JP4336940B2 - Method for producing dicarboxyalicyclic acrylate compound - Google Patents
Method for producing dicarboxyalicyclic acrylate compound Download PDFInfo
- Publication number
- JP4336940B2 JP4336940B2 JP2002376650A JP2002376650A JP4336940B2 JP 4336940 B2 JP4336940 B2 JP 4336940B2 JP 2002376650 A JP2002376650 A JP 2002376650A JP 2002376650 A JP2002376650 A JP 2002376650A JP 4336940 B2 JP4336940 B2 JP 4336940B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- compound represented
- dicarboxy
- dicarboxyalicyclic
- reaction
- 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.)
- Expired - Lifetime
Links
- -1 acrylate compound Chemical class 0.000 title claims description 44
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 238000000034 method Methods 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 229910052750 molybdenum Chemical group 0.000 claims description 3
- 239000011733 molybdenum Chemical group 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 150000003973 alkyl amines Chemical class 0.000 claims 1
- 150000004982 aromatic amines Chemical class 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 39
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- 239000010408 film Substances 0.000 description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 13
- 238000004817 gas chromatography Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- VSIWDRMSJHKGDT-UHFFFAOYSA-N 2-heptyl-3-methylbutanedioic acid Chemical compound CCCCCCCC(C(O)=O)C(C)C(O)=O VSIWDRMSJHKGDT-UHFFFAOYSA-N 0.000 description 11
- 238000004949 mass spectrometry Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 238000006722 reduction reaction Methods 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- 150000002440 hydroxy compounds Chemical class 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 150000004681 metal hydrides Chemical class 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000010898 silica gel chromatography Methods 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 125000002723 alicyclic group Chemical group 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000004891 communication Methods 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000006735 epoxidation reaction Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 4
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- FBZANWBJFUBGEF-UHFFFAOYSA-N 4-oxatetracyclo[6.2.1.02,7.03,5]undecane-9,10-dicarboxylic acid Chemical compound C12C3OC3CC2C2C(C(=O)O)C(C(O)=O)C1C2 FBZANWBJFUBGEF-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- ALEDXSBPMQVUIV-HZJYTTRNSA-N 3-[(8z,11z)-heptadeca-8,11-dienyl]benzene-1,2-diol Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC1=CC=CC(O)=C1O ALEDXSBPMQVUIV-HZJYTTRNSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- YLANJPGPKICYGB-UHFFFAOYSA-N CCCCCCCC1C(C)C(=O)OC1=O Chemical compound CCCCCCCC1C(C)C(=O)OC1=O YLANJPGPKICYGB-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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical class [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 229910000856 hastalloy Inorganic materials 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 2
- 229910052987 metal hydride Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 2
- JABYJIQOLGWMQW-UHFFFAOYSA-N undec-4-ene Chemical compound CCCCCCC=CCCC JABYJIQOLGWMQW-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- TUNPEXUIDOFDKG-UHFFFAOYSA-N 2-ethylhex-2-enoyl chloride Chemical compound CCCC=C(CC)C(Cl)=O TUNPEXUIDOFDKG-UHFFFAOYSA-N 0.000 description 1
- JTQXJDWMNNIVRS-UHFFFAOYSA-N 2-methylpent-2-enoyl chloride Chemical compound CCC=C(C)C(Cl)=O JTQXJDWMNNIVRS-UHFFFAOYSA-N 0.000 description 1
- CJJMAWPEZKYJAP-UHFFFAOYSA-N 3-hydroxyadamantane-1-carboxylic acid Chemical compound C1C(C2)CC3CC2(O)CC1(C(=O)O)C3 CJJMAWPEZKYJAP-UHFFFAOYSA-N 0.000 description 1
- BDUBTLFQHNYXPC-UHFFFAOYSA-N 3-methylbut-2-enoyl chloride Chemical compound CC(C)=CC(Cl)=O BDUBTLFQHNYXPC-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical class C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- RJDBCWIQHUAADL-UHFFFAOYSA-N carboxyoxycarbonyl prop-2-enoate Chemical compound OC(=O)OC(=O)OC(=O)C=C RJDBCWIQHUAADL-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- NEUSVAOJNUQRTM-UHFFFAOYSA-N cetylpyridinium Chemical class CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 NEUSVAOJNUQRTM-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- WIWBLJMBLGWSIN-UHFFFAOYSA-L dichlorotris(triphenylphosphine)ruthenium(ii) Chemical compound [Cl-].[Cl-].[Ru+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 WIWBLJMBLGWSIN-UHFFFAOYSA-L 0.000 description 1
- NIKROVGMTGSETA-UHFFFAOYSA-N dimethyl 4-oxatetracyclo[6.2.1.02,7.03,5]undecane-9,10-dicarboxylate Chemical compound COC(=O)C1C2CC(C3C4OC4CC23)C1C(=O)OC NIKROVGMTGSETA-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical group 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- HDSUWQLDQNJISD-UHFFFAOYSA-N iridium;triphenylphosphane Chemical compound [Ir].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 HDSUWQLDQNJISD-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- RPNNPZHFJPXFQS-UHFFFAOYSA-N methane;rhodium Chemical compound C.[Rh] RPNNPZHFJPXFQS-UHFFFAOYSA-N 0.000 description 1
- ZUZLIXGTXQBUDC-UHFFFAOYSA-N methyltrioctylammonium Chemical class CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC ZUZLIXGTXQBUDC-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
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- 230000000737 periodic effect Effects 0.000 description 1
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- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
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- 229920000642 polymer Polymers 0.000 description 1
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- 239000011736 potassium bicarbonate Substances 0.000 description 1
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- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical compound [Cl-].[Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
本発明は、トリシクロデカンを骨格とするジカルボキシ脂環式アクリレート化合物、アクリロイルオキシ脂環式ジカルボン酸無水物及びジカルボキシ脂環式アルコール化合物並びにそれらの製造法に関する。
【０００２】
本発明で製造されるジカルボキシ脂環式アルコール化合物、ジカルボキシ脂環式アクリレート化合物及びアクリロイルオキシ脂環式ジカルボン酸無水物は、液晶表示素子（ＬＣＤ）に用いられる薄膜トランジスタ（ＴＦＴ）の層間絶縁膜、カラーフィルターの保護膜、平坦化膜、マイクロレンズ材料、有機ＥＬ素子の絶縁膜等を形成する材料及び光通信システムの光導波路分野に好適な感光性樹脂用の新規モノマー又はそれらの架橋剤として有用な新規モノマーに関する。
【０００３】
【従来の技術】
一般に、液晶表示素子、有機ＥＬ素子等のディスプレイ材料においては、電極保護膜、平坦化膜、絶縁膜等が設けられている。これらの材料にはアクリル樹脂、ノボラック樹脂、ポリイミド樹脂などが用いられている。これらの保護膜、平坦化膜、絶縁膜を形成する際には、フォトリソグラフィー法を用いることで必要とするパターン形状を形成している。しかしながら、これまで露光現像に際し、十分な感度を維持しつつ、ポストベーク後に得られる膜の耐熱性、透明性、密着性を維持することは困難であった。一般的にアルカリ可溶性アクリル樹脂を用いた感光性樹脂は透明性が高く、高感度であるものの耐熱性が低く、又基板密着性に難があり樹脂組成物の保存安定性が悪いなどの問題があった。また、光通信システムの光導波路分野においてアクリル系感光性樹脂がその高い光透過性の面から検討されて来ているが、その耐熱性が低いことが実用化を防げていた（例えば非特許文献１参照）。尚、本発明のモノマー合成の中間体であるジカルボキシ脂環式エポキシド化合物は、本願出願人が既に出願し公開されている（特許文献１及び特許文献２）。
【０００４】
【非特許文献１】
高分子学会編「高分子機能材料シリーズー 第６巻 光機能材料」共立出版、１９９１年６月１日、ｐ．１２３−１４２
【特許文献１】
特開２００１−２１３８１７号公報
【特許文献２】
特開２００１−３２８９５９号公報
【０００５】
【発明が解決しようとする課題】
本発明の目的は、上記事情に鑑み、液晶表示素子、有機ＥＬ素子等のディスプレイで用いられる電極保護膜、平坦化膜、絶縁膜あるいは光通信システムの光導波路等の材料として、耐熱性や基板密着性に加え、平坦化性、透明性及び低吸水性などの諸特性を兼ね備えた感光性樹脂の原料となるアクリレートモノマーの提供にある。
【０００６】
【課題を解決するための手段】
本発明者らは、上記課題を解決するため、鋭意研究を行い、本発明を完成した。即ち、本発明は、式［１］
【０００７】
【化１０】
（式中、Ｒ1、Ｒ2、Ｒ3及びＲ4はそれぞれ独立に水素原子又は炭素数１〜１０のアルキル基を表し、ｎは１〜３の整数を表す。）
で表されるジカルボキシ脂環式アクリレート化合物に関する。
【０００９】
また、本発明は、式［２］
【００１０】
【化１１】
（式中、Ｒ1、Ｒ2及びＲ3は水素原子又は炭素数１〜１０のアルキル基を表し、ｎは１〜３の整数を表す。）
で表されるアクリロイルオキシ脂環式ジカルボン酸無水物に関する。
【００１２】
更に、式［４］
【００１３】
【化１２】
（式中、Ｒ4は水素原子又は炭素数１〜１０のアルキル基を表し、ｎは１〜３の整数を表す。）
で表されるジカルボキシ脂環式アルコール化合物に関する。
【００１５】
更にまた本発明は、式［３］
【００１６】
【化１３】
（式中、Ｒ 4 及びｎは前記と同じ意味を表す。）
で表されるジカルボキシ脂環式エポキシド化合物を還元し式［４］
【００１８】
【化１４】
（式中、Ｒ 4 及びｎは前記と同じ意味を表す。）
で表されるジカルボキシ脂環式アルコール化合物を得、更に、このアルコール化合物と式［５］
【００２０】
【化１５】
（式中、Ｒ1、Ｒ2及びＲ3はそれぞれ独立して水素原子又は炭素数１〜１０のアルキル基を表し、Ｘはハロゲン原子を表す。）
で表されるアクリル酸ハライド化合物を塩基存在下で反応させることを特徴とする式［１］
【００２２】
【化１６】
（式中、Ｒ1、Ｒ2、Ｒ3、Ｒ4及びｎは前記と同じ意味を表す。）
で表されるジカルボキシ脂環式アクリレート化合物の製造法に関する。
【００２４】
更に、式［９］
【００２５】
【化１７】
（式中、Ｒ4及びｎは前記と同じ意味を表す。）
で表されるジカルボキシ脂環式不飽和化合物をタングステン又はモリブデンを少なくとも一種含むポリ酸を触媒として、二相溶媒系下で過酸化水素により酸化することを特徴とする式［３］
【００２７】
【化１８】
（式中、Ｒ4及びｎは前記と同じ意味を表す。）
で表されるジカルボキシ脂環式エポキシ化合物の製造法に関する。
【００２９】
【発明の実施の形態】
本発明化合物の製造法は、前述したように次の５つのスキームで表される。
【００３０】
【化１９】
（式中、Ｒ1、Ｒ2、Ｒ3、Ｒ4及びｎは前記と同じ意味を表す。）
以下、順にスキーム（１）から述べる。
【００３２】
出発原料の式［９］の不飽和化合物の製造法は、ｎ＝１の場合次の反応スキームで表される。ｎ＝２，３の場合も同様にして製造される。尚、ｎ＝２，３の場合下記（ａ）の原料は、シクロペンタジエン３量体及びシクロペンタジエン４量体である。原料の入手のし易さからｎ＝１が好ましい。
【００３３】
【化２０】
（式中、Ｒ’は炭素数１〜１０のアルキル基を表す。）
（ａ）の反応は、本出願人が出願した特公平４−６０１００号公報に記載の方法による。即ち、ジシクロペンタジエン（ＤＣＰＤ）を一酸化炭素とアルコ−ルから、塩化第二銅の存在下、パラジウム触媒によって８，９−ビス（アルコキシカルボニル）トリシクロ［５．２．１．０2,6］デセ−３−エン（ＴＣＤＥ）が得られる。
（ｂ）の反応は、ＴＣＤＥを塩基又は酸で加水分解することにより８，９−ジカルボキシトリシクロ［５．２．１．０2,6］デセ−３−エン（ＴＣＤＣ）が得られる。
【００３５】
次にスキーム（１）の不飽和化合物のエポキシ化反応について述べる。この反応は本出願人が出願した２つの方法が知られている。第１の方法は本出願人が特開２００１−３２８９５９号公報に記載した方法で、過酢酸を酸化剤として、１，４−ジオキサン溶媒中均一系での製造法である。この方法は、共存する酢酸の酸性により生成したエポキシ化合物が加水分解したそのジオール体が副生する点や多量の廃酢酸の回収の煩雑さの問題があった。又、工業的に過酢酸は高価であり、この改良法が本出願人が特開２００１−２１３８７１号公報に記載した第２の方法である。
【００３６】
即ち、経済的な過酸化水素を酸化剤とし、過酸化ヘテロポリ酸触媒存在下、アセトニトリルに代表される水を溶解する溶媒中均一系でエポキシ化反応を行う方法である。この方法は、クリーンな過酸化水素を用いながらも、高転化率になるに伴い反応が遅くなり、反応基質に対して数モル倍の過剰な過酸化水素が必要であった。本発明方法において、これらのエポキシ化方法も用いられるが、上記の問題点を改善した方法を用いることが経済的により好ましい。
【００３７】
本発明のエポキシ化方法では、上記第２の方法に於いて、溶媒として、過酸化水素水と不均一になる溶媒系の方法である。この方法には、例えば、クロロホルムや１，２−ジクロロエタン（ＥＤＣ）等のハロゲン化炭化水素類、トルエンやキシレン等の芳香族炭化水素類、ヘキサンやヘプタン等の脂肪族炭化水素類等が挙げられ、特にはトルエンやキシレン等の芳香族炭化水素類が好ましい。これらの溶媒の使用量は、反応基質に対し好ましくは１〜５０質量倍であり、より好ましくは２〜１０質量倍である。
【００３８】
本発明の触媒は、タングステン及びモリブデンを含むポリ酸であり、更には、リンを含むことが好ましい。これらの形態は、タングステン酸、モリブデン酸及びリン酸等がその代表的具体例として挙げられる。その使用量は、反応基質に対して０．０１〜２０モル％が好ましく、特には０．１〜１０モル％が好ましい。
【００３９】
本発明の酸化剤は、過酸化水素であり、その濃度に制限はないが、市販品の３０〜６０％濃度のものをそのまま使用することができる。その使用量は、反応基質に対して１〜２モル倍が好ましく、特には１〜１．５モル倍で目的とするエポキシ化合物が高収率で得られる。
【００４０】
ここで、反応促進させるために、相間移動触媒の添加が有効である。中でも、四級アンモニウム塩、ピリジニウム塩、ホスホニウム塩等が好ましく、具体的には、テトラメチルアンモニウム塩、テトラプロピルアンモニウム塩、テトラブチルアンモニウム塩、トリメチルベンジルアンモニウム塩、トリオクチルメチルアンモニウム塩、セチルピリジニウム塩、テトラブチルホスホニウム塩、硫酸水素テトラブチルアンモニウム塩等を挙げることができる。
【００４１】
これらの使用量は、反応基質に対し好ましくは０．００１〜１０モル％であり、より好ましくは０．００５〜５モル％である。
【００４２】
反応温度は、０〜１５０℃で行うことができ、好ましくは２０〜１００℃が高収率を与える。反応時間は、１〜５０時間で行うことができ、通常２〜２４時間で行うのが実用的ある。この様にして目的のジアルキル３，４−エポキシトリシクロ［５．２．１．０2,6］デカン−８，９−ジカルボキシレート及び３，４−エポキシトリシクロ［５．２．１．０2,6］デカン−８，９−ジカルボン酸が得られる。これらの目的物は、蒸留又は、カラムクロマトグラフィー等で精製することができる。
【００４３】
次に、本発明化合物の製造法の反応スキーム（２）の還元法について述べる。
【００４４】
エポキシ基をヒドロキシ基に変換する種々の一般的還元法が適用できる。これらの中で、アルコキシカルボニル基及びカルボキシル基を残余しつつエポキシ基をヒドロキシ基に変換する接触還元法が経済的である。
【００４５】
例えば、▲１▼金属および金属塩による還元、▲２▼金属水素化物による還元、▲３▼金属水素錯化合物による還元、▲４▼ジボランおよび置換ボランによる還元、▲５▼ヒドラジンによる還元、▲６▼ジイミド還元、▲７▼リン化合物による還元、▲８▼電解還元及び▲９▼接触還元等を挙げることができる。これらの中で、アルコキシカルボニル基及びカルボキシル基を残余しつつエポキシ基をヒドロキシ基に変換する接触還元法が経済的で実用的である。本発明で採用できる接触還元法は以下の通りである。触媒金属としては、周期律表第８族のパラジウム、ルテニウム、ロジウム、白金、ニッケル、コバルト及び鉄、又は第１族の銅等が使用できる。これらの金属は単独で、又は、他の元素と複合させた多元系で使用される。それらの使用形態は、各金属単身、ラネー型触媒、ケイソウ土、アルミナ、ゼオライト、炭素及びその他の担体に担持させた触媒及び錯体触媒等が挙げられる。
【００４６】
具体的には、パラジウム−炭素、ルテニウム−炭素、ロジウム−炭素、白金−炭素、パラジウム−アルミナ、ルテニウム−アルミナ、ロジウム−アルミナ、白金−アルミナ、還元ニッケル、還元コバルト、ラネーニッケル、ラネーコバルト、ラネー銅、酸化銅、銅クロマト、クロロトリス（トリフェニルホスフィン）ロジウム、クロロヒドリドトリス（トリフェニルホスフィン）ルテニウム、ジクロロトリス（トリフェニルホスフィン）ルテニウム及びヒドリドカルボニルトリス（トリフェニルホスフィン）イリジウム等が挙げられる。これらの中で特に好ましいものはパラジウム−炭素及びルテニウム−炭素等である。
【００４７】
触媒の使用量は、５％金属担持触媒として基質に対し０．１〜３０質量％が、特には、０．５〜２０質量％が好ましい。溶媒は、メタノール、エタノール及びプロパノール等に代表されるアルコール類、ジオキサン、テトラヒドロフラン及びジメトキシエタン等に代表されるエーテル類及び酢酸エチル及び酢酸プロピル等に代表されるエステル類等が使用できる。
【００４８】
その使用量は、原料に対し１〜５０質量倍の範囲が、特には、３〜２０質量倍の範囲が好ましい。水素圧は常圧から１０ＭＰａ（１００ｋｇ／ｃｍ2）の範囲が、特には、常圧から５ＭＰａ（５０ｋｇ／ｃｍ2）の範囲が好ましい。反応温度は、０〜２００℃の範囲が、特には、１０〜１８０℃の範囲が好ましい。
【００４９】
反応は、水素吸収量によって追跡することができ、理論水素量の吸収後サンプリングしガスクロマトグラフィーで分析し確認することができる。本反応は、回分式でも連続反応でも可能である。反応後は、濾過により触媒を除いた後、濃縮し、再結晶又は、カラムクロマトグラフィー法で目的のヒドロキシ化合物を精製することができる。
【００５０】
次に、反応スキーム（３）の塩基存在下でのヒドロキシ化合物とアクリル酸ハライド化合物の反応によるアクリレート化合物の製造法について述べる。
【００５１】
アクリル酸ハライド化合物は、アクリル酸化合物をハロゲン化チオニルなどで酸ハライドにして得られる。ハロゲン原子としては、Ｆ、Ｃｌ、Ｂｒ及びＩが挙げられるが、最も安価なＣｌが使用される。具体的には、アクリロイルクロライド、メタアクリロイルクロライド、チグリロイルクロライド、３，３−ジメチルアクリロイルクロライド、２−メチル−２−ペンテノイルクロライド、２−エチル−２−ヘキセノイルクロライド及び２−オクテロイルクロライド等が挙げられる。その使用量は、ヒドロキシ化合物に対し１〜６モル当量が好ましく、Ｒ4がアルキル基の場合は１〜２モル当量が特に好ましい。
【００５２】
本反応は、塩基が必須でありその種類としては、トリメチルアミン、トリエチルアミン及びトリプロピルアミン等に代表される鎖状アルキルアミン化合物、ピリジン、アニリン及びＮ−メチルアニリン等に代表される芳香族アミン化合物、１，５−ジアザビシクロ［４．３．０］ノ−５−ネン（ＤＢＮ）、１，４−ジアザビシクロ［２．２．２］オクタン（ＤＢＯ）及び１，８−ジアザビシクロ［５．４．０］ウンデセ−７−エン（ＤＢＵ）等に代表される環状アルキルアミン化合物、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウム及び炭酸水素カリウム等の金属炭酸塩等が挙げられる。これらの塩基の中で好ましいものは、トリエチルアミンやトリプロピルアミンである。その使用量は、ヒドロキシ化合物に対し１〜６モル当量（酸クロライドと当量）が好ましく、Ｒ4がアルキル基の場合は１〜２モル当量が特に好ましい。
【００５３】
本法は溶媒を使用するのが好ましい。溶媒としては、テトラヒドロフラン（ＴＨＦ）、１，２−ジメトキシエタン及び１，４−ジオキサン等のエーテル化合物、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ），Ｎ−メチルピロリドン及び１，３−ジメチル−２−イミダゾリジノン（ＤＭＩ）等が好ましい。その使用量は、ヒドロキシ化合物に対して１〜１０重量倍が好ましく、特には２〜５重量倍が好ましい。
【００５４】
反応温度は、０〜１００℃、特には０〜５０℃が好ましい。反応後は、水を添加し、残余酸クロライドを加水分解してから、溶媒を留去し、難水溶性溶媒（エーテル系やエステル系）で抽出した後、蒸留又はカラムクロマトグラフィーで精製し、目的のアクリレート化合物を得ることができる。
【００５５】
ヒドロキシ化合物がジカルボン酸化合物の場合は、同様に反応を行っ後、得られたアクリレート化合物の乾燥の程度により、ジカルボキシ脂環式アクリレート化合物が脱水したアクリロイルオキシ脂環式ジカルボン酸無水化合物が得られる。
【００５６】
次に、反応スキーム（４）の塩基又は酸触媒存在下でのヒドロキシ化合物の加水分解反応によるヒドロキシジカルボン酸化合物の製造法について述べる。
【００５７】
通常のアルキルカルボン酸エステルを加水分解してアルキルカルボン酸にする方法が適用できる。塩基としては、アルカリ金属及びアルカリ土類金属の水酸化物を用いるのが経済的に好ましい。具体的には、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム及び水酸化バリウム等であり、特には、水酸化ナトリウムが最も経済的で好ましい。
【００５８】
その使用量は、基質に対し２〜３当量が、特には２〜２．４当量が好ましい。溶媒としては、アルコールと水の混合系が一般的である。アルコールの種類としては、メタノール、エタノール及びプロパノール等の低級アルコールが好ましい。その使用量は、基質に対し１〜２０重量倍が、特には２〜１０重量倍が好ましい。水の添加量は、基質に対し０．１〜２０重量倍が、特には１〜１０重量倍が好ましい。アルコールと水の混合比は、重量比で１：２０から２０：１の間で選択でき、特には１：５から５：１の間で選択するのが好ましい。
【００５９】
反応後は、アルコールを留去した後、水を加えてから酸沈させてヒドロキシジカルボン酸化合物の粗結晶が得られる。これを再結晶法で精製することにより、その純品が得られる。
【００６０】
次に、酸による加水分解方法も可能であるが、一般には、塩基による方法が高収率である。酸の種類としては、塩酸や硫酸などの無機酸類、ｐ−トルエンスルホン酸や蟻酸等の有機酸類が用いられる。反応温度は、５０〜２００℃で行われる。
【００６１】
反応スキーム（５）の塩基存在下でのヒドロキシ化合物とアクリル酸ハライド化合物の反応によるアクリロイルオキシジカルボン酸無水物の製造法は、前述のスキーム（２）と同様に反応を行った後、得られたジカルボキシアクリレート化合物を減圧乾燥することによりそのジカルボン酸無水物が得られる。
【００６２】
以上述べた本発明の反応及び精製は、回分式でも連続式でも可能である。また反応は常圧でも加圧でも行うことができる。
【００６３】
【実施例】
以下に実施例を挙げ、本発明を具体的に説明するが、本発明はこれらに限定されるものではない。尚、実施例で用いた分析法は以下の通りである。
[１] ガスクロマトグラフィー(ＧＣ)
機種 : 島津製作所社製 商品名 ＧＣ−１７Ａ：カラム:キャピラリカラム CBP1-W25-100(25m×0.53mmφ×1μm)、カラム温度:100℃(保持 2min.)〜290℃(保持10min.)、8℃/min.(昇温速度)、注入口温度:290℃、検出器温度:290℃、キャリアガス：ヘリウム、検出法：ＦＩＤ法.
[２] 質量分析(ＭＡＳＳ)
機種 : 日本電子社製 ＬＸ−１０００ 検出法 ： ＦＡＢ 法.
[３] 1Ｈ ＮＭＲ
機種 : ＶＡＲＩＡＮ社製 ＩＮＯＶＡ５００ 測定溶媒：ＣＤＣｌ3
標準物質 : tetramethylsilane （ＴＭＳ）．
[４] 13Ｃ ＮＭＲ
機種: ＶＡＲＩＡＮ社製 ＩＮＯＶＡ５００ 測定溶媒： ＣＤＣｌ3
標準物質: ＣＤＣｌ3(δ:７７．１ｐｐｍ).
[５] 融点（Ｍｐ）
ヤナコ機器開発研究所製：ＭＰ−Ｊ３
実施例１
【００６４】
【化２１】
１００ｍｌ四つ口反応フラスコにジメチルトリシクロ［５．２．１．０2,6］デセ−３−エン−８，９−ジカルボキシレート（ＴＣＤＭＥ）２５．０ｇ（１００ｍｍｏｌ）、Ｈ2ＷＯ4０．９９９ｇ（４ｍｍｏｌ）、８５％リン酸０．１１５ｇ（1ｍｍｏｌ）、９０％トリオクチルメチルアンモニウムクロライド（ＴＯＭＡＣ）１．３５ｇ（３ｍｍｏｌ）及びトルエン５０ｇを仕込み、４５℃で攪拌下に３４％過酸化水素水１４．６ｇ（１５０ｍｍｏｌ）を４５分かけて滴下し、更に５０℃で３時間攪拌した。
【００６６】
ガスクロマトグラフィーで分析の結果、未反応ＴＣＤＭＥが消失し新たなピークが８９．１面積％で出現した。反応終了後トルエンと水を加えて抽出し、トルエン層を水洗後濃縮・乾燥すると油状物２９．４ｇ（純度８８．４％）（収率９７．７％）が得られた。更に、シリカゲルカラムクロマトグラフィー（溶離液／酢酸エチル：ｎ−ヘプタン＝１：９〜１：１）で精製すると油状物２２．８ｇ（純度９８．２％）（収率８４．０％）が得られた。この油状物は、２５℃で静置すると固化した。
【００６７】
この物質の構造は、下記の分析結果からジメチル３，４−エポキシトリシクロ［５．２．１．０2,6］デカン−８，９−ジカルボキシレート（ＤＭＥＤ）であることを確認した。
【００６８】
MASS(FAB+,m/e(%)):267([M+H]+,65),235(100).
1H NMR(500MHz,CDCl3,δppm):1.45(dd,J1=1.22Hz,J2=10.39Hz,1H),1.64(dd,J1=2.75Hz,J2=15.58Hz,1H),1.87(dd,J1=8.86Hz,J2=15.58Hz,1H),2.13(dd,J1=1.53Hz,J2=10.39Hz,1H),2.37-2.43(m,2H),2.47(dd,J1=4.89Hz,J2=9.78Hz,1H),2.62(d,J=4.89Hz,1H),2.86(d,J=9.78Hz,1H),2.92(d,J=9.78Hz,1H),3.28(d,J=9.83Hz,1H),3.49(d,J=2.14Hz,1H),3.57(d,J=5.35Hz,6H).
13C NMR(125MHz,CDCl3,δppm):27.6942,39.7651,41.7337,43.5115,44.2821,44.3661,44.4042,46.9145,51.5079,51.5308,59.1914,60.5725,173.0177,173.2390.
Mp.（℃）：82〜83．
実施例２
【００６９】
【化２２】
１００ｍｌハステロイ製オートクレーブにジメチル３，４−エポキシトリシクロ［５．２．１．０2,6］デカン−８，９−ジカルボキシレート（ＤＭＥＤ）７．０ｇ（純度９８．２％）（２５.８ｍｍｏｌ）、１０％Ｐｄ／Ｃ（Ｈ２Ｏ５５．２５％）０.７８２g（５質量％）、酢酸エチル４９ｇ及び水素圧５ＭＰａ（５０ｋｇ／ｃｍ2）を仕込み、１５０℃で６時間攪拌した。
【００７１】
室温に戻してから脱圧し、内容物を取り出し濾過により触媒を除去し、得られた濾液を濃縮すると油状物７．００ｇ（純度８９．０％）（収率８９．９％）が得られた。ガスクロマトグラフィーで分析の結果、原料が消失し新たな２成分のピーク(ガスクロマトグラフィー面積％＝８２．２（収率８３．０％）：６．８（収率６．９％）)が出現した。この混合物をシリカゲルカラムクロマトグラフィー（溶離液／酢酸エチル：ｎ−ヘプタン＝１：９〜１：１）で分離し、主成分は分析結果からジメチル３−ヒドロキシトリシクロ［５．２．１．０2,6］デカン−８，９−ジカルボキシレート（ＤＭ３ＨＤ）であることを確認した。
【００７２】
MASS(FAB+,m/e(%)):269([M+H]+,18),237(100).
1H NMR(500MHz,CDCl3,δppm):1.44(dd,J1=1.22Hz,J2=10.38Hz,1H),1.47-1.49(m,1H),1.68-1.72(m,2H),1.76-1.83(m,1H),2.09(dd,J1=1.53Hz,J2=10.39Hz,1H),2.90(dd,J1=4.89Hz,J2=11.00Hz,1H),2.34-2.40(m,2H),2.55-2.61(m,2H),2.69(d,J=9.78Hz,1H),2.80(d,J=9.78Hz,1H),3.54 (d,J=2.14Hz,6H),4.07(brs,1H).
13C NMR(125MHz,CDCl3,δppm):23.9245,37.8190,39.8791,42.7176,43.9231,44.0681,44.6938,44.8464,51.5532(2CH3),54.8113,73.7493,173.5209,173.7269.
副成分はＧＣ−ＭＡＳＳ分析結果からＤＭ３ＨＤの異性体のジメチル４−ヒドロキシトリシクロ［５．２．１．０2,6］デカン−８，９−ジカルボキシレート（ＤＭ４ＨＤ）であることを確認した。
実施例３
【００７３】
【化２３】
１００ｍｌ四つ口反応フラスコにＤＭＨＤ（ＤＭ３ＨＤ：ＤＭ４ＨＤ＝９３：７）１．７４ｇ（６．５ｍｍｏｌ）、テトラヒドロフラン（ＴＨＦ）１８ｇ及びトリエチルアミン０．９８７ｇ（９．８ｍｍｏｌ）を仕込み、攪拌しながら氷冷（５℃）下でメタアクリル酸クロライド１．０２ｇ（９．８ｍｍｏｌ）を１０分で滴下した。しだいに室温（２５℃）に戻し１６時間攪拌した。続いて濃縮し、残渣に水と１，２−ジクロロエタン（ＥＤＣ）を加えて抽出した。有機層を分液した後水洗し、濃縮すると油状物１．８５ｇが得られた。油状物をガスクロマトグラフィーで分析すると、新たなピーク（Ａ：Ｂ＝７２．３（収率６１．２％）：５．１（収率４．２％））が出現した。そこで更にシリカゲルカラムクロマトグラフィー（展開溶媒；酢酸エチル／ｎ−ヘプタン＝１／５〜１／１）で精製すると、主成分の油状物０．９１ｇ（収率４１．６％）が得られた。この留分は下記の分析結果からジメチル３−メタアクリロイルオキシトリシクロ［５．２．１．０2,6］デカン−８，９−ジカルボキシレート（ＤＭ３ＡＤ）であることを確認した。
【００７５】
MASS(FAB+,m/e(%)):337([M+H]+,11),305(100),219(28),131(47).
1H NMR(500MHz,CDCl3,δppm):1.43(d,J=1.13Hz,1H),1.50-1.55(m,1H),1.88(s,6H),2.14(dd,J1=1.48Hz,J2=10.34Hz,1H),2.41(d,J=4.89Hz,2H),2.57-2.63(m,2H),2.81(dd,J1=9.77Hz,J2=19.54Hz,2H),3.55(s,6H),5.00(d,J=2.14Hz,1H),5.46(d,J=1.22Hz,1H),5.98(s,1H).
13C NMR(125MHz,CDCl3,δppm):18.0872,24.1532,34.9956,39.9018,42.8470,43.9229,44.0755,44.5867,449148,51.5835(2CH3),52.1481,77.0452,125.0998,136.4611,166.8442,173.2764,173.5511.
副成分はＧＣ−ＭＡＳＳ分析結果からＤＭ３ＡＤの異性体のジメチル４−メタアクリロイルオキシトリシクロ［５．２．１．０2,6］デカン−８，９−ジカルボキシレート（ＤＭ４ＡＤ）であることを確認した。
実施例４
【００７６】
【化２４】
１００ｍｌ四つ口反応フラスコにジメチル３−ヒドロキシトリシクロ［５．２．１．０2,6］デカン−８，９−ジカルボキシレート（ＤＭ３ＨＤ）６．８５ｇ（２５．５ｍｍｏｌ）及びエタノール３１ｇを仕込み氷冷攪拌下に、８５％水酸化カリウム６．７３ｇ（１０２ｍｍｏｌ）を水６．７３ｇに溶解した溶液を滴下した。続いて油浴に移し１１０℃で還流させながら４時間攪した。氷冷後濃塩酸１２ｇを滴下すると結晶が析出した。濾過により結晶を除いてから、濾液を濃縮すると白色結晶６．９３ｇを得た。この結晶をアセトニトリルで抽出・濃縮すると結晶１．３７ｇが得られた。その残渣をアセトンで再抽出・濃縮することにより結晶０．７７ｇが得られた（合計収率３５％）。
この物質の構造は、下記の分析結果から３−ヒドロキシトリシクロ［５．２．１．０2,6］デカン−８，９−ジカルボン酸（３ＨＤＤＣ）であることを確認した。
【００７８】
MASS(FAB-,m/e(%)):239([M-H]+,100),221(22),195(24).
1H NMR(500MHz,CDCl3,δppm):1.31(d,J=9.18Hz,1H),1.41(t,J=5.96Hz1H),1.59-1.63(m,2H),1.66(t,J=10.93Hz1H),2.04(d,J=7.94Hz,1H),3.16(dd,J1=3.81Hz,J2=10.84Hz,1H),2.21(d,J=4.58Hz, 1H),2.36(d,J=4.58Hz,1H),2.43-2.48(m,1H),2.59(d,J=9.78Hz,1H),2.66(t,J=10.85Hz,1H),3.87(s,1H),4.15(brs,1H),11.97(brs,2H).
13C NMR(125MHz,CDCl3,δppm):23.7519,37.6388,39.9965,42.3923,43.5292,43.8726,44.3456,44.4525,54.4861,71.9743,174.2639,174.3936.
ｍｐ（℃）：153〜154.
参考例１
【００７９】
【化２５】
１００ｍｌ四つ口反応フラスコにトリシクロ［５．２．１．０2,6］デセ−３−エン−８，９−ジカルボン酸（ＴＣＤＣ）６．６６ｇ（３０ｍｍｏｌ）、Ｈ2ＷＯ4０．３０ｇ（１．２ｍｍｏｌ）、８５％リン酸０．０３５ｇ（０．３ｍｍｏｌ）、９０％トリオクチルメチルアンモニウムクロライド（ＴＯＭＡＣ）０．４０４ｇ（０．９ｍｍｏｌ）及び１，４−ジオキサン３４ｇを仕込み、５０℃の攪拌下に３４％過酸化水素水４．３７ｇ（４５ｍｍｏｌ）を３０分かけて滴下した。更に５０℃で２０時間攪拌した。ガスクロマトグラフィーで分析の結果、未反応ＴＣＤＣが７．１％残余し新たなピークが７７．０％出現した。反応終了し濃縮後、残渣にトルエンと水を加えて攪拌すると結晶が析出した。これを濾過、トルエンと水で洗浄後、濾取・乾燥すると白色結晶６．７７ｇ（収率９４．８％）が得られた。
【００８１】
この物質の構造は、下記の分析結果から３，４−エポキシトリシクロ［５．２．１．０2,6］デカン−８，９−ジカルボン酸（ＥＤＤＣ）であることを確認した。
【００８２】
MASS(FAB+,m/e(%)):237([M+H]+,100),193(30).
1H NMR(500MHz,CDCl3,δppm):1.34(d,J=9.78Hz,1H),1.71(d,J=7.33Hz,2H),2.07(d,J=9.78Hz,1H),2.24(d,J=3.97Hz,1H),2.29-2.37(m,2H),2.50(d,J=3.97Hz,1H),2.75(d,J=9.78Hz,1H),2.85(d,J=9.78Hz,1H),3.36(d,J=2.19Hz,1H),3.54(d,J=3.75Hz,1H),12.02(brs,2H).
13C NMR(125MHz,CDCl3,δppm):27.6197,39.3472,41.5829,43.2691,44.0855,44.3145,44.3679,46.9774,58.8422,60.4140,174.0953,174.3242.
Mp.（℃）：181〜182．
実施例５
【００８３】
【化２６】
１００ｍｌハステロイ製オートクレーブに３，４−エポキシトリシクロ［５．２．１．０2,6］デカン−８，９−ジカルボン酸（ＥＤＤＣ）２．３８ｇ（１０mmol）、１０％Ｐｄ／Ｃ（Ｈ２Ｏ５５．２５％）０．５３２g（１０質量％）、酢酸エチル２４ｇ及び水素圧３ＭＰａ（３０ｋｇ/ｃｍ2）を仕込み、１３０℃で５時間攪拌した。
【００８５】
室温に戻してから脱圧し、内容物を取り出し濾過により触媒を除去し、得られた濾液を濃縮すると油状物２．１６ｇ（純度６１．５％）（収率５５．３％）が得られた。ガスクロマトグラフィーで分析の結果、新たな２成分のピーク(ガスクロマトグラフィー面積％＝２６．７（収率２４．０％）：３４．８（収率３１．３％）)が出現した。この混合物をシリカゲルカラムクロマトグラフィー（溶離液／酢酸エチル：ｎ−ヘプタン＝１：１〜１：０）で精製し、ＨＤＤＣ（３ＨＤＤＣ：４ＨＤＤＣ＝６３：３７）の留分１．３０ｇを得た。この二成分の構造は、ＭＡＳＳ,13Ｃ ＮＭＲ及び1Ｈ ＮＭＲから６３％が３ＨＤＤＣであり、３７％が４−ヒドロキシトリシクロ［５．２．１．０2,6］デカン−８，９−ジカルボン酸（４ＨＤＤＣ）であることを確認した。
実施例６
【００８６】
【化２７】
１００ｍｌ四つ口反応フラスコに実施例５で得られた３ＨＤＤＣ１．２０ｇ（５．０ｍｍｏｌ）、テトラヒドロフラン（ＴＨＦ）２７ｇ及びトリエチルアミン３．０３ｇ（３０ｍｍｏｌ）を仕込み、攪拌しながら氷冷（５℃）下でメタアクリル酸クロライド３．１４ｇ（３０ｍｍｏｌ）を１５分で滴下した。しだいに室温（２６℃）に戻し５時間攪拌した。続いて水を添加してから濃縮し、残渣に水と１，２−ジクロロエタン（ＥＤＣ）を加えて抽出した。有機層を分液した後水洗し、濃縮すると油状物３．１８ｇが得られた。この油状物をガスクロマトグラフィーで分析すると、新たなピークが出現した。そこでシリカゲルカラムクロマトグラフィー（展開溶媒；酢酸エチル／ｎ−ヘプタン＝１／５〜１／１）で精製すると油状物０．６１ｇ（収率３９．６％）が得られた。この留分は下記の分析結果から３−メタアクリロイルオキシトリシクロ［５．２．１．０2,6］デカン−８，９−ジカルボン酸（３ＭＡＤＣ）であることを確認した。
MASS(FAB-,m/e(%)):307([M-H]+,50),189(100).
13C NMR(125MHz,CDCl3,δppm):17.6373,23.9398,34.4160,37.8572,43.3509,43.4958,43.6408,44.4877,45.5331,51.0649,76.3741,125.7334,136.1180,167.0353,173.0478,173.5285.
実施例７
【００８８】
【化２８】
１００ｍｌ四つ口反応フラスコに実施例５で得られたＨＤＤＣ（３ＨＤＤＣ：４ＨＤＤＣ＝６３：３７）１．３０ｇ（５．４ｍｍｏｌ）、テトラヒドロフラン（ＴＨＦ）２２ｇ及びトリエチルアミン２．１８ｇ（２１．６ｍｍｏｌ）を仕込み、攪拌しながら氷冷（５℃）下でメタアクリル酸クロライド２．２６ｇ（２１．６ｍｍｏｌ）を１５分で滴下した。しだいに室温（２６℃）に戻し７時間攪拌した。続いて水を添加してから濃縮し、残渣に水と１，２−ジクロロエタン（ＥＤＣ）を加えて抽出した。有機層を分液した後水洗し、濃縮すると油状物３．１８ｇが得られた。この油状物をガスクロマトグラフィーで分析すると、新たなピーク（Ａ：Ｂ＝２８．１（収率５３．７％）：１６．７（収率３１．９％））が出現した。そこで更にシリカゲルカラムクロマトグラフィー（展開溶媒；酢酸エチル／ｎ−ヘプタン＝１／５〜１／１）で精製すると、ガスクロマトグラフィーでＡ：Ｂ＝６１．４：３８．６（面積％）の油状物０．８３ｇ（収率４９．８％）が得られた。この留分は下記の分析結果からＡ：３−メタアクリロイルオキシトリシクロ［５．２．１．０2,6］デカン−８，９−ジカルボン酸無水物（３ＭＡＤＡ）であり、Ｂ：４−メタアクリロイルオキシトリシクロ［５．２．１．０2,6］デカン−８，９−ジカルボン酸無水物（４ＭＡＤＡ）であることを確認した。
【００９０】
[３ＭＡＤＡ]
MASS(FAB-,m/e(%)):291([M+H]+,28),207(28),189(60),153(100).
13C NMR(125MHz,CDCl3,δppm):17.9963,24.1767,34.5232,36.0874,36.9420,42.2602,43.7938,45.2969,45.6327,51.4926,76.7102,125.1920,136.2862,166.9289,179.3126,179.8619.
【００９１】
[４ＭＡＤＡ]
MASS(FAB-,m/e(%)):291([M+H]+,28),207(28),189(60),153(100).
13C NMR(125MHz,CDCl3,δppm):18.0192,23.9326,34.5842,36.0874,36.9877,42.2602,43.7938,45.2969,45.6327,55.5137,76.9467,125.0318,136.3702,166.6313,179.3126,179.8619.
【００９２】
【効果】
液晶表示素子、有機ＥＬ素子等のディスプレイで用いられる電極保護膜、平坦化膜、絶縁膜あるいは光通信システムの光導波路等の材料として、耐熱性や基板密着性に加え、平坦化性、透明性及び低吸水性などの諸特性を兼ね備えた感光性樹脂の原料となるアクリレートモノマーを提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a dicarboxy alicyclic acrylate compound having tricyclodecane as a skeleton, an acryloyloxy alicyclic dicarboxylic acid anhydride and a dicarboxy alicyclic alcohol compound, and methods for producing them.
[0002]
The dicarboxy alicyclic alcohol compound, dicarboxy alicyclic acrylate compound and acryloyloxy alicyclic dicarboxylic acid anhydride produced in the present invention are used as an interlayer insulating film of a thin film transistor (TFT) used in a liquid crystal display element (LCD). As a novel monomer for a photosensitive resin or a cross-linking agent thereof suitable for the optical waveguide field of an optical communication system, and a material for forming a protective film for a color filter, a planarizing film, a microlens material, an insulating film for an organic EL element, and the like It relates to useful novel monomers.
[0003]
[Prior art]
In general, in a display material such as a liquid crystal display element and an organic EL element, an electrode protective film, a planarizing film, an insulating film, and the like are provided. Acrylic resin, novolac resin, polyimide resin, or the like is used for these materials. When these protective film, planarizing film, and insulating film are formed, a necessary pattern shape is formed by using a photolithography method. However, it has been difficult to maintain heat resistance, transparency and adhesion of a film obtained after post-baking while maintaining sufficient sensitivity during exposure and development. Generally, a photosensitive resin using an alkali-soluble acrylic resin has high transparency and high sensitivity, but has low heat resistance, difficulty in adhesion to the substrate, and poor storage stability of the resin composition. there were. In addition, acrylic photosensitive resins have been studied in the optical waveguide field of optical communication systems from the viewpoint of their high light transmittance, but their low heat resistance has prevented their practical application (for example, non-patent documents). 1). Incidentally, the dicarboxy alicyclic epoxide compound, which is an intermediate for monomer synthesis of the present invention, has already been filed and published by the present applicant (Patent Document 1 and Patent Document 2).
[0004]
[Non-Patent Document 1]
Edited by The Society of Polymer Science, Japan “Functional Polymer Materials Series Vol. 6 Optical Functional Materials”, Kyoritsu Shuppan, June 1, 1991, p. 123-142
[Patent Document 1]
JP 2001-213817 A
[Patent Document 2]
JP 2001-328959 A
[0005]
[Problems to be solved by the invention]
In view of the above circumstances, an object of the present invention is to provide heat resistance and a substrate as a material such as an electrode protective film, a planarizing film, an insulating film, or an optical waveguide of an optical communication system used in a display such as a liquid crystal display element and an organic EL element. The present invention provides an acrylate monomer which is a raw material for a photosensitive resin having various properties such as flatness, transparency and low water absorption in addition to adhesion.
[0006]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present inventors have conducted intensive research and completed the present invention. That is, the present invention provides the formula [1]
[0007]
[Chemical Formula 10]
(Wherein R1, R2, RThreeAnd RFourEach independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and n represents an integer of 1 to 3. )
It is related with the dicarboxy alicyclic acrylate compound represented by these.
[0009]
Further, the present invention provides the formula [2]
[0010]
Embedded image
(Wherein R1, R2And RThreeRepresents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and n represents an integer of 1 to 3. )
It is related with the acryloyloxy alicyclic dicarboxylic acid anhydride represented by these.
[0012]
Furthermore, Formula [4]
[0013]
Embedded image
(Wherein RFourRepresents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and n represents an integer of 1 to 3. )
It is related with the dicarboxy alicyclic alcohol compound represented by these.
[0015]
Furthermore, the present invention provides the formula [3]
[0016]
Embedded image
(Wherein R Four And n represent the same meaning as described above. )
A dicarboxyalicyclic epoxide compound represented by the formula [4]
[0018]
Embedded image
(Wherein R Four And n represent the same meaning as described above. )
A dicarboxyalicyclic alcohol compound represented by the formula:
[0020]
Embedded image
(Wherein R1, R2And RThreeEach independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and X represents a halogen atom. )
A carboxylic acid halide compound represented by the formula [1]
[0022]
Embedded image
(Wherein R1, R2, RThree, RFourAnd n represent the same meaning as described above. )
The manufacturing method of the dicarboxy alicyclic acrylate compound represented by these.
[0024]
Furthermore, the formula [9]
[0025]
Embedded image
(Wherein RFourAnd n represent the same meaning as described above. )
The dicarboxyalicyclic unsaturated compound represented by the formula [3] is oxidized with hydrogen peroxide under a two-phase solvent system using a polyacid containing at least one tungsten or molybdenum as a catalyst.
[0027]
Embedded image
(Wherein RFourAnd n represent the same meaning as described above. )
The manufacturing method of the dicarboxy alicyclic epoxy compound represented by these.
[0029]
DETAILED DESCRIPTION OF THE INVENTION
The production method of the compound of the present invention is represented by the following five schemes as described above.
[0030]
Embedded image
(Wherein R1, R2, RThree, RFourAnd n represent the same meaning as described above. )
Hereinafter, the scheme (1) will be described in order.
[0032]
The production method of the unsaturated compound of formula [9] as a starting material is represented by the following reaction scheme when n = 1. In the case of n = 2, 3, it is manufactured in the same manner. In the case of n = 2, 3, the raw materials of the following (a) are cyclopentadiene trimer and cyclopentadiene tetramer. From the viewpoint of easy availability of raw materials, n = 1 is preferable.
[0033]
Embedded image
(In the formula, R ′ represents an alkyl group having 1 to 10 carbon atoms.)
The reaction (a) is based on the method described in Japanese Patent Publication No. 4-60100 filed by the present applicant. That is, dicyclopentadiene (DCPD) is converted from carbon monoxide and alcohol into 8,9-bis (alkoxycarbonyl) tricyclo [5.2.1.0] with palladium catalyst in the presence of cupric chloride.2,6Dece-3-ene (TCDE) is obtained.
The reaction of (b) is carried out by hydrolyzing TCDE with a base or an acid to produce 8,9-dicarboxytricyclo [5.2.1.0.2,6Dece-3-ene (TCDC) is obtained.
[0035]
Next, the epoxidation reaction of the unsaturated compound in scheme (1) will be described. For this reaction, two methods filed by the present applicant are known. The first method is a method described in Japanese Patent Application Laid-Open No. 2001-328959 by the present applicant, and is a production method in a homogeneous system in 1,4-dioxane solvent using peracetic acid as an oxidizing agent. This method has problems in that the diol form obtained by hydrolysis of the epoxy compound produced by the acidity of the coexisting acetic acid is produced as a by-product and the complicated recovery of a large amount of waste acetic acid. Further, peracetic acid is industrially expensive, and this improved method is the second method described in Japanese Patent Application Laid-Open No. 2001-213871 by the present applicant.
[0036]
That is, the epoxidation reaction is carried out in a homogeneous system in a solvent that dissolves water typified by acetonitrile using economical hydrogen peroxide as an oxidizing agent and in the presence of a peroxidized heteropolyacid catalyst. In this method, while clean hydrogen peroxide was used, the reaction slowed down as the conversion rate increased, and an excess of hydrogen peroxide several mole times the reaction substrate was required. Although these epoxidation methods are also used in the method of the present invention, it is more economically preferable to use a method in which the above problems are improved.
[0037]
The epoxidation method of the present invention is a solvent-based method that becomes non-uniform with hydrogen peroxide as the solvent in the second method. Examples of this method include halogenated hydrocarbons such as chloroform and 1,2-dichloroethane (EDC), aromatic hydrocarbons such as toluene and xylene, and aliphatic hydrocarbons such as hexane and heptane. In particular, aromatic hydrocarbons such as toluene and xylene are preferred. The amount of these solvents to be used is preferably 1 to 50 times by mass, more preferably 2 to 10 times by mass with respect to the reaction substrate.
[0038]
The catalyst of the present invention is a polyacid containing tungsten and molybdenum, and further preferably contains phosphorus. Typical examples of these forms include tungstic acid, molybdic acid, phosphoric acid, and the like. The amount used is preferably 0.01 to 20 mol%, particularly 0.1 to 10 mol%, based on the reaction substrate.
[0039]
The oxidizing agent of the present invention is hydrogen peroxide, and the concentration thereof is not limited, but a commercially available product having a concentration of 30 to 60% can be used as it is. The amount used is preferably 1 to 2 moles, more preferably 1 to 1.5 moles, and the desired epoxy compound is obtained in high yield.
[0040]
Here, the addition of a phase transfer catalyst is effective for promoting the reaction. Among them, quaternary ammonium salts, pyridinium salts, phosphonium salts and the like are preferable, and specifically, tetramethylammonium salt, tetrapropylammonium salt, tetrabutylammonium salt, trimethylbenzylammonium salt, trioctylmethylammonium salt, cetylpyridinium salt , Tetrabutylphosphonium salt, tetrabutylammonium hydrogen sulfate, and the like.
[0041]
The amount of these used is preferably 0.001 to 10 mol%, more preferably 0.005 to 5 mol%, based on the reaction substrate.
[0042]
The reaction temperature can be 0 to 150 ° C., and preferably 20 to 100 ° C. gives a high yield. The reaction time can be 1 to 50 hours, usually 2 to 24 hours is practical. In this way, the desired dialkyl 3,4-epoxytricyclo [5.2.1.02,6] Decane-8,9-dicarboxylate and 3,4-epoxytricyclo [5.2.1.0]2,6Decane-8,9-dicarboxylic acid is obtained. These objects can be purified by distillation or column chromatography.
[0043]
Next, the reduction method of reaction scheme (2) of the production method of the compound of the present invention will be described.
[0044]
Various general reduction methods for converting an epoxy group into a hydroxy group can be applied. Among these, a catalytic reduction method in which an epoxy group is converted to a hydroxy group while leaving an alkoxycarbonyl group and a carboxyl group is economical.
[0045]
For example, (1) reduction with metal and metal salt, (2) reduction with metal hydride, (3) reduction with metal hydride complex, (4) reduction with diborane and substituted borane, (5) reduction with hydrazine, (6) (7) Reduction with diimide, (7) Reduction with a phosphorus compound, (8) Electrolytic reduction, and (9) Contact reduction. Among these, a catalytic reduction method in which an epoxy group is converted to a hydroxy group while leaving an alkoxycarbonyl group and a carboxyl group is economical and practical. The catalytic reduction method that can be employed in the present invention is as follows. As the catalyst metal, palladium, ruthenium, rhodium, platinum, nickel, cobalt and iron of Group 8 of the periodic table, or copper of Group 1 can be used. These metals are used alone or in a multi-component system combined with other elements. Examples of their use include single metals, Raney-type catalysts, diatomaceous earth, alumina, zeolite, carbon and other catalysts supported on carriers and complex catalysts.
[0046]
Specifically, palladium-carbon, ruthenium-carbon, rhodium-carbon, platinum-carbon, palladium-alumina, ruthenium-alumina, rhodium-alumina, platinum-alumina, reduced nickel, reduced cobalt, Raney nickel, Raney cobalt, Raney copper , Copper oxide, copper chromatography, chlorotris (triphenylphosphine) rhodium, chlorohydridotris (triphenylphosphine) ruthenium, dichlorotris (triphenylphosphine) ruthenium, and hydridocarbonyltris (triphenylphosphine) iridium. Of these, particularly preferred are palladium-carbon and ruthenium-carbon.
[0047]
The amount of the catalyst used is preferably 0.1 to 30% by mass, particularly 0.5 to 20% by mass with respect to the substrate as a 5% metal-supported catalyst. As the solvent, alcohols typified by methanol, ethanol and propanol, ethers typified by dioxane, tetrahydrofuran and dimethoxyethane, and esters typified by ethyl acetate and propyl acetate can be used.
[0048]
The amount used is preferably in the range of 1 to 50 times by mass, particularly in the range of 3 to 20 times by mass with respect to the raw material. The hydrogen pressure is from normal pressure to 10 MPa (100 kg / cm2), In particular, from normal pressure to 5 MPa (50 kg / cm2) Is preferred. The reaction temperature is preferably in the range of 0 to 200 ° C, particularly preferably in the range of 10 to 180 ° C.
[0049]
The reaction can be monitored by the amount of hydrogen absorption, and can be confirmed by sampling after absorption of the theoretical amount of hydrogen and analyzing by gas chromatography. This reaction can be performed batchwise or continuously. After the reaction, the catalyst is removed by filtration, followed by concentration, and the target hydroxy compound can be purified by recrystallization or column chromatography.
[0050]
Next, the manufacturing method of the acrylate compound by reaction of the hydroxy compound and acrylic acid halide compound in presence of the base of reaction scheme (3) is described.
[0051]
The acrylic acid halide compound is obtained by converting an acrylic acid compound into an acid halide with a thionyl halide or the like. Examples of the halogen atom include F, Cl, Br and I, but the cheapest Cl is used. Specifically, acryloyl chloride, methacryloyl chloride, tiglyloyl chloride, 3,3-dimethylacryloyl chloride, 2-methyl-2-pentenoyl chloride, 2-ethyl-2-hexenoyl chloride and 2-octeroyl chloride Etc. The amount used is preferably 1 to 6 molar equivalents relative to the hydroxy compound, RFourWhen is an alkyl group, 1 to 2 molar equivalents are particularly preferred.
[0052]
In this reaction, a base is essential, and the types thereof include chain alkylamine compounds typified by trimethylamine, triethylamine and tripropylamine, aromatic amine compounds typified by pyridine, aniline and N-methylaniline, 1,5-diazabicyclo [4.3.0] no-5-ene (DBN), 1,4-diazabicyclo [2.2.2] octane (DBO) and 1,8-diazabicyclo [5.4.0] Examples thereof include cyclic alkylamine compounds typified by undec-7-ene (DBU) and the like, and metal carbonates such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate and potassium hydrogen carbonate. Among these bases, triethylamine and tripropylamine are preferable. The amount used is preferably 1 to 6 molar equivalents (equivalent to acid chloride) relative to the hydroxy compound, RFourWhen is an alkyl group, 1 to 2 molar equivalents are particularly preferred.
[0053]
The method preferably uses a solvent. Solvents include ether compounds such as tetrahydrofuran (THF), 1,2-dimethoxyethane and 1,4-dioxane, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methylpyrrolidone. And 1,3-dimethyl-2-imidazolidinone (DMI) and the like are preferable. The amount used is preferably 1 to 10 times by weight, more preferably 2 to 5 times by weight, based on the hydroxy compound.
[0054]
The reaction temperature is preferably 0 to 100 ° C, particularly preferably 0 to 50 ° C. After the reaction, water is added to hydrolyze the residual acid chloride, and then the solvent is distilled off, extracted with a hardly water-soluble solvent (ether type or ester type), and then purified by distillation or column chromatography. The target acrylate compound can be obtained.
[0055]
When the hydroxy compound is a dicarboxylic acid compound, an acryloyloxy alicyclic dicarboxylic acid anhydride compound obtained by dehydrating the dicarboxy alicyclic acrylate compound is obtained depending on the degree of drying of the obtained acrylate compound after the same reaction. .
[0056]
Next, a method for producing a hydroxydicarboxylic acid compound by a hydrolysis reaction of a hydroxy compound in the presence of a base or an acid catalyst in reaction scheme (4) will be described.
[0057]
A method of hydrolyzing a normal alkyl carboxylic acid ester to an alkyl carboxylic acid can be applied. As the base, it is economically preferable to use hydroxides of alkali metals and alkaline earth metals. Specific examples include sodium hydroxide, potassium hydroxide, calcium hydroxide and barium hydroxide, and sodium hydroxide is particularly economical and preferred.
[0058]
The amount used is preferably 2 to 3 equivalents, more preferably 2 to 2.4 equivalents, relative to the substrate. As the solvent, a mixed system of alcohol and water is generally used. As the type of alcohol, lower alcohols such as methanol, ethanol and propanol are preferable. The amount used is preferably 1 to 20 times by weight, particularly 2 to 10 times by weight, relative to the substrate. The amount of water added is preferably 0.1 to 20 times by weight, particularly 1 to 10 times by weight, based on the substrate. The mixing ratio of alcohol and water can be selected between 1:20 and 20: 1 by weight, and is preferably selected between 1: 5 and 5: 1.
[0059]
After the reaction, the alcohol is distilled off, and then water is added, followed by acid precipitation to obtain a crude crystal of the hydroxydicarboxylic acid compound. By purifying this by recrystallization, the pure product can be obtained.
[0060]
Next, an acid hydrolysis method is also possible, but in general, a base method provides a high yield. As the type of acid, inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as p-toluenesulfonic acid and formic acid are used. The reaction temperature is 50 to 200 ° C.
[0061]
The production method of acryloyloxydicarboxylic acid anhydride by the reaction of the hydroxy compound and acrylic acid halide compound in the presence of a base in the reaction scheme (5) was obtained after the same reaction as in the above-mentioned scheme (2). The dicarboxylic acid anhydride is obtained by drying the dicarboxyacrylate compound under reduced pressure.
[0062]
The reaction and purification of the present invention described above can be performed batchwise or continuously. The reaction can be carried out at normal pressure or under pressure.
[0063]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The analytical methods used in the examples are as follows.
[1] Gas chromatography (GC)
Model: Shimadzu Corporation Product name GC-17A: Column: Capillary column CBP1-W25-100 (25m × 0.53mmφ × 1μm), Column temperature: 100 ° C (holding 2min.) To 290 ° C (holding 10min.), 8 ° C / min. (Temperature increase rate), inlet temperature: 290 ° C, detector temperature: 290 ° C, carrier gas: helium, detection method: FID method.
[2] Mass spectrometry (MASS)
Model: LX-1000 manufactured by JEOL Ltd. Detection method: FAB method.
[3]1H NMR
Model: VARIAN INOVA500 Measuring solvent: CDClThree
Standard substance: tetramethylsilane (TMS).
[4]13C NMR
Model: VARIAN INOVA500 Measurement solvent: CDClThree
Reference material: CDClThree(δ: 77.1 ppm).
[5] Melting point (Mp)
Yanaco Device Development Laboratory: MP-J3
Example 1
[0064]
Embedded image
In a 100 ml four-necked reaction flask was dimethyltricyclo [5.2.1.0.2,6] Dece-3-ene-8,9-dicarboxylate (TCDME) 25.0 g (100 mmol), H2WOFour0.999 g (4 mmol), 85% phosphoric acid 0.115 g (1 mmol), 90% trioctylmethylammonium chloride (TOMAC) 1.35 g (3 mmol) and toluene 50 g were charged, and 34% peroxidation was performed at 45 ° C. with stirring. Hydrogen water 14.6g (150mmol) was dripped over 45 minutes, and also it stirred at 50 degreeC for 3 hours.
[0066]
As a result of analysis by gas chromatography, unreacted TCDME disappeared and a new peak appeared at 89.1 area%. After completion of the reaction, toluene and water were added for extraction, and the toluene layer was washed with water, concentrated and dried to obtain 29.4 g of oil (purity 88.4%) (yield 97.7%). Further purification by silica gel column chromatography (eluent / ethyl acetate: n-heptane = 1: 9-1: 1) gave 22.8 g (purity 98.2%) of oil (yield 84.0%). It was. The oil solidified upon standing at 25 ° C.
[0067]
The structure of this substance was determined from the following analysis results based on dimethyl 3,4-epoxytricyclo [5.2.1.0.2,6It was confirmed to be decane-8,9-dicarboxylate (DMED).
[0068]
MASS (FAB+, m / e (%)): 267 ([M + H]+, 65), 235 (100).
1H NMR (500MHz, CDClThree, δppm): 1.45 (dd, J1= 1.22Hz, J2= 10.39Hz, 1H), 1.64 (dd, J1= 2.75Hz, J2= 15.58Hz, 1H), 1.87 (dd, J1= 8.86Hz, J2= 15.58Hz, 1H), 2.13 (dd, J1= 1.53Hz, J2= 10.39Hz, 1H), 2.37-2.43 (m, 2H), 2.47 (dd, J1= 4.89Hz, J2= 9.78Hz, 1H), 2.62 (d, J = 4.89Hz, 1H), 2.86 (d, J = 9.78Hz, 1H), 2.92 (d, J = 9.78Hz, 1H), 3.28 (d, J = 9.83 Hz, 1H), 3.49 (d, J = 2.14Hz, 1H), 3.57 (d, J = 5.35Hz, 6H).
13C NMR (125MHz, CDClThree, δppm): 27.6942,39.7651,41.7337,43.5115,44.2821,44.3661,44.4042,46.9145,51.5079,51.5308,59.1914,60.5725,173.0177,173.2390.
Mp. (° C): 82-83.
Example 2
[0069]
Embedded image
In a 100 ml Hastelloy autoclave, dimethyl 3,4-epoxytricyclo [5.2.1.02,6] Decane-8,9-dicarboxylate (DMED) 7.0 g (purity 98.2%) (25.8 mmol), 10% Pd / C (H2O55.25%) 0.782 g (5 mass%), ethyl acetate 49 g and hydrogen pressure 5 MPa (50 kg / cm2) And stirred at 150 ° C. for 6 hours.
[0071]
After returning to room temperature, the pressure was released, the contents were taken out, the catalyst was removed by filtration, and the obtained filtrate was concentrated to obtain 7.00 g (purity 89.0%) (yield 89.9%) of an oily substance. . As a result of analysis by gas chromatography, the raw material disappeared and a new two-component peak (gas chromatography area% = 82.2 (yield 83.0%): 6.8 (yield 6.9%)) Appeared. This mixture was separated by silica gel column chromatography (eluent / ethyl acetate: n-heptane = 1: 9 to 1: 1), and the main component was dimethyl 3-hydroxytricyclo [5.2.1.0 from the analysis result.2,6It was confirmed to be decane-8,9-dicarboxylate (DM3HD).
[0072]
MASS (FAB+, m / e (%)): 269 ([M + H]+, 18), 237 (100).
1H NMR (500MHz, CDClThree, δppm): 1.44 (dd, J1= 1.22Hz, J2= 10.38Hz, 1H), 1.47-1.49 (m, 1H), 1.68-1.72 (m, 2H), 1.76-1.83 (m, 1H), 2.09 (dd, J1= 1.53Hz, J2= 10.39Hz, 1H), 2.90 (dd, J1= 4.89Hz, J2= 11.00Hz, 1H), 2.34-2.40 (m, 2H), 2.55-2.61 (m, 2H), 2.69 (d, J = 9.78Hz, 1H), 2.80 (d, J = 9.78Hz, 1H), 3.54 (d, J = 2.14Hz, 6H), 4.07 (brs, 1H).
13C NMR (125MHz, CDClThree, δppm): 23.9245,37.8190,39.8791,42.7176,43.9231,44.0681,44.6938,44.8464,51.5532 (2CHThree), 54.8113, 73.7493, 173.5209, 173.7269.
As a result of the GC-MASS analysis, the minor component was DM3HD isomer of dimethyl 4-hydroxytricyclo [5.2.1.0.2,6It was confirmed to be decane-8,9-dicarboxylate (DM4HD).
Example 3
[0073]
Embedded image
Into a 100 ml four-necked reaction flask, 1.74 g (6.5 mmol) of DMHD (DM3HD: DM4HD = 93: 7), 18 g of tetrahydrofuran (THF) and 0.987 g (9.8 mmol) of triethylamine were charged with ice cooling ( (5 ° C.), 1.02 g (9.8 mmol) of methacrylic acid chloride was added dropwise over 10 minutes. The mixture was gradually returned to room temperature (25 ° C.) and stirred for 16 hours. Subsequently, the mixture was concentrated, and the residue was extracted by adding water and 1,2-dichloroethane (EDC). The organic layer was separated, washed with water, and concentrated to obtain 1.85 g of an oily substance. When the oily substance was analyzed by gas chromatography, a new peak (A: B = 72.3 (yield 61.2%): 5.1 (yield 4.2%)) appeared. Therefore, further purification by silica gel column chromatography (developing solvent; ethyl acetate / n-heptane = 1/5 to 1/1) gave 0.91 g (yield 41.6%) of the main component oil. From this analysis result, this fraction was dimethyl 3-methacryloyloxytricyclo [5.2.1.0.2,6It was confirmed to be decane-8,9-dicarboxylate (DM3AD).
[0075]
MASS (FAB+, m / e (%)): 337 ([M + H]+, 11), 305 (100), 219 (28), 131 (47).
1H NMR (500MHz, CDClThree, δppm): 1.43 (d, J = 1.13Hz, 1H), 1.50-1.55 (m, 1H), 1.88 (s, 6H), 2.14 (dd, J1= 1.48Hz, J2= 10.34Hz, 1H), 2.41 (d, J = 4.89Hz, 2H), 2.57-2.63 (m, 2H), 2.81 (dd, J1= 9.77Hz, J2= 19.54Hz, 2H), 3.55 (s, 6H), 5.00 (d, J = 2.14Hz, 1H), 5.46 (d, J = 1.22Hz, 1H), 5.98 (s, 1H).
13C NMR (125MHz, CDClThree, δppm): 18.0872,24.1532,34.9956,39.9018,42.8470,43.9229,44.0755,44.5867,449148,51.5835 (2CHThree), 52.1481,77.0452,125.0998,136.4611,166.8442,173.2764,173.5511.
As a result of the GC-MASS analysis, the minor component was DM3AD isomer of dimethyl 4-methacryloyloxytricyclo [5.2.1.0.2,6It was confirmed to be decane-8,9-dicarboxylate (DM4AD).
Example 4
[0076]
Embedded image
Into a 100 ml four-necked reaction flask was dimethyl 3-hydroxytricyclo [5.2.1.0.2,6] 6.85 g (25.5 mmol) of decane-8,9-dicarboxylate (DM3HD) and 31 g of ethanol were charged, and 6.73 g (102 mmol) of 85% potassium hydroxide was dissolved in 6.73 g of water under ice-cooling and stirring. The solution was added dropwise. Subsequently, the mixture was transferred to an oil bath and stirred for 4 hours while refluxing at 110 ° C. After cooling with ice, 12 g of concentrated hydrochloric acid was added dropwise to precipitate crystals. After removing the crystals by filtration, the filtrate was concentrated to obtain 6.93 g of white crystals. The crystals were extracted and concentrated with acetonitrile to obtain 1.37 g of crystals. The residue was re-extracted and concentrated with acetone to obtain 0.77 g of crystals (total yield 35%).
The structure of this substance was determined from the following analysis results based on 3-hydroxytricyclo [5.2.1.0].2,6It was confirmed to be decane-8,9-dicarboxylic acid (3HDDC).
[0078]
MASS (FAB-, m / e (%)): 239 ([M-H]+, 100), 221 (22), 195 (24).
1H NMR (500MHz, CDClThree, δppm): 1.31 (d, J = 9.18Hz, 1H), 1.41 (t, J = 5.96Hz1H), 1.59-1.63 (m, 2H), 1.66 (t, J = 10.93Hz1H), 2.04 (d, J = 7.94Hz, 1H), 3.16 (dd, J1= 3.81Hz, J2= 10.84Hz, 1H), 2.21 (d, J = 4.58Hz, 1H), 2.36 (d, J = 4.58Hz, 1H), 2.43-2.48 (m, 1H), 2.59 (d, J = 9.78Hz, 1H ), 2.66 (t, J = 10.85Hz, 1H), 3.87 (s, 1H), 4.15 (brs, 1H), 11.97 (brs, 2H).
13C NMR (125MHz, CDClThree, δppm): 23.7519,37.6388,39.9965,42.3923,43.5292,43.8726,44.3456,44.4525,54.4861,71.9743,174.2639,174.3936.
mp (° C): 153-154.
Reference example 1
[0079]
Embedded image
Tricyclo [5.2.1.0] in a 100 ml four-neck reaction flask.2,6Dece-3-ene-8,9-dicarboxylic acid (TCDC) 6.66 g (30 mmol), H2WOFour0.30 g (1.2 mmol), 85% phosphoric acid 0.035 g (0.3 mmol), 90% trioctylmethylammonium chloride (TOMAC) 0.404 g (0.9 mmol) and 1,4-dioxane 34 g were charged, Under stirring at 50 ° C., 4.37 g (45 mmol) of 34% aqueous hydrogen peroxide was added dropwise over 30 minutes. The mixture was further stirred at 50 ° C. for 20 hours. As a result of analysis by gas chromatography, 7.1% of unreacted TCDC remained, and 77.0% of a new peak appeared. After completion of the reaction and concentration, toluene and water were added to the residue and stirred to form crystals. This was filtered, washed with toluene and water, filtered and dried to obtain 6.77 g of white crystals (yield 94.8%).
[0081]
The structure of this substance is shown in the following analytical results as 3,4-epoxytricyclo [5.2.1.0].2,6It was confirmed to be decane-8,9-dicarboxylic acid (EDDC).
[0082]
MASS (FAB+, m / e (%)): 237 ([M + H]+, 100), 193 (30).
1H NMR (500MHz, CDClThree, δppm): 1.34 (d, J = 9.78Hz, 1H), 1.71 (d, J = 7.33Hz, 2H), 2.07 (d, J = 9.78Hz, 1H), 2.24 (d, J = 3.97Hz, 1H ), 2.29-2.37 (m, 2H), 2.50 (d, J = 3.97Hz, 1H), 2.75 (d, J = 9.78Hz, 1H), 2.85 (d, J = 9.78Hz, 1H), 3.36 (d , J = 2.19Hz, 1H), 3.54 (d, J = 3.75Hz, 1H), 12.02 (brs, 2H).
13C NMR (125MHz, CDClThree, δppm): 27.6197,39.3472,41.5829,43.2691,44.0855,44.3145,44.3679,46.9774,58.8422,60.4140,174.0953,174.3242.
Mp. (° C): 181-182.
Example 5
[0083]
Embedded image
In a 100 ml Hastelloy autoclave, 3,4-epoxytricyclo [5.2.1.02,6] Decan-8,9-dicarboxylic acid (EDDC) 2.38 g (10 mmol), 10% Pd / C (H2O55.25%) 0.532 g (10% by mass), ethyl acetate 24 g and hydrogen pressure 3 MPa (30 kg / cm2) And stirred at 130 ° C. for 5 hours.
[0085]
After returning to room temperature, the pressure was released, the contents were taken out, the catalyst was removed by filtration, and the obtained filtrate was concentrated to obtain 2.16 g (purity 61.5%) (yield 55.3%) of an oily substance. . As a result of analysis by gas chromatography, a new two-component peak (gas chromatography area% = 26.7 (yield 24.0%): 34.8 (yield 31.3%)) appeared. This mixture was purified by silica gel column chromatography (eluent / ethyl acetate: n-heptane = 1: 1 to 1: 0) to obtain 1.30 g of a fraction of HDDC (3HDDC: 4HDDC = 63: 37). This two-component structure is MASS,13C NMR and1From 1 H NMR, 63% is 3HDDC and 37% is 4-hydroxytricyclo [5.2.1.0.2,6It was confirmed to be decane-8,9-dicarboxylic acid (4HDDC).
Example 6
[0086]
Embedded image
A 100 ml four-necked reaction flask was charged with 1.20 g (5.0 mmol) of 3HDDC obtained in Example 5, 27 g of tetrahydrofuran (THF) and 3.03 g (30 mmol) of triethylamine, and the mixture was stirred under ice cooling (5 ° C.). 3.14 g (30 mmol) of methacrylic acid chloride was added dropwise in 15 minutes. The mixture was gradually returned to room temperature (26 ° C.) and stirred for 5 hours. Subsequently, water was added and the mixture was concentrated. Water and 1,2-dichloroethane (EDC) were added to the residue for extraction. The organic layer was separated, washed with water, and concentrated to obtain 3.18 g of an oily substance. When this oil was analyzed by gas chromatography, a new peak appeared. Therefore, purification by silica gel column chromatography (developing solvent; ethyl acetate / n-heptane = 1/5 to 1/1) gave 0.61 g (yield 39.6%) of an oily substance. From this analysis result, this fraction was analyzed for 3-methacryloyloxytricyclo [5.2.1.0].2,6It was confirmed to be decane-8,9-dicarboxylic acid (3MADC).
MASS (FAB-, m / e (%)): 307 ([M-H]+, 50), 189 (100).
13C NMR (125MHz, CDClThree, δppm): 17.6373,23.9398,34.4160,37.8572,43.3509,43.4958,43.6408,44.4877,45.5331,51.0649,76.3741,125.7334,136.1180,167.0353,173.0478,173.5285.
Example 7
[0088]
Embedded image
A 100 ml four-necked reaction flask was charged with 1.30 g (5.4 mmol) of HDDC (3HDDC: 4HDDC = 63: 37) obtained in Example 5, 22 g of tetrahydrofuran (THF), and 2.18 g (21.6 mmol) of triethylamine. While stirring, 2.26 g (21.6 mmol) of methacrylic acid chloride was added dropwise over 15 minutes under ice cooling (5 ° C.). The mixture was gradually returned to room temperature (26 ° C.) and stirred for 7 hours. Subsequently, water was added and the mixture was concentrated. Water and 1,2-dichloroethane (EDC) were added to the residue for extraction. The organic layer was separated, washed with water, and concentrated to obtain 3.18 g of an oily substance. When this oily substance was analyzed by gas chromatography, a new peak (A: B = 28.1 (yield 53.7%): 16.7 (yield 31.9%)) appeared. Therefore, it was further purified by silica gel column chromatography (developing solvent; ethyl acetate / n-heptane = 1/5 to 1/1), and the oil was A: B = 61.4: 38.6 (area%) by gas chromatography. 0.83 g (yield 49.8%) of the product was obtained. From this analysis result, this fraction was analyzed by A: 3-methacryloyloxytricyclo [5.2.1.0.2,6] Decane-8,9-dicarboxylic anhydride (3MADA) and B: 4-methacryloyloxytricyclo [5.2.1.0].2,6It was confirmed to be decane-8,9-dicarboxylic anhydride (4MADA).
[0090]
[3MADA]
MASS (FAB-, m / e (%)): 291 ([M + H]+, 28), 207 (28), 189 (60), 153 (100).
13C NMR (125MHz, CDClThree, δppm): 17.9963,24.1767,34.5232,36.0874,36.9420,42.2602,43.7938,45.2969,45.6327,51.4926,76.7102,125.1920,136.2862,166.9289,179.3126,179.8619.
[0091]
[4MADA]
MASS (FAB-, m / e (%)): 291 ([M + H]+, 28), 207 (28), 189 (60), 153 (100).
13C NMR (125MHz, CDClThree, δppm): 18.0192,23.9326,34.5842,36.0874,36.9877,42.2602,43.7938,45.2969,45.6327,55.5137,76.9467,125.0318,136.3702,166.6313,179.3126,179.8619.
[0092]
【effect】
As a material for electrode protective films, planarization films, insulating films, optical waveguides for optical communication systems, etc. used in displays such as liquid crystal display elements and organic EL elements, in addition to heat resistance and substrate adhesion, planarization and transparency In addition, it is possible to provide an acrylate monomer that is a raw material for a photosensitive resin having various properties such as low water absorption.
Claims (4)
で表されるジカルボキシ脂環式アルコール化合物。Formula [4]
The dicarboxy alicyclic alcohol compound represented by these.
で表されるジカルボキシ脂環式エポキシド化合物を接触還元し式［４］
で表されるジカルボキシ脂環式アルコール化合物を得、更に、このアルコール化合物と式［５］
で表されるアクリル酸ハライド化合物を塩基存在下で反応させることを特徴とする式［１］
で表されるジカルボキシ脂環式アクリレート化合物の製造法。Formula [3]
In dicarboxy cycloaliphatic epoxide compound catalytic reduction was expression represented [4]
A dicarboxyalicyclic alcohol compound represented by the formula:
A carboxylic acid halide compound represented by the formula [1]
The manufacturing method of the dicarboxy alicyclic acrylate compound represented by these.
で表されるジカルボキシ脂環式不飽和化合物を、タングステン又はモリブデンを少なくとも一種含むポリ酸を触媒として、二相溶媒系下で過酸化水素により酸化して得られる式［３］Formula [3] obtained by oxidizing a dicarboxyalicyclic unsaturated compound represented by the formula (3) with hydrogen peroxide in a two-phase solvent system using a polyacid containing at least one tungsten or molybdenum as a catalyst.
で表されるジカルボキシ脂環式エポキシド化合物を用いることを特徴とする式［１］A dicarboxyalicyclic epoxide compound represented by the formula [1]
で表されるジカルボキシ脂環式アクリレート化合物の製造法。The manufacturing method of the dicarboxy alicyclic acrylate compound represented by these.
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