CN1241570A - 3－位官能化的有机硅烷的新型制备方法 - Google Patents
3－位官能化的有机硅烷的新型制备方法 Download PDFInfo
- Publication number
- CN1241570A CN1241570A CN 99108032 CN99108032A CN1241570A CN 1241570 A CN1241570 A CN 1241570A CN 99108032 CN99108032 CN 99108032 CN 99108032 A CN99108032 A CN 99108032A CN 1241570 A CN1241570 A CN 1241570A
- Authority
- CN
- China
- Prior art keywords
- sulfide
- sulfur
- reaction
- allyl
- thiophene
- 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
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- 238000000034 method Methods 0.000 title claims abstract description 22
- 150000001282 organosilanes Chemical class 0.000 title claims abstract description 5
- 238000002360 preparation method Methods 0.000 title abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- -1 hydrogen silanes Chemical class 0.000 claims abstract description 13
- 239000011593 sulfur Substances 0.000 claims abstract description 13
- 239000003446 ligand Substances 0.000 claims abstract description 11
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 10
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 8
- 239000005052 trichlorosilane Substances 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- WQADWIOXOXRPLN-UHFFFAOYSA-N 1,3-dithiane Chemical compound C1CSCSC1 WQADWIOXOXRPLN-UHFFFAOYSA-N 0.000 claims description 6
- UBJVUCKUDDKUJF-UHFFFAOYSA-N Diallyl sulfide Chemical compound C=CCSCC=C UBJVUCKUDDKUJF-UHFFFAOYSA-N 0.000 claims description 6
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 6
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 claims description 6
- 229930192474 thiophene Natural products 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- LUFPJJNWMYZRQE-UHFFFAOYSA-N benzylsulfanylmethylbenzene Chemical compound C=1C=CC=CC=1CSCC1=CC=CC=C1 LUFPJJNWMYZRQE-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 150000003568 thioethers Chemical class 0.000 claims description 4
- 125000000171 (C1-C6) haloalkyl group Chemical group 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 150000003462 sulfoxides Chemical class 0.000 claims description 3
- YFMZQCCTZUJXEB-UHFFFAOYSA-N tris(methylsulfanyl)methane Chemical compound CSC(SC)SC YFMZQCCTZUJXEB-UHFFFAOYSA-N 0.000 claims description 3
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
- 229910000057 polysulfane Inorganic materials 0.000 claims description 2
- 150000003573 thiols Chemical class 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims 1
- 238000007259 addition reaction Methods 0.000 claims 1
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 abstract description 4
- OOXSLJBUMMHDKW-UHFFFAOYSA-N trichloro(3-chloropropyl)silane Chemical compound ClCCC[Si](Cl)(Cl)Cl OOXSLJBUMMHDKW-UHFFFAOYSA-N 0.000 description 15
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 11
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 5
- 229910019032 PtCl2 Inorganic materials 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 150000003058 platinum compounds Chemical class 0.000 description 4
- UIDUKLCLJMXFEO-UHFFFAOYSA-N propylsilane Chemical compound CCC[SiH3] UIDUKLCLJMXFEO-UHFFFAOYSA-N 0.000 description 4
- 239000005049 silicon tetrachloride Substances 0.000 description 4
- DTOOTUYZFDDTBD-UHFFFAOYSA-N 3-chloropropylsilane Chemical compound [SiH3]CCCCl DTOOTUYZFDDTBD-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 238000006459 hydrosilylation reaction Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- FEVALTJSQBFLEU-UHFFFAOYSA-N 1-methyl-4-methylsulfinylbenzene Chemical compound CC1=CC=C(S(C)=O)C=C1 FEVALTJSQBFLEU-UHFFFAOYSA-N 0.000 description 2
- GWQOOADXMVQEFT-UHFFFAOYSA-N 2,5-Dimethylthiophene Chemical compound CC1=CC=C(C)S1 GWQOOADXMVQEFT-UHFFFAOYSA-N 0.000 description 2
- MOMFXATYAINJML-UHFFFAOYSA-N 2-Acetylthiazole Chemical compound CC(=O)C1=NC=CS1 MOMFXATYAINJML-UHFFFAOYSA-N 0.000 description 2
- WYJOVVXUZNRJQY-UHFFFAOYSA-N 2-Acetylthiophene Chemical compound CC(=O)C1=CC=CS1 WYJOVVXUZNRJQY-UHFFFAOYSA-N 0.000 description 2
- DXYYSGDWQCSKKO-UHFFFAOYSA-N 2-methylbenzothiazole Chemical compound C1=CC=C2SC(C)=NC2=C1 DXYYSGDWQCSKKO-UHFFFAOYSA-N 0.000 description 2
- QMHIMXFNBOYPND-UHFFFAOYSA-N 4-methylthiazole Chemical compound CC1=CSC=N1 QMHIMXFNBOYPND-UHFFFAOYSA-N 0.000 description 2
- BKAWJIRCKVUVED-UHFFFAOYSA-N 5-(2-hydroxyethyl)-4-methylthiazole Chemical compound CC=1N=CSC=1CCO BKAWJIRCKVUVED-UHFFFAOYSA-N 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical class SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 2
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- PFRGXCVKLLPLIP-UHFFFAOYSA-N diallyl disulfide Chemical compound C=CCSSCC=C PFRGXCVKLLPLIP-UHFFFAOYSA-N 0.000 description 2
- GVPWHKZIJBODOX-UHFFFAOYSA-N dibenzyl disulfide Chemical compound C=1C=CC=CC=1CSSCC1=CC=CC=C1 GVPWHKZIJBODOX-UHFFFAOYSA-N 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- ALVPFGSHPUPROW-UHFFFAOYSA-N dipropyl disulfide Chemical compound CCCSSCCC ALVPFGSHPUPROW-UHFFFAOYSA-N 0.000 description 2
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000005053 propyltrichlorosilane Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- DOEHJNBEOVLHGL-UHFFFAOYSA-N trichloro(propyl)silane Chemical compound CCC[Si](Cl)(Cl)Cl DOEHJNBEOVLHGL-UHFFFAOYSA-N 0.000 description 2
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 description 2
- 239000001677 (2R,5R)-1,4-dithiane-2,5-diol Substances 0.000 description 1
- IXULCOYQSDIBFO-UHFFFAOYSA-N (3-bromothiophen-2-yl)methanol Chemical compound OCC=1SC=CC=1Br IXULCOYQSDIBFO-UHFFFAOYSA-N 0.000 description 1
- BMLMGCPTLHPWPY-REOHCLBHSA-N (4R)-2-oxo-4-thiazolidinecarboxylic acid Chemical compound OC(=O)[C@@H]1CSC(=O)N1 BMLMGCPTLHPWPY-REOHCLBHSA-N 0.000 description 1
- JXTGICXCHWMCPM-UHFFFAOYSA-N (methylsulfinyl)benzene Chemical compound CS(=O)C1=CC=CC=C1 JXTGICXCHWMCPM-UHFFFAOYSA-N 0.000 description 1
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 1
- LORRLQMLLQLPSJ-UHFFFAOYSA-N 1,3,5-Trithiane, Natural products C1SCSCS1 LORRLQMLLQLPSJ-UHFFFAOYSA-N 0.000 description 1
- BTTUMVHWIAXYPJ-UHFFFAOYSA-N 1,3-dithian-2-yl(trimethyl)silane Chemical compound C[Si](C)(C)C1SCCCS1 BTTUMVHWIAXYPJ-UHFFFAOYSA-N 0.000 description 1
- RAIPHJJURHTUIC-UHFFFAOYSA-N 1,3-thiazol-2-amine Chemical compound NC1=NC=CS1 RAIPHJJURHTUIC-UHFFFAOYSA-N 0.000 description 1
- ZOBPZXTWZATXDG-UHFFFAOYSA-N 1,3-thiazolidine-2,4-dione Chemical compound O=C1CSC(=O)N1 ZOBPZXTWZATXDG-UHFFFAOYSA-N 0.000 description 1
- WGJCBBASTRWVJL-UHFFFAOYSA-N 1,3-thiazolidine-2-thione Chemical compound SC1=NCCS1 WGJCBBASTRWVJL-UHFFFAOYSA-N 0.000 description 1
- YUIOPHXTILULQC-UHFFFAOYSA-N 1,4-Dithiane-2,5-diol Chemical compound OC1CSC(O)CS1 YUIOPHXTILULQC-UHFFFAOYSA-N 0.000 description 1
- JBYHSSAVUBIJMK-UHFFFAOYSA-N 1,4-oxathiane Chemical compound C1CSCCO1 JBYHSSAVUBIJMK-UHFFFAOYSA-N 0.000 description 1
- RFIRBXAXKBRCTL-UHFFFAOYSA-N 1-(ethylsulfanylmethylsulfinylmethylsulfanyl)ethane Chemical compound CCSCS(=O)CSCC RFIRBXAXKBRCTL-UHFFFAOYSA-N 0.000 description 1
- MYFKLQFBFSHBPA-UHFFFAOYSA-N 1-chloro-2-methylsulfanylethane Chemical compound CSCCCl MYFKLQFBFSHBPA-UHFFFAOYSA-N 0.000 description 1
- NXCKJENHTITELM-UHFFFAOYSA-N 1-nitro-2-[(2-nitrophenyl)disulfanyl]benzene Chemical compound [O-][N+](=O)C1=CC=CC=C1SSC1=CC=CC=C1[N+]([O-])=O NXCKJENHTITELM-UHFFFAOYSA-N 0.000 description 1
- LOXRGHGHQYWXJK-UHFFFAOYSA-N 1-octylsulfanyloctane Chemical compound CCCCCCCCSCCCCCCCC LOXRGHGHQYWXJK-UHFFFAOYSA-N 0.000 description 1
- ZDVBYNCJCIYCFO-UHFFFAOYSA-N 2,2,2-trifluoroethylsulfanylmethylbenzene Chemical compound FC(F)(F)CSCC1=CC=CC=C1 ZDVBYNCJCIYCFO-UHFFFAOYSA-N 0.000 description 1
- ATRJNSFQBYKFSM-UHFFFAOYSA-N 2,3-dibromothiophene Chemical compound BrC=1C=CSC=1Br ATRJNSFQBYKFSM-UHFFFAOYSA-N 0.000 description 1
- XHANCLXYCNTZMM-UHFFFAOYSA-N 2,5-dimethyl-1,3-benzothiazole Chemical compound CC1=CC=C2SC(C)=NC2=C1 XHANCLXYCNTZMM-UHFFFAOYSA-N 0.000 description 1
- KSJBMDCFYZKAFH-UHFFFAOYSA-N 2-(2-sulfanylethylsulfanyl)ethanethiol Chemical compound SCCSCCS KSJBMDCFYZKAFH-UHFFFAOYSA-N 0.000 description 1
- BKCNDTDWDGQHSD-UHFFFAOYSA-N 2-(tert-butyldisulfanyl)-2-methylpropane Chemical compound CC(C)(C)SSC(C)(C)C BKCNDTDWDGQHSD-UHFFFAOYSA-N 0.000 description 1
- MIHADVKEHAFNPG-UHFFFAOYSA-N 2-Amino-5-nitrothiazole Chemical compound NC1=NC=C([N+]([O-])=O)S1 MIHADVKEHAFNPG-UHFFFAOYSA-N 0.000 description 1
- JUIQOABNSLTJSW-UHFFFAOYSA-N 2-Methyl-4,5-dihydro-1,3-thiazole Chemical compound CC1=NCCS1 JUIQOABNSLTJSW-UHFFFAOYSA-N 0.000 description 1
- 229940018167 2-amino-5-nitrothiazole Drugs 0.000 description 1
- UHGULLIUJBCTEF-UHFFFAOYSA-N 2-aminobenzothiazole Chemical compound C1=CC=C2SC(N)=NC2=C1 UHGULLIUJBCTEF-UHFFFAOYSA-N 0.000 description 1
- RXNZFHIEDZEUQM-UHFFFAOYSA-N 2-bromo-1,3-thiazole Chemical compound BrC1=NC=CS1 RXNZFHIEDZEUQM-UHFFFAOYSA-N 0.000 description 1
- RXHZHGKMSAKVQN-UHFFFAOYSA-N 2-bromothiophene Chemical compound BrC1=CC=[C]S1 RXHZHGKMSAKVQN-UHFFFAOYSA-N 0.000 description 1
- BSQLQMLFTHJVKS-UHFFFAOYSA-N 2-chloro-1,3-benzothiazole Chemical compound C1=CC=C2SC(Cl)=NC2=C1 BSQLQMLFTHJVKS-UHFFFAOYSA-N 0.000 description 1
- QDXIHHOPZFCEAP-UHFFFAOYSA-N 2-chloroethylsulfanylbenzene Chemical compound ClCCSC1=CC=CC=C1 QDXIHHOPZFCEAP-UHFFFAOYSA-N 0.000 description 1
- GLSHTINAZAWJBE-UHFFFAOYSA-N 2-chlorothiophene Chemical compound ClC1=CC=[C]S1 GLSHTINAZAWJBE-UHFFFAOYSA-N 0.000 description 1
- JCCCMAAJYSNBPR-UHFFFAOYSA-N 2-ethylthiophene Chemical compound CCC1=CC=CS1 JCCCMAAJYSNBPR-UHFFFAOYSA-N 0.000 description 1
- VMDJWSACUFRJRE-UHFFFAOYSA-N 2-fluoro-3,3-dimethyl-1,2-benzothiazole 1,1-dioxide Chemical compound C1=CC=C2C(C)(C)N(F)S(=O)(=O)C2=C1 VMDJWSACUFRJRE-UHFFFAOYSA-N 0.000 description 1
- ROIMNSWDOJCBFR-UHFFFAOYSA-N 2-iodothiophene Chemical compound IC1=CC=CS1 ROIMNSWDOJCBFR-UHFFFAOYSA-N 0.000 description 1
- OKEHURCMYKPVFW-UHFFFAOYSA-N 2-methoxythiophene Chemical compound COC1=CC=CS1 OKEHURCMYKPVFW-UHFFFAOYSA-N 0.000 description 1
- KXROTPXCYDXGSC-UHFFFAOYSA-N 2-methyl-1,3-dithiane Chemical compound CC1SCCCS1 KXROTPXCYDXGSC-UHFFFAOYSA-N 0.000 description 1
- MBNVSWHUJDDZRH-UHFFFAOYSA-N 2-methylthiirane Chemical compound CC1CS1 MBNVSWHUJDDZRH-UHFFFAOYSA-N 0.000 description 1
- WBBPRCNXBQTYLF-UHFFFAOYSA-N 2-methylthioethanol Chemical compound CSCCO WBBPRCNXBQTYLF-UHFFFAOYSA-N 0.000 description 1
- XQQBUAPQHNYYRS-UHFFFAOYSA-N 2-methylthiophene Chemical compound CC1=CC=CS1 XQQBUAPQHNYYRS-UHFFFAOYSA-N 0.000 description 1
- KWWZHCSQVRVQGF-UHFFFAOYSA-N 2-phenylsulfanylethanol Chemical compound OCCSC1=CC=CC=C1 KWWZHCSQVRVQGF-UHFFFAOYSA-N 0.000 description 1
- SMJRBWINMFUUDS-UHFFFAOYSA-N 2-thienylacetic acid Chemical compound OC(=O)CC1=CC=CS1 SMJRBWINMFUUDS-UHFFFAOYSA-N 0.000 description 1
- CLSHQIDDCJTHAJ-UHFFFAOYSA-N 2-thienylacetonitrile Chemical compound N#CCC1=CC=CS1 CLSHQIDDCJTHAJ-UHFFFAOYSA-N 0.000 description 1
- AJYXPNIENRLELY-UHFFFAOYSA-N 2-thiophen-2-ylacetyl chloride Chemical compound ClC(=O)CC1=CC=CS1 AJYXPNIENRLELY-UHFFFAOYSA-N 0.000 description 1
- RCNOGGGBSSVMAS-UHFFFAOYSA-N 2-thiophen-3-ylacetic acid Chemical compound OC(=O)CC=1C=CSC=1 RCNOGGGBSSVMAS-UHFFFAOYSA-N 0.000 description 1
- GWZCLMWEJWPFFA-UHFFFAOYSA-N 2-thiophen-3-ylacetonitrile Chemical compound N#CCC=1C=CSC=1 GWZCLMWEJWPFFA-UHFFFAOYSA-N 0.000 description 1
- XHTPPQBDONGRAF-UHFFFAOYSA-N 3,3-dimethyl-2h-1,2-benzothiazole 1,1-dioxide Chemical compound C1=CC=C2C(C)(C)NS(=O)(=O)C2=C1 XHTPPQBDONGRAF-UHFFFAOYSA-N 0.000 description 1
- VGKLVWTVCUDISO-UHFFFAOYSA-N 3,4-dibromothiophene Chemical compound BrC1=CSC=C1Br VGKLVWTVCUDISO-UHFFFAOYSA-N 0.000 description 1
- XBNHRNFODJOFRU-UHFFFAOYSA-N 3-(2-benzothiazolylthio)-1-propanesulfonic acid Chemical compound C1=CC=C2SC(SCCCS(=O)(=O)O)=NC2=C1 XBNHRNFODJOFRU-UHFFFAOYSA-N 0.000 description 1
- RNIDWJDZNNVFDY-UHFFFAOYSA-N 3-Acetylthiophene Chemical compound CC(=O)C=1C=CSC=1 RNIDWJDZNNVFDY-UHFFFAOYSA-N 0.000 description 1
- XCMISAPCWHTVNG-UHFFFAOYSA-N 3-bromothiophene Chemical compound BrC=1C=CSC=1 XCMISAPCWHTVNG-UHFFFAOYSA-N 0.000 description 1
- HQFLTUZKIRYQSP-UHFFFAOYSA-N 3-ethyl-2h-1,3-benzothiazole-6-sulfonic acid Chemical compound OS(=O)(=O)C1=CC=C2N(CC)CSC2=C1 HQFLTUZKIRYQSP-UHFFFAOYSA-N 0.000 description 1
- RBIGKSZIQCTIJF-UHFFFAOYSA-N 3-formylthiophene Chemical compound O=CC=1C=CSC=1 RBIGKSZIQCTIJF-UHFFFAOYSA-N 0.000 description 1
- BSQKBHXYEKVKMN-UHFFFAOYSA-N 3-methylthiophene-2-carbaldehyde Chemical compound CC=1C=CSC=1C=O BSQKBHXYEKVKMN-UHFFFAOYSA-N 0.000 description 1
- REGFWZVTTFGQOJ-UHFFFAOYSA-N 4,5-dihydro-1,3-thiazol-2-amine Chemical compound NC1=NCCS1 REGFWZVTTFGQOJ-UHFFFAOYSA-N 0.000 description 1
- XRTJYEIMLZALBD-UHFFFAOYSA-N 4-(6-methyl-1,3-benzothiazol-2-yl)aniline Chemical compound S1C2=CC(C)=CC=C2N=C1C1=CC=C(N)C=C1 XRTJYEIMLZALBD-UHFFFAOYSA-N 0.000 description 1
- VVPUIKNICYCXJZ-UHFFFAOYSA-N 4-iodobutyl benzoate Chemical compound ICCCCOC(=O)C1=CC=CC=C1 VVPUIKNICYCXJZ-UHFFFAOYSA-N 0.000 description 1
- RLYUNPNLXMSXAX-UHFFFAOYSA-N 5-methylthiazole Chemical compound CC1=CN=CS1 RLYUNPNLXMSXAX-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种由氢硅烷和适当烯丙基化合物在具有一个或多个含硫配体的铂催化剂存在下制备3－位官能化的有机硅烷的方法。
Description
本发明提供一种由氢硅烷和烯丙基化合物在铂催化存在下制备3-位官能化的有机硅烷的方法。
已知氢硅烷可例如与烯丙基氯在均相或异相铂催化剂的存在下反应生成3-氯丙基硅烷。一般称该反应为氢化硅烷化反应(如，参见方程式I)。
当采用可溶性铂化合物例如最简单的H2PtCl6·6H2O作催化剂时，该反应被称为均相氢化硅烷化反应(参见DE-OS 28 51 456、CS-PS176 910、US-PS 42 92 433、US-PS 42 92 434、DE-AS 11 87 240、DE-PS 11 65 028)；异相氢化硅烷化反应采用处于载体之上的元素铂或铂化合物(参见US-PS 26 37 738、DE-PS 20 12 229、DE-PS 28 15316)。
例如在烯丙基氯与氢硅烷反应构成3-氯丙基硅烷的反应中，已知部分所使用的烯丙基氯在副反应中与氢硅烷反应生成丙烯，而氢硅烷转化成相应的氯硅烷(如，参见方程式II)
因此，例如在烯丙基氯与三氯硅烷的反应中，25-30mol％的烯丙基氯通过副反应而被转化成丙烯，同时生成等量的四氯化硅。采用粗产物中所生成的氯丙基硅烷与四氯化硅的摩尔比来衡量反应的选择性，其典型数据在2.33∶1(以烯丙基氯计，产率70％)至3∶1(产率75％)之间。
已知在加压容器中采用特殊反应方法可以抑制丙烯的生成。但该方法导致副反应生成的丙烯与所使用的氢硅烷发生进一步的定量反应而生成丙基硅烷。甚至在采用常压的常规反应中，副反应生成的丙烯也与氢硅烷发生进一步的副反应，生成相应的丙基硅烷(参见，DE 34 04703C)(如，参见方程式III)。
因此，例如在工厂中，在装有铂碳的柱中进行烯丙基氯和三氯硅烷的异相铂催化反应时，每生产1000kg 3-氯丙基三氯硅烷可得到高达230kg的丙基三氯硅烷，以转化成目标产物的三氯硅烷的用量计，这意味着需要额外加入28％的三氯硅烷(参见DE 41 19 994A1)。
除需添加额外的氢硅烷外，这些方法中存在的问题还有不需要的丙基硅烷的复杂分离，丙基硅烷在其它场合中用处很少，因而不得不采用昂贵的方法将其处理掉。
这一问题通过权利要求1中的方法得到了改进。
在此方面，提供如下制备3-位官能化的丙基硅烷的方法：反应温度在0℃至200℃之间，压力在800mbar至6bar之间，采用含有一个或多个含硫配体的铂催化剂，在上述条件下将通式I所代表的烯丙基化合物
H2C＝CH-CH2X (I)其中X可为Cl、Br、I、F、CN、SCN、SH、SR、OH、NRR1和OR，R和R1相互独立地为C1-C6烷基或C3-C7芳基，
添加至通式II代表的硅烷中：
R2R3R4SiH (II)其中R2、R3、R4各自独立地为氢、卤素、C1-C6烷基、C1-C6卤代烷基、C3-C6烯丙基、C1-C4烷氧基、苯基、芳基或芳烷基。
在从属权利要求中将对优选实施方案作详述。X优选为卤素，特别优选为氯。
该方法在常压，加压和部分真空的条件下均可进行。优选操作压力在800mbar至6bar之间。800mbar至2bar的压力特别适用。
本发明方法一般是在适当容器中将烯丙基化合物与稍微过量的氢硅烷在0℃至200℃之间的温度下反应，直到所有的烯丙基氯反应完全。
本发明中可用作起始物的硅烷包括结构式II代表的硅烷
R2R3R4SiH (II)其中R2、R3、R4各自独立地为氢、卤素、C1-C6烷基、C1-C6烷氧基、C1-C6卤代烷基、C3-C6烯丙基、苯基、芳基或芳烷基。
用在本发明反应中的硅烷优选为三氯硅烷，或混合取代的硅烷，如甲基、乙基、丙基氢二氯硅烷或二甲基氢氯硅烷。
所采用的铂催化剂可为任何氧化态。理论上可预先制备催化剂而后再加到反应混合物中，或仅在实际反应混合物中生成(原位生成)。催化反应可以是均相或异相的，即所采用的铂化合物也可附于载体上(参见US-PS 26 37 738、DE-PS 20 12 229、DE-PS 28 15 316)。催化剂的用量可以是化学计量的或催化量的，例如以所采用的烯丙基化合物计，用量为0.1至10000ppm，优选为10至500ppm。在“Gmelins无机化学手册(Gmelins Handbuch der Anorganischen Chemie)，第8版，第68卷，D部分(“komplexverbindungen[des Platins]mit neutralenLiganden”)”中概述了铂化合物的制备。
要具有本发明所述的作用，催化剂必须具有一个含硫配体。其中含硫配体要足以在核心铂之间构成简单的供体/受体相互作用。含硫配体可以是单齿或多齿的，可以是硫醚、亚砜、硫烷、多硫烷或硫醇，或总的来说为一硫化物，其中硫的氧化态为-2。本领域的技术人员可从文献中查到这些化合物(Houben-Weyl，第E11卷，G Thieme Verlag，Stuttgart 1985，特别是第158、669、129、147、32页)。可单独使用或混合使用含硫化合物。本发明的方法包括以下结构类型所代表的含硫化合物：
R5SR6、R7S(O)R8、R9SzR10、R9SzR10Sy-R11其中R5、R6、R7、R8、R9、R10、R11可为任何有机基团或H，z、y分别为2至6的整数。可使用的含硫配体的例子为：硫烷，如甲基乙基硫醚、乙基苯基硫醚、烯丙基苯基硫醚、苄基-2，2，2-三氟乙基硫醚、二(2-巯乙基)硫醚、二(三甲基甲硅烷基甲基)硫醚、2-氯乙基甲基硫醚、2-氯乙基苯基硫醚、2-氯-3，4-二甲基-5-苯基-1，3，2-oxazaphospholidine-2-硫醚、氯代二甲基硫醚、氯甲基苯基硫醚、二乙基硫醚、二烯丙基硫醚、二苄基硫醚、二丁基硫醚、二特丁基硫醚、二甲基硫醚、二辛基硫醚、二苯基硫醚、二丙基硫醚、2-羟乙基甲基硫醚、2-羟乙基苯基硫醚、苯基乙烯基硫醚、三硫化四磷、硫化丙烯、二硫化四乙基秋兰姆、二硫化四甲基秋兰姆、三(甲硫基)甲烷、二[3-(三乙氧甲硅烷基)丙基]硫醚；环状硫烷，如1，4-恶噻烷、2，5-二羟基-1，4-二噻烷、1，3-二噻烷、1，3-二噻烷-2-羧酸乙酯、六甲基二硅噻烷、2-甲基-1，3-二噻烷、噻蒽、2-三甲基甲硅烷基-1，3-二噻烷、1，3，5-三噻烷、四氢噻吩，三亚甲基硫醚、1，4，7-三硫代环壬烷、1，4，7-三硫代环癸烷；二硫烷和多硫烷，如二(2-硝基苯基)二硫、二[3-(三乙氧甲硅烷基)丙基]四硫，二[3-(三乙氧甲硅烷基)丙基]二硫、二烯丙基二硫、二苄基二硫、二特丁基二硫、二丁基二硫、二甲基二硫、二苯基二硫、二丙基二硫；亚砜，如烯丙基苯基亚砜、氯甲基苯基亚砜、二苄基亚砜、二甲基亚砜、二苯基亚砜、乙基乙硫基甲基亚砜、DL-甲硫氨酸亚砜、甲基甲硫基甲基亚砜、甲基苯基亚砜、R(+)-甲基-p-甲苯基亚砜、S(-)-甲基-p-甲苯基亚砜、苯基乙烯基亚砜、1-羰基四氢噻吩；噻吩类，如噻吩、2-乙酰噻吩、3-乙酰噻吩、2-乙基噻吩、DL-d-氨基噻吩-2-乙酸、苯并噻吩、2，5-二(5-特丁基苯并恶唑-2-基)噻吩、2，2′-二联噻吩、2-溴噻吩、3-溴噻吩、2-氯噻吩、2，3-二溴噻吩、3，4-二溴噻吩、6，7-二氢-4-苯并[b]噻吩、2，5-二甲基噻吩、2-羟甲基噻吩、2-碘噻吩、甲氧基噻吩、2-甲基噻吩、3-甲基噻吩、3-甲基噻吩-2-甲醛、5-甲基噻吩-2-甲醛、5-甲基噻吩-2-羧酸、2，2′，5′，2″-四噻吩、噻吩-2-乙腈、噻吩-3-乙腈、噻吩-2-乙酰氯、噻吩-2-甲醛、噻吩-3-甲醛、噻吩-2-羧酸、噻吩-3-羧酸、噻吩-2-羧酰氯、噻吩-2-乙酸、噻吩-3-乙酸、噻吩-2-乙酸甲酯、2-巯基噻吩；噻唑类，如噻唑、2-乙酰噻唑、2-氨基苯并噻唑、2-氨基-5-硝基噻唑、2-(4-氨基苯基)-6-甲基苯并噻唑、2-氨基噻唑、2-氨基-2-噻唑啉、2-氨基-4-噻唑基乙酸乙酯、2，2′-吖嗪-二(3-乙基苯并噻唑啉-6-磺酸)、苯并噻唑、3-(苯并噻唑-2-基硫)-1-丙磺酸、2-溴噻唑，2-氯苯并噻唑、2，3-二氢-3，3-二甲基-1，2-苯并异噻唑-1，1-二氧化物、2，5-二甲基苯并噻唑、2，2′-二硫-二(4-甲基噻唑)、2-氟-3，3-二甲基-2，3-二氢-1，2-苯并异噻唑-1，1-二氧化物、5-(2-羟乙基)-4-甲基噻唑、3-羟基-4-甲基-2(3H)-thiazolthion、2-巯基苯并噻唑、2-巯基-2-噻唑啉、2-甲基苯并噻唑、2-(甲基巯基)-2-噻唑啉、2-甲基萘并[1，2-d]噻唑、5-甲基噻唑、2-甲基-2-噻唑啉、R-(-)-2-氧基噻唑烷-4-羧酸、琥珀酰磺胺噻唑、L-噻唑烷-4-羧酸、2，4-噻唑烷二酮、1-(2-噻唑偶氮基)-2-萘酚、4-(2-噻唑偶氮)间苯二酚、R(-)-2-硫代噻唑烷-4-羧酸、2-(三甲基甲硅烷基)噻唑。
特别优选的含硫配体为二乙基硫醚、二甲基亚砜、四氢噻吩、苯并噻唑、噻吩、二苄基硫醚、1，3-二噻烷、三(甲硫基)甲烷、二甲基硫醚、二苄基硫醚、二烯丙基硫醚。
术语“烷基”指“直链”和“支链”烷基。术语“直链烷基”指例如甲基、乙基、正丙基、正丁基、正戊基、正己基的基团。术语“支链烷基”指例如异丙基或特丁基的基团。术语“卤素”指氟、氯、溴或碘。术语“烷氧基”指例如甲氧基、乙氧基、丙氧基、丁氧基、异丙氧基、异丁氧基或戊氧基的基团。
在本发明的上下文中，“芳基”指被C1-C6烷基、C1-C6烷氧基、卤素或杂原子如N、O、酚基、P或S取代的苯基、联苯基或其它类似苯的化合物。对于“芳烷基”来说被N、O、酚、P或S取代。“芳烷基”指上述的“芳基”通过C1-C6烷基链与硅原子键合，其中烷基可被C1-C4烷基或卤素取代。如果“芳基”含有杂原子如O或S，C1-C6烷基链可通过该杂原子与硅原子连接。
当选取取代基如C1-C4烷氧基时，下标的数字指该基团的总碳原子数。
下述实施例1至4描述了本发明的方法。实施例5至7为对照实施例。
此处所给出的选择性是目标产物3-氯丙基三氯硅烷(Cl-PTS)与四氯化硅的摩尔比。本发明实施例所达到的选择性以及3-氯丙基三氯硅烷的产率表明该新方法要比常规方法优越(参见对照实施例5至7)。实施例
实施例1
将100g(472mmol)3-氯丙基三氯硅烷、76.6g(1mol)烯丙基氯和142.3g(1.05mol)三氯硅烷在一个装配有蘑茹状加热器、磁力搅拌器、内置式温度计和强冷至-30℃的回流冷凝器的500ml三颈瓶中混合在一起。然后加入37.0mg(0.10mmol)DMSO(C2H4)PtCl2(V.Y.Kukushkin等人，Inorg.Chim Acta 185(1991)，143)，并将混合物加热至沸腾。由于低沸点组分转化成沸点较高组分，在反应过程中内温上升。当沸腾保持高度稳定相当长时间后，终止反应。然后将反应混合物冷却，并用气相色谱分析所生成的产品混合物。当除去用作溶剂的3-氯丙基三氯硅烷后，发现产品具有以下组成：
2.12wt％ 三氯硅烷(TCS)
0.04wt％ 烯丙基氯(ACl)
16.72wt％ 四氯化硅(STC)
2.73wt％ 丙基三氯硅烷(PTS)
78.38wt％ 3-氯丙基三氯硅烷(Cl-PTS)
因此，以原料用量计，反应的选择性为3.76∶1，以烯丙基氯计，相当于3-氯丙基三氯硅烷的产率为79.0％。
实施例2至4
在类似于实施例1所述的条件下采用多种其它均相催化剂。结果列于下表中
| 催化剂用量 | 产品组成(wt％) | 选择性(以烯丙基氯计算的产率) | |
| 实施例2 | 44.0mg(0.10mmol)THT2PtCl2(THT＝四氢噻吩，E.G.Cox等人，J.Chem.Soc.A(1934)，182) | TCS： 0.04ACl： 0.13STC： 17.80PTS： 1.50Cl-PTS： 80.36 | 3.62∶1(78.4％) |
| 实施例3 | 42.0mg(0.10mmol)DMSO2PtCl2(二甲基亚砜，J.H.Pierce等人，Inorg.Chem.11(1972)，1280) | TCS： 1.03ACI： 0.02STC： 18.23PTS： 2.13Cl-PTS： 77.36 | 3.40∶1(77.3％) |
| 实施例4 | 45.0mg(0.10mmol)(Et2S)2PtCl2(E.G.Cox等人，J.Chem.Soc.A(1934)，182) | TCS： 1.03ACl： 0.02STC： 18.46PTS： 2.09Cl-PTS： 78.37 | 3.40∶1(77.3％) |
实施例5至7(对照实施例)
在类似于实施例1所述的条件下采用多种其它均相催化剂。结果列于下表中。
| 催化剂用量 | 产品组成(wt％) | 选择性(以烯丙基氯计算的产率) | |
| 实施例5 | H2PtCl6·6H2O(CPA)，41mg | TCS： 0.15ACl： 1.67STC： 21.71PTS： 3.54Cl-PTS： 72.88 | 2.69∶1(72.9％) |
| 实施例6 | (Ph3P)2PtCl2(P.J.Stang等人，J.Organomet.Chem.388(1990)，215) | TCS： 1.78ACl： ——STC： 22.77PTS： 2.14Cl-PTS： 73.78 | 2.60∶1(72.2％) |
| 实施例7 | CPA(0.1M丙醇溶液)，0.2ml+dppe(0.1M苯溶液)，0.1ml | TCS： 1.19ACl： ——STC： 20.12PTS： 1.45Cl-PTS： 77.06 | 3.07∶1(75.4％) |
Claims (9)
1、一种制备3-位官能化的有机硅烷的方法，其中，反应温度在0℃至200℃之间，压力在800mbar至6bar之间，采用含有一个或多个含硫配体的铂催化剂，在上述条件下将通式I表示的烯丙基化合物
H2C＝CH-CH2X (I)其中X＝Cl、Br、I、F、CN、SCN、SH、SR、OH、NRR1和OR，R和R1相互独立地为C1-C6烷基或C3-C7芳基，
添加至通式II代表的硅烷中：
R2R3R4SiH (II)其中R2、R3、R4各自独立地为氢、卤素、C1-C6烷基、C1-C6卤代烷基、C3-C6烯丙基、C1-C4烷氧基、苯基、芳基或芳烷基，。
2、如权利要求1所述的方法，其特征在于，X＝F、Cl、Br、或I。
3、如权利要求1或2所述的方法，其特征在于，X＝Cl。
4、如上述任意权利要求所述的方法，其特征在于，三氯硅烷、甲基氢二氯硅烷、乙基氢二氯硅烷、丙基氢二氯硅烷或二甲基氢氯硅烷用作通式II的硅烷。
5、如上述任意权利要求所述的方法，其特征在于，所述含硫配体是单齿或多齿的，并为硫醚、亚砜、硫烷、多硫烷或硫醇。
6、如权利要求5所述的方法，其特征在于，二乙基硫醚、二甲基亚砜、四氢噻吩、苯并噻唑、噻吩、二苄基硫醚、1，3-二噻烷、三(甲硫基)甲烷、二甲基硫醚、二苄基硫醚、二烯丙基硫醚或它们的混合物作为含硫配体。
7、如上述任意权利要求所述的方法，其特征在于，以所采用的烯丙基化合物计，所述催化剂的浓度为0.1至10000ppm，优选为10至500ppm。
8、如上述任意权利要求所述的方法，其特征在于，反应在800mbar至2bar的压力下进行。
9、具有含硫配体的铂催化剂在权利要求1中的加成反应中的应用。
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| CN100352090C (zh) * | 2002-11-26 | 2007-11-28 | 德·诺拉电极股份公司 | 用于电化学氧化反应的金属合金及其制造方法 |
| CN108467486A (zh) * | 2017-12-30 | 2018-08-31 | 深圳市安品有机硅材料有限公司 | 抗硫中毒铂催化剂及其制备方法 |
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| CN100352090C (zh) * | 2002-11-26 | 2007-11-28 | 德·诺拉电极股份公司 | 用于电化学氧化反应的金属合金及其制造方法 |
| CN108467486A (zh) * | 2017-12-30 | 2018-08-31 | 深圳市安品有机硅材料有限公司 | 抗硫中毒铂催化剂及其制备方法 |
| CN108467486B (zh) * | 2017-12-30 | 2021-01-26 | 深圳市安品有机硅材料有限公司 | 抗硫中毒铂催化剂及其制备方法 |
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