JPS635053A - Production of bisphenol derivative - Google Patents
Production of bisphenol derivativeInfo
- Publication number
- JPS635053A JPS635053A JP15056586A JP15056586A JPS635053A JP S635053 A JPS635053 A JP S635053A JP 15056586 A JP15056586 A JP 15056586A JP 15056586 A JP15056586 A JP 15056586A JP S635053 A JPS635053 A JP S635053A
- Authority
- JP
- Japan
- Prior art keywords
- mol
- agent
- carboxylic acid
- acid
- formulas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 16
- -1 bisphenol compound Chemical class 0.000 claims abstract description 14
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 3
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 230000002140 halogenating effect Effects 0.000 claims description 6
- UXCDUFKZSUBXGM-UHFFFAOYSA-N phosphoric tribromide Chemical compound BrP(Br)(Br)=O UXCDUFKZSUBXGM-UHFFFAOYSA-N 0.000 claims description 6
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- HDECRAPHCDXMIJ-UHFFFAOYSA-N 2-methylbenzenesulfonyl chloride Chemical compound CC1=CC=CC=C1S(Cl)(=O)=O HDECRAPHCDXMIJ-UHFFFAOYSA-N 0.000 claims 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 27
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002904 solvent Substances 0.000 abstract description 5
- 238000006704 dehydrohalogenation reaction Methods 0.000 abstract description 4
- 230000026030 halogenation Effects 0.000 abstract 5
- 238000005658 halogenation reaction Methods 0.000 abstract 5
- 230000006866 deterioration Effects 0.000 abstract 1
- 230000003449 preventive effect Effects 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical group ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 3
- ZWHPPPRROACAFE-UHFFFAOYSA-N 2,4-ditert-butyl-6-[1-(3,5-ditert-butyl-2-hydroxyphenyl)butyl]phenol Chemical compound C=1C(C(C)(C)C)=CC(C(C)(C)C)=C(O)C=1C(CCC)C1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1O ZWHPPPRROACAFE-UHFFFAOYSA-N 0.000 description 2
- DXCHWXWXYPEZKM-UHFFFAOYSA-N 2,4-ditert-butyl-6-[1-(3,5-ditert-butyl-2-hydroxyphenyl)ethyl]phenol Chemical compound C=1C(C(C)(C)C)=CC(C(C)(C)C)=C(O)C=1C(C)C1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1O DXCHWXWXYPEZKM-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 229910014033 C-OH Inorganic materials 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229910014570 C—OH Inorganic materials 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 description 1
- ROKOECFNTZMAGR-UHFFFAOYSA-N 2,4-ditert-butyl-6-[(3,5-ditert-butyl-2-hydroxyphenyl)-phenylmethyl]phenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(C(C=2C=CC=CC=2)C=2C(=C(C=C(C=2)C(C)(C)C)C(C)(C)C)O)=C1O ROKOECFNTZMAGR-UHFFFAOYSA-N 0.000 description 1
- ZKUIGIXCJHGITL-UHFFFAOYSA-N 2-[1-[2-hydroxy-3,5-bis(2-methylbutan-2-yl)phenyl]butyl]-4,6-bis(2-methylbutan-2-yl)phenol Chemical compound C=1C(C(C)(C)CC)=CC(C(C)(C)CC)=C(O)C=1C(CCC)C1=CC(C(C)(C)CC)=CC(C(C)(C)CC)=C1O ZKUIGIXCJHGITL-UHFFFAOYSA-N 0.000 description 1
- OBAVEFZNJPQRRC-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-2-hydroxy-5-methylphenyl)-phenylmethyl]-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(C(C=2C=CC=CC=2)C=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O OBAVEFZNJPQRRC-UHFFFAOYSA-N 0.000 description 1
- WYIHUDNDPCJCJL-UHFFFAOYSA-N 2-tert-butyl-6-[1-(3-tert-butyl-2-hydroxy-5-methylphenyl)butyl]-4-methylphenol Chemical compound C=1C(C)=CC(C(C)(C)C)=C(O)C=1C(CCC)C1=CC(C)=CC(C(C)(C)C)=C1O WYIHUDNDPCJCJL-UHFFFAOYSA-N 0.000 description 1
- WXXLULLDFJDEAD-UHFFFAOYSA-N 2-tert-butyl-6-[1-(3-tert-butyl-2-hydroxy-5-methylphenyl)octyl]-4-methylphenol Chemical compound C=1C(C)=CC(C(C)(C)C)=C(O)C=1C(CCCCCCC)C1=CC(C)=CC(C(C)(C)C)=C1O WXXLULLDFJDEAD-UHFFFAOYSA-N 0.000 description 1
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 1
- AZZWZMUXHALBCQ-UHFFFAOYSA-N 4-[(4-hydroxy-3,5-dimethylphenyl)methyl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(CC=2C=C(C)C(O)=C(C)C=2)=C1 AZZWZMUXHALBCQ-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- SBPMVSRBSQIBLG-UHFFFAOYSA-N C(CCC)(C1=C(C(=CC(=C1)C)CCCC)O)C1=C(C(=CC(=C1)C)CCCC)O Chemical compound C(CCC)(C1=C(C(=CC(=C1)C)CCCC)O)C1=C(C(=CC(=C1)C)CCCC)O SBPMVSRBSQIBLG-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- YLCJUZRPEPQSQJ-UHFFFAOYSA-N [2,4-ditert-butyl-6-[1-(3,5-ditert-butyl-2-hydroxyphenyl)butyl]phenyl] prop-2-enoate Chemical compound C=1C(C(C)(C)C)=CC(C(C)(C)C)=C(OC(=O)C=C)C=1C(CCC)C1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1O YLCJUZRPEPQSQJ-UHFFFAOYSA-N 0.000 description 1
- COXFSNIXOAWXRA-UHFFFAOYSA-N [2-[1-[2-hydroxy-3,5-bis(2-methylbutan-2-yl)phenyl]butyl]-4,6-bis(2-methylbutan-2-yl)phenyl] prop-2-enoate Chemical compound C=1C(C(C)(C)CC)=CC(C(C)(C)CC)=C(OC(=O)C=C)C=1C(CCC)C1=CC(C(C)(C)CC)=CC(C(C)(C)CC)=C1O COXFSNIXOAWXRA-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、熱、光あるいは酸素による分解に対して有機
物質を安定化するための劣化防止剤として有用な一般式
（１）
（式中、Ｒ１は炭素数１〜８のアルキル基、炭素数２〜
４のアルケニル基、フェニル基または２−フェニルエチ
ニル基を、Ｒ２、Ｒ３ハ炭素数１〜５のアルキル基を、
Ｒ４は炭素数１〜１１のアルキル基またはフェニル基を
示す。）で示されるビスフェノール誘導体の製造方法に
関する。[Detailed Description of the Invention] <Industrial Application Field> The present invention provides compounds of the general formula (1) (in the formula , R1 is an alkyl group having 1 to 8 carbon atoms, and R1 is an alkyl group having 1 to 8 carbon atoms;
4 is an alkenyl group, phenyl group or 2-phenylethynyl group, R2 and R3 are an alkyl group having 1 to 5 carbon atoms,
R4 represents an alkyl group having 1 to 11 carbon atoms or a phenyl group. ) The present invention relates to a method for producing a bisphenol derivative shown in
〈従来の技術〉
従来より、上記−般式（１）で示されるビスフェノール
誘導体の製造方法としてはカルボン酸を塩化チオニル、
三塩化リン、五塩化リン等の塩素化剤、三臭化リン等の
臭素化剤などのハロゲン化剤を用いて酸ハロゲン化物と
し、次いでその酸ハロゲン化物とビスフェノール類を脱
ノ）ロゲン化水素剤の存在下に反応させる方法（米国特
許第８．９８４１７２号明細書）やピリジン、応させる
方法（特開昭５６−６１８２８号公報）などが知られて
いる。<Prior art> Conventionally, as a method for producing the bisphenol derivative represented by the above general formula (1), carboxylic acid is replaced with thionyl chloride, thionyl chloride,
A halogenating agent such as a chlorinating agent such as phosphorus trichloride or phosphorus pentachloride, or a brominating agent such as phosphorus tribromide is used to form an acid halide, and then the acid halide and bisphenols are removed by hydrogen halogenide. A method of reacting in the presence of an agent (US Pat. No. 8,984,172) and a method of reacting with pyridine (JP-A-56-61828) are known.
〈発明がＭ決しようとする問題点〉
しかし、このような方法による場合には反応工程が二段
階となり、しかも−般に酸ハロゲン化物や酸無水物の収
率が低いため、ビスフェノール誘導体のカルボン酸から
みた収率は非常に低いものにならざるを得なかった。<Problems to be solved by the invention> However, in the case of such a method, the reaction step is two steps, and the yield of acid halides and acid anhydrides is generally low, so that the carbon dioxide of bisphenol derivatives is The yield from the viewpoint of acid had to be very low.
このようなことから、本発明者らはビスフェノール類側
からはもちろん、カルボン酸側からも好収率で前記−般
式（１）で示されるビスフェノール誘導体を製造する方
法について鋭意検討した結果、−段階でしかも荷投率で
目的化合物が得られる新規な製造法を見出し、本発明に
至った。For this reason, the present inventors have conducted intensive studies on a method for producing the bisphenol derivative represented by the general formula (1) in good yield not only from the bisphenol side but also from the carboxylic acid side, and have found that - We have discovered a new manufacturing method that allows the target compound to be obtained in several steps and at a low loading rate, leading to the present invention.
く問題点を解決するための手段〉
本発明は、−般式（ｆｆ）
Ｒ＋−Ｃ−ＯＨ
（式中、Ｒ＋は前記と同じ意味を有する）で示されるカ
ルボン酸と一般式（り
Ｃ式中、Ｒ２，Ｒ３およびＲ４は前記と同じ意味を有す
る）
で示されるビスフェノール類を、脱ハロゲン化水素剤の
存在下にハロゲン化剤を用いて反応させることを特徴と
する前記−般式（Ｉ）で示されるビスフェノール誘導体
の製造法を提供するものである。Means for Solving the Problems> The present invention provides a combination of a carboxylic acid represented by the general formula (ff) R+-C-OH (wherein R+ has the same meaning as above) and a carboxylic acid represented by the general formula (ff) R+-C-OH (wherein R+ has the same meaning as above); wherein R2, R3 and R4 have the same meanings as above) is reacted with a halogenating agent in the presence of a dehydrohalogenating agent. ) provides a method for producing bisphenol derivatives shown in
本発明において、−般式（ｎ）で示されるカルボン酸と
し７て具体的には、酢酸、プロピオン酸、酪酸、アクリ
ル酸、メタクリル酸、クロトン酸、８−ブテン酸、安息
香酸、ケイヒ酸等が例示される。才だ、−般式（１）で
示されるビスフェノール類として具体的には、２・２′
−エチリデンビス（６−ｔ−ブチル−４−メチルフェノ
ール）、２・２′−エチリデンビス（４・６−ジーｔ−
ブチルフェノール）、２・２′−ブチリデンビス（４・
６−シメチルフエノール）、２・２′−ブチリデンビス
（６−Ｌ−ブチル−４−メチルフェノール）、２・２′
−ブチリデンビス（４・６−ジーｔ−ブチルフェノール
）、２・２′−ブチリデンビス（４・６−ｔ−アミルフ
ェノール）、２・２′−オクチリデンビス（６−ｔ−ブ
チル−４−メチルフェノール、２・２′−ドデシリデン
ビス（６−ｔ−ブチル−４−メチルフェノール）２・２
′−ベンジリデンビス（６−ｔ−ブチル−４−メチルフ
ェノール）、２・２′−ベンジリデンビス（４・６−ジ
ーｔ−ブチルフェノール）等が例示される。In the present invention, the carboxylic acids represented by formula (n) include acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, crotonic acid, 8-butenoic acid, benzoic acid, cinnamic acid, etc. is exemplified. -Specifically, the bisphenols represented by the general formula (1) are 2.2'
-ethylidene bis(6-t-butyl-4-methylphenol), 2,2'-ethylidene bis(4,6-di-t-
butylphenol), 2,2'-butylidene bis(4.
6-dimethylphenol), 2,2'-butylidenebis(6-L-butyl-4-methylphenol), 2,2'
-butylidenebis (4,6-di-t-butylphenol), 2,2'-butylidenebis (4,6-t-amylphenol), 2,2'-octylidenebis (6-t-butyl-4-methylphenol, 2. 2'-dodecylidene bis(6-t-butyl-4-methylphenol) 2.2
Examples include '-benzylidene bis(6-t-butyl-4-methylphenol) and 2,2'-benzylidene bis(4,6-di-t-butylphenol).
脱ハロゲン化水素剤として具体的には、トリエチルアミ
ン、ジメチルアニリン、Ｎ、Ｎ−ジメチルベンジルアミ
ン、テトラメチル尿素などの三級アミン類、ピリジン、
４−（Ｎ、Ｎ−ジメチルアミノ）ピリジン等のピリジン
誘導体等が例示される。Specifically, the dehydrohalogenation agent includes tertiary amines such as triethylamine, dimethylaniline, N,N-dimethylbenzylamine, and tetramethylurea, pyridine,
Examples include pyridine derivatives such as 4-(N,N-dimethylamino)pyridine.
ハロゲン化剤としてはオキシ塩化リン、オキシ臭化リン
、０−トルエンスルホニルクロリド、ｐ−トルエンスル
ホニルクロリドなどが例示される。Examples of the halogenating agent include phosphorus oxychloride, phosphorus oxybromide, 0-toluenesulfonyl chloride, p-toluenesulfonyl chloride, and the like.
本発明の反応は、通常は溶媒の存在下に行われ、この溶
媒としては、たとえばｎ−ヘキサン、ｎ−へブタン等の
脂肪族炭化水素、シクロヘキサン等の脂環式炭化水素、
ベンゼン、トルエン、キシレン等の芳香族炭化水素、酢
酸エチル、酢酸ブチル等のエステル類、ジエチルエーテ
ル、テトラヒドロフラン、エチレングリコールジメチル
エーテル等のエーテル類、ジクロロメタン、クロロホル
ム、四塩化炭素、ｌ ＋ ２ ＊りｏ。The reaction of the present invention is usually carried out in the presence of a solvent, such as aliphatic hydrocarbons such as n-hexane and n-hebutane, alicyclic hydrocarbons such as cyclohexane,
Aromatic hydrocarbons such as benzene, toluene and xylene, esters such as ethyl acetate and butyl acetate, ethers such as diethyl ether, tetrahydrofuran and ethylene glycol dimethyl ether, dichloromethane, chloroform, carbon tetrachloride, l + 2 *rio.
エタン等のハロゲン化炭化水素類が挙げられ、また脱ハ
ロゲン化水素剤として例示したもののうち常温で液状の
ものなどが例示される。Examples include halogenated hydrocarbons such as ethane, and among those exemplified as dehydrohalogenating agents, those that are liquid at room temperature are exemplified.
この反応において、カルボン酸およびビスフェノール類
の反応モル比は、通常０．７〜１．５：１でありより好
ましくは０９〜１．２：１である。In this reaction, the reaction molar ratio of carboxylic acid and bisphenols is usually 0.7 to 1.5:1, more preferably 09 to 1.2:1.
また、ハロゲン化剤の使用量は、カルボン酸１モルに対
してオキシ塩化リンおよびオキシ臭化リンの場合は０．
５〜１．０モルの範囲であり、好ましくは、０．６〜０
．９モルの範囲であり、更に好ましくは０．６５〜０．
８モルの範囲、０−またはｐ−トルエンスルホニルクロ
リドの場合は、０．８〜１．６モルの範囲であり好まし
くは０．９〜１．２の範囲である。In addition, the amount of halogenating agent used is 0.00% in the case of phosphorus oxychloride and phosphorus oxybromide per 1 mole of carboxylic acid.
In the range of 5 to 1.0 mol, preferably 0.6 to 0
．． The amount is in the range of 9 mol, more preferably 0.65 to 0.
In the case of 0- or p-toluenesulfonyl chloride, it is in the range of 0.8 to 1.6 moles, preferably in the range of 0.9 to 1.2 moles.
脱ハロゲン化水素剤の使用量は、ハロゲン化剤としてオ
キシ塩化リンおよびオキシ臭化リンを使用する場合は、
オキシ塩化リンまたはオキシ臭化リン１モルに対して２
．７〜８．６当量の範囲、好ましくは２．９〜３．２当
量の範囲であり、また、０−またはｐ−トルエンスルホ
ニルクロリドを使用する場合は、０８〜２，４当量の範
囲、好ましくは０．９〜２．２当量の範囲である。ここ
で１１という表現を用いたのは、テトラメチル尿累のよ
うに１分子でハロゲン化水素２分子を捕捉するものかあ
Ｉるためである。When using phosphorus oxychloride and phosphorus oxybromide as the halogenating agent, the amount of dehydrohalogenating agent to be used is as follows:
2 per mole of phosphorus oxychloride or phosphorus oxybromide
．． In the range of 7 to 8.6 equivalents, preferably in the range of 2.9 to 3.2 equivalents, and in the case of using 0- or p-toluenesulfonyl chloride, in the range of 0.8 to 2.4 equivalents, preferably is in the range of 0.9 to 2.2 equivalents. The expression 11 is used here because some molecules, such as tetramethyl urine, capture two molecules of hydrogen halide with one molecule.
反応温度は一２０°Ｃ−１５０°Ｃの範囲であり、好ま
しくは０°Ｃ〜１２０°Ｃの範囲でありより好ましくは
、２０℃〜１００℃の範囲である。The reaction temperature ranges from -20°C to 150°C, preferably from 0°C to 120°C, and more preferably from 20°C to 100°C.
反応終了後は、脱ハロゲン化水素剤の酸塩を濾過等によ
りあらかじめ分離したのちあるいは分離することなく、
反応液を必要に応じて中和処理したのち水洗し、有機層
から溶媒を留去したり、反応液に水を加え、冷却して析
出晶を取り出す等の種々の方法により目的物を分離する
ことができ、更に再結晶、溶媒洗浄等の公知の方法；こ
より精製することができる。After the reaction is completed, the acid salt of the dehydrohalogenating agent is separated in advance by filtration, etc., or without separation.
After neutralizing the reaction solution as necessary, the target product is separated by various methods, such as washing with water, distilling off the solvent from the organic layer, adding water to the reaction solution, cooling, and removing precipitated crystals. It can be further purified by known methods such as recrystallization and solvent washing.
〈発明の効果〉
カくシて、本発明の方法によればカルボン酸から一段階
で、高収率で、しかも工業的容易に一般式（Ｉ）で示さ
れるビスフェノール誘導体を製造することができる。<Effects of the Invention> According to the method of the present invention, the bisphenol derivative represented by the general formula (I) can be produced from carboxylic acid in one step, in high yield, and industrially easily. .
〈実施例〉 以下、実施例により本発明を説明する。<Example> The present invention will be explained below with reference to Examples.
実施例１
温度計、攪拌装置、冷却管および滴下漏斗を備えた２１
四ロフラスコに２．２７−エチリデンビス（６−ｔ−ブ
チル−４−メチルフェノール）８５４．５９（１，０モ
ル）、アクリル酸７２．０６７（１，０モル）、トルエ
ン５００り及びトリエチルアミン２０９．４７２（２，
０７モル）を仕込み、容器内の空気を窒素置換した後、
攪拌しなからオキシ塩化リン１０５．８ノ（０，６９モ
ル）を滴下する。滴下終了後８０°Ｃで１時間保温する
。その後、有機層を中性になるまで水洗し、トルエンを
減圧留去する。蒸留残渣にｎ−ヘキサンを加えて再結晶
することによって融点１６１〜１６２°Ｃの白色結晶状
の２・２′−エチリデンビス（６−ｔ−−／チルー４−
メチルフェノール）モノアクリレート８８８．２Ｆ（収
率９５チ）を得た。Example 1 21 with thermometer, stirrer, cooling tube and dropping funnel
854.59 (1.0 mol) of 2.27-ethylidenebis(6-t-butyl-4-methylphenol), 72.067 (1.0 mol) of acrylic acid, 500 g of toluene, and 209.9 g of triethylamine were placed in a four-ring flask. 472 (2,
After charging 07 mol) and replacing the air in the container with nitrogen,
While stirring, 105.8 g (0.69 mol) of phosphorus oxychloride is added dropwise. After completion of dropping, keep warm at 80°C for 1 hour. Thereafter, the organic layer is washed with water until it becomes neutral, and toluene is distilled off under reduced pressure. By adding n-hexane to the distillation residue and recrystallizing it, white crystalline 2,2'-ethylidenebis(6-t--/chiru-4-
Methylphenol) monoacrylate 888.2F (yield: 95%) was obtained.
実施例２
実施例１で用いたと同様のフラスコに２・２′−エチリ
デンビス（４・６−ジーｔ−ブチルフェノール）４８８
．７９（１，０モル）、アクリル酸７２．０６ｙ（１，
０モル）、ｎ−へブタン４００２及びトリエチルアミン
２１２．５９ （２，１０モル）を仕込み、容器内の空
気を窒素置換した後、攪拌しなからオキシ臭化リン２０
０．７ＦＪ（０，７０モル）を滴下する。滴下終了後８
０°Ｃで１時間保温した後、水５００２を仕込み、室温
まで冷却した後、性酸物を戸別する。得られた生成物を
、洗液が中性になるまで水洗することによって融点１８
９〜１９０°Ｃの白色結晶状の２．２７−ニチリデンビ
ス（４・６−ジーｔ−ブチルフェノール）モノアクリレ
ート４６８．１ｙを得た。Example 2 In a flask similar to that used in Example 1, 2,2'-ethylidenebis(4,6-di-t-butylphenol) 488
．． 79 (1,0 mol), acrylic acid 72.06y (1,
0 mol), n-hebutane 4002 and triethylamine 212.59 (2.10 mol), and after replacing the air in the container with nitrogen, add 20 phosphorus oxybromide without stirring.
0.7 FJ (0.70 mol) is added dropwise. 8 after completion of dripping
After keeping the temperature at 0°C for 1 hour, water 5002 was added, and after cooling to room temperature, the acidic substance was distributed from house to house. The resulting product was washed with water until the washings became neutral, resulting in a melting point of 18.
2.27-Nycylidenebis(4,6-di-t-butylphenol) monoacrylate 468.1y was obtained in the form of white crystals with a temperature of 9 to 190°C.
実施例８
２・２′−ブチリデンビス（６−ｔ−ブチル−４−メチ
ルフェノール）８８２．６ｉ１．０モル）を用いる以外
は実施例１と同様な条件で反応後処理することにより、
融点１０６〜１０８℃の白色結晶状の２・２′−ブチリ
デンビス（６−ｔ−ブチル−４−メチルフェノール）モ
ノアクリレート４１０．４ｙを得た。Example 8 By post-reaction treatment under the same conditions as in Example 1 except for using 2,2'-butylidenebis(6-t-butyl-4-methylphenol) 882.6i1.0 mol),
A white crystalline 2,2'-butylidenebis(6-t-butyl-4-methylphenol) monoacrylate 410.4y having a melting point of 106-108°C was obtained.
実施例４
実施例１で用いたと同様のフラスコに２・２′−ブチリ
デンビス（４・６−ジーｔ−ブチルフェノール）４６６
．８ｙ（１，０モル）、アクリル酸７２．０６２（１，
０モル）、トルエン６０（１’およびトリエチルアミン
２４２．８６ｙ（２，４モル）を仕込み、容器内の空気
を窒素置換した後、攪拌しなから０−）ルエンスルホニ
ルクロリド２２９．１４ｙ（１，２モル）をｒｍ下する
。滴下終了後９０°Ｃで１時間保温する。その後、有機
層を中性になるまで水洗し、トルエンを減圧留去する。Example 4 In a flask similar to that used in Example 1, 2,2'-butylidene bis(4,6-di-t-butylphenol) 466
．． 8y (1,0 mol), acrylic acid 72.062 (1,
0 mole), toluene 60 (1') and triethylamine 242.86y (2.4 mole) were charged, and the air in the container was replaced with nitrogen. rm). After completion of dropping, keep warm at 90°C for 1 hour. Thereafter, the organic layer is washed with water until it becomes neutral, and toluene is distilled off under reduced pressure.
蒸留残渣にｎ−ヘキサンを加えて再結晶することによっ
て融点１９８〜１９４°Ｃの白色結晶状の２・２′−ブ
チリデンビス（４・６−ジーｔ−ブチルフェノール）モ
ノアクリレート４９７．４９（収率９５．５％）を得た
。By adding n-hexane to the distillation residue and recrystallizing it, white crystalline 2,2'-butylidenebis(4,6-di-t-butylphenol) monoacrylate with a melting point of 198 to 194°C was obtained (yield: 95%). .5%) was obtained.
実施例５
２・２′−ブチリデンビス（４・６−ジ−ｔ−アミルフ
ェノール）５２２．８２（１，０モル）を用いる以外は
実施例４と同様な条件で反応、後処理することにより、
融点１２９〜１１１°Ｃの白色結晶状の２・２′−ブチ
リデンビス（４・６−ジーｔ−アミルフェノール）モノ
アクリレート５Ｂ９．４９Ｃ収率９８．５チ）を得た。Example 5 By reacting and post-treating under the same conditions as in Example 4 except for using 2,2'-butylidenebis(4,6-di-t-amylphenol) 522.82 (1.0 mol),
A white crystalline 2,2'-butylidene bis(4,6-di-t-amylphenol) monoacrylate 5B with a melting point of 129 DEG to 111 DEG C. (yield 98.5 C) was obtained.
実施例６ 。Example 6.
実施例１で用いたと同様のフラスコに２゜２′−ブチリ
デンビス（４・６−シメチルフエノール）２９８．４Ｐ
（１，０モル）、安息香酸１２２．１２Ｐ（１，０モル
）、トルエン５００２およびトリエチルアミン２４２．
８６ ｙ（２，４モル）を仕込み、容器内の空気を＠素
置換した後、攪拌しなからＯ−）ルエンスルホニルクロ
リド２２９．１５５’（１，２モル）を滴下する。滴下
終了後は実施例４と同様に深淵、後処理することにより
、融点１２９〜１３０°Ｃの白色結晶状の２・２′−ブ
チリデンビス（４・６−シメチルフエノール）モノベン
ゾエート８９５．４２（収率９８．２チ）を得た。In a flask similar to that used in Example 1, 298.4P of 2゜2'-butylidene bis(4,6-dimethylphenol) was added.
(1,0 mol), benzoic acid 122.12P (1,0 mol), toluene 5002 and triethylamine 242.
After charging 86y (2.4 mol) and replacing the air in the container with @, 229.155' (1.2 mol) of O-)luenesulfonyl chloride was added dropwise while stirring. After completion of the dropwise addition, the same deep treatment as in Example 4 was carried out to obtain white crystalline 2,2'-butylidene bis(4,6-dimethylphenol) monobenzoate 895.42 (melting point 129-130°C). A yield of 98.2 cm) was obtained.
実施例７
２・２′−オクチリデンビス（６−ｔ−ブチル−４−メ
チルフェノール） ４８８．７ ｙ（１，０モル）を用
いる以外は実施例１と同様な条件で反応、後処理するこ
とにより、融点１０６〜１０７℃の白色結晶状の２・２
′−オクチリデンビス（６−ｔ−ブチル−４−メチルフ
ェノール）モノアクリレート４７８９ （収率９７％）
を得た。Example 7 By reaction and post-treatment under the same conditions as in Example 1 except for using 2,2'-octylidenebis(6-t-butyl-4-methylphenol) 488.7y (1.0 mol). , white crystalline 2.2 with a melting point of 106-107°C
'-Octylidene bis(6-t-butyl-4-methylphenol) monoacrylate 4789 (yield 97%)
I got it.
実施例８
２・２′−オクチリデンビス（４・６−ジーｔ−ブチル
フェノール）５２２．９ｙ（１，０モル）を用いる以外
は、実施例４と同様な条件で反応、後処理することによ
り、融点１２６〜１２７°Ｃの白色結晶状の２・２′−
オクチリデンビス（４・６−ジーｔ−ブチルフェノール
）モノアクリレート５５６．７９（収率９６．５チ）を
得た。Example 8 The melting point of 126-127°C white crystalline 2,2'-
Octylidene bis(4,6-di-t-butylphenol) monoacrylate 556.79% (yield 96.5%) was obtained.
実施例９
温度計、攪拌装置、冷却管、仕込み口を備えた２！四ロ
フラスコに２．２′−ドデシリデンビス（６−ｔ−ブチ
ル−４−メチルフェノール）４９４．８９（１，０モル
）アクリル酸７２．０６９． （１，０モル）および
トリエチルアミン８００Ｓ’を仕込み、容器内の空気を
窒素置換した後、攪拌しなからｐ−）ルエンスルホニル
クロリド８０５．５２５’（１，６モル）を少艦ずつ加
える。仕込終了後、６０°Ｃで１時間攪拌保温し、その
後、室温で生成した塩酸トリエチルアミンをＰ別する。Example 9 2! Equipped with a thermometer, stirring device, cooling pipe, and charging port! 2.2'-dodecylidene bis(6-t-butyl-4-methylphenol) 494.89 (1.0 mol) acrylic acid 72.069. (1.0 mol) and triethylamine 800S' were charged, and after replacing the air in the container with nitrogen, p-)luenesulfonyl chloride 805.525' (1.6 mol) was added in small portions without stirring. After the completion of the preparation, the mixture was stirred and kept at 60°C for 1 hour, and then the triethylamine hydrochloride produced was separated from P at room temperature.
塩酸トリエチルアミンは更にトルエンで洗浄し、Ｆ別お
よびトルエン洗液は混合して中性になるまで水洗する。Triethylamine hydrochloride is further washed with toluene, and the separated F and toluene washings are mixed and washed with water until neutral.
その後、溶媒を減圧留去し、透明油状の２・２′−ドデ
シリデンビス（６−を−ブチル−４−メチルフェノール
）モノアクリレート５８７．９９ （収率９８チ）を得
た。Thereafter, the solvent was distilled off under reduced pressure to obtain 587.99 g of 2,2'-dodecylidene bis(6-butyl-4-methylphenol) monoacrylate (yield: 98 g) as a transparent oil.
実施例１０
２・２′−ベンジリデンビス（６−ｔ−ブチル−４−メ
チルフェノール） ４１６．６ ｌｌ（１，０モル）を
用いる以外は実施例１と同様な条件で反応、後処理する
ことにより、融点１５２〜１５８°Ｃの白色結晶状の２
・２′−ベンジリデンビス（６−ｔ−ブチル−４−メチ
ルフェノール）モノアクリレート４５８．９ノ（収率９
７．５％）を得た。Example 10 Reaction and post-treatment were carried out under the same conditions as in Example 1, except that 416.6 1 (1.0 mol) of 2,2'-benzylidenebis(6-t-butyl-4-methylphenol) was used. white crystalline 2 with a melting point of 152-158°C
・2'-Benzylidene bis(6-t-butyl-4-methylphenol) monoacrylate 458.9 units (yield: 9
7.5%).
実施例１１
２・２′−ベンジリデンビス（４・６−ジーｔ−ブチル
フェノール）５００．８９（１，０モル）を用いる以外
は実施例４と同様な条件で反応、後処理することにより
、融点１６５〜１６７°Ｃの白色結晶状の２・２′−ベ
ンジリデンビス（４・６−ジーｔ−ブチルフェノール）
モノアクリレート５３８．２Ｐ（収率９７％）を得た。Example 11 Melting point 165-167°C white crystalline 2,2'-benzylidene bis(4,6-di-t-butylphenol)
Monoacrylate 538.2P (yield 97%) was obtained.
比較例１
温度計、攪拌装置、冷却管、滴下漏斗を備えた５００ｍ
／四ロフラスコに９９．８％アクリル酸１４４．１ｙ（
２，０モル）、Ｎ、Ｎ−ジメチルホルムアミド２．０ｙ
（０，０８モル）およびハイドロキノン１．４４Ｐ（０
，０１モル）を仕込み、内温を５０°Ｃで攪拌しながら
塩化チオニル２８８．０５’（２，０モル）を滴下する
。Comparative Example 1 500m equipped with thermometer, stirrer, cooling pipe and dropping funnel
/ 144.1y of 99.8% acrylic acid in a four-hole flask (
2.0 mol), N,N-dimethylformamide 2.0y
(0.08 mol) and hydroquinone 1.44P (0
, 01 mol), and 288.05' (2.0 mol) of thionyl chloride was added dropwise while stirring at an internal temperature of 50°C.
滴下終了後３０分保温し、次に塩化第一銅０、１４ Ｆ
（０，ＯＯｌ ８モル）を加え、常圧にて生成物を蒸
留する。７１°Ｃ〜８５°Ｃまでの留分をとって、７０
．６０Ｆ（収率３９％）のアクリル酸クロリドを得た。After dropping, keep warm for 30 minutes, then add cuprous chloride to 0.14 F.
(0,OOl 8 mol) is added and the product is distilled at normal pressure. Take the fraction from 71°C to 85°C, and
．． Acrylic acid chloride of 60F (yield 39%) was obtained.
次に、温度計、攪拌装置、冷却管、滴下漏斗を備えた５
００−四ロフラスコに２．２’−エチリデンビス（６−
ｔ−ブチル−４−メチルフェノール）８５．４Ｆ（０，
２４１モル）、トルエン２００Ｆおよびトリエチルアミ
ン２８．９ｙ（０，２９０モル）を仕込み、容器内の空
気を窒素置換し、攪拌しながらアクリル酸クロリド２５
Ｆ（０，２７６モル）を滴下する。滴下終了後１時間攪
拌を継続した後、希塩酸で過剰のトリエチルアミンを中
和し、生成したトリエチルアミン塩酸塩は水洗して除く
。水洗の終了したトルエン層からトルエンを留去し、得
られた蒸留残渣にｎ−ヘキサン２０りを加えて再結晶す
ると白色結晶（融点１６１〜１６２°Ｃ）の２．２′−
エチリデンビス（６−、ｔ−ブチル−４−メチルフェノ
ール）モノアクリレート９３．１Ｍ’（収率９５％）が
得られた。Next, a
00-2,2'-ethylidene bis(6-
t-butyl-4-methylphenol) 85.4F (0,
241 mol), toluene 200F and triethylamine 28.9y (0,290 mol), the air in the container was replaced with nitrogen, and while stirring, acrylic acid chloride 25
F (0,276 mol) is added dropwise. After continuing stirring for 1 hour after the completion of the dropwise addition, excess triethylamine was neutralized with dilute hydrochloric acid, and the triethylamine hydrochloride formed was removed by washing with water. Toluene is distilled off from the toluene layer that has been washed with water, and the resulting distillation residue is recrystallized by adding 20 g of n-hexane to form white crystals (melting point 161-162°C) of 2.2'-
Ethylidene bis(6-, t-butyl-4-methylphenol) monoacrylate 93.1 M' (yield 95%) was obtained.
Claims (2)
〜４のアルケニル基、フェニル基または２−フェニルエ
テニル基を示す。） で示されるカルボン酸と一般式 ▲数式、化学式、表等があります▼ （式中、Ｒ＿２、Ｒ＿３は炭素数１〜５のアルキル基を
示し、Ｒ＿４は炭素数１〜１１のアルキル基またはフェ
ニル基を示す。） で示されるビスフェノール類を、脱ハロゲン化水素剤の
存在下にハロゲン化剤を用いて反応させることを特徴と
する一般式 ▲数式、化学式、表等があります▼ （式中、Ｒ＿１、Ｒ＿２、Ｒ＿３およびＲ＿４は前記と
同じ意味を有する。） で示されるビスフェノール誘導体の製造方法。(1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 is an alkyl group with 1 to 3 carbon atoms, 2 carbon atoms
~4 alkenyl group, phenyl group or 2-phenylethenyl group. ) Carboxylic acids represented by the general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ that are characterized by reacting bisphenols shown by R_1, R_2, R_3 and R_4 have the same meanings as above.) A method for producing a bisphenol derivative.
、Ｏ−トルエンスルホニルクロリドまたはｐ−トルエン
スルホニルクロリドから選ばれた化合物である特許請求
の範囲第１項に記載の方法。(2) The method according to claim 1, wherein the halogenating agent is a compound selected from phosphorus oxychloride, phosphorus oxybromide, O-toluenesulfonyl chloride, or p-toluenesulfonyl chloride.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15056586A JPS635053A (en) | 1986-06-25 | 1986-06-25 | Production of bisphenol derivative |
| US07/064,461 US4774274A (en) | 1986-06-25 | 1987-06-22 | Thermally stabilized butadiene resins containing a hindered phenolic acrylate or methacrylate |
| CA000540344A CA1307604C (en) | 1986-06-25 | 1987-06-23 | Process for producing bisphenol compounds |
| DE8787305695T DE3784566T2 (en) | 1986-06-25 | 1987-06-25 | COMPOSITIONS CONTAINING BISPHENOL COMPOUNDS. |
| EP87305695A EP0251724B1 (en) | 1986-06-25 | 1987-06-25 | Compositions containing bisphenol compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15056586A JPS635053A (en) | 1986-06-25 | 1986-06-25 | Production of bisphenol derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS635053A true JPS635053A (en) | 1988-01-11 |
Family
ID=15499659
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15056586A Pending JPS635053A (en) | 1986-06-25 | 1986-06-25 | Production of bisphenol derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS635053A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02273643A (en) * | 1989-04-13 | 1990-11-08 | Sumitomo Chem Co Ltd | Phenol-based compound and stabilizer for butadiene-based polymercontaining the same compound as active ingredient |
| JP2006176419A (en) * | 2004-12-21 | 2006-07-06 | Sumitomo Chemical Co Ltd | Method for producing bisphenol monoester |
| WO2014084097A1 (en) * | 2012-11-28 | 2014-06-05 | Dic株式会社 | Compound containing phenolic hydroxy group, composition containing phenolic hydroxy group, resin containing (meth)acryloyl group, curable composition and cured product thereof, and resist material |
| JP2015509513A (en) * | 2012-03-05 | 2015-03-30 | エボニック レーム ゲゼルシャフト ミット ベシュレンクテル ハフツングＥｖｏｎｉｋ Ｒｏｅｈｍ ＧｍｂＨ | Stabilized (meth) acrylic monomer |
| WO2018052026A1 (en) * | 2016-09-13 | 2018-03-22 | 三菱瓦斯化学株式会社 | Compound, resin, composition, resist pattern formation method, and circuit pattern formation method |
-
1986
- 1986-06-25 JP JP15056586A patent/JPS635053A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02273643A (en) * | 1989-04-13 | 1990-11-08 | Sumitomo Chem Co Ltd | Phenol-based compound and stabilizer for butadiene-based polymercontaining the same compound as active ingredient |
| JP2006176419A (en) * | 2004-12-21 | 2006-07-06 | Sumitomo Chemical Co Ltd | Method for producing bisphenol monoester |
| JP2015509513A (en) * | 2012-03-05 | 2015-03-30 | エボニック レーム ゲゼルシャフト ミット ベシュレンクテル ハフツングＥｖｏｎｉｋ Ｒｏｅｈｍ ＧｍｂＨ | Stabilized (meth) acrylic monomer |
| WO2014084097A1 (en) * | 2012-11-28 | 2014-06-05 | Dic株式会社 | Compound containing phenolic hydroxy group, composition containing phenolic hydroxy group, resin containing (meth)acryloyl group, curable composition and cured product thereof, and resist material |
| JP2015091954A (en) * | 2012-11-28 | 2015-05-14 | Dic株式会社 | (meth)acryloyl-containing resin, curable composition, hardened product of the composition and resist material |
| KR20150090094A (en) * | 2012-11-28 | 2015-08-05 | 디아이씨 가부시끼가이샤 | Compound containing phenolic hydroxy group, composition containing phenolic hydroxy group, resin containing (meth)acryloyl group, curable composition and cured product thereof, and resist material |
| WO2018052026A1 (en) * | 2016-09-13 | 2018-03-22 | 三菱瓦斯化学株式会社 | Compound, resin, composition, resist pattern formation method, and circuit pattern formation method |
| JPWO2018052026A1 (en) * | 2016-09-13 | 2019-06-24 | 三菱瓦斯化学株式会社 | Compound, resin, composition, method of forming resist pattern and method of forming circuit pattern |
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