METHOD FOR PRODUCING BISPHENOL DERIVATIVES

Abstract: A method for producing a bisphenol derivative repre­ sented by the formula (I), wherein R represents an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or a phenyl or 2-phenylethenyl group, and each R′ is selected from alkyl groups of 1 to 4 carbon atoms, characterised in that carboxylic acid represented by the formula (II), R - - OH (II) wherein R is as defined above, is reacted with bisphenol represented by the formula (III), wherein each R′ 'is as defined above, using halogenating agent in the presence of dehydrohalogenating agent. By the present invention, bisphenol derivatives represented by the formula (I) can be produced commercially in one step and in good yields from carboxylic acids without handling a strongly irritative acid halide.

Description: METHOD FOR PRODUCING BISPHENOL SDERIVATIVES The present invention relates to a method for producing bisphenol derivatives represented by the formula (I): EMI1.1 wherein R represents an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or a phenyl or 2-phenylethenyl group, and each R' is selected from alkyl groups having 1 to 4 carbon atoms. Bisphenol derivatives represented by the formula (I) are useful as antioxidants. A method for producing them is known in which a carboxylic acid is converted to its acid halide using a halogenating agent such as a chlorinating agent (e.g. thionyl chloride, phosphorus trichloride, phosphorus pentachloride) or brominating agent (e.g. phosphorus tribromide), and the acid halide is then reacted with bisphenol in the presence of a dehydrohalogenating agent (US.Patent No.3,984,372). Such methods, however, are inevitably carried out in two reaction steps and give a poor yield of the bisphenol derivative based -on the carboxylic acid. - Furthermore this two-step reaction requires handling of acid halide intermediate which is strongly irritative to eyes, skin, mucous membrane etc. According to the present invention, there is provided a method for producing bisphenol derivatives represented by the foregoing formula (I) characterized in that carboxylic acid represented by the formula (it) : EMI2.1 wherein R is as defined above, is reacted with bisphenol represented by the formula (III): EMI3.1 wherein each R' is as defined above, using halogenating agent in the presence of dehydrohalogenating agent. In the preset invention, specific examples of the carboxylic acid represented by the formula (11) include for example acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, crotonic acid, 3-butenoic acid, benzoic acid, cinnamic acid and the like. Specific examples of the bisphenols represented by the formula (III) include for example 2,2'-methylenebis(6-tert-butyl-4- methylphenol), 2,2'-metylenebis (6-tert-butyl-4-ethylpheno), 2,2' methylenebis (6-tert-buLyl-4-propylphenol), 2,2 '-methylenebis (6-tertbutyl-4-n-butylpherlol), ), 2,2'-mcthylenebis( 6-tert-butyl-ll-sec-buyl- phenol), and 2,2'-methylenebis (4,6-di-tert-butylphenol). Specific examples of the dehydrohalogenating agent include for example tertiary amines such as triethylamine, dimethylaniline, N,N-dimethylbenzylamine, tetramethylurea, etc., and pyridine compounds such as pyridine, 4-(N,N-dimethylamino)pyridine, etc. Specific examples of the halogenating agent are for example phosphorus oxychloride, phosphorus oxybyomide, -o-toluenesulfonyl chloride, .p-toluenesulfonyl chloride and the like The reaction of the present invention is generally carried out in the presence of a solvent. -Suitable solvents include, for example aliphatic hydrocarbons (e.g. n-hexane, n-heptane), alicyclic ones (e.g. cyclohexane), aromatic ones (e.g. benzene, toluene, xylene), esters (e.g. ethyl acetate, butyl acetate), ethers (e.g. diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether), halogenated Ilydrocarbons (e.g. adichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane), and dehydrohalogenating agents which are liquid at room temperature,(e.g. from those above). In this reaction, the molar ratio of carboxylic acid to bisphenol is preferably 0.7-1.5 1, more preferably 0.9-1.2 : 1. The amount of halogenating agent used is suitably 0.5 to 1.0 mole± preferably 0.6 to 0.9 mole, more preferably 0.65 to 0.8 mole, per mole of the carboxylic acid for phosphorus oxychloride and phosphorus oxybromide, and is suitably 0.8 to 1.6 moles, preferably 0.9 to 1.2 moles, per mole of the acid for o- or p-toluenesulfonyl chloride. The optimum amount of dehydrohalogenating agent used depends upon the kind of halogenating agent used. When the halogenating agent is phosphorus oxychloride or phosphorus oxybromide, said amount is suitably 2.? to 3.6 equivalents, preferably 2.9 to 3.2 equivalents , per mole of the halogenating agent. When the halogcnatig agent is o- or p-toluenesulfonyl chloride, said amount is suitably - 0.8 to 2.4 equivalents, preferably 0.9 to 2.2 equivalents, per mole of the halogenating agent. The expression "equivalent" is used because some dehydrohalogenating agents, for example, tetramethylurea,. will catch two hydrogen halide molecules per one molecule of agent. The reaction temperature is suitably -200C to 1500, preferably O"C to 120 C, more preferably OOC to 1000C. After completion of the reaction, the objective product can be separated from the reaction solution by various methods; for example, optionally after separating the acid salt of the dehydrohalogenating agent by filtration, the reaction solution is neutralized as need arises and washed with water, and the solvent is removed by evaporation from the organic layer; or water is added to the reaction solution which is then cooled, and the deposited crystal is separated. The objective product obtained may further be purified by well-known methods such as recrystallisation, washing with solvents, and the like. By the present invention, bisphenol derivatives represented by the formula (I) can be produced commercially in one step and in good yields from carboxylic acids without handling a strongly irritative acid halide. The present invention is illustrated by the following Examples Example 1 To a 2-liter four-necked flask equipped with a;thermomeer, stirring apparatus, condenser and dropping funnel were added J40*51 g (1.0 mole) of 2,2'-methylencbis (6-tert-butyl-4-mathylphenol) , 2.06 g (1.0 mole) of acrylic acid, 500 g of toueae and 209±47 g (2g07 moles) of triethylamine. After replacing the air in the container with nitrogen, 105.8 g (0.69 mole) of phosphorus oxychloride was added dropwise with stirring. After completion of the dropwise addition, the reaction solution was kept at 800C for 1 hour. Thereafter, the organic layer was washed with water until it became neutral, and toluene was removed under reduced pressure. The residue was then recrystallized from n-hexane to obtain 374.8 g of a white crystalline 2,2'-methylenebis{6-tert-butyl-4-methylphenol) monoacrylate having a melting point of 1320to 134" C. Yield, 95%. Example 2 To the same flask as used in Example 1 were added 340.51 g (1.0 mole) of 2,2 '-methylenebis (6-tert-butyl-4-methylphenol), 72.06 g (1.0 mole) of acrylic acid, 400 g-of n-heptane and 212.5 9 (2.10 moles) of triethylamine. After replacing the air in the container with nitrogen, 200.7 g (0.70 mole) of phosphorus oxybromide was added dropwise with stirring. After completion of the dropwise addition, the reaction solution was kept at 800C for 1 hour. Thereafter, 500 g of water was added, and after cooling to room temperature, the deposited product was filtered off. The product obtained was washed with water until thewashingsbecame neutral to obtain 379.6 g of 2,2'-methylenebis(6-tert-butyl-4-mothylphenol) monoacrylate as white crystals. Malting point, 132-134 c. Yield, 96%. Example 3 To the same flask as used in Example 1 were added 340.51 9 (1.0 mole) of 2,2'-mcthylcnebis (6-tert-butyl-4-methylphenol) , 86.41 g (1.0 mole) of 98.5e methacrylic acid, 500 g of toluene and 242.86 g (2.4 moles) of triethylamine. After replacing the air in the container with nitrogen, 229.14 g (1.2 moles) of o-toluenesulfonyl chloride was added dropwise with stirring. After completion of the dropwise addition, the reaction solution was kept at 900C for 1 hour. Thereafter, the organic layer was washed with water until it became neutral, and toluene was removed under reduced pressure. The residue was recrystallized from n-hexane to obtain 384.1 g of a white crystalline 2, 2'-methylenebis (6-tert-butyl-4-methylphenol) monomethacrylate having a melting point of 1440to 146 CC. Yield, 948. Example 4 To the same flask as used in Example 1 were added 340.51 g (1.0 mole) of 2,2'-methylenebis(6-tert-butyl-4-tnethylphenol), 74.08 g (1.0 mole) of propionic acid, 500 g of toluene and 191.42 g (2.42 moles) of pyridine. After replacing the air in the container with nitrogen, 210.05 g (1.1 moles) of o-toluenesulfonyl chloride was added dropwise with stirring. After completion of the dropwise addition, the reaction solution was kept at 100 0C for 1. hour and then aftertreated in the same manner as in Example 2 to obtain 384.7 g of a white crystalline 2,2'-methylenebis(6-tert-butyl-4methylphenol) monopropiohate having a melting point of 1080to 1100C. Yield, 97%. Example 5 To the same flask as used in Example 1 were added 340.51 g (1.0 mole) of 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 122.12 (1.0 mole) of benzoic acid, 500 g of toluene and 242.86 g (2.4 moles) of triethylamine. After replacing the air in the container with nitrogen, 229.15 g (1.2 moles) of o-to)uenesulfonyl chloride was added dropwise with stirring. After completion of the dropwise addition, temperature maintenance and after-treatment were carried out in the same manner as in Example 3 to obtain 426.83 g of a white crystalline 2,2-methylenebis(6-tert-butyl-4-methylphenol) monobenzoate having a melting point of 1490 to 1510 C. Yield, 96%. Example 6 To a 2-liter four-necked flask equipped with a thermometer, stirring apparatus, condenser and feed inlet were added 340.51 g (1.0 mole) of 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 60.05 g (1.0 mole) of acetic acid and 800 g of triethylamine. After replacing the air in the container with nitrogen, 3uS.52 g 1.6 moles) of p-toluenesulfonyl chloride was added little by little with stirring. After completion of the addition, the reaction solution was kept at 600C for 1 hour with stirring, and then tri ethylamine hydrochloride formcd was filtered off at room temperature. The triethylamine hydrochloride was further washed with toluene, and the filtrate and toluene washing were mixed and washed with water until the mixture became neutral. Thereafter, the solvent was removed under reduced pressure, and the residue was recrystallized from n-hexane to obtain 344.3 g of a white crystalline 2,2' methylenebis(6-tert-buLyl-4-methylphenol) monoacetate having a melting point of 980 to l040C. Yield, 90t. Example 7 To the same flask as used in Example 6 were added 340.51 g (1.0 mole) of 2,2'-methylellebis(6-tert-butyl-4-methylphenol), 151.18 g (1.0 mole) of cinnamic acid, 500 g of tolueneand 118.65 g (1.5 moles) of pyridine. After replacing the air in the container with nitrogen, 286.43 g (1.5 moles) of p-toluenesulfonyl chloride was added little by little with stirring. After completion of the addition, temperature maintenance and after-treatment were carried out in the same manner as in Example 6, and the residue was recrysta llized from toluene to obtain 404.8 g of a white crystalline 2,2' methylenebis(6-tert-butyl-4-metilylphenol) monocinnamoate having a melting point of 164 to 169 C. Yield, 86%. Comparative example 1 To a 500-ml four-necked flask equipped with a thermometer, stirring apparatus, condenser and dropping funnel were added 144.1 g (2.0 moles) of 99.8% acrylic acid, 2.0 g (0.03 mole) of N,N-dimethyl- formamide and 1.44 g (0.01 mole) of hydroquinone, and 238.0 ,9 (2.0 moles) of thionyl chloride was added dropwise with stirring while maintaining the inner temperature at 50 C. After completion of the dropwise addition, temperature maintenance was carried out for 30 minutes, 0.14 g (0.0013 mole) of cuprous chloride was then added and the product was distilled under normal pressure to collect a fraction between 710C antl 85 C. Thus, 70.60 g of acryloyl chloride was obtained. yield, 39. To a 500-ml four-necked flask equipped with a thermometer, stirring apparatus, condenser and dropping funnel were added 82.0 g (0.241 mole) of 2,2'-mehylenebis (6-tert-butyl-4-methylph(anol), 200 methylphenol) 200 g of toluene and 23.9 g (0.290 mole) of triethylamine. After replacing the air in the container with nitrogen, 25 g (0.276 mole) of acryloyl chloride was added dropwise with-stirring. After completion of the dropwise addition, stirring was continued for 1 hour, excess triethylamine was neutralized with dilute hydrochloric acid and the formed.triethylamine hydrochloride was then removed by washing with water. Toluene was then removed by evaporation from the toluene layer after completion of the washing, and the residue obtained was recrystallized from 20 g of n-hexane to obtain 90.0 g of 2,2'-methylcnebis (6-tert-butyl-4-methylphenol) monoacrylate as white crystals. - Melting point, 132-134 C. Yield, 95tt The yield of the product based on acrylic acid was 37.1t. Comparative example 2 To a 2-liter four-necked flask equipped with a thermometer, stirring apparatus, condenser and dropping funnel were added 340.51 g (1.00 mole) of 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 500 g of toluene and 113.41 g (1.12 moles) of triethylamine. After replacing the air in the container with nitrogen, 93.28 g (1.01 mole) of acryloyl chloride was added dropwise with stirring. After completion of the dropwise addition, stirring was continued for 1 hour, excess triethylamine was converted to its hydrochloride with dilute hydrochloric acid, and the formed triethylamine hydrochloridc--was removed by washing with water. After washing with water, toluene was removed by evaporation from the toluene layer, and the residue obtained was recrystallized from 425 g of n-hexane to obtain 286.96 g of 2,2'-methylenebis(6-tertbutyl-4-methylphenol) monoacrylate as white crystals. Melting point, 1320-1340C. Yield, 72.7%. The yield of t!ie product based on acrylic acid was 28.3%. Comparative example 3 Propionyl chloride was obtained from propionic acid and benzoyl chloride according to the method described in J.A.C.S., 60, 1325 (1938). Yield, 89%. Boiling point, 77-78.5 C. Tosa 300-ml four-necked flask equipped with a thermometer, stirring apparatus and condenser were added 34.51 g (0.10 mole) of 2#2'-methylenebis(6-tert-butyl-4-methylphenol)t 50 g of toluene and ll.li g (0.11 mole) of triethylamine. After replacing the air in the container with nitrogen, 10.2Q g (0.11 mole) of propionyl chloride waS added dropwise. After completion of the dropwise addition, aiter-treatment was carried out in the same manner as in Comparative example 1 to obtain 35.0 g of 2,2'-methylenebis(6-tertbutyl-4-methylphenol) monopropionate as white crystals. Melting point, 108-lllt C. Yield, 88.4%. The yield of the product based on propionic acid was 78%.

Claims: C L A I M S 1. A method for producing a bisphenol derivative represented by the formula (I), EMI13.1 wherein R represents an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or a phenyl or 2-phenylethenyl group, and each R' is selected from alkyl groups of 1 to 4 carbon atoms, characterised in that carboxylic acid represented by the formula (it?, EMI13.2 wherein R is as defined above, is reacted with bisphenol represented by the formula (III), EMI13.3 wherein each R' is as defined above, using halogenating agent in the presence of dehydrohaLogenating agent. 2. A method according to claim 1 wherein the carboxylic acid is selected from acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, crotonic acidl 3-butenoic acid, benzoic acid and cinnamic acid. '3. A method according to claim 1 or 2 wherein the bisphenol is selected from 2,2'-methylenebis(6tert-butyl-4-methylphenol), ? '2 '-methylenebis (6-tert- butyl-4-ethylphenol), 2,2' -methylenebis (6-tert-butyl- 4-propylphenol), 2,2'-methylenebis(6-tert-butyl-4-nbutylphenol), 2,2'-methylenebis(6-tert-butyl-4-secbutylpehnol) and 2,2 '-methylenebis (4, 6-di-tert-butyl- phenol). 4. A method according to any preceding claim wherein the dehydrohalogenating agent is a tertiary amine (e.g. selected from triethylamine, dimethylaniline, N,N-dimethylbenzylamine and tetramethylurea) or pyridine compound (e.g. selected from pyridine and 4-(N,N-dimethylamino)pyridine). 5. A method according to any preceding claim wherein the molar ratio-of carboxylic acid. to bisphenol is 0.7-1.5 : 1. 6. A method according to any preceding claim wherein the halogenating agent is phosphorus oxychloride or phosphorus oxybromide, preferably in an amount of O.5- to 1.0 mole per mole of carboxylic acid. 7. A method according to any of claims 1 to 5 wherein the halogenating agent is o- or p-toluenesulfonyl chloride,-preferably in an amount of 0.8 to 1.6 moles per mole of carboxylic acid. 8. A method according to claim 6 wherein the amount of dehydrohalogenating agent used is 2.7 to 3.6 equivalents per mole of halogenating agent. 9. A method according to claim 7 wherein the amount of dehydrohalogenating agent used is 0.8 to 2.4 equivalents per mole of halogenating agent. 10. A method according to any preceding claim wherein the reaction temperature is from -200C to 1500C.

Inventors: ISHII, TAMAKI, TAKAHASHI, YOKOH, TERADA, YUTAKA, YACHIGO, SHINICHI
Applicants: SUMITOMO CHEMICAL COMPANY, LIMITED
Application year: 1983
Main classification: C07C67
IPC codes: C07C69, C07C67