JP2001122883A - Method for producing organosilyl unsaturated carboxylate - Google Patents
Method for producing organosilyl unsaturated carboxylateInfo
- Publication number
- JP2001122883A JP2001122883A JP30348699A JP30348699A JP2001122883A JP 2001122883 A JP2001122883 A JP 2001122883A JP 30348699 A JP30348699 A JP 30348699A JP 30348699 A JP30348699 A JP 30348699A JP 2001122883 A JP2001122883 A JP 2001122883A
- Authority
- JP
- Japan
- Prior art keywords
- group
- organosilyl
- unsaturated
- producing
- palladium
- 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
- 150000007942 carboxylates Chemical class 0.000 title claims abstract description 30
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 39
- -1 norbornene compound Chemical class 0.000 claims abstract description 21
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000002798 polar solvent Substances 0.000 claims abstract description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical group C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 12
- 150000002430 hydrocarbons Chemical group 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000005574 norbornylene group Chemical group 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 5
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 claims description 4
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 claims description 3
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 3
- 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 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 abstract description 14
- 239000006227 byproduct Substances 0.000 abstract description 8
- 150000001735 carboxylic acids Chemical class 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 13
- 229910000077 silane Inorganic materials 0.000 description 13
- 238000004821 distillation Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- PQSIXYSSKXAOFE-UHFFFAOYSA-N tri(propan-2-yl)silyl prop-2-enoate Chemical compound CC(C)[Si](C(C)C)(C(C)C)OC(=O)C=C PQSIXYSSKXAOFE-UHFFFAOYSA-N 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- ZGYICYBLPGRURT-UHFFFAOYSA-N tri(propan-2-yl)silicon Chemical compound CC(C)[Si](C(C)C)C(C)C ZGYICYBLPGRURT-UHFFFAOYSA-N 0.000 description 4
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 4
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- ISEIIPDWJVGTQS-UHFFFAOYSA-N tributylsilicon Chemical compound CCCC[Si](CCCC)CCCC ISEIIPDWJVGTQS-UHFFFAOYSA-N 0.000 description 3
- AKQNYQDSIDKVJZ-UHFFFAOYSA-N triphenylsilane Chemical compound C1=CC=CC=C1[SiH](C=1C=CC=CC=1)C1=CC=CC=C1 AKQNYQDSIDKVJZ-UHFFFAOYSA-N 0.000 description 3
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 2
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- DKBGMFLYIUKQKE-UHFFFAOYSA-N CC(C)(C)[SiH](C(C)(C)C)C(C)(C)C Chemical compound CC(C)(C)[SiH](C(C)(C)C)C(C)(C)C DKBGMFLYIUKQKE-UHFFFAOYSA-N 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 2
- 125000000068 chlorophenyl group Chemical group 0.000 description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- XGZIBBIQQCAYDT-UHFFFAOYSA-N tri(butan-2-yl)silane Chemical compound CCC(C)[SiH](C(C)CC)C(C)CC XGZIBBIQQCAYDT-UHFFFAOYSA-N 0.000 description 2
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 2
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- FEGVSPGUHMGGBO-VOTSOKGWSA-N (E)-2-methoxycinnamic acid Chemical compound COC1=CC=CC=C1\C=C\C(O)=O FEGVSPGUHMGGBO-VOTSOKGWSA-N 0.000 description 1
- KFSQJVOLYQRELE-HWKANZROSA-N (e)-2-ethylbut-2-enoic acid Chemical compound CC\C(=C/C)C(O)=O KFSQJVOLYQRELE-HWKANZROSA-N 0.000 description 1
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- PEXWJYDPDXUVSV-BQYQJAHWSA-N (e)-3-phenylbut-2-enoic acid Chemical compound OC(=O)\C=C(/C)C1=CC=CC=C1 PEXWJYDPDXUVSV-BQYQJAHWSA-N 0.000 description 1
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- JQZUMFHYRULBEN-UHFFFAOYSA-N diethyl(methyl)silicon Chemical compound CC[Si](C)CC JQZUMFHYRULBEN-UHFFFAOYSA-N 0.000 description 1
- QWVFZGVJZUJZGG-UHFFFAOYSA-N diethyl(phenyl)silicon Chemical compound CC[Si](CC)C1=CC=CC=C1 QWVFZGVJZUJZGG-UHFFFAOYSA-N 0.000 description 1
- OIKHZBFJHONJJB-UHFFFAOYSA-N dimethyl(phenyl)silicon Chemical compound C[Si](C)C1=CC=CC=C1 OIKHZBFJHONJJB-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- DRUOQOFQRYFQGB-UHFFFAOYSA-N ethoxy(dimethyl)silicon Chemical compound CCO[Si](C)C DRUOQOFQRYFQGB-UHFFFAOYSA-N 0.000 description 1
- QGBMSFLTRRZTGI-UHFFFAOYSA-N ethyl(dimethyl)silane Chemical compound CC[SiH](C)C QGBMSFLTRRZTGI-UHFFFAOYSA-N 0.000 description 1
- MGOBEGBHSBJTJR-UHFFFAOYSA-N ethyl(diphenyl)silicon Chemical compound C=1C=CC=CC=1[Si](CC)C1=CC=CC=C1 MGOBEGBHSBJTJR-UHFFFAOYSA-N 0.000 description 1
- SCRLEJODSSWXCE-UHFFFAOYSA-N ethyl-methyl-phenylsilane Chemical compound CC[SiH](C)C1=CC=CC=C1 SCRLEJODSSWXCE-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 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
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- LDHQCZJRKDOVOX-IHWYPQMZSA-N isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 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
- OKHRRIGNGQFVEE-UHFFFAOYSA-N methyl(diphenyl)silicon Chemical compound C=1C=CC=CC=1[Si](C)C1=CC=CC=C1 OKHRRIGNGQFVEE-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- 150000001367 organochlorosilanes Chemical class 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- ACECBHHKGNTVPB-UHFFFAOYSA-N silylformic acid Chemical compound OC([SiH3])=O ACECBHHKGNTVPB-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- MHMUCYJKZUZMNJ-OWOJBTEDSA-N trans-3-chloroacrylic acid Chemical compound OC(=O)\C=C\Cl MHMUCYJKZUZMNJ-OWOJBTEDSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- HVMNIRCQQXUXRP-UHFFFAOYSA-N triphenylsilyl prop-2-enoate Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(OC(=O)C=C)C1=CC=CC=C1 HVMNIRCQQXUXRP-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の技術分野】本発明は、オルガノシリル不飽和カ
ルボキシレートの製造法に関する。さらに詳しくは、不
飽和カルボン酸とオルガノハイドロシランとを反応さ
せ、オルガノシリル不飽和カルボキシレートを製造する
方法に関する。TECHNICAL FIELD The present invention relates to a method for producing an organosilyl unsaturated carboxylate. More specifically, the present invention relates to a method for producing an organosilyl unsaturated carboxylate by reacting an unsaturated carboxylic acid with an organohydrosilane.
【０００２】[0002]
【発明の技術的背景とその問題点】オルガノシリル不飽
和カルボキシレートの製造方法としては、不飽和カルボ
ン酸の金属塩にクロロシランを反応させる方法が知られ
ている（D.N.Andreev,et.al.,Chem.Abstr. No.55 1533
2）。しかしこの反応では反応収率が低く、クロロシラ
ンが残存し、目的生成物の純度を下げるという欠点があ
った。BACKGROUND OF THE INVENTION As a method for producing an organosilyl unsaturated carboxylate, a method of reacting a metal salt of an unsaturated carboxylic acid with chlorosilane is known (DNAndreev, et. Al., Chem. .Abstr. No.55 1533
2). However, this reaction has the disadvantage that the reaction yield is low, chlorosilane remains, and the purity of the target product decreases.
【０００３】また、不飽和カルボン酸とオルガノクロロ
シランとをトリエチルアミンのような塩基の存在下で脱
塩化水素反応を行い、目的生成物を得る方法もある。し
かし、この方法では副生する塩酸塩を除去しなければな
らず、工程が煩雑になり、濾過工程の際に目的生成物が
塩酸塩に吸着して著しく収率が低下し、更に反応混合物
を蒸留によって精製する場合に塩酸塩が昇華・留出しや
すく、目的生成物の純度を下げるなどの欠点があった。There is also a method in which an unsaturated carboxylic acid and an organochlorosilane are subjected to a dehydrochlorination reaction in the presence of a base such as triethylamine to obtain a desired product. However, in this method, the hydrochloride produced as a by-product must be removed, the process becomes complicated, the target product is adsorbed to the hydrochloride during the filtration step, and the yield is significantly reduced. In the case of purification by distillation, the hydrochloride tends to sublimate and distill, and has the drawbacks of lowering the purity of the target product.
【０００４】一方、カルボン酸とハイドロシランをパラ
ジウム、ニッケル、ロジウムなどの金属または金属化合
物を含んだ触媒の存在下で反応させて、シリルカルボキ
シレートを製造する方法が知られている（L.H.Sommer,
J.E.Lyons,J.Am.Chem.Soc.,91,7061(1969) ）。しか
し、この反応を、不飽和カルボン酸とオルガノハイドロ
シランを用いて行うと反応中に発生した水素により、不
飽和カルボン酸の二重結合が還元（水素添加）されてオ
ルガノシリル飽和カルボキシレートが多量に副生すると
いう問題があった。さらに、この際、目的のオルガノシ
リル不飽和カルボキシレートを精製するためには、蒸留
が必要であるが、副生したオルガノシリル飽和カルボキ
シレートと目的のオルガノシリル不飽和カルボキシレー
トとの沸点が非常に近いために蒸留による精製が難し
く、高純度のオルガノシリル不飽和カルボキシレートを
得るのは困難であった。On the other hand, there is known a method for producing a silylcarboxylate by reacting a carboxylic acid with hydrosilane in the presence of a catalyst containing a metal or a metal compound such as palladium, nickel and rhodium (LHSommer,
JELyons, J. Am. Chem. Soc., 91 , 7061 (1969)). However, when this reaction is carried out using an unsaturated carboxylic acid and an organohydrosilane, the hydrogen generated during the reaction reduces (hydrogenates) the double bond of the unsaturated carboxylic acid, resulting in a large amount of organosilyl saturated carboxylate. There was a problem of by-product. Further, at this time, distillation is necessary in order to purify the target organosilyl unsaturated carboxylate, but the boiling point between the by-produced organosilyl saturated carboxylate and the target organosilyl unsaturated carboxylate is extremely low. Because of the closeness, purification by distillation was difficult, and it was difficult to obtain high-purity organosilyl unsaturated carboxylate.
【０００５】そこで、不飽和カルボン酸とオルガノハイ
ドロシランとの反応によるオルガノシリル不飽和カルボ
キシレートの製造において、オルガノシリル飽和カルボ
キシレートの副生を抑制する方法として、特公平７−６
８２５５号公報にはパラジウム触媒と配位子の存在下で
行う方法が、特許第２５４２１１７号公報にはパラジウ
ム触媒と非プロトン性極性溶媒の存在下で行う方法が、
それぞれ提案されている。しかし、これらの方法では、
特に不飽和カルボン酸がアクリル酸の場合において、オ
ルガノシリル飽和カルボキシレートの生成が多く、満足
できる品質かつ収率で、目的のオルガノシリル不飽和カ
ルボキシレートを得ることができなかった。In producing organosilyl unsaturated carboxylate by reacting unsaturated carboxylic acid with organohydrosilane, a method for suppressing by-product of organosilyl saturated carboxylate is disclosed in JP-B-7-6.
No. 8255 discloses a method performed in the presence of a palladium catalyst and a ligand, and Patent No. 2542117 discloses a method performed in the presence of a palladium catalyst and an aprotic polar solvent.
Each has been proposed. But with these methods,
In particular, when the unsaturated carboxylic acid is acrylic acid, organosilyl saturated carboxylate is often produced, and the desired organosilyl unsaturated carboxylate cannot be obtained with satisfactory quality and yield.
【０００６】また、これを解決するために、特開平１０
−２１２２９３号公報には還元性の二重結合を有する化
合物を共存させることが提案されている。しかし、この
公報で提案された還元性の二重結合を有する化合物では
水素の捕捉能力が十分でないためにオルガノシリル飽和
カルボキシレートの副生を十分に抑制することができな
かった。また、提案された還元性の二重結合を有する化
合物自体が高いラジカル重合性を有しているために、加
熱を必要とする反応や蒸留精製などの工程において、当
該化合物自身または目的のオルガノシリル不飽和カルボ
キシレートとの重合が起こり、不均一系触媒を凝集させ
て触媒活性を低下させたり、著しく収率を低下させると
いう問題があった。In order to solve this problem, Japanese Patent Laid-Open No.
JP-A-212293 proposes coexistence of a compound having a reducing double bond. However, the compounds having a reducing double bond proposed in this publication cannot sufficiently suppress the by-product of organosilyl-saturated carboxylate because of insufficient hydrogen-capturing ability. In addition, since the proposed compound having a reducing double bond itself has high radical polymerizability, the compound itself or the intended organosilyl compound is used in a step such as a reaction requiring heating or purification by distillation. There has been a problem that polymerization with an unsaturated carboxylate occurs, and the heterogeneous catalyst is agglomerated to lower the catalytic activity or to significantly lower the yield.
【０００７】[0007]
【発明の目的】本発明は、このような従来の技術の欠点
に鑑み、好ましくない副生成物であるオルガノシリル飽
和カルボキシレートを生成することなく、目的のオルガ
ノシリル不飽和カルボキシレートを、高純度かつ高収率
で製造する方法を提供することを課題とする。SUMMARY OF THE INVENTION In view of the above-mentioned drawbacks of the prior art, the present invention provides a method for producing a desired organosilyl unsaturated carboxylate without producing an undesirable by-product, organosilyl saturated carboxylate. Another object of the present invention is to provide a method for producing a high yield.
【０００８】[0008]
【発明の構成】本発明者らは、かかる課題を達成するた
めに鋭意検討した結果、不飽和カルボン酸とオルガノハ
イドロシランとを、パラジウム触媒、非プロトン性極性
溶媒及びノルボルネン化合物の存在下で反応させると、
不飽和カルボン酸の二重結合の還元が抑制され、オルガ
ノシリル不飽和カルボキシレートを高純度かつ高収率で
製造できることを見出し、本発明に至った。The present inventors have conducted intensive studies in order to achieve the object, and as a result, reacted an unsaturated carboxylic acid with an organohydrosilane in the presence of a palladium catalyst, an aprotic polar solvent and a norbornene compound. When you do
The present inventors have found that the reduction of the double bond of the unsaturated carboxylic acid can be suppressed, and that organosilyl unsaturated carboxylate can be produced with high purity and high yield.
【０００９】すなわち本発明は、一般式（Ｉ）；That is, the present invention provides a compound represented by the general formula (I):
【００１０】[0010]
【化４】 Embedded image
【００１１】（式中、R1、R2及びR3は、同一または異な
った、水素原子、ハロゲン原子又は置換もしくは非置換
の１価の炭化水素基を表す）で示される不飽和カルボン
酸と、一般式（II）；Wherein R 1 , R 2 and R 3 are the same or different and represent a hydrogen atom, a halogen atom or a substituted or unsubstituted monovalent hydrocarbon group; , A general formula (II);
【００１２】[0012]
【化５】 Embedded image
【００１３】（式中、R4、R5及びR6は、同一または異な
った、アルコキシ基又は置換もしくは非置換の１価炭化
水素基を表す）で示されるオルガノハイドロシランと
を、パラジウム触媒、非プロトン性極性溶媒及びノルボ
ルネン化合物の存在下に反応させることを特徴とする、
一般式（III)；Wherein R 4 , R 5 and R 6 are the same or different and represent an alkoxy group or a substituted or unsubstituted monovalent hydrocarbon group, and a palladium catalyst; Characterized by reacting in the presence of an aprotic polar solvent and a norbornene compound,
General formula (III);
【００１４】[0014]
【化６】 Embedded image
【００１５】（式中、R1〜R6は前述の通り）で示される
オルガノシリル不飽和カルボキシレートの製造方法に関
する。(Wherein, R 1 to R 6 are as described above) and a method for producing an organosilyl unsaturated carboxylate represented by the formula:
【００１６】[0016]
【発明の実施の形態】本発明に使用される一般式（Ｉ）
で示される不飽和カルボン酸において、R1、R2及びR
3は、同一または異なった、水素原子、ハロゲン原子又
は置換もしくは非置換の１価炭化水素基を表す。例え
ば、このR1、R2およびR3としては、水素原子；メチル
基、エチル基、プロピル基、ブチル基、ペンチル基、ヘ
キシル基、ヘプチル基、オクチル基、ノニル基、デシル
基、ドデシル基のようなアルキル基；シクロペンチル
基、シクロヘキシル基のようなシクロアルキル基；２−
フェニルエチル基、２−フェニルプロピル基のようなア
ラルキル基；フェニル基、トリル基のようなアリール
基；カルボキシル基及びこれらの１価炭化水素基の炭素
原子に結合した水素原子が部分的にハロゲン原子、アミ
ノ基、シアノ基、アルコキシ基、水酸基などで置換され
たクロロメチル基、クロロフェニル基、3,3,3 −トリフ
ルオロプロピル基、アミノエチル基、シアノエチル基、
ｏ−メトキシフェニル基、ｏ−ヒドロキシフェニル基の
ような置換炭化水素基が例示される。これらの中でも原
料の入手が容易なことから、水素原子、アルキル基、ア
ラルキル基及びアリール基が好ましく、特に水素原子、
アルキル基が好ましい。DETAILED DESCRIPTION OF THE INVENTION The general formula (I) used in the present invention
In the unsaturated carboxylic acid represented by R 1 , R 2 and R
3 represents the same or different, a hydrogen atom, a halogen atom or a substituted or unsubstituted monovalent hydrocarbon group. For example, as R 1 , R 2 and R 3 , a hydrogen atom; methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group Such an alkyl group; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group;
Aralkyl groups such as phenylethyl group and 2-phenylpropyl group; aryl groups such as phenyl group and tolyl group; carboxyl groups and hydrogen atoms bonded to carbon atoms of these monovalent hydrocarbon groups are partially halogen atoms An amino group, a cyano group, an alkoxy group, a chloromethyl group substituted with a hydroxyl group, a chlorophenyl group, a 3,3,3-trifluoropropyl group, an aminoethyl group, a cyanoethyl group,
Examples thereof include substituted hydrocarbon groups such as an o-methoxyphenyl group and an o-hydroxyphenyl group. Of these, a hydrogen atom, an alkyl group, an aralkyl group, and an aryl group are preferable because raw materials are easily available, and particularly, a hydrogen atom,
Alkyl groups are preferred.
【００１７】このような不飽和カルボン酸としては、ア
クリル酸、メタクリル酸、２−エチルアクリル酸、クロ
トン酸、イソクロトン酸、２−エチルクロトン酸、アン
ゲリカ酸、２−クロロアクリル酸、３−クロロアクリル
酸、ケイ皮酸、α−メチルケイ皮酸、β−メチルケイ皮
酸、ｏ−メトキシケイ皮酸、マレイン酸、フマル酸など
が例示されるが、これらの中でも入手及び合成が容易な
ことから、アクリル酸、メタクリル酸が好ましい。Examples of such unsaturated carboxylic acids include acrylic acid, methacrylic acid, 2-ethylacrylic acid, crotonic acid, isocrotonic acid, 2-ethylcrotonic acid, angelic acid, 2-chloroacrylic acid and 3-chloroacrylic acid. Acid, cinnamic acid, α-methylcinnamic acid, β-methylcinnamic acid, o-methoxycinnamic acid, maleic acid, fumaric acid, etc. are exemplified. Acids and methacrylic acid are preferred.
【００１８】本発明において使用される一般式（II）で
示されるオルガノハイドロシランにおいて、R4、R5及び
R6は、同一または異なった、アルコキシ基又は置換もし
くは非置換の１価炭化水素基を表す。例えばR4、R5及び
R6としては、メトキシ基、エトキシ基、ブトキシ基、フ
ェノキシ基などのアルコキシ基；メチル基、エチル基、
ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソ
ブチル基、sec −ブチル基、tert−ブチル基、ペンチル
基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、
デシル基、ドデシル基のようなアルキル基；シクロペン
チル基、シクロヘキシル基のようなシクロアルキル基；
２−フェニルエチル基、２−フェニルプロピル基のよう
なアラルキル基；フェニル基、トリル基のようなアリー
ル基及びこれらの１価炭化水素基の炭素原子に結合した
水素原子が部分的にハロゲン原子、アミノ基、シアノ
基、アルコキシ基、水酸基などで置換されたクロロメチ
ル基、クロロフェニル基、3,3,3 −トリフルオロプロピ
ル基、アミノエチル基、シアノエチル基、ｏ−メトキシ
フェニル基、ｏ−ヒドロキシフェニル基のような置換炭
化水素基が例示される。これらの中でも原料の入手及び
合成が容易なことから、アルキル基及びアリール基が好
ましく、特にメチル基、エチル基、ｎ−プロピル基、イ
ソプロピル基、ｎ−ブチル基、イソブチル基、 sec−ブ
チル基、tert−ブチル基及びフェニル基が好ましい。In the organohydrosilane represented by the general formula (II) used in the present invention, R 4 , R 5 and
R 6 represents the same or different alkoxy groups or substituted or unsubstituted monovalent hydrocarbon groups. For example, R 4 , R 5 and
R 6 is an alkoxy group such as a methoxy group, an ethoxy group, a butoxy group, and a phenoxy group; a methyl group, an ethyl group,
n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group,
Alkyl groups such as decyl group and dodecyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group;
An aralkyl group such as a 2-phenylethyl group or a 2-phenylpropyl group; an aryl group such as a phenyl group or a tolyl group, and a hydrogen atom bonded to a carbon atom of these monovalent hydrocarbon groups is partially a halogen atom; Chloromethyl group, chlorophenyl group, 3,3,3-trifluoropropyl group, aminoethyl group, cyanoethyl group, o-methoxyphenyl group, o-hydroxyphenyl substituted with amino group, cyano group, alkoxy group, hydroxyl group, etc. Examples are substituted hydrocarbon groups such as groups. Among them, an alkyl group and an aryl group are preferable because of easy availability and synthesis of raw materials, and in particular, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, Tert-butyl and phenyl are preferred.
【００１９】このようなオルガノハイドロシランとして
は、トリメチルシラン、トリエチルシラン、トリ−ｎ−
プロピルシラン、トリイソプロピルシラン、トリ−ｎ−
ブチルシラン、トリイソブチルシラン、トリ−sec −ブ
チルシラン、トリ−tert−ブチルシラン、トリフェニル
シラン、メチルジエチルシラン、ジメチルエチルシラ
ン、メチルジブチルシラン、ジメチルブチルシラン、エ
チルジブチルシラン、ジエチルブチルシラン、メチルジ
フェニルシラン、ジメチルフェニルシラン、エチルジフ
ェニルシラン、ジエチルフェニルシラン、ブチルジフェ
ニルシラン、ジブチルフェニルシラン、メチルエチルブ
チルシラン、メチルエチルフェニルシラン、メチルブチ
ルフェニルシラン、エチルブチルフェニルシラン、メチ
ルジエトキシシラン、ジメチルエトキシシランなどが例
示されるが、これらの中でも入手及び合成が容易なこと
から、トリメチルシラン、トリエチルシラン、トリ−ｎ
−プロピルシラン、トリイソプロピルシラン、トリ−ｎ
−ブチルシラン、トリイソブチルシラン、トリ−sec −
ブチルシラン、トリ−tert−ブチルシラン及びトリフェ
ニルシランが好ましい。As such organohydrosilanes, trimethylsilane, triethylsilane, tri-n-
Propylsilane, triisopropylsilane, tri-n-
Butylsilane, triisobutylsilane, tri-sec-butylsilane, tri-tert-butylsilane, triphenylsilane, methyldiethylsilane, dimethylethylsilane, methyldibutylsilane, dimethylbutylsilane, ethyldibutylsilane, diethylbutylsilane, methyldiphenylsilane, Dimethylphenylsilane, ethyldiphenylsilane, diethylphenylsilane, butyldiphenylsilane, dibutylphenylsilane, methylethylbutylsilane, methylethylphenylsilane, methylbutylphenylsilane, ethylbutylphenylsilane, methyldiethoxysilane, dimethylethoxysilane, etc. Examples include, among these, trimethylsilane, triethylsilane, tri-n
-Propylsilane, triisopropylsilane, tri-n
-Butylsilane, triisobutylsilane, tri-sec-
Butylsilane, tri-tert-butylsilane and triphenylsilane are preferred.
【００２０】本発明において使用されるパラジウム触媒
としては、パラジウム金属の配位化合物、パラジウム金
属粉末、炭素上に担持されたパラジウム金属及びパラジ
ウム塩などがあげられ、配位化合物におけるパラジウム
はいかなる原子価を有していてもよい。これらの触媒と
しては、PdCl2 、PdCl2(PPh3)2、Pd(OCOCH3)2 、PdCl
2(PhCN)2のような均一系触媒、パラジウム−炭素のよう
な不均一系触媒などが例示されるが、これらの中でも回
収、再生が可能な点から、パラジウム−炭素が好まし
い。パラジウム触媒の使用量は特に制限されず、原料の
種類、反応温度、反応時間などを考慮して変えることが
できるが、反応性、経済性の点からオルガノハイドロシ
ランに対して50〜500ppmが好ましい。Palladium catalyst used in the present invention
As a coordination compound of palladium metal, palladium gold
Powder, palladium metal supported on carbon and palladium
Palladium in coordination compounds
May have any valence. With these catalysts
Then, PdClTwo, PdClTwo(PPhThree)Two, Pd (OCOCHThree)Two, PdCl
Two(PhCN)TwoHomogeneous catalysts such as palladium-carbon
Heterogeneous catalysts and the like are exemplified.
Palladium-carbon is preferred because it can be recovered and regenerated.
No. The amount of palladium catalyst used is not particularly limited,
It can be changed considering the type, reaction temperature, reaction time, etc.
Can be used, but from the viewpoint of reactivity and economy
50 to 500 ppm for the run is preferred.
【００２１】また、パラジウム触媒の活性を制御するた
めにパラジウムに対して配位子として作用する配位性化
合物を使用することもできる。このような配位性化合物
としては、トリブチルホスフィンなどのアルキルホスフ
ィン、トリフェニルホスフィンなどのアリールホスフィ
ン等のホスフィン系化合物、及びベンゾニトリル、オク
タジエンなどが例示されるが、これらの中でも比較的優
れた効果を示すことから、ホスフィン系化合物であるこ
とが好ましく、特にトリフェニルホスフィンが好まし
い。配位子の使用量は特に制限されず、配位子の種類、
パラジウム触媒の種類等によって変えることができる
が、効果・経済性の点からパラジウム原子に対して０〜
1.5 当量が好ましい。In order to control the activity of the palladium catalyst, a coordinating compound acting as a ligand for palladium can be used. Examples of such a coordinating compound include alkylphosphines such as tributylphosphine, phosphine compounds such as arylphosphines such as triphenylphosphine, and benzonitrile and octadiene. Thus, a phosphine compound is preferable, and triphenylphosphine is particularly preferable. The amount of the ligand used is not particularly limited, and the type of the ligand,
It can be changed depending on the type of palladium catalyst, etc.
1.5 equivalents are preferred.
【００２２】本発明において使用される非プロトン性極
性溶媒としては、ジメチルスルホキシド（ＤＭＳＯ）、
Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、ヘキサメチ
ルホスホルアミド（ＨＭＰＡ）、ニトロメタン、Ｎ−メ
チルピロリドン、アセトニトリル、アセトン、テトラヒ
ドロフランなどが例示され、これらのうちのいくつかを
混合して使用してもよい。これらの中でも優れた効果を
示すことなどから、Ｎ，Ｎ−ジメチルホルムアミド、ジ
メチルスルホキシド、ヘキサメチルホスホルアミドが好
ましい。なお、反応温度の制御、原料の溶解などのため
に、他の溶媒を併用して反応溶媒とすることは可能であ
り、そのような溶媒としては、例えばベンゼン、トルエ
ン、キシレン、ｎ−ヘキサン、シクロヘキサンなどが挙
げられるが、反応性の点で反応溶媒中に非プロトン性極
性溶媒を５重量％以上含有していることが好ましい。The aprotic polar solvent used in the present invention includes dimethyl sulfoxide (DMSO),
Examples thereof include N, N-dimethylformamide (DMF), hexamethylphosphoramide (HMPA), nitromethane, N-methylpyrrolidone, acetonitrile, acetone, tetrahydrofuran, and the like. Good. Among these, N, N-dimethylformamide, dimethylsulfoxide, and hexamethylphosphoramide are preferred because they exhibit excellent effects. In addition, for controlling the reaction temperature, dissolving the raw materials, and the like, it is possible to use another solvent in combination as a reaction solvent. Examples of such a solvent include benzene, toluene, xylene, n-hexane, and the like. Examples thereof include cyclohexane, and the reaction solvent preferably contains an aprotic polar solvent in an amount of 5% by weight or more in terms of reactivity.
【００２３】また、本発明において使用されるノルボル
ネン化合物とは、分子内に二環式オレフィンのノルボル
ネン骨格を有するものであり、そのような化合物であれ
ば特に限定はないが、ノルボルニレン（ノルボルネ
ン）、５−エチリデン−２−ノルボルネン、５−ビニル
−２−ノルボルネン、ノルボルナジエンなどの二環式オ
レフィン化合物、あるいはジシクロペンタジエンなどの
三環式オレフィン化合物などが例示されるが、副生する
水素の捕捉性や工業的な入手の容易さの点で、ノルボル
ニレン、５−エチリデン−２−ノルボルネン、５−ビニ
ル−２−ノルボルネンが好ましい。ノルボルネン化合物
の使用量は特に制限されず、原料の種類、反応温度、反
応時間などを考慮して変えることができるが、水素の捕
捉性や経済性の点からオルガノハイロドシランに対して
0.5 〜２当量が好ましい。The norbornene compound used in the present invention is a compound having a norbornene skeleton of a bicyclic olefin in the molecule, and is not particularly limited as long as it is such a compound, but is not particularly limited to norbornene (norbornene), Examples thereof include bicyclic olefin compounds such as 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene and norbornadiene, and tricyclic olefin compounds such as dicyclopentadiene. Norbornylene, 5-ethylidene-2-norbornene, and 5-vinyl-2-norbornene are preferred from the viewpoint of industrial availability. The amount of the norbornene compound to be used is not particularly limited and can be changed in consideration of the type of the raw material, the reaction temperature, the reaction time, and the like.
0.5 to 2 equivalents are preferred.
【００２４】本発明の製造方法において、反応温度は40
〜160 ℃、好ましくは70〜120 ℃の範囲である。この温
度範囲内で不飽和カルボン酸をオルガノハイドロシラン
に対して好ましくは当量（モル）以上、２倍当量（モ
ル）以下、更に好ましくは1.1倍当量（モル）以上、1.5
倍当量（モル）以下反応させることにより、副生成物
の発生を抑え、収率良く目的生成物を製造することがで
きる。反応生成物からは、通常の精製方法、例えば蒸留
などにより純度の高い目的生成物を得ることができる。In the production method of the present invention, the reaction temperature is 40
To 160.degree. C., preferably 70 to 120.degree. Within this temperature range, the unsaturated carboxylic acid is preferably at least equivalent (mol) to double equivalent (mol) to organohydrosilane, more preferably at least 1.1 equivalent (mol), and not more than 1.5 equivalent (mol).
By performing the reaction at a double equivalent (mol) or less, generation of by-products can be suppressed, and the target product can be produced with high yield. From the reaction product, a high-purity target product can be obtained by a usual purification method, for example, distillation.
【００２５】また、本発明の製造方法においては、原料
の不飽和カルボン酸や、生成物の不飽和カルボキシレー
トの重合を防止するために、酸素、ヒドロキノン、ｐ−
メトキシフェノールなどの重合防止剤を添加することが
好ましい。また反応中に副生する水素は、窒素ガス、酸
素−窒素混合ガス（空気も含む）、アルゴンガス、ヘリ
ウムガスなどを反応液に吹き込んで系外に除去してもよ
い。Further, in the production method of the present invention, oxygen, hydroquinone, p-type, and the like are used in order to prevent the polymerization of the unsaturated carboxylic acid as the raw material and the unsaturated carboxylate of the product.
It is preferable to add a polymerization inhibitor such as methoxyphenol. Hydrogen by-produced during the reaction may be removed from the system by blowing nitrogen gas, oxygen-nitrogen mixed gas (including air), argon gas, helium gas, or the like into the reaction solution.
【００２６】[0026]
【発明の効果】本発明の製造方法によれば、不飽和カル
ボン酸とオルガノハイドロシランとを反応させ、オルガ
ノシリル不飽和カルボキシレートを製造する際に、オル
ガノシリル飽和カルボキシレートの副生を抑制し、高純
度かつ高収率で得ることができる。According to the production method of the present invention, when an unsaturated carboxylic acid is reacted with an organohydrosilane to produce an organosilyl unsaturated carboxylate, the by-product of the organosilyl saturated carboxylate is suppressed. , High purity and high yield.
【００２７】[0027]
【実施例】以下に実施例および比較例により、本発明を
具体的に説明する。純度および不飽和／飽和比（重量
比）については、ガスクロマトグラフィにより測定し
た。不飽和／飽和比は、本発明の目的化合物であるオル
ガノシリル不飽和カルボキシレートとその二重結合が還
元されたオルガノシリル飽和カルボキシレートとの重量
比である。収率は使用したトリオルガノシランに基づく
収率である。 実施例１ 温度計、攪拌機、還流冷却器を備えたフラスコに、トル
エン1450ｇ、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）
250 ｇ、５％パラジウム−炭素3.2 ｇ（シランに対し20
0ppm）及びノルボルニレン612 ｇ（6.5 モル、シランに
対し1.3 当量）を入れ、窒素雰囲気とした後、攪拌しな
がら90℃まで加熱した。次いで、トリイソプロピルシラ
ン792 ｇ（5.0 モル）、アクリル酸396 ｇ（5.5 モル、
シランに対し1.1 当量）及びｐ−メトキシフェノール2.
0 ｇを１時間かけて滴下し、さらに90℃で３時間加熱攪
拌を行った。The present invention will be specifically described below with reference to examples and comparative examples. The purity and the unsaturated / saturated ratio (weight ratio) were measured by gas chromatography. The unsaturated / saturated ratio is the weight ratio between the organosilyl unsaturated carboxylate, which is the target compound of the present invention, and the organosilyl saturated carboxylate whose double bond has been reduced. The yield is based on the triorganosilane used. Example 1 A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 1450 g of toluene and N, N-dimethylformamide (DMF).
250 g, 5% palladium-carbon 3.2 g (20
0 ppm) and 612 g (6.5 mol, 1.3 equivalents to silane) of norbornylene, and the mixture was heated to 90 ° C. while stirring under a nitrogen atmosphere. Then, 792 g (5.0 mol) of triisopropylsilane and 396 g (5.5 mol,
1.1 equivalents to silane) and p-methoxyphenol 2.
0 g was added dropwise over 1 hour, and the mixture was further heated and stirred at 90 ° C. for 3 hours.
【００２８】その後、室温まで冷却し、パラジウム−炭
素を濾別したのち、減圧蒸留することによってトリイソ
プロピルシリルアクリレート留分1051ｇ（Mw228.4g/mo
l、b.p.85〜87℃／3mmHg 、収率92.0％、純度87.4％）
を得た。不飽和／飽和比＝88.1／11.9であった。 実施例２ 温度計、攪拌機、還流冷却器を備えたフラスコに、トル
エン1450ｇ、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）
250 ｇ、５％パラジウム−炭素3.2 ｇ（シランに対し20
0ppm）及びノルボルニレン612 ｇ（6.5 モル、シランに
対し1.3 当量）を入れ、窒素雰囲気とした後、攪拌しな
がら90℃まで加熱した。次いで、トリ−ｎ−ブチルシラ
ン1002ｇ（5.0 モル）、メタクリル酸474 ｇ（5.5 モ
ル、シランに対し1.1 当量）及びｐ−メトキシフェノー
ル2.0 ｇを１時間かけて滴下し、さらに90℃で３時間加
熱攪拌を行った。Thereafter, the mixture was cooled to room temperature, palladium-carbon was removed by filtration, and the mixture was distilled under reduced pressure, whereby 1051 g of a triisopropylsilyl acrylate fraction (Mw: 228.4 g / mo
l, bp 85-87 ° C / 3mmHg, yield 92.0%, purity 87.4%)
I got Unsaturation / saturation ratio = 88.1 / 11.9. Example 2 A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 1450 g of toluene and N, N-dimethylformamide (DMF).
250 g, 5% palladium-carbon 3.2 g (20
0 ppm) and 612 g (6.5 mol, 1.3 equivalents to silane) of norbornylene, and the mixture was heated to 90 ° C. while stirring under a nitrogen atmosphere. Then, 1002 g (5.0 mol) of tri-n-butylsilane, 474 g (5.5 mol, 1.1 equivalent to silane) of methacrylic acid and 2.0 g of p-methoxyphenol were added dropwise over 1 hour, and the mixture was further heated and stirred at 90 ° C. for 3 hours. Was done.
【００２９】その後、室温まで冷却し、パラジウム−炭
素を濾別したのち、減圧蒸留することによってトリ−ｎ
−ブチルシリルメタクリレート留分1320ｇ（Mw284.5g/m
ol、b.p.115 〜117 ℃／3mmHg 、収率92.8％、純度95.1
％）を得た。不飽和／飽和比＝95.4／4.6 であった。 実施例３ 実施例１において、ノルボルニレンの代わりに５−エチ
リデン−２−ノルボルネン781 ｇ（6.5 モル、シランに
対し1.3 当量）を使用した以外は実施例１と同様に反応
を行った。Thereafter, the mixture was cooled to room temperature, palladium-carbon was filtered off, and then distilled under reduced pressure to obtain tri-n.
-Butylsilyl methacrylate fraction 1320 g (Mw 284.5 g / m
ol, bp 115-117 ° C / 3 mmHg, yield 92.8%, purity 95.1
%). The unsaturated / saturated ratio was 95.4 / 4.6. Example 3 A reaction was carried out in the same manner as in Example 1 except that 781 g (6.5 mol, 1.3 equivalents to silane) of 5-ethylidene-2-norbornene was used instead of norbornylene.
【００３０】そして、減圧蒸留することによってトリイ
ソプロピルシリルアクリレート留分1056ｇ（Mw228.4g/m
ol、b.p.85〜87℃／3mmHg 、収率92.5％、純度86.9％）
を得た。不飽和／飽和比＝87.6／12.4であった。 実施例４ 実施例３において、トリイソプロピルシラン、アクリル
酸及びｐ−メトキシフェノールの混合物の滴下とその後
の加熱攪拌の間、乾燥した酸素−窒素混合ガス（酸素／
窒素＝20／80）を反応液中へバブリングした以外は実施
例３と同様に反応を行った。The mixture was distilled under reduced pressure to obtain a triisopropylsilyl acrylate fraction (1056 g, Mw: 228.4 g / m 2).
ol, bp 85-87 ° C / 3mmHg, yield 92.5%, purity 86.9%)
I got Unsaturation / saturation ratio was 87.6 / 12.4. Example 4 In Example 3, a dry oxygen-nitrogen mixed gas (oxygen / oxygen / gas) was added during the dropwise addition of the mixture of triisopropylsilane, acrylic acid and p-methoxyphenol and the subsequent heating and stirring.
The reaction was carried out in the same manner as in Example 3 except that nitrogen (20/80) was bubbled into the reaction solution.
【００３１】そして、減圧蒸留することによってトリイ
ソプロピルシリルアクリレート留分1062ｇ（Mw228.4g/m
ol、b.p.85〜87℃／3mmHg 、収率93.0％、純度96.8％）
を得た。不飽和／飽和比＝97.8／2.2 であった。 実施例５ 温度計、攪拌機、還流冷却器を備えたフラスコに、トル
エン850 ｇ、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）
850 ｇ、５％パラジウム−炭素3.2 ｇ（シランに対し20
0ppm）及びノルボルナジエン599 ｇ（6.5 モル、シラン
に対し1.3 当量）を入れ、窒素雰囲気とした後、攪拌し
ながら110 ℃まで加熱した。次いで、ジイソプロピル−
ｎ−ブチルシラン861.9 ｇ（5.0 モル）、メタクリル酸
474 ｇ（5.5 モル、シランに対し1.1 当量）及びｐ−メ
トキシフェノール2.0 ｇを１時間かけて滴下し、さらに
110 ℃で３時間加熱攪拌を行った。The mixture was distilled under reduced pressure to obtain a diisopropylsilyl acrylate fraction (1062 g, Mw: 228.4 g / m 2).
ol, bp 85-87 ° C / 3mmHg, yield 93.0%, purity 96.8%)
I got The unsaturated / saturation ratio was 97.8 / 2.2. Example 5 A flask equipped with a thermometer, a stirrer and a reflux condenser was charged with 850 g of toluene and N, N-dimethylformamide (DMF).
850 g, 5% palladium-carbon 3.2 g (20 parts per silane)
0 ppm) and 599 g (6.5 mol, 1.3 equivalents based on silane) of norbornadiene were added, and the mixture was heated to 110 ° C. while stirring under a nitrogen atmosphere. Then, diisopropyl-
861.9 g (5.0 mol) of n-butylsilane, methacrylic acid
474 g (5.5 mol, 1.1 equivalent to silane) and 2.0 g of p-methoxyphenol were added dropwise over 1 hour.
The mixture was heated and stirred at 110 ° C. for 3 hours.
【００３２】その後、室温まで冷却し、パラジウム−炭
素を濾別したのち、減圧蒸留することによってジイソプ
ロピル−ｎ−ブチルシリルメタクリレート留分1197ｇ
（Mw256.5g/mol、b.p.96〜98℃／3mmHg 、収率93.3％、
純度95.2％）を得た。不飽和／飽和比＝95.6／4.4 であ
った。 実施例６ 温度計、攪拌機、還流冷却器を備えたフラスコに、トル
エン850 ｇ、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）
850 ｇ、５％パラジウム−炭素3.2 ｇ（シランに対し20
0ppm）、トリフェニルホスフィン0.39ｇ（パラジウムに
対し１当量）及び５−ビニル−２−ノルボルネン781 ｇ
（6.5 モル、シランに対し1.3 当量）を入れ、窒素雰囲
気とした後、攪拌しながら110 ℃まで加熱した。次い
で、トリフェニルシラン1302ｇ（5.0 モル）、アクリル
酸393 ｇ（5.5 モル、シランに対し1.1 当量）及びｐ−
メトキシフェノール2.0 ｇを１時間かけて滴下し、さら
に110 ℃で３時間加熱攪拌を行った。Thereafter, the mixture was cooled to room temperature, palladium-carbon was filtered off, and then distilled under reduced pressure to obtain 1197 g of a diisopropyl-n-butylsilyl methacrylate fraction.
(Mw 256.5 g / mol, bp 96-98 ° C./3 mmHg, yield 93.3%,
Purity 95.2%). The unsaturated / saturated ratio was 95.6 / 4.4. Example 6 A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 850 g of toluene and N, N-dimethylformamide (DMF).
850 g, 5% palladium-carbon 3.2 g (20 parts per silane)
0 ppm), 0.39 g of triphenylphosphine (1 equivalent to palladium) and 781 g of 5-vinyl-2-norbornene
(6.5 mol, 1.3 equivalents to silane), and the mixture was heated to 110 ° C. while stirring under a nitrogen atmosphere. Then, 1302 g (5.0 mol) of triphenylsilane, 393 g (5.5 mol, 1.1 equivalents to silane) of acrylic acid and p-
2.0 g of methoxyphenol was added dropwise over 1 hour, and the mixture was further heated and stirred at 110 ° C. for 3 hours.
【００３３】その後、室温まで冷却し、パラジウム−炭
素を濾別したのち、減圧蒸留することによってトリフェ
ニルシリルアクリレート留分1517ｇ（Mw330.5g/mol、b.
p.135 〜145 ℃／2mmHg 、収率91.8％、純度95.5％）を
得た。不飽和／飽和比＝97.2／2.8 であった。 比較例１ 実施例１において、ノルボルニレンを使用しない以外は
実施例１と同様に反応を行った。そして、減圧蒸留する
ことによってトリイソプロピルシリルアクリレート留分
1036ｇ（Mw228.4g/mol、b.p.85〜87℃／3mmHg 、収率9
0.7％、純度15.3％）を得た。不飽和／飽和比＝17.2／8
2.8であった。 比較例２ 実施例１において、ノルボルニレンの代わりに酢酸ビニ
ル560 ｇ(6.5モル、シランに対し1.3 当量) を使用した
以外は実施例１と同様に反応を行った。Thereafter, the mixture was cooled to room temperature, palladium-carbon was removed by filtration, and then distilled under reduced pressure to obtain a triphenylsilyl acrylate fraction of 1517 g (Mw: 330.5 g / mol, b.
135-145 ° C / 2 mmHg, yield 91.8%, purity 95.5%). The unsaturated / saturated ratio was 97.2 / 2.8. Comparative Example 1 The reaction was performed in the same manner as in Example 1 except that no norbornylene was used. Then, the triisopropylsilyl acrylate fraction is distilled under reduced pressure.
1036 g (Mw 228.4 g / mol, bp 85-87 ° C./3 mmHg, yield 9
0.7%, purity 15.3%). Unsaturation / saturation ratio = 17.2 / 8
It was 2.8. Comparative Example 2 A reaction was carried out in the same manner as in Example 1 except that 560 g (6.5 mol, 1.3 equivalents to silane) of vinyl acetate was used instead of norbornylene.
【００３４】そして、減圧蒸留することによってトリイ
ソプロピルシリルアクリレート留分1022ｇ（Mw228.4g/m
ol、b.p.85〜87℃／3mmHg 、収率89.5％、純度42.7％）
を得た。不飽和／飽和比＝44.3／55.7であった。 比較例３ 実施例１において、ノルボルニレンの代わりにアクリル
酸エチル651 ｇ（6.5モル、シランに対し1.3 当量）を
使用した以外は実施例１と同様に反応を行った。この
際、加熱攪拌の終点付近において、パラジウム−炭素が
凝集し、フラスコの壁面や攪拌羽に付着した。The mixture was distilled under reduced pressure to obtain a triisopropylsilyl acrylate fraction (1022 g, Mw: 228.4 g / m 2).
ol, bp 85-87 ° C / 3mmHg, yield 89.5%, purity 42.7%)
I got Unsaturation / saturation ratio was 44.3 / 55.7. Comparative Example 3 A reaction was carried out in the same manner as in Example 1 except that 651 g of ethyl acrylate (6.5 mol, 1.3 equivalents to silane) was used instead of norbornylene. At this time, near the end point of the heating and stirring, the palladium-carbon aggregated and adhered to the wall surface of the flask and the stirring blade.
【００３５】そして、減圧蒸留を行った結果、トリイソ
プロピルシリルアクリレート563g（Mw228.4g/mol、b.p.
85〜87℃／3mmHg 、収率49.3％、純度66.8％）が得られ
た。不飽和／飽和比＝69.2／30.8であった。なお、この
減圧蒸留の際に重合が併発したため、多量の重合体を蒸
留残渣として回収した。Then, as a result of vacuum distillation, 563 g of triisopropylsilyl acrylate (Mw: 228.4 g / mol, bp
85-87 ° C / 3 mmHg, yield 49.3%, purity 66.8%). Unsaturation / saturation ratio was 69.2 / 30.8. In addition, a large amount of the polymer was recovered as a distillation residue because polymerization occurred simultaneously during the distillation under reduced pressure.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4H039 CA92 CD10 4H049 VN01 VP01 VQ02 VQ20 VR23 VR41 VS02 VT17 VT39 VV12 VW02 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4H039 CA92 CD10 4H049 VN01 VP01 VQ02 VQ20 VR23 VR41 VS02 VT17 VT39 VV12 VW02
Claims (4)
子、ハロゲン原子又は置換もしくは非置換の１価の炭化
水素基を表す）で示される不飽和カルボン酸と、一般式
（II）； 【化２】 （式中、R4、R5及びR6は、同一または異なった、アルコ
キシ基又は置換もしくは非置換の１価炭化水素基を表
す）で示されるオルガノハイドロシランとを、パラジウ
ム触媒、非プロトン性極性溶媒及びノルボルネン化合物
の存在下に反応させることを特徴とする、一般式（II
I)； 【化３】 （式中、R1〜R6は前述の通り）で示されるオルガノシリ
ル不飽和カルボキシレートの製造方法。1. A compound of the general formula (I): Wherein R 1 , R 2 and R 3 are the same or different and represent a hydrogen atom, a halogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and an unsaturated carboxylic acid represented by the general formula: (II); Wherein R 4 , R 5 and R 6 are the same or different and represent an alkoxy group or a substituted or unsubstituted monovalent hydrocarbon group, and a palladium catalyst, an aprotic The reaction is carried out in the presence of a polar solvent and a norbornene compound.
I); (Wherein, R 1 to R 6 are as described above).
５−エチリデン−２−ノルボルネン、５−ビニル−２−
ノルボルネン、ノルボルナジエンおよびジシクロペンタ
ジエンから選択される化合物である請求項１記載のオル
ガノシリル不飽和カルボキシレートの製造方法。2. The norbornene compound is norbornylene,
5-ethylidene-2-norbornene, 5-vinyl-2-
The method for producing an organosilyl unsaturated carboxylate according to claim 1, which is a compound selected from norbornene, norbornadiene and dicyclopentadiene.
る請求項１記載のオルガノシリル不飽和カルボキシレー
トの製造方法。3. The method for producing an organosilyl unsaturated carboxylate according to claim 1, wherein the palladium catalyst is palladium-carbon.
アミドである請求項１記載のオルガノシリル不飽和カル
ボキシレートの製造方法。4. The process for producing an organosilyl unsaturated carboxylate according to claim 1, wherein the aprotic polar solvent is dimethylformamide.
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|---|---|---|---|
| JP30348699A JP2001122883A (en) | 1999-10-26 | 1999-10-26 | Method for producing organosilyl unsaturated carboxylate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30348699A JP2001122883A (en) | 1999-10-26 | 1999-10-26 | Method for producing organosilyl unsaturated carboxylate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009078394A1 (en) * | 2007-12-19 | 2009-06-25 | Dow Corning Toray Co., Ltd. | 4-hydroxyphenylalkylamine derivative |
| CN108840882A (en) * | 2018-06-15 | 2018-11-20 | 扬州三友合成化工有限公司 | A kind of preparation method of triisopropylsilyl acrylate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6485981A (en) * | 1987-09-28 | 1989-03-30 | Toshiba Silicone | Vinylsilane compound |
| JPH10212293A (en) * | 1997-01-31 | 1998-08-11 | Nitto Kasei Co Ltd | Production of polymerizable triorganosilyl unsaturated carboxylate |
| JPH1135630A (en) * | 1997-05-20 | 1999-02-09 | Kanegafuchi Chem Ind Co Ltd | Promotion of hydrosilylation |
-
1999
- 1999-10-26 JP JP30348699A patent/JP2001122883A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6485981A (en) * | 1987-09-28 | 1989-03-30 | Toshiba Silicone | Vinylsilane compound |
| JPH10212293A (en) * | 1997-01-31 | 1998-08-11 | Nitto Kasei Co Ltd | Production of polymerizable triorganosilyl unsaturated carboxylate |
| JPH1135630A (en) * | 1997-05-20 | 1999-02-09 | Kanegafuchi Chem Ind Co Ltd | Promotion of hydrosilylation |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009078394A1 (en) * | 2007-12-19 | 2009-06-25 | Dow Corning Toray Co., Ltd. | 4-hydroxyphenylalkylamine derivative |
| CN101903332A (en) * | 2007-12-19 | 2010-12-01 | 道康宁东丽株式会社 | 4-hydroxyphenylalkylamine derivative |
| US8624064B2 (en) | 2007-12-19 | 2014-01-07 | Dow Corning Toray Company, Ltd. | 4-hydroxyphenylalkylamine derivative |
| CN108840882A (en) * | 2018-06-15 | 2018-11-20 | 扬州三友合成化工有限公司 | A kind of preparation method of triisopropylsilyl acrylate |
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