ethanethiol or dodecyl mercaptan.
6. The method according to claim 1, wherein in step II, the reaction solvent is toluene, xylene or carbon tetrachloride, the reaction temperature is 20-70 ℃, and the reaction time is 1-10 hours; the molar ratio of the compound of formula 4 to the compound of formula 3 is 1.9-2.2: 1.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0219294A1 (en) * | 1985-10-08 | 1987-04-22 | Mitsui Petrochemical Industries, Ltd. | Triphenol and polycarbonate polymer prepared therefrom |
| JPS63145245A (en) * | 1986-12-09 | 1988-06-17 | Mitsui Petrochem Ind Ltd | Novel 2,2,2'-tris(hydroxycyclohexyl)diisopropylbenzenes and production thereof |
| US5534382A (en) * | 1994-04-07 | 1996-07-09 | Fuji Photo Film Co., Ltd. | Positive photoresist composition |
| CN1224716A (en) * | 1998-01-26 | 1999-08-04 | 西安近代化学研究所 | Synthesis of hymexazole |
| CN102428061A (en) * | 2009-05-19 | 2012-04-25 | 本州化学工业株式会社 | Method for producing trisphenols and monoester derivatives thereof, and 4-acylaralkylphenol derivatives |
| CN104311397A (en) * | 2014-10-13 | 2015-01-28 | 武汉船舶职业技术学院 | Novel fluorine-containing bisphenol compound and preparation method thereof |
-
2017
- 2017-03-15 CN CN201710153709.9A patent/CN107011124B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0219294A1 (en) * | 1985-10-08 | 1987-04-22 | Mitsui Petrochemical Industries, Ltd. | Triphenol and polycarbonate polymer prepared therefrom |
| JPS63145245A (en) * | 1986-12-09 | 1988-06-17 | Mitsui Petrochem Ind Ltd | Novel 2,2,2'-tris(hydroxycyclohexyl)diisopropylbenzenes and production thereof |
| US5534382A (en) * | 1994-04-07 | 1996-07-09 | Fuji Photo Film Co., Ltd. | Positive photoresist composition |
| CN1224716A (en) * | 1998-01-26 | 1999-08-04 | 西安近代化学研究所 | Synthesis of hymexazole |
| CN102428061A (en) * | 2009-05-19 | 2012-04-25 | 本州化学工业株式会社 | Method for producing trisphenols and monoester derivatives thereof, and 4-acylaralkylphenol derivatives |
| CN104311397A (en) * | 2014-10-13 | 2015-01-28 | 武汉船舶职业技术学院 | Novel fluorine-containing bisphenol compound and preparation method thereof |
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