KR100306574B1 - Dehydrohalogenative coupling reaction of alkyl halides with silane - Google Patents
Dehydrohalogenative coupling reaction of alkyl halides with silane Download PDFInfo
- Publication number
- KR100306574B1 KR100306574B1 KR1019990013006A KR19990013006A KR100306574B1 KR 100306574 B1 KR100306574 B1 KR 100306574B1 KR 1019990013006 A KR1019990013006 A KR 1019990013006A KR 19990013006 A KR19990013006 A KR 19990013006A KR 100306574 B1 KR100306574 B1 KR 100306574B1
- Authority
- KR
- South Korea
- Prior art keywords
- mmol
- formula
- reaction
- trichlorosilane
- yield
- Prior art date
Links
- 229910000077 silane Inorganic materials 0.000 title claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title description 5
- 150000001350 alkyl halides Chemical class 0.000 title 1
- 238000005859 coupling reaction Methods 0.000 title 1
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 20
- -1 chlorosilane compound Chemical class 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 150000002896 organic halogen compounds Chemical class 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 71
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 8
- 125000001246 bromo group Chemical group Br* 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 238000006704 dehydrohalogenation reaction Methods 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 125000001188 haloalkyl group Chemical group 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 abstract description 4
- 239000010703 silicon Substances 0.000 abstract description 4
- 239000005046 Chlorosilane Substances 0.000 abstract description 3
- 238000005695 dehalogenation reaction Methods 0.000 abstract description 3
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 43
- 239000005052 trichlorosilane Substances 0.000 description 43
- 238000009835 boiling Methods 0.000 description 32
- 229910001220 stainless steel Inorganic materials 0.000 description 31
- 239000010935 stainless steel Substances 0.000 description 31
- 238000005160 1H NMR spectroscopy Methods 0.000 description 30
- 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 20
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 12
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 10
- 229940073608 benzyl chloride Drugs 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 10
- 239000005047 Allyltrichlorosilane Substances 0.000 description 8
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 8
- HKFSBKQQYCMCKO-UHFFFAOYSA-N trichloro(prop-2-enyl)silane Chemical compound Cl[Si](Cl)(Cl)CC=C HKFSBKQQYCMCKO-UHFFFAOYSA-N 0.000 description 8
- MLRVZFYXUZQSRU-UHFFFAOYSA-N 1-chlorohexane Chemical compound CCCCCCCl MLRVZFYXUZQSRU-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 description 6
- 239000005048 methyldichlorosilane Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- 150000003961 organosilicon compounds Chemical class 0.000 description 5
- 238000007033 dehydrochlorination reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 125000005270 trialkylamine group Chemical group 0.000 description 4
- MLDKTCCADNRZEK-UHFFFAOYSA-N trichloro(3-trichlorosilylpropyl)silane Chemical compound Cl[Si](Cl)(Cl)CCC[Si](Cl)(Cl)Cl MLDKTCCADNRZEK-UHFFFAOYSA-N 0.000 description 4
- ABDDAHLAEXNYRC-UHFFFAOYSA-N trichloro(trichlorosilylmethyl)silane Chemical compound Cl[Si](Cl)(Cl)C[Si](Cl)(Cl)Cl ABDDAHLAEXNYRC-UHFFFAOYSA-N 0.000 description 4
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 4
- 229940094989 trimethylsilane Drugs 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 3
- NZWWDFFNRDNYFO-UHFFFAOYSA-N benzyl-dichloro-methylsilane Chemical compound C[Si](Cl)(Cl)CC1=CC=CC=C1 NZWWDFFNRDNYFO-UHFFFAOYSA-N 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- LFXJGGDONSCPOF-UHFFFAOYSA-N trichloro(hexyl)silane Chemical compound CCCCCC[Si](Cl)(Cl)Cl LFXJGGDONSCPOF-UHFFFAOYSA-N 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- FMGGHNGKHRCJLL-UHFFFAOYSA-N 1,2-bis(chloromethyl)benzene Chemical compound ClCC1=CC=CC=C1CCl FMGGHNGKHRCJLL-UHFFFAOYSA-N 0.000 description 2
- YHRUOJUYPBUZOS-UHFFFAOYSA-N 1,3-dichloropropane Chemical compound ClCCCCl YHRUOJUYPBUZOS-UHFFFAOYSA-N 0.000 description 2
- ZZHIDJWUJRKHGX-UHFFFAOYSA-N 1,4-bis(chloromethyl)benzene Chemical compound ClCC1=CC=C(CCl)C=C1 ZZHIDJWUJRKHGX-UHFFFAOYSA-N 0.000 description 2
- KJDRSWPQXHESDQ-UHFFFAOYSA-N 1,4-dichlorobutane Chemical compound ClCCCCCl KJDRSWPQXHESDQ-UHFFFAOYSA-N 0.000 description 2
- IZXWCDITFDNEBY-UHFFFAOYSA-N 1-(chloromethyl)-4-fluorobenzene Chemical compound FC1=CC=C(CCl)C=C1 IZXWCDITFDNEBY-UHFFFAOYSA-N 0.000 description 2
- MOHYOXXOKFQHDC-UHFFFAOYSA-N 1-(chloromethyl)-4-methoxybenzene Chemical compound COC1=CC=C(CCl)C=C1 MOHYOXXOKFQHDC-UHFFFAOYSA-N 0.000 description 2
- HLQZCRVEEQKNMS-UHFFFAOYSA-N 1-(chloromethyl)-4-phenylbenzene Chemical compound C1=CC(CCl)=CC=C1C1=CC=CC=C1 HLQZCRVEEQKNMS-UHFFFAOYSA-N 0.000 description 2
- JQZAEUFPPSRDOP-UHFFFAOYSA-N 1-chloro-4-(chloromethyl)benzene Chemical compound ClCC1=CC=C(Cl)C=C1 JQZAEUFPPSRDOP-UHFFFAOYSA-N 0.000 description 2
- HPWWMXONAIDFQW-UHFFFAOYSA-N 2-chloroethyl(trimethyl)silane Chemical compound C[Si](C)(C)CCCl HPWWMXONAIDFQW-UHFFFAOYSA-N 0.000 description 2
- ZPIFKCVYZBVZIV-UHFFFAOYSA-N 3-chloro-1,1,1-trifluoropropane Chemical compound FC(F)(F)CCCl ZPIFKCVYZBVZIV-UHFFFAOYSA-N 0.000 description 2
- QXDDDCNYAAJLBT-UHFFFAOYSA-N 3-chloropropyl(trimethyl)silane Chemical compound C[Si](C)(C)CCCCl QXDDDCNYAAJLBT-UHFFFAOYSA-N 0.000 description 2
- MFESCIUQSIBMSM-UHFFFAOYSA-N I-BCP Chemical compound ClCCCBr MFESCIUQSIBMSM-UHFFFAOYSA-N 0.000 description 2
- FYTPGBJPTDQJCG-UHFFFAOYSA-N Trichloro(chloromethyl)silane Chemical compound ClC[Si](Cl)(Cl)Cl FYTPGBJPTDQJCG-UHFFFAOYSA-N 0.000 description 2
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- ZJDOJJKRTWHPOY-UHFFFAOYSA-N but-2-enyl(trichloro)silane Chemical compound CC=CC[Si](Cl)(Cl)Cl ZJDOJJKRTWHPOY-UHFFFAOYSA-N 0.000 description 2
- ITKVLPYNJQOCPW-UHFFFAOYSA-N chloro-(chloromethyl)-dimethylsilane Chemical compound C[Si](C)(Cl)CCl ITKVLPYNJQOCPW-UHFFFAOYSA-N 0.000 description 2
- KBZVJUSTKXSFCR-UHFFFAOYSA-N chloro-(dichlorosilylmethyl)-dimethylsilane Chemical compound C[Si](C)(Cl)C[SiH](Cl)Cl KBZVJUSTKXSFCR-UHFFFAOYSA-N 0.000 description 2
- YTKRILODNOEEPX-NSCUHMNNSA-N crotyl chloride Chemical compound C\C=C\CCl YTKRILODNOEEPX-NSCUHMNNSA-N 0.000 description 2
- NYKYPUSQZAJABL-UHFFFAOYSA-N dichloro(hexyl)silane Chemical compound CCCCCC[SiH](Cl)Cl NYKYPUSQZAJABL-UHFFFAOYSA-N 0.000 description 2
- MJVFSDBAXDCTOC-UHFFFAOYSA-N dichloro(prop-2-enyl)silicon Chemical compound Cl[Si](Cl)CC=C MJVFSDBAXDCTOC-UHFFFAOYSA-N 0.000 description 2
- JAYBZWYBCUJLNQ-UHFFFAOYSA-N dichloro-(chloromethyl)-methylsilane Chemical compound C[Si](Cl)(Cl)CCl JAYBZWYBCUJLNQ-UHFFFAOYSA-N 0.000 description 2
- LOFPLWQPZAOILI-UHFFFAOYSA-N dichloro-(dichlorosilylmethyl)-methylsilane Chemical compound C[Si](Cl)(Cl)C[SiH](Cl)Cl LOFPLWQPZAOILI-UHFFFAOYSA-N 0.000 description 2
- YCEQUKAYVABWTE-UHFFFAOYSA-N dichloro-methyl-prop-2-enylsilane Chemical compound C[Si](Cl)(Cl)CC=C YCEQUKAYVABWTE-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000002894 organic compounds Chemical group 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].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.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000005053 propyltrichlorosilane Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- WDVUXWDZTPZIIE-UHFFFAOYSA-N trichloro(2-trichlorosilylethyl)silane Chemical compound Cl[Si](Cl)(Cl)CC[Si](Cl)(Cl)Cl WDVUXWDZTPZIIE-UHFFFAOYSA-N 0.000 description 2
- WEUBQNJHVBMUMD-UHFFFAOYSA-N trichloro(3,3,3-trifluoropropyl)silane Chemical compound FC(F)(F)CC[Si](Cl)(Cl)Cl WEUBQNJHVBMUMD-UHFFFAOYSA-N 0.000 description 2
- ZTNLXKSEJCGJRH-UHFFFAOYSA-N trichloro(dichlorosilylmethyl)silane Chemical compound Cl[SiH](Cl)C[Si](Cl)(Cl)Cl ZTNLXKSEJCGJRH-UHFFFAOYSA-N 0.000 description 2
- DOEHJNBEOVLHGL-UHFFFAOYSA-N trichloro(propyl)silane Chemical compound CCC[Si](Cl)(Cl)Cl DOEHJNBEOVLHGL-UHFFFAOYSA-N 0.000 description 2
- JOTSLPSOZKUZIU-UHFFFAOYSA-N trichloro(trimethylsilylmethyl)silane Chemical compound C[Si](C)(C)C[Si](Cl)(Cl)Cl JOTSLPSOZKUZIU-UHFFFAOYSA-N 0.000 description 2
- CQHJBQDGWRDUML-UHFFFAOYSA-N trichloro-[(4-chlorophenyl)methyl]silane Chemical compound ClC1=CC=C(C[Si](Cl)(Cl)Cl)C=C1 CQHJBQDGWRDUML-UHFFFAOYSA-N 0.000 description 2
- RUDCZOITHPYDRZ-UHFFFAOYSA-N trichloro-[(4-fluorophenyl)methyl]silane Chemical compound FC1=CC=C(C[Si](Cl)(Cl)Cl)C=C1 RUDCZOITHPYDRZ-UHFFFAOYSA-N 0.000 description 2
- CDVJPOXUZPVGOJ-UHFFFAOYSA-N trichloro-[(4-methoxyphenyl)methyl]silane Chemical compound COC1=CC=C(C[Si](Cl)(Cl)Cl)C=C1 CDVJPOXUZPVGOJ-UHFFFAOYSA-N 0.000 description 2
- GUAVBESCPOPILP-UHFFFAOYSA-N trichloro-[(4-phenylphenyl)methyl]silane Chemical compound C1=CC(C[Si](Cl)(Cl)Cl)=CC=C1C1=CC=CC=C1 GUAVBESCPOPILP-UHFFFAOYSA-N 0.000 description 2
- MFRSILUPXHDCGQ-UHFFFAOYSA-N trichloro-[[2-(chloromethyl)phenyl]methyl]silane Chemical compound ClCC1=CC=CC=C1C[Si](Cl)(Cl)Cl MFRSILUPXHDCGQ-UHFFFAOYSA-N 0.000 description 2
- QOUJYSRCDNANNE-UHFFFAOYSA-N trichloro-[[4-(chloromethyl)phenyl]methyl]silane Chemical compound ClCC1=CC=C(C[Si](Cl)(Cl)Cl)C=C1 QOUJYSRCDNANNE-UHFFFAOYSA-N 0.000 description 2
- JKILEHKJCUCORS-UHFFFAOYSA-N trichloro-[[4-(trichlorosilylmethyl)phenyl]methyl]silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=C(C[Si](Cl)(Cl)Cl)C=C1 JKILEHKJCUCORS-UHFFFAOYSA-N 0.000 description 2
- GJIIJSWYRBEOCZ-UHFFFAOYSA-N trichloro-[[chloro(dimethyl)silyl]methyl]silane Chemical compound C[Si](C)(Cl)C[Si](Cl)(Cl)Cl GJIIJSWYRBEOCZ-UHFFFAOYSA-N 0.000 description 2
- ABVUXBPCPLBFHM-UHFFFAOYSA-N trichloro-[[dichloro(methyl)silyl]methyl]silane Chemical compound C[Si](Cl)(Cl)C[Si](Cl)(Cl)Cl ABVUXBPCPLBFHM-UHFFFAOYSA-N 0.000 description 2
- PPDADIYYMSXQJK-UHFFFAOYSA-N trichlorosilicon Chemical group Cl[Si](Cl)Cl PPDADIYYMSXQJK-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DOJYIHBHHDTFPH-UHFFFAOYSA-N N(Cl)(Cl)Cl.Cl Chemical compound N(Cl)(Cl)Cl.Cl DOJYIHBHHDTFPH-UHFFFAOYSA-N 0.000 description 1
- XRBZWUQAUXLFDY-UHFFFAOYSA-N benzyl(dichloro)silane Chemical compound Cl[SiH](Cl)CC1=CC=CC=C1 XRBZWUQAUXLFDY-UHFFFAOYSA-N 0.000 description 1
- JOYFJVNRFXOGFH-UHFFFAOYSA-N bis(trichlorosilyl)methyl-trichlorosilane Chemical compound Cl[Si](Cl)(Cl)C([Si](Cl)(Cl)Cl)[Si](Cl)(Cl)Cl JOYFJVNRFXOGFH-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- MIHBEVRKYFBXIK-UHFFFAOYSA-N chloro-(2-chloroethyl)-dimethylsilane Chemical compound C[Si](C)(Cl)CCCl MIHBEVRKYFBXIK-UHFFFAOYSA-N 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- OOCUOKHIVGWCTJ-UHFFFAOYSA-N chloromethyl(trimethyl)silane Chemical compound C[Si](C)(C)CCl OOCUOKHIVGWCTJ-UHFFFAOYSA-N 0.000 description 1
- DGUPEYLBWVTFTE-UHFFFAOYSA-N chlorosilylmethyl(trimethyl)silane Chemical compound C[Si](C)(C)C[SiH2]Cl DGUPEYLBWVTFTE-UHFFFAOYSA-N 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- KKRMHVJQWMXYBZ-UHFFFAOYSA-N dichloro-hexyl-methylsilane Chemical compound CCCCCC[Si](C)(Cl)Cl KKRMHVJQWMXYBZ-UHFFFAOYSA-N 0.000 description 1
- LZJINVYTYPELPM-UHFFFAOYSA-N dichlorosilylmethyl(trimethyl)silane Chemical compound C[Si](C)(C)C[SiH](Cl)Cl LZJINVYTYPELPM-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- OOXSLJBUMMHDKW-UHFFFAOYSA-N trichloro(3-chloropropyl)silane Chemical compound ClCCC[Si](Cl)(Cl)Cl OOXSLJBUMMHDKW-UHFFFAOYSA-N 0.000 description 1
- OBQPCBCKBUQQHH-UHFFFAOYSA-N trichloro(3-trichlorosilylbutan-2-yl)silane Chemical compound Cl[Si](Cl)(Cl)C(C)C(C)[Si](Cl)(Cl)Cl OBQPCBCKBUQQHH-UHFFFAOYSA-N 0.000 description 1
- MMJWAVCCBPOYAP-UHFFFAOYSA-N trichloro(4-trichlorosilylbutyl)silane Chemical compound Cl[Si](Cl)(Cl)CCCC[Si](Cl)(Cl)Cl MMJWAVCCBPOYAP-UHFFFAOYSA-N 0.000 description 1
- YWUUHVWMPSPGQO-UHFFFAOYSA-N trichloro(trichloromethyl)silane Chemical compound ClC(Cl)(Cl)[Si](Cl)(Cl)Cl YWUUHVWMPSPGQO-UHFFFAOYSA-N 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
- C07F7/14—Preparation thereof from optionally substituted halogenated silanes and hydrocarbons hydrosilylation reactions
Abstract
3차 유기 포스핀 촉매 존재 하에, 수소-규소 결합을 갖는 다음 화학식 1의 클로로실란 화합물과 화학식 2의 유기 할로겐 화합물을 탈할로겐화수소 반응으로 결합시켜 화학식 3의 화합물들을 제조하는 방법이 제공된다.In the presence of a tertiary organic phosphine catalyst, a method of preparing the compounds of formula 3 is provided by combining a chlorosilane compound of formula 1 having an hydrogen-silicon bond with an organic halogen compound of formula 2 by a dehalogenation reaction.
HSiR1Cl2+ R2CH2R3CH2SiR1Cl2+ HXHSiR 1 Cl 2 + R 2 CH 2 R 3 CH 2 SiR 1 Cl 2 + HX
(1) (2) (3)(1) (2) (3)
(식 중, R1, X, R2및 R3는 하기 정의되는 바와 같다)(Wherein R 1 , X, R 2 and R 3 are as defined below)
Description
본 발명은 3차 유기 포스핀 촉매 하에 수소-규소 결합을 갖는 클로로실란 화합물과 유기 할로겐 화합물을 탈할로겐화수소반응에 의해 결합시키는 방법에 관한 것이다.The present invention relates to a method of combining an organic halogen compound with a chlorosilane compound having a hydrogen-silicon bond under a tertiary organic phosphine catalyst by a dehalogenation reaction.
1968년, 벤케서와 스미스는 처음으로 트리클로로실란과 트리알킬아민의 1:1 혼합물로 사염화탄소를 클로로포름으로 환원시키는 반응을 보고하였다 (Benkeser, R.A.; Smith, W. E.J. Am. Chem. Soc.1968, 90, 5307). 이 환원반응은 트리클로로실란과 사염화탄소 및 트리알킬아민이 반응하여 염화수소가 빠지는 반응을 일으켜 트리클로로메틸트리클로로실란이 형성되었다가 트리알킬암모늄 클로라이드에 의해 클로로포름과 테트라클로로실란으로 분해된다고 보고되었다. 벤케서와 그의 공동연구자들은 1969년에 다시 벤질 클로라이드와 1,1,1-트리클로로에탄이 트리클로로실란과 트리알킬아민의 1:1 혼합물과 반응하여 탈염화수소반응으로 클로로 대신 트리클로로실릴기가 치환된 화합물이 생성된다고 보고하였다 (Benkeser, R.A.; Gaul, J. M.; Smith, W.E.,J. Am. Chem. Soc. 1969, 91, 3666).In 1968, Benkeser and Smith reported for the first time the reaction of reducing carbon tetrachloride to chloroform with a 1: 1 mixture of trichlorosilane and trialkylamine (Benkeser, RA; Smith, WE J. Am. Chem. Soc. 1968 , 90, 5307). It has been reported that trichlorosilane reacts with carbon tetrachloride and trialkylamine to release hydrogen chloride, forming trichloromethyltrichlorosilane, which is then decomposed into trichloroammonium chloride by chloroform and tetrachlorosilane. Benkeser and his co-workers reinvented the reaction of benzyl chloride and 1,1,1-trichloroethane with a 1: 1 mixture of trichlorosilane and trialkylamine in 1969, replacing trichlorosilyl groups with dehydrochlorination. Reported compounds (Benkeser, RA; Gaul, JM; Smith, WE, J. Am. Chem. Soc . 1969, 91, 3666).
1975년에는 일본의 후루야와 수카와가 알릴클로라이드에 트리클로로실란과 트리알킬아민의 1:1 혼합물을 반응시키는데 구리염화물을 촉매로 사용하면 높은 수율로 알릴트리클로로실란이 얻어진다고 보고하였다 (Furuya, N.; Sukawa, T.,J. Organometal. Chem.1985, 96, C1).In 1975, Furuya and Sukawa of Japan reported a 1: 1 mixture of trichlorosilane and trialkylamine with allyl chloride, and copper chloride was used as a catalyst to obtain allyl trichlorosilane in high yield (Furuya, N .; Sukawa, T., J. Organometal.Chem. 1985, 96, C1).
최근, 프랑스의 꼬류와 그의 공동연구자들은 과량의 트리부틸아민을 사용하여 클로로포름과 트리클로로실란을 반응시켜 비스(트리클로로실릴)메탄과 트리스(트리클로로실릴)메탄을 합성하였다고 보고하였다 (Corriur, R. J. P.: Granier, M.; Lanneau, G.F.J. Organometal. Chem.1998, 562, 79).Recently, French pods and their co-workers reported the synthesis of bis (trichlorosilyl) methane and tris (trichlorosilyl) methane by reacting chloroform with trichlorosilane using excess tributylamine (Corriur, RJP Granier, M .; Lanneau, GF J. Organometal.Chem. 1998, 562, 79).
상기 종래기술에 따르면 클로로메틸기를 갖는 유기규소화합물이 유기염기 존재 하에서 트리클로로실란과 반응하여 탈염화수소반응으로 결합한다는 것을 알 수 있다.According to the prior art, it can be seen that the organosilicon compound having a chloromethyl group is reacted with trichlorosilane in the presence of an organic base to bind with a dehydrochlorination reaction.
이 탈염화수소반응은 탄소와 규소의 결합을 형성시키는 새로운 반응으로 유기규소화합물을 합성하는데 매우 유용한 반응이다. 그러나 벤질클로라이드나 알릴클로라이드와 같은 활성화된 염화알칸이 트리클로로실란과 탈염화수소반응으로 결합한다는 보고는 있으나 단순한 염화알칸이 이와 같은 반응을 한다는 것은 이제까지 보고된 바 없다. 이 반응에서도 강한 염기성을 갖는 3차 아민이 과량으로 사용되므로 이 반응에서 아민을 촉매라고 하기보다는 염화수소를 잡아주는 반응물질이라고 보는 것이 타당하다. 이것은 염화수소를 중화하고 아민을 회수하는데 많은 비용이 들어 공업적으로 많이 활용되기 어렵다. 따라서, 아민을 소량 사용하여 반응시키거나 다른 촉매를 찾는 것이 이 공정의 경제성을 높이는 관건이 된다.This dehydrochlorination reaction is a new reaction that forms a bond between carbon and silicon and is very useful for synthesizing organosilicon compounds. However, although it has been reported that activated alkane chlorides such as benzyl chloride and allyl chloride are combined with trichlorosilane in a dehydrochlorination reaction, it has never been reported that simple alkane chloride reacts as such. In this reaction, since the tertiary amine having a strong basicity is used in excess, it is reasonable to regard the amine as a reactant that catches hydrogen chloride rather than a catalyst in this reaction. It is expensive to neutralize hydrogen chloride and recover amines, making it difficult for industrial use. Therefore, using a small amount of amine to react or finding another catalyst is the key to increasing the economics of this process.
본 발명자들은 상기한 종래기술의 문제점을 해결하고자 연구하던 중, 3차 유기 포스핀을 촉매로 사용하여 수소-규소 결합을 갖는 화학식 1의 클로로실란 화합물과 화학식 2의 유기 할로겐 화합물을 탈할로겐화수소 반응으로 결합시킴으로써 화학식 3의 화합물들을 제조할 수 있음을 발견하였다. 이를 다음 반응식 1에 나타내었다.The present inventors have been studying to solve the above problems of the prior art, using a tertiary organic phosphine as a catalyst to dehydrohalogenation reaction of the chlorosilane compound of Formula 1 and the organic halogen compound of Formula 2 having a hydrogen-silicon bond It was found that the compounds of the formula 3 can be prepared by binding to. This is shown in Scheme 1 below.
화학식 1Formula 1
HSiR1Cl2 HSiR 1 Cl 2
화학식 2Formula 2
R2CH2XR 2 CH 2 X
화학식 3Formula 3
R3CH2SiR1Cl2 R 3 CH 2 SiR 1 Cl 2
(1) (2) (3)(1) (2) (3)
[화학식 1 및 화학식 3에서, R1은 수소, 클로로 또는 메틸기;[Formula 1 and Formula 3, R 1 is hydrogen, chloro or methyl group;
화학식 2에서 X는 클로로 또는 브로모;X in formula 2 is chloro or bromo;
화학식 2 및 화학식 3에서 R2및 R3는 탄소수 1 내지 17개의 알킬기, 플루오로가 1개 이상 치환된 탄소수 1 내지 10개의 알킬기, 불포화 결합을 함유하는 탄소수 1 내지 5개의 알켄기, (CH2)nSiMe3-mClm으로 표시되는 알킬기 (이 때 n은 0 내지 2의 정수, m은 0 내지 3의 정수임), Ar(R')q로 표시되는 방향족기 (이 때 Ar은 탄소수 6 내지 14개의 방향족 탄화수소이고 R'은 탄소수 1 내지 4개의 알킬기, 할로겐, 알콕시, 또는 비닐이며, q는 0 내지 5의 정수임), (CH2)pX로 표시되는 할로알킬기 (이 때, p는 1 내지 9의 정수이고 X는 클로로 또는 브로모임), 또는 ArCH2X로 표시되는 할로메틸 방향족기 (이 때 Ar은 탄소수 6 내지 14개의 방향족 탄화수소이고 X는 클로로 또는 브로모임)이고,In Formulas 2 and 3, R 2 and R 3 are each an alkyl group having 1 to 17 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with at least one fluoro, an alken group having 1 to 5 carbon atoms containing an unsaturated bond, and (CH 2 ) n SiMe alkyl group represented by 3-m Cl m (where n is an integer of 0 to 2, m is an integer of 0 to 3), an aromatic group represented by Ar (R ′) q (where Ar is 6 carbon atoms) To 14 aromatic hydrocarbons and R 'is an alkyl group having 1 to 4 carbon atoms, halogen, alkoxy, or vinyl, q is an integer of 0 to 5, and a haloalkyl group represented by (CH 2 ) p X, wherein p is An integer of 1 to 9 and X is chloro or bromo), or a halomethyl aromatic group represented by ArCH 2 X, wherein Ar is an aromatic hydrocarbon having 6 to 14 carbon atoms and X is chloro or bromo,
단, 화학식 2의 R2가 (CH2)pX이거나 ArCH2X인 경우 화학식 3의 R3는 (CH2)pSiR1Cl2이거나 ArCH2SiR1Cl2가 될 수 있다]Provided that when R 2 in Formula 2 is (CH 2 ) p X or ArCH 2 X, R 3 in Formula 3 may be (CH 2 ) p SiR 1 Cl 2 or ArCH 2 SiR 1 Cl 2 ]
즉, 본 발명자들은 유기 아민보다 염기성이 낮은 3차 유기 포스핀 화합물을 촉매로 사용하여 벤질클로라이드나 알릴클로라이드와 같은 활성화된 염화알칸 뿐만 아니라 단순한 유기 할로겐 화합물과 할로겐이 치환된 알킬기를 갖는 유기규소 화합물도 Si-H 결합을 갖는 실란을 탈할로겐화수소 반응으로 결합시키는 방법을 발견하였다. 압력에 견디는 반응조에 화학식 1의 화합물과 화학식 2의 유기 할로겐 화합물 그리고 촉매로 3차 유기 포스핀 화합물을 화학식 2의 화합물에 대해 1 내지 100몰%, 바람직하게는 5 내지 20몰% 정도 넣고 섭씨 10-200℃, 바람직하게는 100 - 200℃로 가열시켜 화학식 3과 같은 유기실란을 합성하였다 (반응식 1 참조).That is, the present inventors use a tertiary organic phosphine compound having a lower basicity than an organic amine as a catalyst, and an organosilicon compound having a simple organic halogen compound and a halogen-substituted alkyl group as well as an activated alkane chloride such as benzyl chloride or allyl chloride. Also found is a method of combining silanes having Si—H bonds in a dehalogenated hydrogen reaction. In a pressure-resistant reactor, a compound of formula 1, an organic halogen compound of formula 2, and a tertiary organic phosphine compound are added in an amount of 1 to 100 mol%, preferably 5 to 20 mol%, based on 10 Organosilanes represented by Formula 3 were synthesized by heating to -200 ° C, preferably 100-200 ° C (see Scheme 1).
3차 유기 포스핀 화합물을 촉매로 사용하여 할로겐 원소가 치환된 유기화합물과 Si-H 결합을 갖는 실란을 반응시켜 화학식 2의 할로겐을 실릴기로 치환시켜 유기규소 화합물을 합성하는 본 발명의 전형적인 합성공정은, 질소 대기하에서 화학식 2와 같은 할로겐이 치환된 유기화합물과 3차 유기 포스핀 화합물이나 3차 유기 포스핀 화합물을 리간드로 갖고 있는 금속염의 촉매를 압력에 견디는 스텐리스 관으로 된 반응조에 넣은 후에 화학식 1의 실란을 넣고 마개를 닫고 반응시키는 것으로 된다. 화학식 1의 실란은 화학식 2의 유기 할로겐에 대하여 몰비로 1-5배 사용한다. 3차 유기 포스핀 화합물 촉매는 화학식 2의 화합물에 대해 1 내지 30 몰%, 바람직하게는 2-10몰%의 양으로 사용한다. 반응 용매는 반응물에 따라서 사용하기도 하고 사용하지 않아도 된다. 반응온도는 10-200℃, 바람직하게는 100-200℃로 유지시키고 1-48시간 정도 교반시킨다. 반응이 끝나면 상압 또는 감압하에서 증류하여 생성물을 분리한다.Typical synthesis process of the present invention using a tertiary organic phosphine compound as a catalyst to react an organic compound substituted with a halogen element and a silane having a Si-H bond to replace an halogen of Formula 2 with a silyl group to synthesize an organosilicon compound In a nitrogen atmosphere, a catalyst of a halogen-substituted organic compound, such as Formula 2, and a metal salt having a tertiary organic phosphine compound or a tertiary organic phosphine compound as a ligand is placed in a stainless steel tube that is pressure-resistant. The silane of Formula 1 is added and the stopper is closed to react. The silane of Formula 1 is used 1-5 times in molar ratio with respect to the organic halogen of Formula 2. The tertiary organic phosphine compound catalyst is used in an amount of 1 to 30 mol%, preferably 2-10 mol%, based on the compound of formula (2). The reaction solvent may or may not be used depending on the reactants. The reaction temperature is maintained at 10-200 ° C., preferably 100-200 ° C. and stirred for 1-48 hours. After the reaction, the product is separated by distillation under normal or reduced pressure.
다음에 실시예를 들어 본 발명을 더욱 상세히 설명하나 본 발명의 범위가 이들 실시예로 한정되는 것은 아니다.The present invention will be described in more detail with reference to the following Examples, but the scope of the present invention is not limited to these Examples.
실시예 1. 1-클로로헥산과 트리클로로실란의 반응Example 1 Reaction of 1-Chlorohexane with Trichlorosilane
오븐에서 건조된 25 ml 들이 스텐리스 관으로 된 반응조를 건조된 질소기체 하에서 냉각시킨 후에 0.15 g (0.75 mmol)의 트리노말부틸포스핀 촉매와 0.90g (7.5 mmol)의 1-클로로헥산 및 5.08g (37.5 mmol)의 트리클로로실란을 넣었다. 반응조의 입구를 마개로 밀봉하고 150℃에서 12시간 동안 교반시켰다. 반응물을 상압에서 증류하여 1.1 g의 n-헥실트리클로로실란 (끓는점 215-219℃, 수율 65%)을 얻었다.The reactor, which was dried in an oven in a 25 ml stainless steel tube, was cooled under a dried nitrogen gas, followed by 0.15 g (0.75 mmol) of trinormalyl phosphine catalyst, 0.90 g (7.5 mmol) of 1-chlorohexane and 5.08 g. (37.5 mmol) trichlorosilane was added. The inlet of the reactor was sealed with a stopper and stirred at 150 ° C. for 12 hours. The reaction was distilled at atmospheric pressure to give 1.1 g of n-hexyltrichlorosilane (boiling point 215-219 ° C., yield 65%).
n-헥실트리클로로실란의 H-NMR (CDCl3, ppm) 0.88-0.94 (m, 3H, CH 3), 1.30-1.45 (m, 6H, (CH 2)4), 1.52-1.63 (m, 2H, SiCH 2)H-NMR of n-hexyltrichlorosilane (CDCl 3 , ppm) 0.88-0.94 (m, 3H, C H 3 ), 1.30-1.45 (m, 6H, (C H 2 ) 4 ), 1.52-1.63 (m , 2H, SiC H 2 )
실시예 2. 1-클로로-3,3,3-트리플루오로프로판과 트리클로로실란의 반응Example 2. Reaction of 1-chloro-3,3,3-trifluoropropane with trichlorosilane
실시예 1과 같은 방법으로 25 ml 들이 스텐리스 관에 0.15 g (0.75 mmol)의 트리노말부틸 포스핀 촉매와 1.33 g (10.0 mmol)의 1-클로로-3,3,3-트리플루오로프로판 및 6.77 g (50.0 mmol)의 트리클로로실란을 넣고 150℃에서 15시간 동안 교반시켰다. 반응물을 상압에서 증류하여 2.1 g의 (3,3,3-트리플루오로프로필)트리클로로실란 (끓는점 114℃, 수율 90%)을 얻었다.In the same manner as in Example 1, 0.15 g (0.75 mmol) of trinormalyl phosphine catalyst and 1.33 g (10.0 mmol) of 1-chloro-3,3,3-trifluoropropane in a 25 ml stainless steel tube; 6.77 g (50.0 mmol) of trichlorosilane was added thereto and stirred at 150 ° C. for 15 hours. The reaction was distilled at atmospheric pressure to give 2.1 g of (3,3,3-trifluoropropyl) trichlorosilane (boiling point 114 ° C., yield 90%).
(3,3,3-트리플루오로프로필)트리클로로실란의 MS (70eV EI) m/z (상대강도); 137(24), 135(71), 133(72), 98(11), 78(87), 77(100), 69(20), 63(21), 59(26), 51(11).MS (70eV EI) m / z (relative intensity) of (3,3,3-trifluoropropyl) trichlorosilane; 137 (24), 135 (71), 133 (72), 98 (11), 78 (87), 77 (100), 69 (20), 63 (21), 59 (26), 51 (11).
실시예 3. 1-클로로헥산과 디클로로실란의 반응Example 3. Reaction of 1-chlorohexane with dichlorosilane
실시예 1과 같은 방법으로 25 ml 들이 스텐리스 관에 0.21 ml (0.86 mmol)의 트리노말부틸포스핀 촉매와 1.18 ml (8.6 mmol)의 1-클로로헥산 및 4.3 g (43 mmol)의 디클로로실란을 넣고 150℃에서 12시간 동안 교반시켰다. 반응물을 상압에서 증류하여 0.93 g의 n-헥실트리클로로실란 (수율 33 %)과 n-헥실디클로로실란 (수율 18%)을 얻었다.In the same manner as in Example 1, 0.21 ml (0.86 mmol) tri-normal butylphosphine catalyst, 1.18 ml (8.6 mmol) 1-chlorohexane and 4.3 g (43 mmol) dichlorosilane were added to a 25 ml stainless steel tube. Put and stirred at 150 ℃ for 12 hours. The reaction was distilled at atmospheric pressure to give 0.93 g of n-hexyltrichlorosilane (yield 33%) and n-hexyldichlorosilane (yield 18%).
n-헥실디클로로실란의 H-NMR (CDCl3, ppm) 0.88-0.94 (m, 3H, CH 3), 1.30-1.45 (m, 6H, (CH 2)4, 1.49-1.60 (m, 2H, SiCH 2), 5.47 (t, J=1.8Hz, 1H, SiH).H-NMR of n-hexyldichlorosilane (CDCl 3 , ppm) 0.88-0.94 (m, 3H, C H 3 ), 1.30-1.45 (m, 6H, (C H 2 ) 4 , 1.49-1.60 (m, 2H , SiC H 2 ), 5.47 (t, J = 1.8 Hz, 1H, Si H ).
실시예 4. 1-클로로헥산과 메틸디클로로실란의 반응Example 4. Reaction of 1-chlorohexane with Methyldichlorosilane
실시예 1과 같은 방법으로 25 ml 들이 스텐리스 관에 0.15 g (0.75 mmol)의 트리노말부틸포스핀 촉매와 0.90 g (7.5 mmol)의 1-클로로헥산 및 3.90 ml (37.5 mmol)의 메틸디클로로실란을 넣고 150℃에서 12시간 동안 교반시켰다. 반응물을 상압에서 증류하여 0.25 g의 2,2,-디클로로-2-실라옥탄 (수율 16%)을 얻었다.In the same manner as in Example 1, 0.15 g (0.75 mmol) tri-normal butylphosphine catalyst, 0.90 g (7.5 mmol) 1-chlorohexane and 3.90 ml (37.5 mmol) methyldichlorosilane in a 25 ml stainless steel tube. Was added and stirred at 150 ° C. for 12 hours. The reaction was distilled at atmospheric pressure to afford 0.25 g of 2,2, -dichloro-2-silaoctane (yield 16%).
2,2-디클로로-2-실라옥탄의 H-NMR (CDCl3, ppm) 0.88-0.91 (m, 3H, CH 3), 0.94 (s, 3H, SiCH 3), 1.30-1.45 (m, 6H, (CH 2)4, 1.45-1.60 (m, 2H, SiCH 2).H-NMR of 2,2-dichloro-2-silaoctane (CDCl 3 , ppm) 0.88-0.91 (m, 3H, C H 3 ), 0.94 (s, 3H, SiC H 3 ), 1.30-1.45 (m, 6H, (C H 2 ) 4 , 1.45-1.60 (m, 2H, SiC H 2 ).
실시예 5. (클로로메틸)트리클로로실란과 트리클로로실란의 반응Example 5 Reaction of (Chloromethyl) trichlorosilane with Trichlorosilane
실시예 1과 같은 방법으로 25 ml 들이 스텐리스 관에 0.20 g (0.75 mmol)의 트리페닐포스핀 촉매와 0.92 g (7.5 mmol)의 (클로로메틸)트리클로로실란 및 5.08 g (37.5 mmol)의 트리클로로실란을 넣고 150℃에서 42시간 동안 반응시켰다. 반응물을 상압에서 증류하여 1.1 g의 1,1,1,3,3,3,-헥사클로로-1,3-디실라프로판 (끓는점 173-174℃, 수율 50%)을 얻고 부산물로 0.3 g의 1,1,1,3,3-펜타클로로-1,3-디실라프로판 (끓는점 166-16℃, 수율 16%)을 얻었다.In the same manner as in Example 1, 0.20 g (0.75 mmol) of triphenylphosphine catalyst, 0.92 g (7.5 mmol) of (chloromethyl) trichlorosilane and 5.08 g (37.5 mmol) of Triclo in a 25 ml stainless steel tube. Rosilane was added and reacted at 150 ° C. for 42 hours. The reaction was distilled at atmospheric pressure to give 1.1 g of 1,1,1,3,3,3, -hexachloro-1,3-disilapropane (boiling point 173-174 ° C., yield 50%) and 0.3 g of as a byproduct. 1,1,1,3,3-pentachloro-1,3-disilapropane (boiling point 166-16 ° C., yield 16%) was obtained.
1,1,1,3,3,3-헥사클로로-1,3-디실라프로판의 H-NMR (CDCl3, ppm) 1.87 (s, SiCH 2Si)H-NMR of 1,1,1,3,3,3-hexachloro-1,3-disilapropane (CDCl 3 , ppm) 1.87 (s, SiC H 2 Si)
1,1,1,3,3-펜타클로로-1,3-디실라프로판의 H-NMR (CDCl3, ppm) 1.64 (d, J=2.2Hz, 2H, SiCH 2Si), 5.72 (t, J=2,2Hz, 1H, SiH).H-NMR of 1,1,1,3,3-pentachloro-1,3-disilapropane (CDCl 3 , ppm) 1.64 (d, J = 2.2 Hz, 2H, SiC H 2 Si), 5.72 (t , J = 2,2 Hz, 1H, Si H ).
실시예 6. (클로로메틸)메틸디클로로실란과 트리클로로실란의 반응Example 6 Reaction of (Chloromethyl) methyldichlorosilane with Trichlorosilane
실시예 1과 같은 방법으로 25 ml 들이 스텐리스 관에 0.20 g (0.75 mmol)의 트리페닐포스핀 촉매와 1.07 g (7.5 mmol)의 (클로로메틸)메틸디클로로실란 및 5.08 g (37.5 mmol)의 트리클로로실란을 넣고 150℃에서 24시간 동안 반응시켰다. 반응물을 상압에서 증류하여 1.0 g의 1,1,1,3,3-펜타클로로-1,3-디실라부탄 (끓는점 181-182℃, 수율 58%)을 얻고 부산물로 0.1 g의 1,1,3,3-테트라클로로-1,3-디실라부탄 (끓는점 166-167℃, 수율 14%)을 얻었다.In the same manner as in Example 1, 0.20 g (0.75 mmol) of triphenylphosphine catalyst, 1.07 g (7.5 mmol) of (chloromethyl) methyldichlorosilane and 5.08 g (37.5 mmol) of Triclo in a 25 ml stainless steel tube Rosilane was added and reacted at 150 ° C. for 24 hours. The reaction was distilled at atmospheric pressure to yield 1.0 g of 1,1,1,3,3-pentachloro-1,3-disilabutane (boiling point 181-182 ° C., yield 58%) and as a byproduct 0.1 g of 1,1 , 3,3-tetrachloro-1,3-disilabutane (boiling point 166-167 ° C., yield 14%) was obtained.
1,1,1,3,3-펜타클로로-1,3-디실라부탄의 H-NMR (CDCl3, ppm) 0.94 (s, 3H, SiCH 3), 1.58 (s, SiCH 2Si)H-NMR of 1,1,1,3,3-pentachloro-1,3-disilabutane (CDCl 3 , ppm) 0.94 (s, 3H, SiC H 3 ), 1.58 (s, SiC H 2 Si)
1,1,3,3-테트라클로로-1,3-디실라부탄의 H-NMR (CDCl3, ppm) 0.94 (s, 3H, SiCH 3), 1.34 (d, J=2.3Hz, 2H, SiCH 2Si), 5.69 (t, J=2.3Hz, 1H, SiH).H-NMR of 1,1,3,3-tetrachloro-1,3-disilabutane (CDCl 3 , ppm) 0.94 (s, 3H, SiC H 3 ), 1.34 (d, J = 2.3 Hz, 2H, SiC H 2 Si), 5.69 (t, J = 2.3 Hz, 1H, SiH).
실시예 7. (클로로메틸)디메틸클로로실란과 트리클로로실란의 반응Example 7.Reaction of (Chloromethyl) dimethylchlorosilane with Trichlorosilane
실시예 1과 같은 방법으로 50 ml 들이 스텐리스 관에 1.0 g (3.8 mmol)의 트리페닐포스핀 촉매와 6.21 g (38.0 mmol)의 (클로로메틸)디메틸클로로실란 및 25.7 g (190.0 mmol)의 트리클로로실란을 넣고 150℃에서 12시간 동안 반응시켰다. 반응물을 상압에서 증류하여 5.8 g의 1,1,1,3-테트라클로로-3-메틸-1,3-디실라부탄 (끓는점 169-170℃, 수율 58%)을 얻고 부산물로 1.2 g의 1,1,3-트리클로로-3-메틸-1,3-디실라부탄 (끓는점 153-155℃, 수율 8%)을 얻었다.In the same manner as in Example 1, 1.0 g (3.8 mmol) of triphenylphosphine catalyst, 6.21 g (38.0 mmol) of (chloromethyl) dimethylchlorosilane and 25.7 g (190.0 mmol) of Triclo were placed in a 50 ml stainless steel tube. Rosilane was added and reacted at 150 ° C. for 12 hours. The reaction was distilled at atmospheric pressure to give 5.8 g of 1,1,1,3-tetrachloro-3-methyl-1,3-disilabutane (boiling point 169-170 ° C., yield 58%) and as a byproduct 1.2 g of 1 , 1,3-trichloro-3-methyl-1,3-disilabutane (boiling point 153-155 ° C., yield 8%) was obtained.
1,1,1,3-테트라클로로-3-메틸-1,3-디실라부탄의 H-NMR (CDCl3, ppm) 0.62 (s, 6H,SiCH 3), 1.28 (s, 2H, SiCH 2Si)H-NMR of 1,1,1,3-tetrachloro-3-methyl-1,3-disilabutane (CDCl 3 , ppm) 0.62 (s, 6H, SiC H 3 ), 1.28 (s, 2H, SiC H 2 Si)
1,1,3-트리클로로-3-메틸-1,3-디실라부탄의 H-NMR (CDCl3, ppm) 0.58 (s, 6H, SiCH 3), 1.00 (d, J=2.3Hz, 2H, SiCH 2Si), 5.65 (t, J=2,3Hz, 1H, SiH).H-NMR of 1,1,3-trichloro-3-methyl-1,3-disilabutane (CDCl 3 , ppm) 0.58 (s, 6H, SiC H 3 ), 1.00 (d, J = 2.3 Hz, 2H, SiC H 2 Si), 5.65 (t, J = 2,3 Hz, 1H, Si H ).
실시예 8. (클로로메틸)트리메틸실란과 트리클로로실란의 반응Example 8 Reaction of (Chloromethyl) trimethylsilane with Trichlorosilane
실시예 1과 같은 방법으로 25 ml 들이 스텐리스 관에 0.20 g (0.75 mmol)의 트리페닐포스핀 촉매와 1.38 g (7.5 mmol)의 (클로로메틸)트리메틸클로로실란 및 5.08 g (35.7 mmol)의 트리클로로실란을 넣고 150℃에서 10시간 동안 반응시켰다. 반응물을 상압에서 증류하여 1.2 g의 1,1,1-트리클로로-3,3-디메틸-1,3-디실라부탄 (끓는점 173-174℃, 수율 70%)을 얻고 부산물로 0.1 g의 1,1-3ㅣ클로로-3,3-디메틸-1,3-디실라부탄 (끓는점 157-159℃, 수율 7%)을 얻었다.In a 25 ml stainless steel tube in the same manner as in Example 1, 0.20 g (0.75 mmol) of triphenylphosphine catalyst, 1.38 g (7.5 mmol) of (chloromethyl) trimethylchlorosilane and 5.08 g (35.7 mmol) of Triclo Rosilane was added and reacted at 150 ° C. for 10 hours. The reaction was distilled at atmospheric pressure to yield 1.2 g of 1,1,1-trichloro-3,3-dimethyl-1,3-disilabutane (boiling point 173-174 ° C., yield 70%) and as a byproduct 0.1 g of 1 , 1-3 ㅣ chloro-3,3-dimethyl-1,3-disilabutane (boiling point 157-159 ° C., yield 7%) was obtained.
1,1,1-트리클로로-3,3-디메틸-1,3-디실라부탄의 H-NMR (CDCl3, ppm) 0.25 (s, 9H, SiCH 3), 0.85 (s, 2H, SiCH 2Si).H-NMR (CDCl 3 , ppm) of 1,1,1-trichloro-3,3-dimethyl-1,3-disilabutane 0.25 (s, 9H, SiC H 3 ), 0.85 (s, 2H, SiC H 2 Si).
1,1-디클로로-3,3-디메틸-1,3-디실라부탄의 H-NMR (CDCl3, ppm) 0.17 (s, 9H, SiCH 3), 0.59 (d, J=2.4Hz, 2H, SiCH 2Si), 5.60 (t, J=2.4Hz, 1H, SiH).H-NMR of 1,1-dichloro-3,3-dimethyl-1,3-disilabutane (CDCl 3 , ppm) 0.17 (s, 9H, SiC H 3 ), 0.59 (d, J = 2.4 Hz, 2H , SiC H 2 Si), 5.60 (t, J = 2.4 Hz, 1H, Si H ).
실시예 9. (2-클로로에틸)트리메틸실란과 트리클로로실란의 반응Example 9 Reaction of (2-Chloroethyl) trimethylsilane with Trichlorosilane
실시예 1에서와 같은 방법으로 25 ml 들이 스텐리스 관에 0.46g (0.40 mmol)의 테트라키스(트리페닐포스핀)팔라듐 (0) 촉매와 1.03 g (7.5 mmol)의 (2-클로로에틸)트리메틸실란 및 5.08 g (37.5 mmol)의 트리클로로실란을 넣고 150℃에서 12시간동안 교반시켰다. 반응물을 상압에서 증류하여 1.06 g의 [(2-트리클로로실릴)에틸]트리메틸실란 (끓는점 236℃, 수율 60%)을 얻었다.In a 25 ml stainless steel tube in the same manner as in Example 1, 0.46 g (0.40 mmol) of tetrakis (triphenylphosphine) palladium (0) catalyst and 1.03 g (7.5 mmol) of (2-chloroethyl) trimethyl Silane and 5.08 g (37.5 mmol) of trichlorosilane were added thereto and stirred at 150 ° C. for 12 hours. The reaction was distilled at atmospheric pressure to yield 1.06 g of [(2-trichlorosilyl) ethyl] trimethylsilane (boiling point 236 ° C., yield 60%).
[(2-트리클로로실릴)에틸]트리메틸실란의 H-NMR (CDCl3, ppm) 0.02 (s, 9H, Si(CH 3)3), 0.50 (m, 2H, CH 2SiMe3), 1,54 (m, 2H, Cl3SiCH 2).H-NMR of [(2-trichlorosilyl) ethyl] trimethylsilane (CDCl 3 , ppm) 0.02 (s, 9H, Si (C H 3 ) 3 ), 0.50 (m, 2H, C H 2 SiMe 3 ), 1,54 (m, 2H, Cl 3 SiC H 2 ).
실시예 10. (3-클로로프로필)트리메틸실란과 트리클로로실란의 반응Example 10 Reaction of (3-Chloropropyl) trimethylsilane with Trichlorosilane
실시예 1과 같은 방법으로 25 ml 들이 스텐리스 관에 0.15 g (0.75 mmol)의 트리노말부틸포스핀 촉매와 1.61 g (7.5 mmol)의 (3-클로로프로필)트리메틸실란 및 5.08 g (37.5 mmol)의 트리클로로실란을 넣고 150℃에서 12시간 동안 교반시켰다. 반응물을 상압에서 증류하여 1.06 g의 [(3-트리클로로실릴)프로필]트리메틸실란 (끓는점 250-258℃, 수율 86%)을 얻었다.In the same manner as in Example 1, 0.15 g (0.75 mmol) of trinormalyl phosphine catalyst, 1.61 g (7.5 mmol) of (3-chloropropyl) trimethylsilane and 5.08 g (37.5 mmol) in a 25 ml stainless steel tube. Trichlorosilane was added and stirred at 150 ° C. for 12 hours. The reaction was distilled at atmospheric pressure to yield 1.06 g of [(3-trichlorosilyl) propyl] trimethylsilane (boiling point 250-258 ° C., yield 86%).
[(3-트리클로로실릴)프로필]트리메틸실란의 H-NMR (CDCl3, ppm) 0.02 (s, 9H, SiCH 3), 0.66 (m, 2H, Me3SiCH 2), 1.47 (m, 2H, CH 2), 1.61 (m, 2H, CH 2SiCl3).H-NMR of [(3-trichlorosilyl) propyl] trimethylsilane (CDCl 3 , ppm) 0.02 (s, 9H, SiC H 3 ), 0.66 (m, 2H, Me 3 SiC H 2 ), 1.47 (m, 2H, C H 2 ), 1.61 (m, 2H, C H 2 SiCl 3 ).
실시예 11. 알릴 클로라이드와 트리클로로실란의 반응 (촉매로서 PPh3만 사용)Example 11 Reaction of Allyl Chloride with Trichlorosilane (Use Only PPh 3 as Catalyst)
실시예 1과 같은 방법으로 25 ml 들이 스텐리스 관에 0.037 g (0.14 mmol)의 트리페닐포스핀 촉매와 1.07 g (14.0 mmol)의 알릴클로라이드 및 9.48 g (70.0 mmol)의트리클로로실란을 넣고 150℃에서 10시간 동안 교반시켰다. 반응물을 상압에서 증류하여 1.2 g의 알릴트리클로로실란 (끓는점 117-8℃, 수율 49%)얻고 부산물로 0.12 g의 프로필트리클로로실란 (끓는점 123-5℃, 수율 5%)과 0.24 g (3-클로로프로필)트리클로로실란 (끓는점 181-2℃, 수율 8%)을 얻었다.In the same manner as in Example 1, 150 ml of 0.037 g (0.14 mmol) triphenylphosphine catalyst, 1.07 g (14.0 mmol) allyl chloride and 9.48 g (70.0 mmol) trichlorosilane were added to a 25 ml stainless steel tube. Stir at 10 ° C. for 10 hours. The reaction was distilled at atmospheric pressure to obtain 1.2 g of allyltrichlorosilane (boiling point 117-8 ° C., yield 49%) and as a byproduct 0.12 g of propyltrichlorosilane (boiling point 123-5 ° C., yield 5%) and 0.24 g (3 -Chloropropyl) trichlorosilane (boiling point 181-2 ° C., yield 8%) was obtained.
알릴트리클로로실란의 H-NMR (CDCl3, ppm) 2.35-2.37 (d, 2H, CH 2), 5.18-5.24 (m, 2H, CH 2=), 5.71-5.85 (m, 1H, -CH=).H-NMR of allyltrichlorosilane (CDCl 3 , ppm) 2.35-2.37 (d, 2H, C H 2 ), 5.18-5.24 (m, 2H, C H 2 =), 5.71-5.85 (m, 1H, − C H =).
3-(클로로프로필)트리클로로실란의 H-NMR (CDCl3, ppm) 1.58 (m, 2H, SiCH 2-), 2.06 (m, 2H, CH 2), 3.61 (t, J=6.48, 2H, CH 2Cl).H-NMR of 3- (chloropropyl) trichlorosilane (CDCl 3 , ppm) 1.58 (m, 2H, SiC H 2- ), 2.06 (m, 2H, C H 2 ), 3.61 (t, J = 6.48, 2H, C H 2 Cl).
실시예 12. 알릴클로라이드와 트리클로로실란의 반응 (촉매로 PPh3와 CuCl 사용).Example 12 Reaction of Allylchloride with Trichlorosilane (Use PPh 3 and CuCl as Catalyst).
실시예 1과 같은 방법으로 25 ml 들이 스텐리스 관에 0.037 g (0.14 mmol)의 트리페닐포스핀과 1.4 mg (0.014 mmol)의 쿠퍼 클로라이드 (CuCl) 촉매와 1.07 g (14.0 mmol)의 알릴 클로라이드 및 9.48 g (70.0 mmol)의 트리클로로실란을 넣고 150℃에서 10시간 동안 교반시켰다. 반응물을 상압에서 증류하여 0.5g의 알릴트리클로로실란 (끓는점 117-8℃, 수율 20%)을 얻고 부산물로 0.51 g의 프로필트리클로로실란 (끓는점 123-5℃, 수율 20%)과 0.73g의 1,3-비스(트리클로로실릴)프로판 (끓는점 88-90℃/12.5 mmHg, 수율 17%)을 얻었다.In the same manner as in Example 1, 0.037 g (0.14 mmol) of triphenylphosphine, 1.4 mg (0.014 mmol) of copper chloride (CuCl) catalyst and 1.07 g (14.0 mmol) of allyl chloride were added to a 25 ml stainless steel tube. 9.48 g (70.0 mmol) of trichlorosilane was added thereto and stirred at 150 ° C. for 10 hours. The reaction was distilled at atmospheric pressure to obtain 0.5 g of allyltrichlorosilane (boiling point 117-8 ° C., yield 20%) and as a byproduct 0.51 g of propyltrichlorosilane (boiling point 123-5 ° C., yield 20%) and 0.73 g of 1,3-bis (trichlorosilyl) propane (boiling point 88-90 ° C./12.5 mmHg, yield 17%) was obtained.
알릴트리클로로실란의 H-NMR (CDCl3, ppm) 2.35-2.37 (d, 2H, CH 2), 5.18-5.24 (m, 2H, CH 2=), 5.71-5.85 (m, 1H, -CH=).H-NMR of allyltrichlorosilane (CDCl 3 , ppm) 2.35-2.37 (d, 2H, C H 2 ), 5.18-5.24 (m, 2H, C H 2 =), 5.71-5.85 (m, 1H, − C H =).
실시예 13. 알릴브로마이드와 트리클로로실란의 반응Example 13. Reaction of Allylbromide with Trichlorosilane
실시예 1과 같은 방법으로 25 ml 들이 스텐리스 관에 0.037 g (0.14 mmol)의 트리페닐포스핀 촉매와 1.69 g (14.0 mmol)의 알릴 브로마이드 및 9.48 g (70.0 mmol)의 트리클로로실란을 넣고 150℃에서 2시간 동안 교반시켰다. 반응물을 상압에서 증류하여 2.37 g의 알릴트리클로로실란 (끓는점 117-8℃, 수율 95%)을 얻었다.In the same manner as in Example 1, 150 ml of 0.037 g (0.14 mmol) triphenylphosphine catalyst, 1.69 g (14.0 mmol) allyl bromide and 9.48 g (70.0 mmol) trichlorosilane were added to a 25 ml stainless steel tube. Stir at 2 ° C. for 2 hours. The reaction was distilled at atmospheric pressure to yield 2.37 g of allyltrichlorosilane (boiling point 117-8 ° C., yield 95%).
알릴트리클로로실란의 H-NMR (CDCl3, ppm) 2.35-2.37 (d, 2H, CH 2), 5.18-5.24 (m, 2H, CH 2=), 5.71-5.85 (m, 1H, -CH=).H-NMR of allyltrichlorosilane (CDCl 3 , ppm) 2.35-2.37 (d, 2H, C H 2 ), 5.18-5.24 (m, 2H, C H 2 =), 5.71-5.85 (m, 1H, − C H =).
실시예 14. 크로틸 클로라이드와 트리클로로실란의 반응Example 14 Reaction of Crotyl Chloride with Trichlorosilane
실시예 1과 같은 방법으로 25 ml 들이 스텐리스 관에 0.061 g (0.30 mmol)의 트리부틸포스핀 촉매와 0.272 g (14.9 mmol)의 크로틸 클로라이드 및 2.02 g (70.0 mmol)의 트리클로로실란을 넣고 150℃에서 1시간 30분동안 교반시켰다. 반응물을 상압에서 증류하여 0.40 g의 크로틸트리클로로실란 (수율 65%)을 얻었다.In the same manner as in Example 1, 0.061 g (0.30 mmol) tributylphosphine catalyst, 0.272 g (14.9 mmol) crotyl chloride and 2.02 g (70.0 mmol) trichlorosilane were added to a 25 ml stainless steel tube. Stirred at 150 ° C. for 1 hour 30 minutes. The reaction was distilled at atmospheric pressure to yield 0.40 g of crotyltrichlorosilane (yield 65%).
크로틸트리클로로실란의 MS (70 eV EI) m/z (상대 강도); 190(7), 188(7), 135(10, 63(7), 56(6), 55(100), 54 (11), 53(8).MS (70 eV EI) m / z (relative strength) of crotyltrichlorosilane; 190 (7), 188 (7), 135 (10, 63 (7), 56 (6), 55 (100), 54 (11), 53 (8).
실시예 15. 벤질 클로라이드와 트리클로로실란의 반응Example 15 Reaction of Benzyl Chloride with Trichlorosilane
실시예 1과 같은 방법으로 25 ml 들이 스텐리스 관에 0.15 g (0.75 mmol)의 트리노말부틸포스핀 촉매와 0.95 g (7.5 mmol)의 벤질 클로라이드 및 5.08 g (37.5 mmol)의 트리클로로실란을 넣고 150℃에서 2시간 동안 교반시켰다. 반응물을 감압하에서 증류하여 1.6 g의 벤질트리클로로실란 (끓는점 140-2℃/10 mmHg, 수율 96%)을 얻었다.In the same manner as in Example 1, 0.15 g (0.75 mmol) of trinormalyl phosphine catalyst, 0.95 g (7.5 mmol) of benzyl chloride and 5.08 g (37.5 mmol) of trichlorosilane were added to a 25 ml stainless steel tube. Stir at 150 ° C. for 2 hours. The reaction was distilled off under reduced pressure to afford 1.6 g of benzyltrichlorosilane (boiling point 140-2 ° C./10 mmHg, yield 96%).
벤질트리클로로실란의 H-NMR (CDCl3, ppm) 2.92 (s, 2H, CH 2), 7.29-7.36 (m, 5H, ArH).H-NMR of benzyltrichlorosilane (CDCl 3 , ppm) 2.92 (s, 2H, C H 2 ), 7.29-7.36 (m, 5H, Ar H ).
실시예 16. 4-플루오로벤질 클로라이드와 트리클로로실란의 반응Example 16 Reaction of 4-Fluorobenzyl Chloride with Trichlorosilane
실시예 1과 같은 방법으로 25 ml 들이 스텐리스 관에 0.15 g (0.75 mmol)의 트리노말부틸포스핀 촉매와 1.08g (7.5 mmol)의 4-플루오로벤질 클로라이드 및 5.08 g (37.5 mmol)의 트리클로로실란을 넣고 150℃에서 2시간 동안 교반시켰다. 반응물을 감압하에서 증류하여 1.6 g의 (4-플루오로벤질)트리클로로실란 (끓는점 56℃/13 mmHg, 수율 96%)을 얻었다.In the same manner as in Example 1, in a 25 ml stainless steel tube, 0.15 g (0.75 mmol) of trinormalylphosphine catalyst, 1.08 g (7.5 mmol) of 4-fluorobenzyl chloride and 5.08 g (37.5 mmol) of Triclo Rosilane was added and stirred at 150 ° C. for 2 hours. The reaction was distilled off under reduced pressure to afford 1.6 g of (4-fluorobenzyl) trichlorosilane (boiling point 56 ° C./13 mmHg, yield 96%).
(4-플루오로벤질)트리클로로실란의 H-NMR (CDCl3, ppm) 2.89 (s, 2H, CH 2), 7.00-7.20 (m, 4H, ArH).H-NMR of (4-fluorobenzyl) trichlorosilane (CDCl 3 , ppm) 2.89 (s, 2H, C H 2 ), 7.00-7.20 (m, 4H, Ar H ).
실시예 17. 4-클로로벤질 클로라이드와 트리클로로실란의 반응Example 17. Reaction of 4-chlorobenzyl chloride with trichlorosilane
실시예 1과 같은 방법으로 25 ml 들이 스텐리스 관에 0.15 g (0.75 mmol)의 트리노말부틸포스핀 촉매와 1.21 g (7.5 mmol)의 4-클로로벤질 클로라이드 및 5.08g (37.5 mmol)의 트리클로로실란을 넣고 150℃에서 2시간 동안 교반시켰다. 반응물을 감압하에서 증류하여 1.8 g의 (4-클로로벤질)트리클로로실란 (끓는점 80℃/10 mmHg, 수율 92%)을 얻었다.In the same manner as in Example 1, 0.15 g (0.75 mmol) of trinormalylphosphine catalyst, 1.21 g (7.5 mmol) of 4-chlorobenzyl chloride and 5.08 g (37.5 mmol) of trichlorous in a 25 ml stainless steel tube. Silane was added and stirred at 150 ° C. for 2 hours. The reaction was distilled off under reduced pressure to afford 1.8 g of (4-chlorobenzyl) trichlorosilane (boiling point 80 ° C / 10 mmHg, yield 92%).
(4-클로로벤질)트리클로로실란의 H-NMR (CDCl3, ppm) 2.93 (s, 2H, CH 2), 7.29-7.38 (m, 4H, ArH).H-NMR of (4-chlorobenzyl) trichlorosilane (CDCl 3 , ppm) 2.93 (s, 2H, C H 2 ), 7.29-7.38 (m, 4H, Ar H ).
실시예 18. 4-메톡시벤질 클로라이드와 트리클로로실란의 반응Example 18. Reaction of 4-methoxybenzyl chloride with trichlorosilane
실시예 1과 같은 방법으로 25 ml 들이 스텐리스 관에 0.056 g (0.2 mmol)의 트리시클로헥실포스핀 촉매와 0.271 ml (2.0 mmol)의 4-메톡시벤질 클로라이드 및 1.00ml (9.91 mmol)의 트리클로로실란을 넣고 150℃에서 2시간 동안 반응시켰다. 반응물을 감압하에 증류하여 0.23 g의 1-(트리클로로실릴메틸)-4-메톡시벤젠 (수율 47%)을 얻었다.In the same manner as in Example 1, 0.056 g (0.2 mmol) of tricyclohexylphosphine catalyst, 0.271 ml (2.0 mmol) of 4-methoxybenzyl chloride and 1.00 ml (9.91 mmol) of Triclo in a 25 ml stainless steel tube. Rosilane was added and reacted at 150 ° C. for 2 hours. The reaction was distilled off under reduced pressure to afford 0.23 g of 1- (trichlorosilylmethyl) -4-methoxybenzene (yield 47%).
1-(트리클로로실릴메틸)-4-메톡시벤젠의 MS (70eV EI) m/z (상대 강도); 256(7), 254(7), 135(5), 133(5), 122(9), 121(100), 78(10), 77(8), 51(6).MS (70eV EI) m / z (relative strength) of 1- (trichlorosilylmethyl) -4-methoxybenzene; 256 (7), 254 (7), 135 (5), 133 (5), 122 (9), 121 (100), 78 (10), 77 (8), 51 (6).
실시예 19. 4-페닐벤질 클로라이드와 트리클로로실란의 반응.Example 19. Reaction of 4-phenylbenzyl chloride with trichlorosilane.
실시예 1과 같은 방법으로 25 ml 들이 스텐리스 관에 0.15 g (0.75 mmol)의 트리노말부틸포스핀 촉매와 1.52 g (7.5 mmol)의 4-페닐벤질 클로라이드 및 5.08 g (37.5 mmol)의 트리클로로실란을 넣고 150℃에서 2시간 동안 교반시켰다. 반응물을 감압하에서 증류하여 2.0 g의 (4-페닐벤질)트리클로로실란 (녹는점 60-65℃, 수율 90%)을 얻었다. In the same manner as in Example 1, in a 25 ml stainless steel tube, 0.15 g (0.75 mmol) of trinormalylphosphine catalyst, 1.52 g (7.5 mmol) of 4-phenylbenzyl chloride and 5.08 g (37.5 mmol) of trichloro Silane was added and stirred at 150 ° C. for 2 hours. The reaction was distilled off under reduced pressure to yield 2.0 g of (4-phenylbenzyl) trichlorosilane (melting point 60-65 ° C., yield 90%).
(4-페닐벤질)트리클로로실란의 H-NMR(CDCl3, ppm) 2.90 (s, 2H, CH 2), 7.20-7.40 (m, 9H, ArH).H-NMR (CDCl 3 , ppm) 2.90 (s, 2H, C H 2 ), 7.20-7.40 (m, 9H, Ar H ) of (4-phenylbenzyl) trichlorosilane.
실시예 20. 알릴 클로라이드와 메틸디클로로실란의 반응Example 20 Reaction of Allyl Chloride with Methyldichlorosilane
실시예 1에서와 같은 방법으로 25 ml 들이 스텐리스 관에 0.34 g (1.4 mmol)의 트리페닐포스핀 촉매와 1.07 g (14.0 mmol)의 알릴 클로라이드 및 8.05 g (70.0 mmol)의 메틸디클로로실란을 넣고 150℃에서 10시간 동안 교반시켰다. 반응물을 상압에서 증류하여 0.4 g의 알릴메틸디클로로실란 (끓는점 119-120℃, 수율 20%)을 얻고 부산물로 0.1 g의 알릴메틸클로로실란 (끓는점 85-90℃, 수율 5%)을 얻었다.In the same manner as in Example 1, 0.34 g (1.4 mmol) of triphenylphosphine catalyst, 1.07 g (14.0 mmol) of allyl chloride and 8.05 g (70.0 mmol) of methyldichlorosilane were added to a 25 ml stainless steel tube. Stir at 150 ° C. for 10 hours. The reaction was distilled at atmospheric pressure to obtain 0.4 g of allylmethyldichlorosilane (boiling point 119-120 ° C., yield 20%) and to obtain 0.1 g of allylmethylchlorosilane (boiling point 85-90 ° C., yield 5%) as a byproduct.
알릴메틸디클로로실란의 MS (70eV EI) m/z (상대 강도); 156(13), 154(18), 141(13), 139(20), 117(13), 115(70), 114(9), 113(1000, 65(7), 63(22).MS (70eV EI) m / z (relative strength) of allylmethyldichlorosilane; 156 (13), 154 (18), 141 (13), 139 (20), 117 (13), 115 (70), 114 (9), 113 (1000, 65 (7), 63 (22).
실시예 21. 벤질 클로라이드와 메틸디클로로실란의 반응Example 21. Reaction of Benzyl Chloride with Methyldichlorosilane
실시예 1과 같은 방법으로 25 ml 들이 스텐리스 관에 0.15 g (0.75 mmol)의 트리노말부틸포스핀 촉매와 0.95 g (7.5 mmol)의 벤질 클로라이드 및 4.31 g (37.5 mmol)의 메틸디클로로실란을 넣고 200℃에서 2시간 동안 교반시켰다. 반응물을 상압에서 증류하여 0.31 g의 벤질메틸디클로로실란 (끓는점 214-215℃/740 mmHg, 수율 20%)을 얻었다.In the same manner as in Example 1, 0.15 g (0.75 mmol) of trinormalylphosphine catalyst, 0.95 g (7.5 mmol) of benzyl chloride and 4.31 g (37.5 mmol) of methyldichlorosilane were added to a 25 ml stainless steel tube. Stir at 200 ° C. for 2 hours. The reaction was distilled at atmospheric pressure to yield 0.31 g of benzylmethyldichlorosilane (boiling point 214-215 ° C./740 mmHg, yield 20%).
벤질메틸디클로로실란의 H-NMR (CDCl3, ppm) 0.96 (s, 3H, SiCH 3), 2.85(s, 2H, CH 2), 7.29-7.36 (m, 5H, ArH).H-NMR of benzylmethyldichlorosilane (CDCl 3 , ppm) 0.96 (s, 3H, SiC H 3 ), 2.85 (s, 2H, C H 2 ), 7.29-7.36 (m, 5H, Ar H ).
실시예 22. 벤질 클로라이드와 디클로로실란의 반응Example 22. Reaction of Benzyl Chloride with Dichlorosilane
실시예 1과 같은 방법으로 25 ml 들이 스텐리스 관에 0.21 ml (0.84 mmol)의 트리노말부틸포스핀 촉매와 0.97 ml (8.4 mmol)의 벤질 클로라이드 및 1.7 g (16.8 mmol)의 디클로로실란을 넣고 150℃에서 3시간 동안 반응시켰다. 반응물을 감압하에서 증류하여 1.51 g의 벤질디클로로실란 (수율 23%)와 벤질트리클로로실란 (수율 60%)을 얻었다.In the same manner as in Example 1, 150 ml of 0.21 ml (0.84 mmol) tri-normal butylphosphine catalyst, 0.97 ml (8.4 mmol) benzyl chloride and 1.7 g (16.8 mmol) dichlorosilane were added to a 25 ml stainless steel tube. The reaction was carried out at 3 ° C. for 3 hours. The reaction was distilled off under reduced pressure to yield 1.51 g of benzyldichlorosilane (yield 23%) and benzyltrichlorosilane (yield 60%).
벤질메틸디클로로실란의 H-NMR (CDCl3, ppm) 2.76 (s, J=2.0Hz, 2H, CH 2), 5.54 9t, J=2.0Hz, 1H, SiH), 7.18-7.37 (m, 5H, ArH).H-NMR of benzylmethyldichlorosilane (CDCl 3 , ppm) 2.76 (s, J = 2.0 Hz, 2H, C H 2 ), 5.54 9t, J = 2.0 Hz, 1H, Si H ), 7.18-7.37 (m, 5H, Ar H ).
실시예 23. 알릴 클로라이드와 디클로로실란의 반응Example 23. Reaction of Allyl Chloride with Dichlorosilane
실시예 1과 같은 방법으로 25 ml 들이 스텐리스관에 0.80 g (3.1 mmol)의 트리페닐포스핀 촉매와 1.25 ml (15.3 mmol)의 알릴 클로라이드 및 3.1 g (31 mmol)의 디클로로실란을 넣고 150℃에서 1시간 20분 동안 반응시켰다. 반응물을 상압에서 증류하여 1.00 g의 알릴디클로로실란 (수율 13%)과 알릴트리클로로실란 (수율 20%)의 혼합물을 얻었다.In the same manner as in Example 1, 0.80 g (3.1 mmol) triphenylphosphine catalyst, 1.25 ml (15.3 mmol) allyl chloride and 3.1 g (31 mmol) dichlorosilane were added to a 25 ml stainless steel tube at 150 ° C. The reaction was carried out for 1 hour 20 minutes. The reaction was distilled at atmospheric pressure to give a mixture of 1.00 g of allyldichlorosilane (yield 13%) and allyltrichlorosilane (yield 20%).
알릴디클로로실란의 H-NMR (CDCl3, ppm) 2.17-2.19 (d, 2H, SiCH 2), 5.13-5.18 (m, 2H, CH 2=), 5.47 (t, J=1.8Hz, 1H, SiH), 5.71-5.85 (m, 1H, CH=).H-NMR of allyldichlorosilane (CDCl 3 , ppm) 2.17-2.19 (d, 2H, SiC H 2 ), 5.13-5.18 (m, 2H, C H 2 =), 5.47 (t, J = 1.8 Hz, 1H , Si H ), 5.71-5.85 (m, 1H, C H =).
실시예 24. 디클로로메탄과 트리클로로실란의 반응Example 24 Reaction of Dichloromethane with Trichlorosilane
실시예 1과 같은 방법으로 25 ml 들이 스텐리스 관에 0.30 g (1.5 mmol)의 트리노말부틸포스핀 촉매와 0.64 g (7.5 mmol)의 디클로로메탄 및 10.2 g (75.0 mmol)의 트리클로로실란을 넣고 150℃에서 6시간 동안 교반시켰다. 반응물을 상압에서 증류하여 소량의 비스(트리클로로실릴)메탄을 얻었다.In the same manner as in Example 1, 0.30 g (1.5 mmol) tri-normal butylphosphine catalyst, 0.64 g (7.5 mmol) dichloromethane and 10.2 g (75.0 mmol) trichlorosilane were added to a 25 ml stainless steel tube. Stir at 150 ° C. for 6 hours. The reaction was distilled at atmospheric pressure to afford a small amount of bis (trichlorosilyl) methane.
비스(트리클로로실릴)메탄의 H-NMR (CDCl3, ppm) 1.59 (s, SiCH 2).H-NMR of bis (trichlorosilyl) methane (CDCl 3 , ppm) 1.59 (s, SiC H 2 ).
실시예 25. 1,2-디클로로에탄과 트리클로로실란의 반응Example 25 Reaction of 1,2-dichloroethane with Trichlorosilane
실시예 1과 같은 방법으로 25 ml 들이 스텐리스 관에 0.30 g (1.5 mmol)의 트리노말부틸포스핀 촉매와 0.74 g (7.5 mmol)의 1,2-디클로로에탄 및 10.2 g (75.0 mmol)의 트리클로로실란을 넣고 150℃에서 12시간 동안 교반시켰다. 반응물을 상압에서 증류하여 1.5 g의 1,2-비스(트리클로로실릴)에탄 (끓는점 201℃, 수율 67%)을 얻고 부산물로 0.1 g의 2-(클로로에틸)트리클로로실란 (끓는점 152-3℃, 수율 5%)을 얻었다.In the same manner as in Example 1, 0.30 g (1.5 mmol) of trinormalyl phosphine catalyst, 0.74 g (7.5 mmol) of 1,2-dichloroethane and 10.2 g (75.0 mmol) of Triclo in a 25 ml stainless steel tube Rosilane was added and stirred at 150 ° C. for 12 hours. The reaction was distilled at atmospheric pressure to yield 1.5 g of 1,2-bis (trichlorosilyl) ethane (boiling point 201 ° C., yield 67%) and as a byproduct 0.1 g of 2- (chloroethyl) trichlorosilane (boiling point 152-3 C, yield 5%) was obtained.
1,2-비스(트리클로로실릴)에탄의 H-NMR (CDCl3, ppm) 1.59 (s, 4H, SiCH 2).H-NMR (CDCl 3 , ppm) of 1,2-bis (trichlorosilyl) ethane 1.59 (s, 4H, SiC H 2 ).
실시예 26. 1,3-디클로로프로판과 트리클로로실란의 반응Example 26. Reaction of 1,3-dichloropropane with trichlorosilane
실시예 1과 같은 방법으로 25 ml 들이 스텐리스 관에 0.30 g (1.5 mmol)의 트리노말부틸포스핀 촉매와 0.85 g (7.5 mmol)의 1,3-디클로로프로판 및 10.2 g (75.0 mmol)의 트리클로로실란을 넣고 150℃에서 12시간 동안 교반시켰다. 반응물을 감압하에서 증류하여 1.6 g의 1,3-비스(트리클로로실릴)프로판 (끓는점 104℃/12.5 mmHg, 수율 70%)을 얻고 부산물로 0.3 g의 3-(클로로프로필)트리클로로실란 (끓는점 88-90℃/12.5 mmHg, 수율 20%)을 얻었다.In the same manner as in Example 1, 0.30 g (1.5 mmol) of trinormalylphosphine catalyst, 0.85 g (7.5 mmol) of 1,3-dichloropropane and 10.2 g (75.0 mmol) of Triclo in a 25 ml stainless steel tube Rosilane was added and stirred at 150 ° C. for 12 hours. The reaction was distilled off under reduced pressure to yield 1.6 g of 1,3-bis (trichlorosilyl) propane (boiling point 104 ° C./12.5 mmHg, yield 70%) and 0.3 g of 3- (chloropropyl) trichlorosilane (boiling point) as a by-product. 88-90 ° C./12.5 mmHg, yield 20%).
1,3-비스(트리클로로실릴)프로판의 H-NMR (CDCl3, ppm) 1.56 (m, 4H, SiCH 2), 1.92 (m, 2H, CH 2).H-NMR (CDCl 3 , ppm) 1.56 (m, 4H, SiC H 2 ), 1.92 (m, 2H, C H 2 ) of 1,3-bis (trichlorosilyl) propane.
3-(클로로프로필)트리클로로실란의 H-NMR (CDCl3, ppm) 1.58 (m, 2H, SiCH 2), 2.06 (m, 2H, CH 2), 3.61 (t, J=6.48, 2H, CH 2Cl).H-NMR of 3- (chloropropyl) trichlorosilane (CDCl 3 , ppm) 1.58 (m, 2H, SiC H 2 ), 2.06 (m, 2H, C H 2 ), 3.61 (t, J = 6.48, 2H , C H 2 Cl).
실시예 27. 1-브로모-3-클로로프로판과 트리클로로실란의 반응Example 27. Reaction of 1-bromo-3-chloropropane with trichlorosilane
실시예 1과 같은 방법으로 25 ml 들이 스텐리스 관에 0.30 g (1.5 mmol)의 트리노말부틸포스핀 촉매와 1.18 g (7.5 mmol)의 1-브로모-3-클로로프로판 및 10.2 g (75 mmol)의 트리클로로실란을 넣고 150℃에서 18시간 동안 교반시켰다. 반응물을 감압하에서 증류하여 1.1g의 1,3-비스(트리클로로실릴)프로판 (끓는점 104℃/12.5mmHg, 수율 48%)을 얻고 부산물로 0.3g의 3-(브로모프로필)트리클로로실릴 (수율 21%)과 0.2g의 3-(클로로프로필)트리클로로실란 (끓는점 88-90℃/12.5 mmHg, 수율 11%)을 얻었다.In the same manner as in Example 1, 0.30 g (1.5 mmol) of trinormalylphosphine catalyst, 1.18 g (7.5 mmol) of 1-bromo-3-chloropropane and 10.2 g (75 mmol) in a 25 ml stainless steel tube. ) Trichlorosilane was added and stirred at 150 ° C. for 18 hours. The reaction was distilled off under reduced pressure to give 1.1 g of 1,3-bis (trichlorosilyl) propane (boiling point 104 ° C./12.5 mmHg, yield 48%) and as a byproduct 0.3 g of 3- (bromopropyl) trichlorosilyl ( Yield 21%) and 0.2 g of 3- (chloropropyl) trichlorosilane (boiling point 88-90 ° C./12.5 mmHg, yield 11%) were obtained.
3-(클로로프로필)트리클로로실란의 H-NMR (CDCl3, ppm) 1.58 (m, 2H, SiCH 2), 2.06 (m, 2H, CH 2), 3.61 (t, J=6.5Hz, 2H, CH 2Cl).H-NMR of 3- (chloropropyl) trichlorosilane (CDCl 3 , ppm) 1.58 (m, 2H, SiC H 2 ), 2.06 (m, 2H, C H 2 ), 3.61 (t, J = 6.5 Hz, 2H, C H 2 Cl).
실시예 28. 1,4-디클로로부탄과 트리클로로실란의 반응Example 28. Reaction of 1,4-dichlorobutane with trichlorosilane
실시예 1과 같은 방법으로 25 ml 들이 스텐리스 관에 0.30 g(1.5 mmol)의 트리노말부틸포스핀 촉매와 0.96 g (7.5 mmol)의 1,4-디클로로부탄 및 10.2 g (75.0 mmol)의 트리클로로실란을 넣고 150℃에서 24시간 동안교반시켰다. 반응물을 감압하에서 증류하여 2.0g의 1,4-비스(트리클로로실릴)부탄 (끓는점 104℃/12.5 mmHg, 수율 84%)을 얻었다.In the same manner as in Example 1, 0.30 g (1.5 mmol) of trinormalyl phosphine catalyst, 0.96 g (7.5 mmol) of 1,4-dichlorobutane and 10.2 g (75.0 mmol) of Triclo in a 25 ml stainless steel tube. Rosilane was added and stirred at 150 ° C. for 24 hours. The reaction was distilled off under reduced pressure to yield 2.0 g of 1,4-bis (trichlorosilyl) butane (boiling point 104 ° C./12.5 mmHg, yield 84%).
1,4-(비스(트리클로로실릴)부탄의 H-NMR (CDCl3, ppm) 1.46(m, 4H, SiCH 2), 1.73 (m, 4H, CH 2).H-NMR (CDCl 3 , ppm) of 1,4- (bis (trichlorosilyl) butane) 1.46 (m, 4H, SiC H 2 ), 1.73 (m, 4H, C H 2 ).
실시예 29. 1,4-비스(클로로메틸)벤젠과 트리클로로실란의 반응Example 29. Reaction of 1,4-bis (chloromethyl) benzene with trichlorosilane
실시예 1과 같은 방법으로 25 ml 들이 스텐리스 관에 0.040 g (0.2 mmol)의 트리부틸포스핀 촉매와 0.35 g (2.0 mmol)의 1,4-비스(클로로메틸)벤젠 및 1.34 g (9.91 mmol)의 트리클로로실란, 벤젠 10 ml를 넣고 150℃에서 1시간 30분 동안 반응시켰다. 반응물을 감압하에서 증류하여 0.19 g의 1-클로로메틸-4-(트리클로로실릴메틸)벤젠 (수율 34%)과 0.21 g의 1,4-비스(트리클로로실릴메틸)벤젠 (수율 28%)을 분리하였다.In the same manner as in Example 1, 0.040 g (0.2 mmol) tributylphosphine catalyst, 0.35 g (2.0 mmol) of 1,4-bis (chloromethyl) benzene and 1.34 g (9.91 mmol) in a 25 ml stainless steel tube. 10 ml of trichlorosilane and benzene were added and reacted at 150 ° C. for 1 hour 30 minutes. The reaction was distilled off under reduced pressure to afford 0.19 g of 1-chloromethyl-4- (trichlorosilylmethyl) benzene (yield 34%) and 0.21 g of 1,4-bis (trichlorosilylmethyl) benzene (yield 28%). Separated.
1-클로로메틸-4-(트리클로로실릴메틸)벤젠의 MS (70eV EI) m/z (상대강도); 274 923), 272(17), 241(37), 239(99), 238(17), 237(100), 139(33), 104(39), 103(32), 77(20).MS (70eV EI) m / z (relative strength) of 1-chloromethyl-4- (trichlorosilylmethyl) benzene; 274 923), 272 (17), 241 (37), 239 (99), 238 (17), 237 (100), 139 (33), 104 (39), 103 (32), 77 (20).
1,4-비스(트리클로로실릴메틸)벤젠의 MS (70eV EI) m/z (상대 강도); 372(15), 241(38), 240(16), 239(99), 238(17), 237(100), 134(13), 132(14), 104(27), 103(19).MS (70eV EI) m / z (relative strength) of 1,4-bis (trichlorosilylmethyl) benzene; 372 (15), 241 (38), 240 (16), 239 (99), 238 (17), 237 (100), 134 (13), 132 (14), 104 (27), and 103 (19).
실시예 30. 1,2-비스(클로로메틸)벤젠과 디클로로실란의 반응.Example 30. Reaction of 1,2-bis (chloromethyl) benzene with dichlorosilane.
실시예 1과 같은 방법으로 25 ml 들이 스텐리스 관에 0.73 g (2.8 mmol)의 트리페닐포스핀 촉매와 4.9 g (28 mmol)의 1,2-비스(클로로메틸)벤젠 및 1.7 g (17 mmol)의 디클로로실란, 벤젠 10 ml를 넣고 150℃에서 3시간 동안 반응시켰다. 반응물을 감압하에서 증류하여 2.33 g의 1-클로로메틸-2-(트리클로로실릴메틸)벤젠 (수율 50%)을 분리하였다.In the same manner as in Example 1, 0.73 g (2.8 mmol) of triphenylphosphine catalyst, 4.9 g (28 mmol) of 1,2-bis (chloromethyl) benzene and 1.7 g (17 mmol) in a 25 ml stainless steel tube. 10 ml of dichlorosilane and benzene were added and reacted at 150 ° C. for 3 hours. The reaction was distilled off under reduced pressure to separate 2.33 g of 1-chloromethyl-2- (trichlorosilylmethyl) benzene (yield 50%).
1-클로로메틸-2-(트리클로로실릴메틸)벤젠의 MS (70eV EI) m/z (상대 강도); 274(28), 272(22), 241(37), 239(100), 237(100), 139(57), 104(50), 103(54), 78(24), 77(33).MS (70eV EI) m / z (relative strength) of 1-chloromethyl-2- (trichlorosilylmethyl) benzene; 274 (28), 272 (22), 241 (37), 239 (100), 237 (100), 139 (57), 104 (50), 103 (54), 78 (24), 77 (33).
본 발명에 따라, 유기 아민보다 염기성이 낮은 3차 유기 포스핀 화합물을 촉매로 사용함으로써 벤질클로라이드나 알릴클로라이드와 같은 활성화된 염화알칸 뿐만 아니라 단순한 유기 할로겐 화합물과 할로겐이 치환된 알킬기를 갖는 유기규소 화합물도 Si-H 결합을 갖는 실란을 탈할로겐화수소 반응으로 결합시키는 것이 가능하다.According to the present invention, by using a tertiary organic phosphine compound having a lower basicity than the organic amine as a catalyst, an organosilicon compound having a simple organic halogen compound and a halogen-substituted alkyl group as well as an activated alkane chloride such as benzyl chloride or allyl chloride It is possible to bond silanes having a Si-H bond in a dehalogenation reaction.
Claims (6)
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1019990013006A KR100306574B1 (en) | 1999-04-13 | 1999-04-13 | Dehydrohalogenative coupling reaction of alkyl halides with silane |
JP2000015275A JP3361498B2 (en) | 1999-04-13 | 2000-01-25 | Method for producing organosilicon compound |
US09/543,546 US6251057B1 (en) | 1999-04-13 | 2000-04-05 | Dehydrohalogenative coupling reaction of organic halides with silanes |
DE10018101A DE10018101C2 (en) | 1999-04-13 | 2000-04-12 | Dehydrohalogenating coupling reaction of organic halides with silanes |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1019990013006A KR100306574B1 (en) | 1999-04-13 | 1999-04-13 | Dehydrohalogenative coupling reaction of alkyl halides with silane |
Publications (2)
Publication Number | Publication Date |
---|---|
KR20000066127A KR20000066127A (en) | 2000-11-15 |
KR100306574B1 true KR100306574B1 (en) | 2001-09-13 |
Family
ID=19579779
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
KR1019990013006A KR100306574B1 (en) | 1999-04-13 | 1999-04-13 | Dehydrohalogenative coupling reaction of alkyl halides with silane |
Country Status (2)
Country | Link |
---|---|
JP (1) | JP3361498B2 (en) |
KR (1) | KR100306574B1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100491960B1 (en) * | 2002-05-07 | 2005-05-30 | 한국과학기술연구원 | Double Silylation of Unsaturated Organic Compounds with Trichlorosilane |
EP1705180A1 (en) | 2005-03-21 | 2006-09-27 | Korea Institute of Science and Technology | (Organothiomethyl)chlorosilanes and their preparation methods |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100453211B1 (en) * | 2000-11-01 | 2004-10-15 | 한국과학기술연구원 | A process for preparing organic silanes |
KR100487904B1 (en) * | 2002-04-16 | 2005-05-06 | 한국과학기술연구원 | A preparation method of organochlorosilanes by reductive deoxysilation reaction of aldehydes or ketones |
EP1787319A4 (en) * | 2004-08-31 | 2011-06-29 | Silecs Oy | Novel polyorganosiloxane dielectric materials |
KR100928942B1 (en) * | 2008-05-26 | 2009-11-30 | 제이에스아이실리콘주식회사 | Preparation method of linear and cyclic trisilaalkanes |
DE102009046121A1 (en) * | 2009-10-28 | 2011-05-05 | Wacker Chemie Ag | Process for the preparation of organosilanes |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55145693A (en) * | 1979-05-02 | 1980-11-13 | Chisso Corp | Preparation of 3-chloropropyltrichlorosilane |
-
1999
- 1999-04-13 KR KR1019990013006A patent/KR100306574B1/en not_active IP Right Cessation
-
2000
- 2000-01-25 JP JP2000015275A patent/JP3361498B2/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55145693A (en) * | 1979-05-02 | 1980-11-13 | Chisso Corp | Preparation of 3-chloropropyltrichlorosilane |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100491960B1 (en) * | 2002-05-07 | 2005-05-30 | 한국과학기술연구원 | Double Silylation of Unsaturated Organic Compounds with Trichlorosilane |
EP1705180A1 (en) | 2005-03-21 | 2006-09-27 | Korea Institute of Science and Technology | (Organothiomethyl)chlorosilanes and their preparation methods |
Also Published As
Publication number | Publication date |
---|---|
JP3361498B2 (en) | 2003-01-07 |
JP2000297091A (en) | 2000-10-24 |
KR20000066127A (en) | 2000-11-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP3856081B2 (en) | Method for producing halopropyldimethylchlorosilane compound | |
KR940010290B1 (en) | Bis(silyl)methanes and process for the preparation thereof | |
KR950002860B1 (en) | Chloroakdenylsilanes and its method of preparation | |
US6251057B1 (en) | Dehydrohalogenative coupling reaction of organic halides with silanes | |
KR100306574B1 (en) | Dehydrohalogenative coupling reaction of alkyl halides with silane | |
US6392077B1 (en) | Process for preparing organochlorosilanes by dehydrohalogenative coupling reaction of alkyl halides with chlorosilanes | |
US5629439A (en) | Method for preparation of allylsilanes | |
JP4821991B2 (en) | Method for producing 1- (alkoxysilyl) ethyl-1,1,3,3-tetramethyldisiloxane | |
JP2612991B2 (en) | Method for chlorinating silicon compounds | |
JP3612504B2 (en) | Method for producing organosilane | |
JPH10316688A (en) | Production of alkenylsilane | |
KR100356692B1 (en) | Preparation method of organosilanes by dehydrochlorinative reaction | |
JP4527351B2 (en) | Improved organosilane production process | |
JP4411077B2 (en) | Method for producing triorgano-monoalkoxysilane and method for producing triorgano-monochlorosilane | |
US5210255A (en) | Process for the preparation of methylchlorosilanes | |
KR100979578B1 (en) | Preparation of organosilanes and their derivatives in a novel grignard process | |
KR102585616B1 (en) | Dehydrogenation method of dichlorosilane | |
KR20060121283A (en) | Grignard processes with increased content of diphenylchlorosilanes | |
KR20060123433A (en) | Grignard processes with improved yields of diphenylchlorosilanes as products | |
KR20100031628A (en) | Process for converting si-h compounds to si-halogen compounds | |
KR20200015644A (en) | Process for Preparing Polysilylalkane | |
KR20160036020A (en) | Process for Preparing Polysilylalkane | |
JP3427145B2 (en) | Method for producing 3-chloropropyltrimethoxysilane | |
KR20150101288A (en) | Process for Preparing Polysilylalkane | |
KR950004175B1 (en) | Tris(silyl)alkanes and method of preparing the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A201 | Request for examination | ||
E902 | Notification of reason for refusal | ||
E701 | Decision to grant or registration of patent right | ||
GRNT | Written decision to grant | ||
FPAY | Annual fee payment |
Payment date: 20070731 Year of fee payment: 7 |
|
LAPS | Lapse due to unpaid annual fee |