GB2234511A - Electrochemical synthesis of organosilicon compounds - Google Patents
Electrochemical synthesis of organosilicon compounds Download PDFInfo
- Publication number
- GB2234511A GB2234511A GB9016403A GB9016403A GB2234511A GB 2234511 A GB2234511 A GB 2234511A GB 9016403 A GB9016403 A GB 9016403A GB 9016403 A GB9016403 A GB 9016403A GB 2234511 A GB2234511 A GB 2234511A
- Authority
- GB
- United Kingdom
- Prior art keywords
- compound
- atoms
- groups
- group
- silicon
- 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.)
- Granted
Links
- 150000003961 organosilicon compounds Chemical class 0.000 title claims description 14
- 230000015572 biosynthetic process Effects 0.000 title description 7
- 238000003786 synthesis reaction Methods 0.000 title description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 52
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- 229910000077 silane Inorganic materials 0.000 claims abstract description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 15
- 125000005843 halogen group Chemical group 0.000 claims abstract description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 14
- 125000001424 substituent group Chemical group 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 229910018540 Si C Inorganic materials 0.000 claims abstract description 8
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229920003257 polycarbosilane Polymers 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 125000000962 organic group Chemical group 0.000 claims abstract description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 4
- 125000004437 phosphorous atom Chemical group 0.000 claims abstract description 3
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 25
- 125000004429 atom Chemical group 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 239000008139 complexing agent Substances 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
- 239000004411 aluminium Substances 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 2
- 229910000971 Silver steel Inorganic materials 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- -1 methyl- Chemical group 0.000 abstract description 38
- 150000004756 silanes Chemical class 0.000 abstract description 9
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 8
- OOCUOKHIVGWCTJ-UHFFFAOYSA-N chloromethyl(trimethyl)silane Chemical compound C[Si](C)(C)CCl OOCUOKHIVGWCTJ-UHFFFAOYSA-N 0.000 abstract description 6
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052736 halogen Inorganic materials 0.000 abstract description 6
- 239000005055 methyl trichlorosilane Substances 0.000 abstract description 6
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 abstract description 6
- BWROMPNXPAWQEP-UHFFFAOYSA-N chloro(chloromethyl)silane Chemical class ClC[SiH2]Cl BWROMPNXPAWQEP-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001923 cyclic compounds Chemical class 0.000 abstract description 2
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 abstract description 2
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 abstract description 2
- 239000005048 methyldichlorosilane Substances 0.000 abstract description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 125000004430 oxygen atom Chemical group O* 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 30
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000011541 reaction mixture Substances 0.000 description 12
- 239000005051 trimethylchlorosilane Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000003487 electrochemical reaction Methods 0.000 description 8
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 8
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 8
- ITKVLPYNJQOCPW-UHFFFAOYSA-N chloro-(chloromethyl)-dimethylsilane Chemical compound C[Si](C)(Cl)CCl ITKVLPYNJQOCPW-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000010926 purge Methods 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 150000002367 halogens Chemical group 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- JKDNLUGVHCNUTB-UHFFFAOYSA-N 1,1,3,3-tetramethyl-1,3-disiletane Chemical compound C[Si]1(C)C[Si](C)(C)C1 JKDNLUGVHCNUTB-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- BJLJNLUARMMMLW-UHFFFAOYSA-N chloro-(3-chloropropyl)-dimethylsilane Chemical compound C[Si](C)(Cl)CCCCl BJLJNLUARMMMLW-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- SWSOIFQIPTXLOI-HNQUOIGGSA-N (e)-1,4-dichlorobut-1-ene Chemical compound ClCC\C=C\Cl SWSOIFQIPTXLOI-HNQUOIGGSA-N 0.000 description 1
- ICSWLKDKQBNKAY-UHFFFAOYSA-N 1,1,3,3,5,5-hexamethyl-1,3,5-trisilinane Chemical compound C[Si]1(C)C[Si](C)(C)C[Si](C)(C)C1 ICSWLKDKQBNKAY-UHFFFAOYSA-N 0.000 description 1
- COSWCAGTKRUTQV-UHFFFAOYSA-N 1,1,3-trimethylurea Chemical compound CNC(=O)N(C)C COSWCAGTKRUTQV-UHFFFAOYSA-N 0.000 description 1
- PASYEMKYRSIVTP-UHFFFAOYSA-N 1,1-dichlorosiletane Chemical compound Cl[Si]1(Cl)CCC1 PASYEMKYRSIVTP-UHFFFAOYSA-N 0.000 description 1
- UWTUEMKLYAGTNQ-UHFFFAOYSA-N 1,2-dibromoethene Chemical group BrC=CBr UWTUEMKLYAGTNQ-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- FZWGHFKXHHRNRD-UHFFFAOYSA-N 1,5-dimethyl-3,4-dihydro-2h-silole Chemical compound CC1=[Si](C)CCC1 FZWGHFKXHHRNRD-UHFFFAOYSA-N 0.000 description 1
- QVTRVYIELYPWQM-UHFFFAOYSA-N 2,2,4,4-tetramethylsiletane Chemical compound CC1(CC([SiH2]1)(C)C)C QVTRVYIELYPWQM-UHFFFAOYSA-N 0.000 description 1
- NYTGRMZNKJWWBE-UHFFFAOYSA-N 2,2-dibromoethenyl(dimethyl)silane Chemical compound BrC(=C[SiH](C)C)Br NYTGRMZNKJWWBE-UHFFFAOYSA-N 0.000 description 1
- XGLVDUUYFKXKPL-UHFFFAOYSA-N 2-(2-methoxyethoxy)-n,n-bis[2-(2-methoxyethoxy)ethyl]ethanamine Chemical compound COCCOCCN(CCOCCOC)CCOCCOC XGLVDUUYFKXKPL-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- BFLIHMZBIRUXDK-UHFFFAOYSA-N 2-trichlorosilylacetic acid Chemical compound OC(=O)C[Si](Cl)(Cl)Cl BFLIHMZBIRUXDK-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- UIFBMBZYGZSWQE-UHFFFAOYSA-N 4-[dichloro(methyl)silyl]butanenitrile Chemical compound C[Si](Cl)(Cl)CCCC#N UIFBMBZYGZSWQE-UHFFFAOYSA-N 0.000 description 1
- QKFFSWPNFCXGIQ-UHFFFAOYSA-M 4-methylbenzenesulfonate;tetraethylazanium Chemical compound CC[N+](CC)(CC)CC.CC1=CC=C(S([O-])(=O)=O)C=C1 QKFFSWPNFCXGIQ-UHFFFAOYSA-M 0.000 description 1
- RJAUOJTXSQGHIN-UHFFFAOYSA-N 5,6-dichloro-5,6-dimethylcyclohexa-1,3-diene Chemical group CC1(Cl)C=CC=CC1(C)Cl RJAUOJTXSQGHIN-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910017048 AsF6 Inorganic materials 0.000 description 1
- 229910015898 BF4 Inorganic materials 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- JIQBIYSSYZCYRL-UHFFFAOYSA-N C[Si](C)(C)C([Si](C)(C)C)[SiH3] Chemical compound C[Si](C)(C)C([Si](C)(C)C)[SiH3] JIQBIYSSYZCYRL-UHFFFAOYSA-N 0.000 description 1
- 241001323490 Colias gigantea Species 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- FYTPGBJPTDQJCG-UHFFFAOYSA-N Trichloro(chloromethyl)silane Chemical compound ClC[Si](Cl)(Cl)Cl FYTPGBJPTDQJCG-UHFFFAOYSA-N 0.000 description 1
- 238000006621 Wurtz reaction Methods 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000004450 alkenylene group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 125000004419 alkynylene group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 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
- UWAXDPWQPGZNIO-UHFFFAOYSA-N benzylsilane Chemical class [SiH3]CC1=CC=CC=C1 UWAXDPWQPGZNIO-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000006278 bromobenzyl group Chemical group 0.000 description 1
- GRADOOOISCPIDG-UHFFFAOYSA-N buta-1,3-diyne Chemical group [C]#CC#C GRADOOOISCPIDG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LOZIVUPXZAKVDI-UHFFFAOYSA-N butyl-(chloromethyl)-dimethylsilane Chemical compound CCCC[Si](C)(C)CCl LOZIVUPXZAKVDI-UHFFFAOYSA-N 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- HJPCYQFRJQEXSL-UHFFFAOYSA-N chloro(trichloromethyl)silane Chemical compound Cl[SiH2]C(Cl)(Cl)Cl HJPCYQFRJQEXSL-UHFFFAOYSA-N 0.000 description 1
- VTFMVORNFLEGJJ-UHFFFAOYSA-N chloro-(chloromethyl)-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound C[Si](Cl)(CCl)CCCOCC1CO1 VTFMVORNFLEGJJ-UHFFFAOYSA-N 0.000 description 1
- WXDJZYHLNMELOZ-UHFFFAOYSA-N chloro-(dichloromethyl)-methylsilane Chemical compound C[SiH](C(Cl)Cl)Cl WXDJZYHLNMELOZ-UHFFFAOYSA-N 0.000 description 1
- CKNVNQHQPPZERM-UHFFFAOYSA-N chloro-bis(chloromethyl)-methylsilane Chemical compound ClC[Si](Cl)(C)CCl CKNVNQHQPPZERM-UHFFFAOYSA-N 0.000 description 1
- HXVPUKPVLPTVCQ-UHFFFAOYSA-N chloro-dimethyl-propylsilane Chemical compound CCC[Si](C)(C)Cl HXVPUKPVLPTVCQ-UHFFFAOYSA-N 0.000 description 1
- OJZNZOXALZKPEA-UHFFFAOYSA-N chloro-methyl-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](Cl)(C)C1=CC=CC=C1 OJZNZOXALZKPEA-UHFFFAOYSA-N 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- LSXNTNKAPQBWLB-UHFFFAOYSA-N dichloro(dichloromethyl)silane Chemical compound ClC(Cl)[SiH](Cl)Cl LSXNTNKAPQBWLB-UHFFFAOYSA-N 0.000 description 1
- JAYBZWYBCUJLNQ-UHFFFAOYSA-N dichloro-(chloromethyl)-methylsilane Chemical compound C[Si](Cl)(Cl)CCl JAYBZWYBCUJLNQ-UHFFFAOYSA-N 0.000 description 1
- GNEPOXWQWFSSOU-UHFFFAOYSA-N dichloro-methyl-phenylsilane Chemical compound C[Si](Cl)(Cl)C1=CC=CC=C1 GNEPOXWQWFSSOU-UHFFFAOYSA-N 0.000 description 1
- 125000004772 dichloromethyl group Chemical group [H]C(Cl)(Cl)* 0.000 description 1
- CWADKGYQSVGONA-UHFFFAOYSA-N dichloromethyl(dimethyl)silane Chemical compound C[SiH](C)C(Cl)Cl CWADKGYQSVGONA-UHFFFAOYSA-N 0.000 description 1
- UWGIJJRGSGDBFJ-UHFFFAOYSA-N dichloromethylsilane Chemical compound [SiH3]C(Cl)Cl UWGIJJRGSGDBFJ-UHFFFAOYSA-N 0.000 description 1
- 229960004132 diethyl ether Drugs 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000000262 haloalkenyl group Chemical group 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000003106 haloaryl group Chemical group 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- FQDIANVAWVHZIR-OWOJBTEDSA-N trans-1,4-Dichlorobutene Chemical compound ClC\C=C\CCl FQDIANVAWVHZIR-OWOJBTEDSA-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
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 1
- SZHYQYMXVMIXEP-UHFFFAOYSA-N trimethyl(4-trimethylsilylbut-1-enyl)silane Chemical compound C[Si](C)(C)CCC=C[Si](C)(C)C SZHYQYMXVMIXEP-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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 Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
- C07F7/121—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20
- C07F7/122—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20 by reactions involving the formation of Si-C linkages
-
- 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 Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0801—General processes
-
- 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 Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/0827—Syntheses with formation of a Si-C bond
-
- 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 Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
- C07F7/121—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20
- C07F7/127—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20 by reactions not affecting the linkages to the silicon atom
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
Abstract
A method of making silanes, carbosilanes or polycarbosilanes having at least one silicon-bonded organic group, linked to the silicon atom via a Si-C bond by electroreduction of a compound (I), having a substituent -RX wherein R is a divalent carbon or hydrocarbon compound which may be substituted and X is halogen in the presence of (II), a silane of the general formula R'4-a-bSiXa(RX)b wherein R' is hydrogen, a hydrocarbon group, a group containing H, C and O atoms, S atoms and/or P atoms and groups consisting of C, H and N atoms, a has a value of 1 to 4, b has a value of 0 to 3 and a+b has a value of 2, 3 or 4. Examples of compound (I) include carbohalides, e.g. methyl-, benzyl-, phenyl- and vinyl-halides, silanes, e.g. trimethylchloromethylsilane and siloxanes. Examples of compound (II) include dimethyldichlorosilane, methyltrichlorosilane, methyldichlorosilane and dichlorosilane. Alternatively, the same reagent for compound (I) and compound (II) may be used, e.g. a silane having at least one silicon-bonded halogen atom and one or more groups -RX, e.g. chloromethylchlorosilanes. The products may be linear and/or cyclic compounds.
Description
ELECTROCHEMICAL SYNTHESIS OF ORGANOSILICON COMPOUNDS
This invention relates to an electrochemical method of synthesising organosilicon compounds, in particular polycarbosilane compounds.
The term organosilicon compounds where used herein denotes those compounds in which at least one organic group is attached to a silicon atom via a Si-C bond. These compounds include silanes having one silicon atom and at least one organic substituent which is linked to the silicon atom via a silicon-carbon linkage and carbosilane compounds having at least two silicon atoms which are linked via a group R, which denotes a divalent carbon or hydrocarbon group which may be substituted, linked to each silicon atom via a Si-C bond. Said carbosilanes include silanes of the general formula -Si-R-Si- and polycarbosilanes having at least 2 units of the general structure -(R-Si)-, wherein R is as defined above.
The formation of Si-C and Si-CH2-Si bonds is usually obtained via Grignard or Wurtz reactions involving the use of metals such as magnesium, sodium and lithium. These methods are complicated and costly and require the protection of any additional functional groups which may be present on the reagents.
Electrochemical synthesis is known and has been practised in organic chemistry for some time. Recently it has been shown that silylation of certain compounds with trimethylchlorosilane is possible via electrochemical synthesis. Shono et al (Chem. Letters 1985, pages 463 466) have demonstrated the electrochemical reduction of benzyl and allyl halides in the presence of trimethylchlorosilane to give the corresponding benzylsilanes and allylsilanes. They also show electroreduction or 1,4 dichloro butene to give 1,4 bis(trimethylsilyl)butene.
P. Pons et al (J. Organometallic Chemistry 1988, pages 31 37) disclose the electroreduction of carbon tetrachloride, chloroform and methylene chloride with trimethylchlorosilane to give the corresponding trimethylsilyl substituted compounds in the presence of a sacrificial electrode. They also exemplify the electro-reduction of trimethylchloromethylsilane with trimethylchlorosilane to obtain hexamethylsilmethylene.
We have now found that it is possible to use electrochemical synthesis for the production of organosilicon compounds as defined above by using dihalosilanes, trihalosilanes, tetrahalosilanes or halocarbohalosilanes.
According to the invention there is provided a method of making organosilicon compounds having at least one silicon-bonded organic group linked to the silicon atom via a Si-C bond by electroreduction of a compound (I) having a substituent of the general formula -RX, wherein R denotes a divalent carbon or hydrocarbon compound which may be substituted, and X is a halogen atom in the presence of (II) a silane of the general formula R'4 a bSiXa(RX)b wherein R' is selected from hydrogen, hydrocarbon groups, groups containing H, C and 0 atoms, S atoms and/or P atoms and groups consisting of C, H and N atoms and optionally 0 atoms wherein N does not form part of an amino group, X and
R are as defined above, a has a value of 1, 2, 3 or 4, b has a value of 0, 1, 2 or 3 and a+b has a value of 2, 3 or 4.
Compound (I) for use in the method of the invention may be any compound which has a halogen substituted carbon atom. The halogen atom is preferably chlorine, bromine or iodine, the latter being the most reactive. For reasons oz commercial availability and for cost purposes however, chlorine and bromine are preferred. The halogen atom is linked to a compound which may be purely organic or which may be a compound having both organic and inorganic parts, for example an organosilicon compound or an organogermanium compound. The group R, to which a halogen atom is linked, is a diva lent carbon or hydrocarbon group which may be substitued. Carbon groups include e.g. acetylene and 1,3 butadiynylene. Hydrocarbon R groups can vary from methylene groups to very large hydrocarbon groups.These may be saturated alkylene groups, e.g. ethylene, isopropylene, hexylene and octadecylene, unsaturated aliphatic groups for example alkenylene or alkynylene, e.g. vinylene, propenylene, butadienylene, hexynylene, propynylene and 1,4 octadecenylene, aromatic groups, e.g. phenylene, benzylene, tolylene and phenylethylene. Substituted hydrocarbon groups are those in which the carbon atoms have one or more substituents which may be any groups which are not reactive with the halogen groups of compound (II) under reaction conditions. Such substituents include fluorine, cyano groups, nitro groups, oxyethylene groups, silyl groups, siloxane groups, carbosilyl groups. Examples of such substituted hydrocarbon groups include hexafluoropropylene, oxyethyleneoxypropylene substituted groups, acetyl substituted groups, ether substituted groups and ester substituted groups.It is preferred that the group R is an aromatically unsaturated, aliphatically unsaturated or aliphatically saturated hydrocarbon, e.g. benzylene, propenylene, isopentylene, butylene, propylene, ethylene or phenylene. Most preferred are methylene and vinylene. The
R group may be linked at the other side to any atom or group. These include e.g. hydrogen atoms, hydrocarbon groups, organosilicon groups, organofunctional groups, e.g. sulphur containing groups, phosphor containing groups and even halogen atoms. Preferably the R group is linked on the other side from the X group to a hydrogen atom or a halogen atom.Examples of compound (I) include carbohalides for example methylhalide, e.g. methylchloride, dichloromethane, benzylhalide, e.g. benzylchloride, phenyl- halide, vinylhalide, 1,4 dichloro 2-butene, dibromoethylene, 1,2,bis- chloromethylbenzene, silanes, e.g.
trimethylchloromethylsilane, dimethylchloromethylchlorosilane, siloxanes, e.g. those having at least one unit of the general formula 4 x (CH2X)y wherein R' is as 2 defined above but is preferably hydrogen, a hydrocarbon, e.g. alkyl, aryl, alkenyl or alkaryl or a group containing
C, H and optionally N or 0 atoms, x has a value of 0, 1 or 2, y has a value of 1, 2 or 3 and x+y are not more than 3, any other units when present having the average formula O4zSiR' wherein R' is as defined above and z has a value 2 of 0, 1, 2 or 3, or those having at least one unit of the general formula O4ySiR x(RCH2X) y wherein R, R', x and 2 are as defined above. Preferably siloxanes are avoided as it is difficult to control the nature of the reaction product.
Compound (II) for use in the method of the invention is a silane which has at least two halogen containing substituents of which at least one is a silicon-bonded halogen atom. Iodine is the most reactive halogen but for reasons of commercial availability and for cost reasons chlorine and bromine atoms are preferred. Non siliconbonded halogen atoms are linked to the silicon atom via a group R as defined above for compound (I). Examples of these halogen containing substituents are haloalkyl, e.g.
chloromethyl, chloroisopropyl, bromoheptyl, haloalkenyl, e.g. chlorovinyl, bromopropenyl, haloaryl groups, e.g.
chlorophenyl and bromobenzyl. Non-halogen containing substituents R' when present, include hydrogen, hydrocarbon groups, for example alkyl, aryl, alkaryl, aralkyl, alkenyl, alkynyl, groups containing C, H and 0 atoms for example carboxyl group containing substituents, C=O containing groups, aldehyde containing groups and epoxy containing groups, ether containing groups, sulphur containing groups or groups containing C, H and N atoms wherein N does not form part of an amino group, for example cyano group containing substituents and NO2 containing substituents.
Examples of such groups are methyl, ethyl, propyl, phenyl, phenylethyl, tolyl, vinyl, allyl, hexenyl, ethynyl, buta diynyl, stearyl, lauryl, ethoxy, methoxy, polyoxyethyl and benzyl. Preferably R' is hydrogen, alkyl or aryl, most preferably methyl or phenyl. It is preferred that the value of a+b is equal to 2, there being two R' groups which independently denote a substituent as described above. The values for a and b are preferably either 1 and 1 respectively or 2 and 0. Examples of compound (11) include dimethyldichlorosilane, dimethylchloromethylchlorosilane, methyltrichlorosilane, carboxymethyltrichlorosilane, phenylmethyldichlorosilane, diphenyldichlorosilane, methylcyanopropyldichlorosilane, methyldichlorosilane, dichlorosilane, methylbis(chloromethyl)chlorosilane and methylglycidoxypropylchloromethylchlorosilane.
Depending on which organosilicon compound one desires to synthesise certain types of compounds (I) and (II) should be selected. Additional compounds may also be added. Organosilicon compounds which may be made by the method of the invention include silanes. Silanes would be produced if (I) is a purely organic compound not having a silicon atom in its structure, and if only one -RX group is present in (I) or if more than one -RX group is present in (I) only a sufficient amount of (II) is provided to allow reaction with one -RX group of (I). Resulting silanes include e.g. methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, tetramethylsilane, chloromethyltrimethylsilane, chloromethyldimethylbutylsilane, dibromovinyldimethylsilane and many others.Carbosilanes as defined above would be provided by the elctrochemical reaction of a compound (I) with more than one -RX groups or a compound I of the formula XRX and a sufficient amount of compound (II) to react with at least two of these -RX groups or X atoms linked to R, or provision of sufficient of compound (I) having only one -RX group with compound (II) having more than one silicon-bonded halogen atoms, or the provision of certain silicon containing compounds (I), for example those having one -RX group and one SiX group for reaction with a compound (II) which may be the same.
As a general rule the value of a+b in compound (II) will, in most cases, determine the general character of the carbosilane produced. Where a+b is 2 using such compound (II) will extend the chain length of the organosilicon compound produced, whereas if a+b has a value of 3 or 4 it will introduce a certain amount of branching in the organosilicon compound leading to a three dimensional structure in some cases. Mixture of compound (II) where a+b is two and compound (Il) where a+b is 3 or 4 can lead to basically linear carbosilanes with some branching, whereas an increase in the amount of compound (II) having a value of 3 or 4 will increase the amount of branching eventually leading to a resin type carbosilane reaction product.
Depending on the nature of the desired carbosilane compound, one type of each compounds (I) and (II) may be reacted together or a mixture of different types of compound (I) and/or compound (II) may be reacted together.
It is also possible to use the same reagent for compound (I) and compound (II), for example a silane having one or more silicon-bonded halogen atoms and one or more groups -RX. For example chloromethylchlorosilanes fall within the definition of both compounds (I) and (II) can react with each other . Such reaction results in the formation of a polycarbosilane having repeating units of the formula -[Si(R')2CH]-. These compounds may be linear or cyclic or a mixture of linear and cyclic organosilicon compounds.
When linear polycarbosilanes are desired it may be preferred to add other compounds, for example end-blocking compounds which may be silanes of the formula R'3SiX, wherein R' and X are as defined above. For example in order to obtain a linear polymer having the general formula R'[Si(R')2-R]mSiR'3 the reagents should include, as well as compounds (I) and (it), a silane of the general formula R' 3SiX in sufficient amount to act as end-blocker of a polymer of the desired chain length.
it is, however, preferred to make relatively small molecules, e.g. polycarbosilanes having 2 or 3 silicon atoms which may then be used as precursors for higher molecuiar weight materials using e.g. conventional polymerisation techniques.
The reaction may be carried out in any convenient way using a cell having a cathode and an anode. The cell may be a single chamber cell but it is preferred to have two chambers which are separated by a membrane, for example a sintered disc. The cell is provided with a potentiostat and/or a galvanostat to regulate the potential or intensity of the current. The electrodes which may be used as cathode or working electrode are preferably made of an inert metal such as gold, silver or platinum, most prefer- ably silver, or of another metal or alloy which is reasonably inert, e.g. stainless steel whilst the counter electrode (anode) is either inert or may be sacrificial to some extent. The choice of counter electrode sometimes depends on the desired reaction.In certain cases a relatively inert counter electrode is preferred whilst in other cases a sacrifical electrode will perform better. Useful metals for the manufacture of the counter electrode include e.g. C, Al, Pt, Ni, Zn and Mg, C being particularly preferred as inert electrode and Al being particularly preferred as sacrificial electrode.
It is preferred to use a complexing agent in conjunction with a sacrificial Al electrode. The use of complexing agents counteracts the catalytic activity of the
Lewis acids formed. Lewis acids, e.g. All3, are known catalysts for ring opening of e.g. tetramethylsilacyclobutane and even tetrahydrofuran which is suitable as a solvent for the method according to the invention.
Suitable complexing agents are known to the persons skilled in the art and include tris(dioxa-3,6 heptyl)amine and hexamethylpho sphoramide.
The cell is filled with a solution of an electrolyte which may be any of those which are commercially available and soluble in the solvent used for the reagents. These electrolytes are salts of the general formula M+Y wherein
M denotes for example Li, Na, NBu4, NMe4, NEt4 and Y denotes for example C104, C1, Br, I, NO3, BF4, AsF6, BPh4,
PF6, All4, CF3SO3 and SCN wherein Bu, Me, Et and Ph respectively denote a butyl, methyl, ethyl and phenyl group. Examples of suitable electrolytes include tetraethyl ammonium p-toluene sulphonic acid, tetrabutyl ammonium hexafluoro phosphate, tetrabutyl ammonium bromide, tetraethyl ammonium tetrafluoro borate, lithium chloride and magnesium chloride.
Solvents which dissolve both reagents and electrolytes are usually employed. Suitable solvents are those in which the reagent is at least partially soluble under operating conditions of concentration and temperature.
They include tetrahydrofuran, acetonitrile, y butyrolactone, dimethoxyethane with nitromethane, 1,3 dioxolane, liquid SO2, trimethylurea and dimethylformamide. The electrochemical reaction may be carried out by keeping the intensity constant at predetermined levels or by retaining a constant potential which has been determined by cyclic voltametry. Standard electrochemical techniques are applied cable to the method of the invention.
There now follow a number of examples which illustrate the invention in which all parts and percentages are expressed by weight unless otherwise stated.
Example 1
A one compartment cell equipped with a nitrogen inlet, agitation and an air cooling system was charged with 50ml of a 0.2 molar solution of tetrabutylammonium. hexafluorophosphate In tetrahydrofuran and 8.5g of chloromethyldimethylchlorosilane. A constant current density of 125mA was applied via a galvanostat/potentiostat using aluminium foil as anode and a silver wire as cathode. The current was applied over a period of 22 hours in order to apply 1.9 Faraday per mole of C1CH2.A reaction product mixture was obtained which was analysed by gas chromotography/mass spectrometry and was found to consist of about 50% cyclic compounds of which about 65% had the formula [(CH3)2Si-CH2]2, about 35% had the formula [(CH3)2Si-CH2]3 and of about 50% linear compounds of the formula ClCH2SiCCH3)2[CH2SiCCH3)2]nCl where 84% had a value for n equal to 3, about 5 to 8% each of compounds where n had the value of 2, 4 and 5 and traces of the compound where n had the value of 1.
Example 2
A 250ml flask was equipped with a nitrogen purge, magnetic stirrer, condenser and air cooling device. 100ml of a 0.2 molar solution of tetrabutylammonium hexafluorophosphate in tetrahydrofuran and 15.4g of 3-chloropropyl dimethylchlorosilane were added. An electrochemical reaction was carried out using a model 362 potentiostat galvanostat. The cathode was a silver wire (5cm length and 0.25mm diameter) and the anode was 4 aluminium strips (3 x 5 x 0.01cm).A constant current was applied during 25 hours (giving 2.5 Faraday per mole of silane) at a temperature of 23"C. The resulting reaction mixture was analysed by gas chromatography/mass spectrometry. 83.71 was l,l-dimethyl-l-silacyclobutane, 8.1 unreacted 3-chloropropyl dimethylchlorosilane and 7.9 propyl dimethylchlorosilane.
Example 3
A 250ml flask was equipped with a nitrogen purge, magnetic stirrer, condenser and air cooling device. 150ml of a 0.2 molar solution of tetrabutylammonium hexafluorophosphate in tetrahydrofuran and 25.5g of chloromethyl dimethylchlorosilane were added. An electrochemical reaction was carried out as in the previous example except that 2.8 Faraday was applied per mole of silane at a temperature of 30"C. The resulting reaction mixture was analysed as above. 62.6% was 1,1,3,3-tetramethyl-1,3- disilacyclobutane and 31.4% 1,1,3,3,5,5-hexamethyl-1,3,5trisilacyclohexane.
Example 4
A 250ml flask was equipped with a nitrogen purge, magnetic stirrer, condenser and air cooling device. 100ml of a 0.2 molar solution of tetrabutylammonium hexafluorophosphate in tetrahydrofuran and 5.24g of a,a,o-dichloroxylene and 4g of dichlorodimethylsilane were added. AI1 electrochemical reaction was carried out as in the previous example except that 4.8 Faraday was applied per mole of o-dichloroxylene. The resulting reaction mixture was washed in water, extracted with diethylether, dried and analvsed as above. 65% had the formula
Example 5
A 250ml flask was equipped with a nitrogen purge, magnetic stirrer, condenser and air cooling device. 100ml of a 0.2 molar solution of tetrabutylammonium hexafluorophosphate in tetrahydrofuran, 3.70g of cis-dichlorobutene and 4g of dichlorodimethylsilane were added.An electrochemical reaction was carried out as in the previous example except that 2.13 Faraday was applied per mole of cis-dichlorobutene. The resulting reaction mixture was analysed and showed 15% dimethylsilacyclopentene.
Example 6
A 250ml flask was equipped with a nitrogen purge, magnetic stirrer, condenser and air cooling device. 100ml of a 0.2 molar solution of tetrabutylammonium hexafluorophosphate in tetrahydrofuran, 12.5g of chloromethyltrimethylsilane and 6.5g of dichloromethylsilane were added.
An electrochemical reaction was carried out as in the previous example except that 2.3 Faraday was applied per mole of chloromethyltrimethylsilane. The resulting reaction mixture was analysed and showed 25% bis(trimethylsilyl)methylsilane.
Example 7
A Schlenk tube was equipped with an aluminium rod as anode (99.5% pure, 6.35mm diameter) and a cylindrical stainless steel gauze as cathode (20 mesh, 30cm2). A solution of 14.3ml of tetrahydrofuran, 0.08g of tetraethylammonium tetrafluoroborate, 3.6ml of hexamethylphosphoramide and O.lml of trimethylchlorosilane was preelectrolysed at lOOmA for 2 hours. 2.28g of chloromethyl- dimethylchlorosilane were added. An electrochemical reaction was carried out by applying a constant current during 10 hours (giving 2.3 Faraday per mole of silane) at a temperature of 23"C. The resulting reaction mixture was filtered and stripped under reduced pressure to give 11.68g of distillate.Analysis by gas chromatography/mass spectrometry yielded 69% of 1,1,3,3-tetramethyl-1,3- disilacyclobutane.
Example 8
Using the set-up of Example 7, 4.24g of chloropropyltrichlorosilane was added to the reaction product of the previous example and the electrolysis continued at 200mA for almost 6 hours. After three and a half hours a maximum conversion to dichlorosilacyclobutane of 45% was observed.
Example 9
The set-up of Example 7 was used except that a condenser, cooled with solid carbon dioxide, was added to minimise loss of reagents. A solution of 8.45ml of tetrahydrofuran, 0.08g of tetraethylammonium tetrafluoroborate, 2.lml of hexamethylphosphoramide, 6.4ml of dichloromethane and O.lml of trimethylchlorosilane was pre-electrolysed at 50mA for 2 hours. 3.03ml of chloromethyldimethylchlorosilane were added. An electrochemical reaction was carried out by applying a constant current during 53 hours (giving 4 Faraday per mole of silane) at a temperature of 23"C.
The resulting reaction mixture was analysed by gas chromatography/mass spectrometry yielding 74% of dimethyldichloromethylsilane.
Example 10
The set-up of Example 9 was used. A solution of 9.16ml of tetrahydrofuran, 0.08g of tetraethylammonium tetrafluoroborate, 2.29my of hexamethylphosphoramide, 1.28ml of dichloromethane and O.lml of trimethylchlorosilane was pre-electrolysed at 50mA for 2 hours. 7.27ml of dimethyldichlorosilane was added and the electrolysis continued at 50mA for 24 hours giving 2.2 Faraday per mole of silane). The resulting reaction mixture was analysed by gas chromatography/mass spectrometry yielding 81% (based on reacted silane) of chlorodimethyl chloromethylsilane.
Example 11
The set-up of Example 9 was used. A solution of 12.67ml of tetrahydrofuran, 0.08g of tetraethylammonium tetrafluoroborate, 3.12ml of hexamethylphosphoramide, 0.85ml of dichloromethane and O.lml of trimethylchlorosilane was pre-electrolysed at 50mA for 2 hours. 4.48ml of methyltrichlorosilane was added and the electrolysis continued at 50mA for 12.5 hours giving 2.2 Faraday per mole of silane). The resulting reaction mixture was analysed by gas chromatography/mass spectrometry yielding 62% of methyldichloro chloromethylsilane and 13% of methylchlorodichloromethylsilane.
Example 12
The set-up of Example 9 was used. A solution of 11.8ml of tetrahydrofuran, 0.08g of tetraethylammonium tetrafluoroborate, 2.95my of hexamethylphosphoramide, 0.64ml of dichloromethane and O.lml of trimethylchlorosilane was pre-electrolysed at 50mA for 2 hours. 6.79g of tetrachlorosilane was added and the electrolysis continued at 50mA for 12.5 hours (giving 2.2 Faraday per mole of silane). The resulting reaction mixture was analysed by gas chromatography/mass spectrometry yielding 58% of trichlorochloromethylsilane, 15% of dichloro dichloromethylsilane and 3% of chloro trichloromethylsilane.
Example 13
The set-up of Example 9 was used. A solution of 12.37m1 of tetrahydrofuran, 0.08g of tetraethylammonium tetrafluoroborate, 3.09ml of hexamethylphosphoramide, 1.12ml of phenylchloride and O.lml of trimethylchlorosilane was pre-electrolysed at 50mA for 2 hours. 4.48g of methyltrichlorosilane was added and the electrolysis continued at 50mA for 12.5 hours (giving 2.2 Faraday per mole of silane). The resulting reaction mIxture was analysed by gas chromatography/mass spectrometry yielding 65% dichlorophenylmethylsilane, 10% of methylchlorodiphenylsilane and 6% of dichloromethyl silphenylene.
Example 14
The set-up of Example 9 was used. A solution of 11.52ml of tetrahydrofuran, 0.08g of tetraethylammonium tetrafluoroborate, 2.88my of hexamethylphosphoramide, 1.12ml of phenylchloride and O.lml of trimethylchlorosilane was pre-electrolysed at 50mA for 2 hours. 6.79g of methyltrichlorosilane was added and the electrolysis continued at 50mA for 12.5 hours (giving 2.2 Faraday per mole of silane). The resulting reaction mixture was analysed by gas chromatography/mass spectrometry yielding 68% trichlorophenylsilane, 10% of dichlorodiphenylsilane and 8% of trichloro silphenylene.
Claims (18)
- I. A method of making organosilicon compounds having at least one silicon-bonded organic group, linked to the silicon atom via a Si-C bond by electroreduction of a compound (I) having a substituent of the general formula -RX wherein R denotes a divalent carbon or hydrocarbon compound which may be substituted and X is a halogen atom in the presence of (II), a silane of the general formula R 4~a~bSiXa(RX)b wherein R' is selected from hydrogen, hydrocarbon groups, groups containing H, C and 0 atoms, S atoms and/or P atoms and groups consisting of C, H and N atoms and optionally 0 atoms wherein N does not form part of an amino group, X and R are as defined above, a has a value of 1, 2, 3 or 4, b has a value of 0, 1, 2 or 3 and a+b has a value of 2, 3 or 4.
- 2. A method according to Claim 1 wherein X is chlorine.
- 3. A method according to either Claim 1 or Claim 2 wherein the group R in compound (I) is an aromatically unsaturated, aliphatically unsaturated or aliphatically saturated hydrocarbon.
- 4. A method according to any one of the preceding claims wherein in compound (II) R' is hydrogen, alkyl or aryl.
- 5. A method according to Claim 4 wherein R' is methyl or phenyl.
- 6. A method according to any one of the preceding claims wherein in compound (II) the value of a+b is equal to 2.
- 7. A method according to any one of the preceding claims carried out in a cell having two chambers which are separated by a membrane.
- 8. A method according to any one of the preceding claims wherein the cathode is made of silver or stainless steel.
- 9. A method according to any one of the preceding claims wherein the anode is inert.
- 10. A method according to Claim 9 wherein the anode is made from C.
- 11. A method according to any one of Claims 1 to 8 wherein the anode is sacrifical to some extent.
- 12. A method according to Claim 11 in which the anode is made of aluminium.
- 13. A method according to any one of the preceding claims wherein a complexing agent is used.
- 14. An organosilicon compound in which at least one organic group is attached to a silicon atom via a Si-C bond, made by a method, according to any one of the preceding claims.
- 15. A silane having one silicon atom and at least one organic substituent which is linked to the silicon atom via a siliconcarbon linkage, made by a method, according to any one of Claims I to 13.
- 16. A carbosilane having at least two silicon atoms which are linked via a group R which denotes a divalent carbon or hydrocarbon group which may be substituted, linked to the silicon atoms via Si-C bonds, made by a method, according to any one of Claims 1 to 13.
- 17. A polycarbosilane having at least 2 units of the general structure -(R-Si)- wherein R is as defined above, made by a method, according to any one of Claims 1 to 13.
- 18. A method for making organosilicon compounds essentially as described herein with reference to any one of the examples.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9016403A GB2234511B (en) | 1989-08-03 | 1990-07-26 | Electrochemical synthesis of organosilicon compounds |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB898917725A GB8917725D0 (en) | 1989-08-03 | 1989-08-03 | Electrochemical synthesis of organosilicon compounds |
GB9016403A GB2234511B (en) | 1989-08-03 | 1990-07-26 | Electrochemical synthesis of organosilicon compounds |
Publications (3)
Publication Number | Publication Date |
---|---|
GB9016403D0 GB9016403D0 (en) | 1990-09-12 |
GB2234511A true GB2234511A (en) | 1991-02-06 |
GB2234511B GB2234511B (en) | 1993-04-14 |
Family
ID=26295696
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB9016403A Expired - Fee Related GB2234511B (en) | 1989-08-03 | 1990-07-26 | Electrochemical synthesis of organosilicon compounds |
Country Status (1)
Country | Link |
---|---|
GB (1) | GB2234511B (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2681866A1 (en) * | 1991-09-27 | 1993-04-02 | Rhone Poulenc Chimie | Process for the synthesis of organosilicon compounds and organosilicon compounds |
EP0629718A1 (en) * | 1993-06-17 | 1994-12-21 | Wacker-Chemie GmbH | Process for electrochemical synthesis of organic silicon compounds as well as an apparatus for carrying outsaid process and the use of said apparatus for preparing said organic silicon compounds |
WO1996008519A2 (en) * | 1994-09-12 | 1996-03-21 | The Dow Chemical Company | Silylium cationic polymerization activators for metallocene complexes |
FR2791705A1 (en) * | 1999-04-01 | 2000-10-06 | Rhodia Chimie Sa | Preparation of a silylated carbonylated and halogenated derivative by electrolysis of a polyhalogenated or fluorinated carbonylated substrate in the presence of a silylating agent |
WO2014070270A1 (en) * | 2012-11-02 | 2014-05-08 | Dow Corning Corporation | Electrochemical route to prepare hydrocarbyl-functional silicon compounds |
CN107835815A (en) * | 2015-05-27 | 2018-03-23 | 陶氏环球技术有限责任公司 | The method for preparing double (chloromethyl) dichlorosilanes and double (chloromethyl) (aryl) chlorosilanes |
WO2023222245A1 (en) | 2022-05-20 | 2023-11-23 | Wacker Chemie Ag | Process for producing organosilicon compounds |
-
1990
- 1990-07-26 GB GB9016403A patent/GB2234511B/en not_active Expired - Fee Related
Non-Patent Citations (3)
Title |
---|
1988,P.PONS et al pages 31-37 * |
Benzylsilanes", pages 463-466 Journal of ORGANOMETALLIC CHEMISTRY * |
CHEMISTRY LETTERS,1985, T.SHONO et al,"An Electroreductive systhesis of Allylsilanes and * |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2681866A1 (en) * | 1991-09-27 | 1993-04-02 | Rhone Poulenc Chimie | Process for the synthesis of organosilicon compounds and organosilicon compounds |
EP0629718A1 (en) * | 1993-06-17 | 1994-12-21 | Wacker-Chemie GmbH | Process for electrochemical synthesis of organic silicon compounds as well as an apparatus for carrying outsaid process and the use of said apparatus for preparing said organic silicon compounds |
US5538618A (en) * | 1993-06-17 | 1996-07-23 | Wacker-Chemie Gmbh | Process for the electrochemical synthesis of organosilicon compounds, and an appliance for carrying out the process, and use thereof for preparing organosilicon compounds |
WO1996008519A2 (en) * | 1994-09-12 | 1996-03-21 | The Dow Chemical Company | Silylium cationic polymerization activators for metallocene complexes |
WO1996008519A3 (en) * | 1994-09-12 | 1996-06-13 | Dow Chemical Co | Silylium cationic polymerization activators for metallocene complexes |
FR2791705A1 (en) * | 1999-04-01 | 2000-10-06 | Rhodia Chimie Sa | Preparation of a silylated carbonylated and halogenated derivative by electrolysis of a polyhalogenated or fluorinated carbonylated substrate in the presence of a silylating agent |
WO2000060139A1 (en) * | 1999-04-01 | 2000-10-12 | Rhodia Chimie | Method for preparing silylated, carbonylated and halogenated derivatives by electrolysis |
WO2014070270A1 (en) * | 2012-11-02 | 2014-05-08 | Dow Corning Corporation | Electrochemical route to prepare hydrocarbyl-functional silicon compounds |
CN107835815A (en) * | 2015-05-27 | 2018-03-23 | 陶氏环球技术有限责任公司 | The method for preparing double (chloromethyl) dichlorosilanes and double (chloromethyl) (aryl) chlorosilanes |
CN107835815B (en) * | 2015-05-27 | 2021-02-26 | 陶氏环球技术有限责任公司 | Process for preparing bis (chloromethyl) dichlorosilane and bis (chloromethyl) (aryl) chlorosilane |
WO2023222245A1 (en) | 2022-05-20 | 2023-11-23 | Wacker Chemie Ag | Process for producing organosilicon compounds |
Also Published As
Publication number | Publication date |
---|---|
GB2234511B (en) | 1993-04-14 |
GB9016403D0 (en) | 1990-09-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Chandrasekhar et al. | Recent developments in the synthesis and structure of organosilanols | |
Kumada et al. | Aliphatic organopolysilanes | |
JP4351058B2 (en) | Alkene-platinum-silyl complex | |
EP1013699A2 (en) | Polyorganosiloxanes having at least one organofunctional group with multiple hydrolyzable groups | |
US5527935A (en) | Organopolysiloxanes having bifunctional terminal siloxane units | |
JPH06172535A (en) | Preparation of cluster azasilacycloalkyl- functional polysiloxane | |
US11008349B2 (en) | Process for the production of organohydridochlorosilanes | |
Michalska | Reactions of organosilicon hydrides with organosilanols catalysed by homogeneous and silica-supported rhodium (L) complexes | |
GB2234511A (en) | Electrochemical synthesis of organosilicon compounds | |
EP0405560B1 (en) | Preparation of tertiary-hydrocarbylsilyl compounds | |
US3793357A (en) | Process for the redistribution of alkylsilanes and alkylhydrosilanes | |
US3535092A (en) | Reduction of halogen-containing silicon compounds | |
CA2022184A1 (en) | Electrochemical synthesis of organosilicon compounds | |
Lewis et al. | Platinum catalysed hydrosilylation of alkynes: Comparison of rates of addition of terminal olefins to internal alkynes | |
US5281736A (en) | Method for the preparation of 1-aza-2-silacyclopentane compounds | |
US5852153A (en) | Trimethylsiloxy group-containing polysiloxane and a process for producing the same | |
US3529007A (en) | New organosilicon compounds,their preparation and their use | |
US5239099A (en) | Azasilacycloalkyl functional alkoxysilanes and azasilacycloalkyl functional tetramethyldisiloxanes | |
US3746732A (en) | Synthesis of silylmetallic complexes | |
Andrianov et al. | The Hydride Addition of Organohydrosiloxanes to Compounds with a Multiple Carbon–Carbon Bond | |
Luderer et al. | Preparation and Synthetic Utility of 1‐Trimethylsiloxyalkyl‐bis (trimethylsilyl) silanes,(Me3Si) 2SiH–C (OSiMe3) R1R2 | |
EP0195997B1 (en) | Chlorosilane compounds | |
EP1668018B1 (en) | Preparation of a halosilylated chain hydrocarbon | |
US5281737A (en) | 1-aza-2-silacyclobutane compounds and method for their preparation | |
JPH0786117B2 (en) | Alkoxy silane |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19970726 |