WO2005123811A1 - Method for electrochemically linking silicon-carbon bonds and silicon-hydrogen bonds by using a hydrogen electrode - Google Patents
Method for electrochemically linking silicon-carbon bonds and silicon-hydrogen bonds by using a hydrogen electrode Download PDFInfo
- Publication number
- WO2005123811A1 WO2005123811A1 PCT/EP2005/006225 EP2005006225W WO2005123811A1 WO 2005123811 A1 WO2005123811 A1 WO 2005123811A1 EP 2005006225 W EP2005006225 W EP 2005006225W WO 2005123811 A1 WO2005123811 A1 WO 2005123811A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hydrogen
- alkyl
- alkenyl
- radical
- group
- Prior art date
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 61
- 239000001257 hydrogen Substances 0.000 title claims abstract description 59
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims description 41
- -1 iso-butyl - Chemical class 0.000 claims description 38
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 239000005062 Polybutadiene Substances 0.000 claims description 5
- 239000008139 complexing agent Substances 0.000 claims description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
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- 235000010980 cellulose Nutrition 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 239000002608 ionic liquid Substances 0.000 claims description 4
- 229920002857 polybutadiene Polymers 0.000 claims description 4
- 239000005033 polyvinylidene chloride Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 3
- 239000000010 aprotic solvent Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 229920001195 polyisoprene Polymers 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 125000005353 silylalkyl group Chemical group 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 2
- 244000043261 Hevea brasiliensis Species 0.000 claims description 2
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical compound CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 239000005018 casein Substances 0.000 claims description 2
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 claims description 2
- 235000021240 caseins Nutrition 0.000 claims description 2
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 2
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 235000010981 methylcellulose Nutrition 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000003136 n-heptyl 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])* 0.000 claims description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 229920003052 natural elastomer Polymers 0.000 claims description 2
- 229920001194 natural rubber Polymers 0.000 claims description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 125000005561 phenanthryl group Chemical group 0.000 claims description 2
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
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- 239000003153 chemical reaction reagent Substances 0.000 claims 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims 1
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- 238000002360 preparation method Methods 0.000 description 7
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- 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
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052794 bromium Inorganic materials 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
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 125000000000 cycloalkoxy group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 239000012039 electrophile Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 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
- 150000004820 halides Chemical class 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000012493 hydrazine sulfate Substances 0.000 description 1
- 229910000377 hydrazine sulfate Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 125000006608 n-octyloxy group Chemical group 0.000 description 1
- 125000005484 neopentoxy group Chemical group 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 229920003257 polycarbosilane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- KXFSUVJPEQYUGN-UHFFFAOYSA-N trimethyl(phenyl)silane Chemical compound C[Si](C)(C)C1=CC=CC=C1 KXFSUVJPEQYUGN-UHFFFAOYSA-N 0.000 description 1
- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 description 1
- SCHZCUMIENIQMY-UHFFFAOYSA-N tris(trimethylsilyl)silicon Chemical compound C[Si](C)(C)[Si]([Si](C)(C)C)[Si](C)(C)C SCHZCUMIENIQMY-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
-
- 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
- C25B3/23—Oxidation
-
- 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
- C25B3/29—Coupling reactions
Definitions
- the invention relates to an electrochemical process for forming silicon-carbon and silicon-hydrogen bonds (Si-C and Si-H bonds) using a hydrogen anode (H 2 anode).
- EP 0 446 578 B1, EP 0 558 760 B1, EP 0 671 487 B1, JP 3104893 B2, JP 3264683 B2 and JP 09-255785 A2 describe processes for the electrochemical production of polysilanes, i.e. Formation of Si-Si bonds from halogen monosilanes.
- Si-Si bonds are formed from halosilanes by electrochemical reaction using an anode, which is surrounded by a halogen scavenger (especially hydrogen).
- the object of the present invention was therefore to provide an electrochemical process which can be used to produce silicon-carbon and silicon-hydrogen bonds, while avoiding undesirable side reactions, for example caused by halogens or metal halides.
- the task was surprisingly achieved by using a hydrogen anode for the electrochemical formation of silicon-carbon and silicon-hydrogen bonds (Si-C and Si-H bonds).
- the invention therefore relates to a process for the electrochemical formation of silicon-carbon and silicon-hydrogen bonds, characterized in that a hydrogen anode is used as the anode.
- the invention further relates to a process for the electrochemical formation of silicon-carbon and silicon-hydrogen bonds, characterized in that a substituted silane of the general formula (1)
- R 1 independently of one another a radical selected from the group comprising hydrogen, C 6 -C ⁇ 8 aryl, C 3 -C ⁇ 8 - heteroaryl, C ⁇ -C3 n-alkyl, C 2 -C 30 alkenyl, C 3 -C 30 - alkynyl, -C-C 3 o-alkoxy, C 2 -C 3 o-alkenyloxy, C3-C30-alkynyloxy, C 6 -C 8 -aryl -CC-C 3 o-alkyl -, C 3 -C 8 heteroaryl -C -C 30 alkyl-, C 6 -Ci 8 -aryl-C 2 -C 3 o-alkenyl-, C 3 -C 8 - heteroaryl-C 2 -C 3 o -Alkenyl-, -CC 8 -alkoxy-C 3 -C 3 -alkyl-, -C 8 -alkoxycarbon
- X independently of one another is a radical selected from the group consisting of halogen atom and OR 2 , R 2 is a C 1 -C 4 -alkyl radical and n is 1, 2, 3 and 4
- R 3 independently of one another a radical selected from the group consisting of hydrogen, unsubstituted or substituted C ⁇ -Ci ⁇ -aryl, C 3 8 -C ⁇ heteroaryl, C ⁇ -C 3 _ o alkyl, C 2 -C 30 alkenyl , C 3 -C 3 n-alkynyl, C 6 -C 8 aryl-C 30 -C 30 alkyl, C 3 -C 8 heteroaryl-C 3 -C 3 o-alkyl, C 6 -C 8 - Aryl- C 2 -C 30 alkenyl, C 3 -C ⁇ 8 heteroaryl-C 2 -C 3 o-alkenyl, -C ⁇ -C ⁇ 8 ⁇ alkoxy-C ⁇ -C 3 o-alkyl, -C ⁇ ⁇ C ⁇ 8 - Alkoxycarbonyl, -CC 8 ⁇ alkoxy-C 2 -C 30 alkenyl, C 6 -C 8 -aryloxy
- Y independently of one another is a radical selected from the group containing hydrogen and halogen atom
- radical R 1 is a substituted radical
- this substituent is preferably selected from the group of optionally substituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, hydroxy, alkoxy, acyloxy, silyloxy, Carboxylate, alkoxycarbonyl, amino, nitro or halogen radicals.
- radical R 1 contains a heteroatom, it is preferably 0, N, S, P or Si.
- Preferred monomeric radicals R 1 are C 1 -C 30 alkyl, C 2 -C 3 o-alkenyl, C 3 -C 8 cycloalkyl, C 6 -C 8 aryl, C 6 -C 8 aryl-C ⁇ -C 3 o-alkyl and C 1 -C30 alkoxy, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert. -Butyl-, n-pentyl-, iso-pentyl-, neo-pentyl-, tert.
- -Pentyl- n-hexyl, n-heptyl, n-octyl, iso-octyl, n-decyl, n-dodecyl, n-octadecyl, vinyl, allyl, cyclopentyl, cyclohexyl, cycloheptyl, methylcyclohexyl, phenyl -, naphthyl, anthryl, phenanthryl, o-tolyl, m-tolyl, p-tolyl, xylyl and ethylphenyl, benzyl, ⁇ -phenylethyl, ß-phenylethyl, methoxy, ethoxy, n-propyloxy, iso-propyloxy, n-butoxy, iso-butoxy, tert-butoxy, n-pentyloxy, iso-pentyloxy
- Preferred oligomeric and polymeric radicals R 1 are, for example, the polymers polyvinyl chloride, polyethylene, polypropylene, polyvinyl acetate, polycarbonate, polyacrylate, polymethacrylate, polymethyl methacrylate, polystyrene, polyacrylonitrile, polyvinylidene chloride (PVC), polyvinyl fluoride, polyvinylidene fluoride, polyvinylidene cyanide, polybutadiene, polyisophenene, polyisophenylene Polyamide, polyimide, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyethylene glycol and their derivatives and the like, as well as copolymers, such as styrene-acrylate copolymers, vinyl acetate-acrylate copolymers, ethylene-vinyl acetate copolymers, ethylene-propylene-terpolymers (EPDM), ethylene-propylene- Rubber (EPM), poly
- Oligomers and polymeric radicals R 1 are, for example, also natural oligomers and polymers, such as cellulose, starch, casein and natural rubber, as well as semisynthetic oligomers and polymers, such as cellulose derivatives, methyl cellulose, hydroxymethyl cellulose, carboxymethyl cellulose, silicone polymers and organosilyl-functionalized organopolysiloxane resins.
- natural oligomers and polymers such as cellulose, starch, casein and natural rubber
- semisynthetic oligomers and polymers such as cellulose derivatives, methyl cellulose, hydroxymethyl cellulose, carboxymethyl cellulose, silicone polymers and organosilyl-functionalized organopolysiloxane resins.
- radicals R 1 are the methyl, ethyl, phenyl, vinyl, cyclohexyl, methoxy and ethoxy radical.
- the substituent X is preferably selected from the group comprising the chloride, bromide, iodide and alkoxy radical -OR 2 , where X particularly preferably denotes the chloride, methoxy or ethoxy radical.
- radical R 3 is a substituted radical
- this substituent is preferably selected from the group of optionally substituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, hydroxy, alkoxy, acyloxy, silyloxy, Carboxylate, alkoxycarbonyl, amino, nitro or halogen radicals.
- R 3 radicals are hydrogen, methyl, ethyl, substituted and unsubstituted phenyl, substituted silylalkyl and polyvinyl radicals.
- the substituent Y is preferably selected from the group containing hydrogen and chloride.
- Particularly preferred compounds of the general formula (2) are hydrogen (H 2 ), CH 3 C1 and C 6 H 5 C1.
- any mixtures or combinations of compounds of the general formulas (1) can be used, the electrochemical reaction of the individual components being able to take place both simultaneously and in succession.
- the process can be carried out in the presence or absence of complexing agents.
- work is carried out, for example, in the presence of hexamethylphosphoric triamide (HMPT) or N, N'-dimethylpropyleneurea (DMPH).
- HMPT hexamethylphosphoric triamide
- DMPH N, N'-dimethylpropyleneurea
- the use of toxicologically questionable complexing agents is preferably avoided.
- a conductive salt is preferably added.
- Inert salts or mixtures thereof which do not react with the reaction components are used as conductive salts.
- Examples of conductive salts are salts of the general formula M + Y ⁇ , in which M preferably Mg, Li, Na, NBu 4 , NMe 4 or NEt 4 and Y preferably C10 4 , Cl, Br, I, N0 3 , BF 4 , ASF 6 , BPh 4 , PF 6 , A1C1 4 , CF3SO3 and SCN mean, in which Bu, Me, Et or Ph denotes a butyl, methyl, ethyl or phenyl group.
- Suitable electrolytes include tetraethylammonium tetrafluoroborate, tetrabutylammonium tetrafluoroborate and tetrabutylammonium bromide.
- Magnesium and lithium chloride and mixtures thereof are particularly preferred conductive salts.
- the process preferably takes place in a solvent.
- All aprotic solvents which do not react with the compounds of the general formulas (1) and (2) and which are inert under the given electrochemical conditions can be used as solvents.
- Suitable solvents are all in which the compounds used are at least partially soluble under operating conditions with regard to concentration and temperature.
- the compounds of the general formulas (1) and (2) themselves can also be used as solvents serve.
- Suitable solvents are ethers, such as, for example, tetrahydrofuran (THF), 1,2-dimethoxyethane, 1,3-dioxolane or bis (2-methoxy-ethyl) ether, dioxane, acetonitrile, ⁇ -butyrolactone, nitromethane, liquid sulfur dioxide, Tris (dioxa-3, 6-heptyl) amine, trimethylurea, dimethylformamide, dimethyl sulfoxide, and mixtures of these solvents.
- Supercritical media such as supercritical CO 2 or ionic liquids can also be used as solvents. If ionic liquids are used as the solvent, this preferably takes over the function of the conductive salt.
- the solvents are preferably dry.
- a particularly preferred solvent is tetrahydrof ran.
- the anode is constructed in a manner known to those skilled in the art. It can consist of all materials which have sufficient electrical conductivity, are chemically inert under the selected reaction conditions and are coated with a precious metal or an alloy which contains one or more noble metals, or already consist thereof, the noble metals being rhenium, Ruthenium, rhodium, osmium, iridium, platinum or palladium are used and of which the group containing platinum and palladium and their alloys. If it is a coated anode, silicon carbide, iron silicide or graphite is preferred as the anode material to be coated. Graphite is particularly preferred as the base material and platinum or palladium or alloys which contain platinum and / or palladium as the coating material.
- the anode is reacted under gaseous hydrogen or mixtures of hydrogen and one or more inert gases, such as helium, nitrogen or flows around argon.
- Hydrogen is preferably used alone or a mixture of nitrogen and hydrogen. Pure hydrogen or forming gas (90% nitrogen, 10% hydrogen) are particularly preferred.
- the hydrogen or the gas mixture containing hydrogen is metered, for example, in such a way that a gas inlet tube is attached below the anode and through this the hydrogen or its mixture is introduced into the system.
- a porous graphite tube coated with platinum or palladium or with alloys containing platinum and / or palladium is used as the anode.
- the amount of hydrogen or hydrogen-containing gas mixture depends on the size of the apparatus, the design of the anode and the design of the electrolysis cell and must be set so that the anode is completely surrounded by the hydrogen or hydrogen-containing gas mixture during the electrolysis.
- the counter electrode can also consist of all materials that have sufficient electrical conductivity and are chemically stable under the selected reaction conditions. Preferred are graphite or a chemically stable metal such as gold, silver, platinum, rhenium, ruthenium, rhodium, osmium, iridium and palladium or another metal or alloy that is sufficiently stable, such as stainless steel.
- a hydrogen anode is a long-lasting, stable electrode which also enables a simpler cell design, since no electrode change, as in the case of sacrificial anodes, is necessary.
- the use of sacrificial anodes in Si-H bond formation is only possible to a limited extent, since these can be attacked by the protons necessary for the reaction (acid addition).
- the present invention is all the more surprising since a person skilled in the art must assume that when using a hydrogen electrode instead of a sacrificial anode, such as Mg, for example, the desired product cannot be formed in the Si-C bond formation, but other reactions are in the foreground. This is due to the fact that the carbanion primarily generated at the cathode by electroreduction should only react with the protons formed at the anode from H 2 (secondary reaction 1), since the protons, in contrast to the uncharged, bulky Si, due to their size and charge -Electrophiles, migrate faster towards the cathode, the place of origin of the carbanions, and react there.
- Si-C bond formation anode reaction: H 2 - ⁇ . 2 H ⁇ + 2 e ⁇ ⁇ cathode reaction: R 3 C-CI + 2 e ⁇ R 3 C! ⁇ + Cl ⁇ side reaction 1: H anode + R 3 C: ⁇ a thode ⁇ R3G- UH // * side reaction 2: 2 H A node + 2 e ⁇ // H 2
- the process can be carried out in any conventional way using an electrolytic cell with a cathode and a hydrogen anode.
- the electrolytic cell can be a divided or undivided electrolytic cell, the undivided electrolytic cell being preferred since it is the simplest in construction.
- the process preferably takes place under an inert gas atmosphere, nitrogen, argon or helium being preferred as inert gases.
- the electrolysis cell is preferably provided with a potentiostat or a galvanostat (constant current flow) in order to regulate the potential or the intensity of the current.
- the implementation can be carried out with and without controlled potential.
- the method preferably takes place under the influence of ultrasound.
- the temperature in the process is preferably -50 ° C to 150 ° C, particularly preferably -10 to 50 ° C. All of the above symbols of the above formulas have their meanings independently of one another.
- the silicon atom is tetravalent in all formulas.
- the cell Before the electrolysis begins, the cell is heated and, if necessary, the Kryomat is given sufficient time to cool to the desired temperature. Then the hydrogen flow is adjusted to about 60 mbar (graphite anode) above normal pressure before adding the electrolyte and starting materials so that the pores of the hydrogen electrode cannot soak up with the reaction solution while the cell is being filled. Only then are the electrolyte, organic halide (only for Si-C bond formation) and silane transferred into the cell in a nitrogen countercurrent. The electrolysis is carried out in a cooled ultrasound bath and / or with stirring at a current of 45 mA. The electrolytes have special dryness requirements. The THF is therefore distilled over potassium or dried using an ion exchange column. The conductive salts are used in the quality "puriss.” Or “for electrochemical purposes"; LiCl and MgCl 2 are dried for 5-6 hours at 0.5 torr with heating just prior to use. H 2 graphite anode
- a graphite cylinder from SIGRI (MKSl) is brought into the appropriate shape so that the copper and stainless steel power and gas supply lines can then be inserted into the cylinder.
- the transition from graphite to copper / stainless steel is sealed gas-tight and the graphite part is then coated with platinum.
- a mixture of 3% ammonia and 5% hydrazine sulfate solution is then applied for reduction.
- the electrode is then dried in the drying cabinet.
- a stainless steel or silver electrode is used as the cathode.
- Tetraethylammonium tetrafluoroborate Et 4 NBF 4 0.2 mol'L -1 in 80 mL of a mixture of THF and HMPT (3: 1 v / v)) was introduced into the electrolytic cell. Then chlorobenzene (8.0 mL; 79 mmol) and trimethylchlorosilane (Me 3 SiCl, 10.0 mL; 79 mmol) are added in succession and the electrolysis started. After 18 hours, the product can already be detected using GC-MS. The reaction is stopped after 190 hours.
- Example 4 The experimental procedure is analogous to Example 4 with 15 g of Amberlyst ® A-21 and a solution of trimethylchlorosilane (Me 3 SiCl, 4.5 g; 41 mmol) and methylene chloride (about 25 g; 0.5 mol) obtained by a reflux condenser (-70 ° C ) is condensed.
- the electrolysis is carried out at room temperature, the boiling methyl chloride is kept in the electrolysis cell by the reflux condenser. After 2.2 F, the product tetramethylsilane is obtained in about 25% yield.
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Abstract
The invention relates to an electrochemical method for linking silicon-carbon bonds and silicon-hydrogen bonds (Si-C and Si-H-bonds) by using a hydrogen anode (H2 anode).
Description
Verfahren zur elektrochemischen Knüpfung von Silicium- Kohlenstoff- und Silicium-Wasserstoff-Bindungen unter Verwendung einer Wasserstoff-Elektrode Process for the electrochemical formation of silicon-carbon and silicon-hydrogen bonds using a hydrogen electrode
Die Erfindung betrifft ein elektrochemisches Verfahren zur Knüpfung von Silicium-Kohlenstoff- und Silicium-Wasserstoff- Bindungen (Si-C- und Si-H-Bindungen) unter Verwendung einer Wasserstoffanode (H2-Anode) .The invention relates to an electrochemical process for forming silicon-carbon and silicon-hydrogen bonds (Si-C and Si-H bonds) using a hydrogen anode (H 2 anode).
Verfahren zur elektrochemischen Synthese von Organosiliciumver- bindungen sind bereits bekannt. Beispielsweise werden in den Patentschriften EP 0 446 578 Bl, EP 0 558 760 Bl, EP 0 671 487 Bl, JP 3104893 B2, JP 3264683 B2 und JP 09-255785 A2 Verfahren zur elektrochemischen Herstellung von Polysilanen, d.h. Knüpfung von Si-Si-Bindungen aus Halogenmonosilanen beschrieben.Processes for the electrochemical synthesis of organosilicon compounds are already known. For example, EP 0 446 578 B1, EP 0 558 760 B1, EP 0 671 487 B1, JP 3104893 B2, JP 3264683 B2 and JP 09-255785 A2 describe processes for the electrochemical production of polysilanes, i.e. Formation of Si-Si bonds from halogen monosilanes.
Aus den Patenschriften DE 40 24 600 AI, DE 102 23 939 AI und JP53-031673 A2 sind Verfahren zur Herstellung von Carbosilanen und Polycarbosilanen aus (Halogenalkyl) -halogensilanen bekannt (Knüpfung von Si-C-Bindungen). Pons et al. beschreiben ein elektrochemisches Verfahren zur Ausbildung von Si-C-Bindungen durch Umsetzung von Chlorsilanen mit halogenorganischen Verbindungen (J. Organomet. Chem. 358 (1988), 31; J. Organomet. Chem. 321 (1987) , C27) .Processes for the production of carbosilanes and polycarbosilanes from (haloalkyl) halosilanes are known from patents DE 40 24 600 AI, DE 102 23 939 AI and JP53-031673 A2 (formation of Si-C bonds). Pons et al. describe an electrochemical process for the formation of Si-C bonds by reacting chlorosilanes with halogen-organic compounds (J. Organomet. Chem. 358 (1988), 31; J. Organomet. Chem. 321 (1987), C27).
Allen diesen elektrochemischen Verfahren ist gemeinsam, dass sich während der Reaktion unerwünschte Nebenprodukte bilden, die entweder den Reaktionsverlauf negativ beeinflussen oder schwer zu entsorgen sind. Dies ist immer auf die Wahl der Anode zurückzuführen .
Falls wie in der deutsche Offenlegungsschrift DE 40 24 600 AI beschrieben, bei dem elektrochemischen Verfahren eine im wesentlichen inerte Anode, beispielsweise aus Pt oder C, verwendet wird, bildet sich beim Einsatz einer derartigen Elektrode in einer nicht definierte Anodenreaktion elementares Halogen, das wiederum unerwünschte Reaktionen, beispielsweise mit dem Lösungsmittel in Form der Halogenierung des Lösungsmittels, eingehen kann.All these electrochemical processes have in common that undesired by-products are formed during the reaction, which either negatively influence the course of the reaction or are difficult to dispose of. This is always due to the choice of the anode. If, as described in German Offenlegungsschrift DE 40 24 600 AI, an essentially inert anode, for example made of Pt or C, is used in the electrochemical process, elemental halogen is formed when an electrode of this type is used in an undefined anode reaction, which in turn is undesirable Reactions, for example with the solvent in the form of halogenation of the solvent.
Falls, wie auch in den anderen beschriebenen Fällen, eine nicht vollständig inerte Anode (Opferanode) zur Anwendung kommt, wird zwar die Bildung des Halogens verhindert, jedoch bilden sich dabei erhebliche Mengen an Metallhalogeniden, die entsprechend aufgearbeitet und entsorgt werden müssen. Darüber hinaus wird die Anode während der Reaktion verbraucht und muss nach einer gewissen Zeit ersetzt werden.If, as in the other cases described, a not completely inert anode (sacrificial anode) is used, the formation of the halogen is prevented, but considerable amounts of metal halides are formed, which have to be worked up and disposed of accordingly. In addition, the anode is consumed during the reaction and must be replaced after a certain time.
Die Verwendung einer H2-Anode wurde bereits für die Knüpfung von Si-Si-Bindungen beschrieben. EP 0 629 718 Bl beansprucht ein Verfahren zur elektrochemischen Synthese und eine Vorrichtung zur Durchführung dieser zur Herstellung von Organosilicium-Verbindungen. Dabei werden Si-Si-Bindungen aus Halogensilanen durch elektrochemische Reaktion unter Verwendung einer Anode, die von einem Halogenfänger (insbesondere Wasserstoff) umspült wird, geknüpft.The use of an H 2 anode has already been described for the formation of Si-Si bonds. EP 0 629 718 B1 claims a method for electrochemical synthesis and an apparatus for carrying it out for the production of organosilicon compounds. Here, Si-Si bonds are formed from halosilanes by electrochemical reaction using an anode, which is surrounded by a halogen scavenger (especially hydrogen).
Die Aufgabe der vorliegenden Erfindung war somit, ein elektrochemisches Verfahren zur Verfügung zu stellen, mit dem Silicium-Kohlenstoff- und Silicium-Wasserstoff-Bindungen erzeugt werden können, wobei störende Nebenreaktionen, wie beispielsweise verursacht durch Halogene oder Metallhalogenide, vermieden werden können.
Die Aufgabe konnte überraschend durch die Verwendung einer Wasserstoffanode zur elektrochemischen Knüpfung von Silicium- Kohlenstoff- und Silicium-Wasserstoff-Bindungen (Si-C- und Si- H-Bindungen) gelöst werden.The object of the present invention was therefore to provide an electrochemical process which can be used to produce silicon-carbon and silicon-hydrogen bonds, while avoiding undesirable side reactions, for example caused by halogens or metal halides. The task was surprisingly achieved by using a hydrogen anode for the electrochemical formation of silicon-carbon and silicon-hydrogen bonds (Si-C and Si-H bonds).
Gegenstand der Erfindung ist daher ein Verfahren zur elektrochemischen Knüpfung von Silicium-Kohlenstoff- und Silicium-Wasserstoff-Bindungen, dadurch gekennzeichnet, dass als Anode eine Wasserstoffanode verwendetet wird.The invention therefore relates to a process for the electrochemical formation of silicon-carbon and silicon-hydrogen bonds, characterized in that a hydrogen anode is used as the anode.
Gegenstand der Erfindung ist weiterhin ein Verfahren zur elektrochemischen Knüpfung von Silicium-Kohlenstoff- und Silicium-Wasserstoff-Bindungen, dadurch gekennzeichnet, dass ein substituiertes Silan der allgemeinen Formel (1)The invention further relates to a process for the electrochemical formation of silicon-carbon and silicon-hydrogen bonds, characterized in that a substituted silane of the general formula (1)
[SiR1 (4-n)Xn] (1), wobei[SiR 1 (4 -n) Xn] (1 ) , where
R1 unabhängig von einander einen Rest ausgewählt aus der Gruppe enthaltend Wasserstoff, C6-Cι8-Aryl-, C3-Cι8- Heteroaryl-, Cι-C3n-Alkyl-, C2-C30-Alkenyl-, C3-C30- Alkinyl-, Cι-C3o-Alkoxy-, C2-C3o-Alkenyloxy-, C3-C30- Alkinyloxy-, C6-Cι8-Aryl-Cι-C3o-Alkyl-, C3-Cι8-Heteroaryl- Cι-C30-Alkyl-, C6-Ci8-Aryl-C2-C3o-Alkenyl-, C3-Cι8- Heteroaryl-C2-C3o-Alkenyl-, Cι-Cι8-Alkoxy-Cι-C3o-Alkyl-, Cι-Cι8-Alkoxycarbonyl-, Cι-Cι8-Alkoxy-C2-C3o-Alkenyl-, ζ- Cι8-Aryloxy-Cι-C3o-Alkyl-, C5-Cι8-Aryloxy-C2-C3o-Alkenyl-, C3-C8-Cycloalkyl-, C3-C8-Cycloalkyloxy-, C3-C8- Cycloalkyl-Cι-C30-Alkyl- oder C3-C8-Cycloalkyl-C2-C3o- Alkenylrest, Silyl- und Silyloxyrest, Oligomer und Polymer, organosilylfunktionalisiertes Si02, organo-
silylfunktionalisierte Harze und organosilylfunktiona- lisierte Partikel,R 1 independently of one another a radical selected from the group comprising hydrogen, C 6 -Cι 8 aryl, C 3 -Cι 8 - heteroaryl, Cι-C3 n-alkyl, C 2 -C 30 alkenyl, C 3 -C 30 - alkynyl, -C-C 3 o-alkoxy, C 2 -C 3 o-alkenyloxy, C3-C30-alkynyloxy, C 6 -C 8 -aryl -CC-C 3 o-alkyl -, C 3 -C 8 heteroaryl -C -C 30 alkyl-, C 6 -Ci 8 -aryl-C 2 -C 3 o-alkenyl-, C 3 -C 8 - heteroaryl-C 2 -C 3 o -Alkenyl-, -CC 8 -alkoxy-C 3 -C 3 -alkyl-, -C 8 -alkoxycarbonyl-, -C 8 -alkoxy-C 2 -C 3 o-alkenyl-, C 8 -C 8 - aryloxy-Cι-C 3 o-alkyl, C 5 -Cι 8 aryloxy-C 2 -C 3 O-alkenyl, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyloxy, C 3 - C 8 - Cycloalkyl -CC 30 alkyl or C 3 -C 8 cycloalkyl-C 2 -C 3 o-alkenyl radical, silyl and silyloxy radical, oligomer and polymer, organosilyl-functionalized Si0 2 , organo- silyl-functionalized resins and organosilyl-functionalized particles,
X unabhängig von einander einen Rest ausgewählt aus der Gruppe enthaltend Halogenatom und OR2, R2 einen Cι-Cι0-Alkylrest und n einen Wert 1, 2, 3 und 4X independently of one another is a radical selected from the group consisting of halogen atom and OR 2 , R 2 is a C 1 -C 4 -alkyl radical and n is 1, 2, 3 and 4
bedeuten,mean,
einer Verbindung der allgemeinen Formel (2)a compound of the general formula (2)
R3-Y (2),R 3 -Y (2),
wobeiin which
R3 unabhängig von einander einen Rest ausgewählt aus der Gruppe enthaltend Wasserstoff, unsubstituierten oder substituierten Cβ-Ciβ-Aryl-, C3-Cι8-Heteroaryl-, Cι-C3o_ Alkyl-, C2-C30-Alkenyl-, C3-C3n-Alkinyl-, C6-Cι8-Aryl-Cι- C30-Alkyl-, C3-Cι8-Heteroaryl-Cι-C3o-Alkyl-, C6-Cι8-Aryl- C2-C30-Alkenyl-, C3-Cι8-Heteroaryl-C2-C3o-Alkenyl-, Cι-Cι8~ Alkoxy-Cι-C3o-Alkyl-, Cι~Cι8-Alkoxycarbonyl-, Cι-Cι8~ Alkoxy-C2-C30-Alkenyl-, C6-Cι8-Aryloxy-Cι-C30-Alkyl-, C6- Cι8-Aryloxy-C2-C30-Alkenyl-, C3-C8-Cycloalkyl-, C3-Cg- Cycloalkyl-Cι-C30-Alkyl- oder C3-C8-Cycloalkyl-C2-C3o- Alkenylrest, Silyl-, Silyloxy- und Silylalkylrest, Oligomer und Polymer undR 3 independently of one another a radical selected from the group consisting of hydrogen, unsubstituted or substituted Cβ-Ciβ-aryl, C 3 8 -Cι heteroaryl, Cι-C 3 _ o alkyl, C 2 -C 30 alkenyl , C 3 -C 3 n-alkynyl, C 6 -C 8 aryl-C 30 -C 30 alkyl, C 3 -C 8 heteroaryl-C 3 -C 3 o-alkyl, C 6 -C 8 - Aryl- C 2 -C 30 alkenyl, C 3 -Cι 8 heteroaryl-C 2 -C 3 o-alkenyl, -Cι-Cι 8 ~ alkoxy-Cι-C 3 o-alkyl, -Cι ~ Cι 8 - Alkoxycarbonyl, -CC 8 ~ alkoxy-C 2 -C 30 alkenyl, C 6 -C 8 -aryloxy-C-C 30 alkyl-, C 6 -C 8 -aryloxy-C 2 -C 30 alkenyl -, C 3 -C 8 cycloalkyl, C 3 -Cg cycloalkyl -CC 30 alkyl or C 3 -C 8 cycloalkyl-C 2 -C 3 alkenyl radical, silyl, silyloxy and silylalkyl radical, oligomer and polymer and
Y unabhängig von einander einen Rest ausgewählt aus der Gruppe enthaltend Wasserstoff und HalogenatomY independently of one another is a radical selected from the group containing hydrogen and halogen atom
bedeuten,
unter Verwendung einer Wasserstoffanode elektrochemisch umgesetzt wird, so dass eine Verbindung der allgemeinen Formel (3)mean, is electrochemically reacted using a hydrogen anode, so that a compound of the general formula (3)
[ S lR (4-n) X (n-m) Ym] ( 3 ) , wobei n, m Werte 1, 2, 3 oder 4 bedeuten, mit der Maßgabe, dass m kleiner oder gleich n sein kann,[S 1R (4-n) X (n-m) Ym] (3), where n, m are values 1, 2, 3 or 4, with the proviso that m can be less than or equal to n,
erhalten wird.is obtained.
Soweit es sich beim Rest R1 um einen substituierten Rest handelt, wird dieser Substituent vorzugsweise ausgewählt aus der Gruppe der gegebenenfalls wiederum substituierten Alkyl-, Alkenyl-, Alkinyl-, Aryl-, Heteroaryl-, Hydroxy, Alkoxy-, Acyloxy, Silyloxy-, Carboxylat-, Alkoxycarbonyl-, Amino-, Nitro- oder Halogenreste.If the radical R 1 is a substituted radical, this substituent is preferably selected from the group of optionally substituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, hydroxy, alkoxy, acyloxy, silyloxy, Carboxylate, alkoxycarbonyl, amino, nitro or halogen radicals.
Soweit der vorstehend genannte Rest R1 ein Heteroatom enthält, handelt es sich dabei vorzugsweise um 0, N, S, P oder Si.If the above-mentioned radical R 1 contains a heteroatom, it is preferably 0, N, S, P or Si.
Bevorzugte monomere Reste R1 sind Cι-C30-Alkyl-, C2-C3o-Alkenyl-, C3-C8-Cycloalkyl, C6-Cι8-Aryl-, C6-Cι8-Aryl-Cι-C3o-Alkyl und C1-C30- Alkoxyreste, wie beispielsweise Methyl-, Ethyl-, n- Propyl-, iso-Propyl-, n-Butyl-, iso-Butyl-, tert . -Butyl-, n-Pentyl-, iso-Pentyl-, neo-Pentyl-, tert . -Pentyl-, n-Hexyl, n-Heptyl, n- Octyl, iso-Octyl, n-Decyl, n-Dodecyl, n-Octadecyl, Vinyl-, Allyl, Cyclopentyl-, Cyclohexyl-, Cycloheptyl-, Methylcyclohexyl-, Phenyl-, Naphthyl, Anthryl-, Phenanthryl-, o-Tolyl-, m-Tolyl-, p-Tolyl-, Xylyl- und Ethylphenyl-, Benzyl-,
α-Phenylethyl-, ß-Phenylethyl-, Methoxy-, Ethoxy-, n- Propyloxy-, iso-Propyloxy-, n-Butoxy-, iso-Butoxy-, tert.- Butoxy-, n-Pentyloxy-, iso-Pentyloxy-, neo-Pentyloxy-, tert.- Pentyloxy-, n-Hexyloxy-, n-Heptyloxy- und n-Octyloxyrest .Preferred monomeric radicals R 1 are C 1 -C 30 alkyl, C 2 -C 3 o-alkenyl, C 3 -C 8 cycloalkyl, C 6 -C 8 aryl, C 6 -C 8 aryl-Cι -C 3 o-alkyl and C 1 -C30 alkoxy, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert. -Butyl-, n-pentyl-, iso-pentyl-, neo-pentyl-, tert. -Pentyl-, n-hexyl, n-heptyl, n-octyl, iso-octyl, n-decyl, n-dodecyl, n-octadecyl, vinyl, allyl, cyclopentyl, cyclohexyl, cycloheptyl, methylcyclohexyl, phenyl -, naphthyl, anthryl, phenanthryl, o-tolyl, m-tolyl, p-tolyl, xylyl and ethylphenyl, benzyl, α-phenylethyl, ß-phenylethyl, methoxy, ethoxy, n-propyloxy, iso-propyloxy, n-butoxy, iso-butoxy, tert-butoxy, n-pentyloxy, iso-pentyloxy -, neo-pentyloxy, tert-pentyloxy, n-hexyloxy, n-heptyloxy and n-octyloxy.
Bevorzugte oligomere und polymere Reste R1 sind beispielsweise die Polymere Polyvinylchlorid, Polyethylen, Polypropylen, Polyvinylacetat, Polycarbonat, Polyacrylat, Polymethacrylat, Polymethylmethacrylat, Polystyrol, Polyacrylnitril, Polyvinylidenchlorid (PVC) , Polyvinylfluorid, Polyvinylidenfluorid, Polyvinylidencyanid, Polybutadien, Polyisopren, Polyether, Polyester, Polyamid, Polyimid, Polyvinylalkohol, Polyvinylpyrrolidon, Polyacrylamid, Polyethylenglykol und deren Derivate und ähnliche, sowie Copolymere, wie beipsielsweise Styrol-Acrylat Copolymere, Vinylacetat-Acrylat Copolymere, Ethylen-Vinylacetat Copolymere, Ethylen-Propylen-Terpolymere (EPDM) , Ethylen-Propylen-Kautschuk (EPM) , Polybutadien (BR) Poly-Isobuten-Isopren (Butylkautschuk, JJR) , Polyisopren (IR) und Styrol-Butadien-Kautschuk (SBR) . Oligomere und polymere Reste R1 sind beispielsweise auch natürliche Oligomere und Polymere, wie Cellulose, Stärke, Casein und natürliches Gummi, sowie halbsynthetische Oligomere und Polymere, wie beispielsweise Cellulosederivate, Methylcellulose, Hydroxymethylcellulose, Carboxymethylcellulose, Siliconpolymere und organosilylfunktionalisierte Organopolysiloxanharze .Preferred oligomeric and polymeric radicals R 1 are, for example, the polymers polyvinyl chloride, polyethylene, polypropylene, polyvinyl acetate, polycarbonate, polyacrylate, polymethacrylate, polymethyl methacrylate, polystyrene, polyacrylonitrile, polyvinylidene chloride (PVC), polyvinyl fluoride, polyvinylidene fluoride, polyvinylidene cyanide, polybutadiene, polyisophenene, polyisophenylene Polyamide, polyimide, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyethylene glycol and their derivatives and the like, as well as copolymers, such as styrene-acrylate copolymers, vinyl acetate-acrylate copolymers, ethylene-vinyl acetate copolymers, ethylene-propylene-terpolymers (EPDM), ethylene-propylene- Rubber (EPM), polybutadiene (BR), poly-isobutene-isoprene (butyl rubber, JJR), polyisoprene (IR) and styrene-butadiene rubber (SBR). Oligomers and polymeric radicals R 1 are, for example, also natural oligomers and polymers, such as cellulose, starch, casein and natural rubber, as well as semisynthetic oligomers and polymers, such as cellulose derivatives, methyl cellulose, hydroxymethyl cellulose, carboxymethyl cellulose, silicone polymers and organosilyl-functionalized organopolysiloxane resins.
Besonders bevorzugte Reste R1 sind der Methyl-, Ethyl-, Phenyl- , Vinyl-, Cyclohexyl-, Methoxy- und Ethoxyrest.Particularly preferred radicals R 1 are the methyl, ethyl, phenyl, vinyl, cyclohexyl, methoxy and ethoxy radical.
Der Substituent X wird bevorzugt ausgewählt aus der Gruppe enthaltend den Chlorid-, Bromid-, Jodid und Alkoxyrest -OR2,
wobei X besonders bevorzugt den Chlorid-, Methoxy- oder Ethoxyrest bedeutet.The substituent X is preferably selected from the group comprising the chloride, bromide, iodide and alkoxy radical -OR 2 , where X particularly preferably denotes the chloride, methoxy or ethoxy radical.
Soweit es sich bei dem Rest R3 um einen substituierten Rest handelt, wird dieser Substituent vorzugsweise ausgewählt aus der Gruppe der gegebenenfalls wiederum substituierten Alkyl-, Alkenyl-, Alkinyl-, Aryl-, Heteroaryl-, Hydroxy, Alkoxy-, Acyloxy, Silyloxy, Carboxylat-, Alkoxycarbonyl-, Amino-, Nitro- oder Halogenreste.If the radical R 3 is a substituted radical, this substituent is preferably selected from the group of optionally substituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, hydroxy, alkoxy, acyloxy, silyloxy, Carboxylate, alkoxycarbonyl, amino, nitro or halogen radicals.
Bevorzugte Reste R3 sind Wasserstoff, Methyl-, Ethyl-, substituierter und unsubstituierter Phenyl-, substituierter Silylalkyl- und Polyvinylrest .Preferred R 3 radicals are hydrogen, methyl, ethyl, substituted and unsubstituted phenyl, substituted silylalkyl and polyvinyl radicals.
Der Substituent Y wird bevorzugt ausgewählt aus der Gruppe enthaltend Wasserstoff und Clorid.The substituent Y is preferably selected from the group containing hydrogen and chloride.
Besonders bevorzugte Verbindungen der allgemeinen Formel (2) sind Wasserstoff (H2) , CH3C1 und C6H5C1.Particularly preferred compounds of the general formula (2) are hydrogen (H 2 ), CH 3 C1 and C 6 H 5 C1.
In einer weiteren bevorzugten Ausführungsform können auch beliebige Mischungen oder Kombinationen aus Verbindungen der allgemeinen Formeln (1) eingesetzt werden, wobei die elektrochemische Reaktion der einzelnen Komponenten sowohl gleichzeitig als auch nacheinander ablaufen kann.In a further preferred embodiment, any mixtures or combinations of compounds of the general formulas (1) can be used, the electrochemical reaction of the individual components being able to take place both simultaneously and in succession.
Das Verfahren kann in An- bzw. Abwesenheit von Komplexierungsmitteln durchgeführt werden. Im Fall der Anwesenheit solcher Komplexierungsmittel wird beispielsweise in Gegenwart von Hexamethylphosphorsäuretriamid (HMPT) oder N,N'- Dimethylpropylenharnstoff (DMPH) gearbeitet. Bevorzugt wird auf den Einsatz von toxikologisch bedenklichen Komplexierungsmitteln verzichtet .
Das Verfahren kann in An- bzw. Abwesenheit von Basen wie beispielsweise Triethylamin, Pyridin bzw. Ionenaustauschern wie beispielsweise Amberlyst® A21 oder auch Molekularsieben durchgeführt werden. Wird als Agens der allgemeinen Formel (2) Wasserstoff (R3 = H und Y = H) verwendet, wird bevorzugt in Anwesenheit von Triethylamin oder Ionenaustauschern gearbeitet .The process can be carried out in the presence or absence of complexing agents. In the case of the presence of such complexing agents, work is carried out, for example, in the presence of hexamethylphosphoric triamide (HMPT) or N, N'-dimethylpropyleneurea (DMPH). The use of toxicologically questionable complexing agents is preferably avoided. The method may for example, Amberlyst A21 ® or molecular sieves also be carried out in the presence or absence of bases such as triethylamine, pyridine or ion exchangers. If hydrogen (R 3 = H and Y = H) is used as the agent of the general formula (2), preference is given to working in the presence of triethylamine or ion exchangers.
Um eine ausreichende Leitfähigkeit der Reaktionsmischung zu erreichen, wird vorzugsweise ein Leitsalz zugesetzt. Als Leitsalze werden inerte Salze oder deren Gemische verwendet, die nicht mit den Reaktionskomponenten reagieren. Beispiele für Leitsalze sind Salze der allgemeinen Formel M+Y~, worin M vorzugsweise Mg, Li, Na, NBu4, NMe4 oder NEt4 und Y vorzugsweise C104, Cl, Br, I, N03, BF4, ASF6, BPh4, PF6, A1C14, CF3SO3 und SCN bedeuten, worin Bu, Me, Et bzw. Ph eine Butyl-, Methyl-, Ethyl- bzw. Phenylgruppe bezeichnet. Beispiele geeigneter Elektrolyte schließen Tetraethylammoniumtetrafluoro- borat, Tetrabutylammoniumtetrafluoroborat und Tetrabutylammoniumbromid ein. Besonders bevorzugte Leitsalze sind Magnesium- und Lithiumchlorid sowie deren Gemische.In order to achieve a sufficient conductivity of the reaction mixture, a conductive salt is preferably added. Inert salts or mixtures thereof which do not react with the reaction components are used as conductive salts. Examples of conductive salts are salts of the general formula M + Y ~ , in which M preferably Mg, Li, Na, NBu 4 , NMe 4 or NEt 4 and Y preferably C10 4 , Cl, Br, I, N0 3 , BF 4 , ASF 6 , BPh 4 , PF 6 , A1C1 4 , CF3SO3 and SCN mean, in which Bu, Me, Et or Ph denotes a butyl, methyl, ethyl or phenyl group. Examples of suitable electrolytes include tetraethylammonium tetrafluoroborate, tetrabutylammonium tetrafluoroborate and tetrabutylammonium bromide. Magnesium and lithium chloride and mixtures thereof are particularly preferred conductive salts.
Das Verfahren findet vorzugsweise in einem Lösungsmittel statt. Als Lösungsmittel können alle aprotischen Lösungsmittel verwendet werden, die nicht mit den Verbindungen der allgemeinen Formeln (1) und (2) reagieren und die unter den gegebenen elektrochemischen Bedingungen inert sind. Geeignete Lösungsmittel sind alle, in denen zumindest teilweise die eingesetzten Verbindungen unter Betriebsbedingungen bezüglich Konzentration und Temperatur löslich sind. In einer speziellen Ausführungsform können auch die eingesetzten Verbindungen der allgemeinen Formeln (1) und (2) selbst als Lösungsmittel
dienen. Beispiele für geeignete Lösungsmittel sind Ether, wie beispielsweise Tetrahydrofuran (THF) , 1, 2-Dimethoxyethan, 1,3- Dioxolan oder Bis (2-Methoxy-ethyl) -ether, Dioxan, Acetonitril, γ-Butyrolacton, Nitromethan, flüssiges Schwefeldioxid, Tris (dioxa-3, 6-heptyl) amin, Trimethylharnstoff, Dimethylformamid, Dimethylsulfoxid, sowie Gemische dieser Lösungsmittel. Als Lösungsmittel können auch überkritische Medien, wie beispielsweise überkritisches C02 oder ionische Flüssigkeiten verwendet werden. Im Falle der Verwendung von ionischen Flüssigkeiten als Lösungsmittel übernimmt dieses bevorzugt die Funktion des Leitsalzes. Die Lösungsmittel sind bevorzugt trocken. Ein besonders bevorzugtes Lösungsmittel ist Tetrahydrof ran .The process preferably takes place in a solvent. All aprotic solvents which do not react with the compounds of the general formulas (1) and (2) and which are inert under the given electrochemical conditions can be used as solvents. Suitable solvents are all in which the compounds used are at least partially soluble under operating conditions with regard to concentration and temperature. In a special embodiment, the compounds of the general formulas (1) and (2) themselves can also be used as solvents serve. Examples of suitable solvents are ethers, such as, for example, tetrahydrofuran (THF), 1,2-dimethoxyethane, 1,3-dioxolane or bis (2-methoxy-ethyl) ether, dioxane, acetonitrile, γ-butyrolactone, nitromethane, liquid sulfur dioxide, Tris (dioxa-3, 6-heptyl) amine, trimethylurea, dimethylformamide, dimethyl sulfoxide, and mixtures of these solvents. Supercritical media such as supercritical CO 2 or ionic liquids can also be used as solvents. If ionic liquids are used as the solvent, this preferably takes over the function of the conductive salt. The solvents are preferably dry. A particularly preferred solvent is tetrahydrof ran.
Die Anode ist in einer dem Fachmann bekannten Weise aufgebaut. Sie kann aus allen Werkstoffen bestehen, die eine ausreichende elektrische Leitfähigkeit besitzen, sich unter den gewählten Reaktionsbedingungen chemisch inert verhalten und mit einem Edelmetall oder einer Legierung, die ein oder mehrere Edelmetalle enthält, beschichtet sind bzw. bereits daraus bestehen, wobei als Edelmetalle Rhenium, Ruthenium, Rhodium, Osmium, Iridium, Platin oder Palladium verwendet werden und wovon die Gruppe enthaltend Platin und Palladium sowie deren Legierungen. Falls es sich um eine beschichtete Anode handelt, ist als zu beschichtendes Anoden Grundmaterial Siliciumcarbid, Eisensilicid oder Graphit bevorzugt. Besonders bevorzugt ist als Grundmaterial Graphit und als Beschichtungsmaterial Platin oder Palladium oder Legierungen, die Platin und/oder Palladium enthalten.The anode is constructed in a manner known to those skilled in the art. It can consist of all materials which have sufficient electrical conductivity, are chemically inert under the selected reaction conditions and are coated with a precious metal or an alloy which contains one or more noble metals, or already consist thereof, the noble metals being rhenium, Ruthenium, rhodium, osmium, iridium, platinum or palladium are used and of which the group containing platinum and palladium and their alloys. If it is a coated anode, silicon carbide, iron silicide or graphite is preferred as the anode material to be coated. Graphite is particularly preferred as the base material and platinum or palladium or alloys which contain platinum and / or palladium as the coating material.
Die Anode wird unter Reaktionsbedingungen von gasförmigem Wasserstoff oder Mischungen aus Wasserstoff und einem oder mehrerer inerten Gasen, wie beispielsweise Helium, Stickstoff
oder Argon umströmt. Bevorzugt wird Wasserstoff alleine oder eine Mischung aus Stickstoff und Wasserstoff verwendet. Besonders bevorzugt sind reiner Wasserstoff bzw. Formiergas (90% Stickstoff, 10 % Wasserstoff) . Der Wasserstoff oder die Wasserstoff enthaltende Gasmischung wird beispielsweise so dosiert, dass unterhalb der Anode ein Gaseinleitungsrohr angebracht ist und durch dieses der Wasserstoff oder dessen Mischung in das System eingeleitet wird. In einer besonders bevorzugten Ausführung wird als Anode ein mit Platin oder Palladium oder mit Legierungen, die Platin und/oder Palladium enthalten, beschichtetes, poröses Graphitrohr eingesetzt. Die Menge an Wasserstoff oder Wasserstoff enthaltenden Gasgemisches hängt von der Größe der Apparatur, der Bauart der Anode und der Bauart der Elektrolysezelle ab und muss so eingestellt werden, dass die Anode während der Elektrolyse vollständig vom Wasserstoff oder dem Wasserstoff enthaltenden Gasgemisch umspült wird.The anode is reacted under gaseous hydrogen or mixtures of hydrogen and one or more inert gases, such as helium, nitrogen or flows around argon. Hydrogen is preferably used alone or a mixture of nitrogen and hydrogen. Pure hydrogen or forming gas (90% nitrogen, 10% hydrogen) are particularly preferred. The hydrogen or the gas mixture containing hydrogen is metered, for example, in such a way that a gas inlet tube is attached below the anode and through this the hydrogen or its mixture is introduced into the system. In a particularly preferred embodiment, a porous graphite tube coated with platinum or palladium or with alloys containing platinum and / or palladium is used as the anode. The amount of hydrogen or hydrogen-containing gas mixture depends on the size of the apparatus, the design of the anode and the design of the electrolysis cell and must be set so that the anode is completely surrounded by the hydrogen or hydrogen-containing gas mixture during the electrolysis.
In einer bevorzugten Variante des Verfahrens dient der Wasserstoff oder der in der Gasmischung enthaltene Wasserstoff als Agens der allgemeinen Formel (2) (R3 = H und Y = H) .In a preferred variant of the process, the hydrogen or the hydrogen contained in the gas mixture serves as an agent of the general formula (2) (R 3 = H and Y = H).
Die Gegenelektrode (Kathode) kann ebenfalls aus allen Werkstoffen bestehen, die eine ausreichende elektrische Leitfähigkeit besitzen und sich unter den gewählten Reaktionsbedingungen chemisch stabil verhalten. Bevorzugt sind Graphit oder ein chemisch stabiles Metall, wie beispielsweise Gold, Silber, Platin, Rhenium, Ruthenium, Rhodium, Osmium, Iridium und Palladium oder ein anderes Metall oder eine Legierung, die ausreichend stabil sind, wie beispielsweise rostfreier Stahl.
Eine Wasserstoffanode ist im Gegensatz zu den im Stand der Technik verwendeten Opferanoden eine langlebige, stabile Elektrode, die zudem ein einfacheres Zellendesign ermöglicht, da kein Elektrodenwechsel, wie im Falle von Opferanoden, notwendig ist. Zusätzlich ist die Verwendung von Opferanoden bei der Si-H-Bindungsknüpfung nur beschränkt möglich, da diese durch die für die Reaktion notwendigen Protonen (Säurezugabe) angegriffen werden können.The counter electrode (cathode) can also consist of all materials that have sufficient electrical conductivity and are chemically stable under the selected reaction conditions. Preferred are graphite or a chemically stable metal such as gold, silver, platinum, rhenium, ruthenium, rhodium, osmium, iridium and palladium or another metal or alloy that is sufficiently stable, such as stainless steel. In contrast to the sacrificial anodes used in the prior art, a hydrogen anode is a long-lasting, stable electrode which also enables a simpler cell design, since no electrode change, as in the case of sacrificial anodes, is necessary. In addition, the use of sacrificial anodes in Si-H bond formation is only possible to a limited extent, since these can be attacked by the protons necessary for the reaction (acid addition).
Die Verwendung einer Wasserstoffanode für die genannten Reaktionen ermöglicht eine elektrochemische Reaktion, die im Vergleich zur Verwendung der bekannten Opferelektroden, wesentlich wirtschaftlicher betrieben werden kann.The use of a hydrogen anode for the reactions mentioned enables an electrochemical reaction which can be operated much more economically compared to the use of the known sacrificial electrodes.
Die vorliegende Erfindung ist umso überraschender, als ein Fachmann davon ausgehen muss, dass bei Verwendung einer Wasserstoffelektrode anstelle einer Opferanode wie beispielsweise Mg bei der Si-C-Bindungsknüpfung nicht das gewünschte Produkt entstehen kann, sondern andere Reaktionen im Vordergrund stehen. Dies begründet sich darin, dass das primär an der Kathode durch Elektroreduktion entstehende Carbanion ausschließlich mit den an der Anode aus H2 entstehenden Protonen reagieren sollte (Nebenreaktion 1) , da die Protonen, aufgrund ihrer Größe und Ladung im Gegensatz zu den ungeladenen, sperrigen Si-Elektrophilen, schneller in Richtung der Kathode, dem Entstehungsort der Carbanionen, wandern und dort reagieren. Für die Knüpfung von Si-C- und Si-H-Bindungen gilt gleichermaßen, dass die stärker mobilen Protonen an der Kathode zu Wasserstoff reduziert werden sollten (Nebenreaktion 2) . Es entsteht ein sogenannter „Wasserstoffkreislauf", bei dem als Hauptreaktion an der Anode Wasserstoff zu Protonen oxidiert wird, diese zur Kathode wandern, um dort wieder zu Wasserstoff reduziert zu werden.
Si-C-Bindungsknüpfung: Anodenreaktion: H2 -^. 2 Hβ + 2 eΘ Θ Kathodenreaktion: R3C-CI + 2 e ^ R3C!θ + Clθ Nebenreaktion 1 : H Anode + R3C:κathode π R3G- UH // * Nebenreaktion 2: 2 H Anode + 2 e~ // H2 The present invention is all the more surprising since a person skilled in the art must assume that when using a hydrogen electrode instead of a sacrificial anode, such as Mg, for example, the desired product cannot be formed in the Si-C bond formation, but other reactions are in the foreground. This is due to the fact that the carbanion primarily generated at the cathode by electroreduction should only react with the protons formed at the anode from H 2 (secondary reaction 1), since the protons, in contrast to the uncharged, bulky Si, due to their size and charge -Electrophiles, migrate faster towards the cathode, the place of origin of the carbanions, and react there. For the formation of Si-C and Si-H bonds, the same applies that the more mobile protons at the cathode should be reduced to hydrogen (side reaction 2). A so-called "hydrogen cycle" is formed, in which the main reaction at the anode is hydrogen, which is oxidized to protons, which migrate to the cathode, where they are reduced again to hydrogen. Si-C bond formation: anode reaction: H 2 - ^. 2 H β + 2 e Θ Θ cathode reaction: R 3 C-CI + 2 e ^ R 3 C! θ + Cl θ side reaction 1: H anode + R 3 C: κ a thode π R3G- UH // * side reaction 2: 2 H A node + 2 e ~ // H 2
Produktbildung: R3C:Θ + R'3Si-CI R'3Si-CR3 + Clθ Abbildung: Beispiel für die bei der Si-C-Bindungsknüpfung möglichen ReaktionspfadeProduct formation: R 3 C: Θ + R ' 3 Si-CI R' 3 Si-CR 3 + Cl θ Figure: Example of the possible reaction pathways for Si-C bond formation
Die Folge wäre die Knüpfung einer C-H- bzw. die einer H-H- Bindung. Diese Reaktionen werden unter den in der vorliegenden Erfindung beschriebenen Bedingungen überraschenderweise jedoch nur in vernachlässigbarem Ausmaß beobachtet.The result would be the formation of a C-H or an H-H bond. Surprisingly, however, these reactions are observed only to a negligible extent under the conditions described in the present invention.
Das Verfahren kann auf jedem üblichen Weg unter Verwendung einer Elektrolysezelle mit einer Kathode und einer Wasserstoffanode durchgeführt werden. Die Elektrolysezelle kann eine geteilte oder ungeteilte Elektrolysezelle sein, wobei die ungeteilte Elektrolysezelle bevorzugt ist, da sie vom Aufbau am einfachsten ist. Das Verfahren findet bevorzugt unter Inertgasatmosphäre statt, wobei als Inertgase Stickstoff, Argon oder Helium bevorzugt werden. Die Elektrolysezelle wird vorzugsweise mit einem Potentiostaten oder einem Galvanostaten (konstanter Stromfluss) versehen, um das Potential oder die Intensität des Stromes zu regeln. Die Umsetzung kann mit und ohne kontrolliertem Potential durchgeführt werden.The process can be carried out in any conventional way using an electrolytic cell with a cathode and a hydrogen anode. The electrolytic cell can be a divided or undivided electrolytic cell, the undivided electrolytic cell being preferred since it is the simplest in construction. The process preferably takes place under an inert gas atmosphere, nitrogen, argon or helium being preferred as inert gases. The electrolysis cell is preferably provided with a potentiostat or a galvanostat (constant current flow) in order to regulate the potential or the intensity of the current. The implementation can be carried out with and without controlled potential.
Das Verfahren findet bevorzugt unter Einfluss von Ultraschall statt.The method preferably takes place under the influence of ultrasound.
Die Temperatur beträgt bei dem Verfahren vorzugsweise -50 °C bis 150°C, besonders bevorzugt -10 bis 50°C.
Alle vorstehenden Symbole der vorstehenden Formeln weisen ihre Bedeutungen jeweils unabhängig voneinander auf. In allen Formeln ist das Siliciu atom vierwertig.The temperature in the process is preferably -50 ° C to 150 ° C, particularly preferably -10 to 50 ° C. All of the above symbols of the above formulas have their meanings independently of one another. The silicon atom is tetravalent in all formulas.
BeispieleExamples
Das erfindungsgemäße Verfahren wird anhand einer bevorzugten Ausführungsform beschrieben.The method according to the invention is described on the basis of a preferred embodiment.
Elektrolysenaufbauelectrolysis construction
Vor Beginn der Elektrolyse wird die Zelle ausgeheizt und gegebenenfalls dem Kryomat ausreichend Zeit gegeben, um auf die gewünschte Temperatur zu kühlen. Dann wird vor Zugabe von Elektrolyt und Edukten der Wasserstoffström auf ca. 60 mbar (Graphitanode) über Normaldruck eingestellt, damit sich die Poren der Wasserstoffelektrode während der Befüllung der Zelle nicht mit der Reaktionslösung voll saugen können. Erst anschließend werden nacheinander Elektrolyt, organisches Halogenid (nur für die Si-C-Bindungsknüpfung) und Silan im Stickstoffgegenstrom in die Zelle überführt. Die Elektrolyse wird im gekühlten Ultraschallbad und/oder unter Rührung bei einer Stromstärke von 45 mA durchgeführt. An die Elektrolyten werden besondere Anforderungen bezüglich Trockenheit gestellt. Daher wird das THF über Kalium destilliert oder mit Hilfe einer Ionenaustauschersäule getrocknet. Die Leitsalze werden in der Qualität „puriss." oder „für elektrochemische Zwecke" verwendet; LiCl und MgCl2 werden direkt vor der Verwendung für 5-6 Stunden bei 0,5 Torr unter Erwärmung getrocknet.
H2-Graphit-AnodeBefore the electrolysis begins, the cell is heated and, if necessary, the Kryomat is given sufficient time to cool to the desired temperature. Then the hydrogen flow is adjusted to about 60 mbar (graphite anode) above normal pressure before adding the electrolyte and starting materials so that the pores of the hydrogen electrode cannot soak up with the reaction solution while the cell is being filled. Only then are the electrolyte, organic halide (only for Si-C bond formation) and silane transferred into the cell in a nitrogen countercurrent. The electrolysis is carried out in a cooled ultrasound bath and / or with stirring at a current of 45 mA. The electrolytes have special dryness requirements. The THF is therefore distilled over potassium or dried using an ion exchange column. The conductive salts are used in the quality "puriss." Or "for electrochemical purposes"; LiCl and MgCl 2 are dried for 5-6 hours at 0.5 torr with heating just prior to use. H 2 graphite anode
Ein Graphitzylinder der Fa. SIGRI (MKSl) wird in die passende Form gebracht, so dass dann die Strom- und Gaszuleitung aus Kupfer oder Edelstahl in den Zylinder gesteckt werden können. Der Übergang von Graphit zu Kupfer/Edelstahl wird gasdicht abgedichtet und der Graphitteil anschließend mit Platin beschichtet. Dazu wird zuerst eine 2%ige H2PtCl6_Lösung auf den Graphit gepinselt, die Oberfläche getrocknet und der Vorgang wiederholt. Danach wird zur Reduktion eine Mischung aus 3%iger Ammoniak- und 5%iger Hydrazinsulfatlösung aufgetragen. Die Elektrode wird dann im Trockenschrank getrocknet. Als Kathode wir eine Edelstahl- bzw. Silberelektrode verwendet.A graphite cylinder from SIGRI (MKSl) is brought into the appropriate shape so that the copper and stainless steel power and gas supply lines can then be inserted into the cylinder. The transition from graphite to copper / stainless steel is sealed gas-tight and the graphite part is then coated with platinum. To do this, first brush a 2% H2PtCl6 _ solution onto the graphite, dry the surface and repeat the process. A mixture of 3% ammonia and 5% hydrazine sulfate solution is then applied for reduction. The electrode is then dried in the drying cabinet. A stainless steel or silver electrode is used as the cathode.
Beispiel 1 : Darstellung von TrimethylphenylsilanExample 1: Preparation of trimethylphenylsilane
Zunächst wird der Elektrolyt (Lösung vonFirst the electrolyte (solution of
Tetraethylammoniumtetrafluoroborat Et4NBF4, 0.2 mol'L-1 in 80 mL einer Mischung aus THF und HMPT (3:1 v/v)) in die Elektrolysezelle eingebracht. Anschließend werden nacheinander Chlorbenzol (8.0 mL; 79 mmol) und Trimethylchlorosilan (Me3SiCl, 10.0 mL; 79 mmol) zugegeben und die Elektrolyse gestartet. Nach 18 Stunden kann bereits das Produkt mittels GC- MS detektiert werden. Nach 190 Stunden wird die Reaktion abgebrochen. Nach destillativer Reinigung im Ölpumpenvakuum (0.5 Torr) wird 0.3 g des Produkts erhalten (leichte Verunreinigung durch HMPT, Benzol, Me3SiPhSiMe3) . 29Si-NMR: δ -1.6 ppm.Tetraethylammonium tetrafluoroborate Et 4 NBF 4 , 0.2 mol'L -1 in 80 mL of a mixture of THF and HMPT (3: 1 v / v)) was introduced into the electrolytic cell. Then chlorobenzene (8.0 mL; 79 mmol) and trimethylchlorosilane (Me 3 SiCl, 10.0 mL; 79 mmol) are added in succession and the electrolysis started. After 18 hours, the product can already be detected using GC-MS. The reaction is stopped after 190 hours. After cleaning by distillation in an oil pump vacuum (0.5 Torr), 0.3 g of the product is obtained (slight contamination by HMPT, benzene, Me 3 SiPhSiMe 3 ). 29 Si NMR: δ -1.6 ppm.
Beispiel 2: Darstellung von 1 ,1 ,1,3 ,3 ,3-Hexamethyl-2- (tri- methylsilyl) -trisilanExample 2: Preparation of 1, 1, 1,3, 3, 3-hexamethyl-2- (trimethylsilyl) trisilane
Die Versuchsdurchführung erfolgt analog Beispiel 1. Jedoch wird eine Lösung von ( (CH3) 3Si) 3SiCl (1.3 g; 5 mmol) in THF (5 mL)
mit einer Pumpe in den vorgelegten Elektrolyten gelöst in einer gesättigten Lösung von Tetrabutylammoniumbromid in 80 ml THF und 8 ml HMPT mit einer Geschwindigkeit von 6.5'10~8 rnol's"1 zudosiert. Die Reaktionstemperatur wird mittels Kryomat auf - 10 °C eingeregelt. Der Umsatz ist vollständig. Neben dem Produkt wird lediglich ( (CH3) 3Si) Si (Verunreinigung aus dem Edukt) gefunden. 29Si-NMR: δ -11.56; -115.72The experiment is carried out analogously to Example 1. However, a solution of ((CH 3 ) 3 Si) 3 SiCl (1.3 g; 5 mmol) in THF (5 mL) with a pump in the submitted electrolyte dissolved in a saturated solution of tetrabutylammonium bromide in 80 ml THF and 8 ml HMPT at a rate of 6.5'10 ~ 8 rnol's "1. The reaction temperature is regulated to -10 ° C. using Kryomat. The conversion In addition to the product, only ((CH 3 ) 3 Si) Si (impurity from the starting material) is found 29 Si NMR: δ -11.56; -115.72
Beispiel 3a: Darstellung von DimethylphenylsilanExample 3a: Preparation of dimethylphenylsilane
Die Versuchsdurchführung erfolgt analog Beispiel 1 mit einer Lösung von Diphenylmethylchlorsilan (Ph2MeSiCl, 4 mL; 19 mmol) und Triethylamin (NEt3, 6.0 L; 43 mmol) in einer Lösung von Lithiumchlorid (0.5 mol'L-1) und Magnesiumchlorid (0.25 mol'L-1) in THF (88 mL) bei einer Temperatur von ca. 20°C. Nach 64 Stunden (5.5 F) wird die Reaktion abgebrochen (vollständiger Umsatz, 40% Stromausbeute) . 2Si-NMR: δ -17.60The experiment is carried out analogously to Example 1 with a solution of diphenylmethylchlorosilane (Ph 2 MeSiCl, 4 mL; 19 mmol) and triethylamine (NEt 3 , 6.0 L; 43 mmol) in a solution of lithium chloride (0.5 mol'L -1 ) and magnesium chloride ( 0.25 mol'L -1 ) in THF (88 mL) at a temperature of approx. 20 ° C. After 64 hours (5.5 F) the reaction is stopped (complete conversion, 40% electricity yield). 2 Si NMR: δ -17.60
Beispiel 3b: Darstellung von DimethylphenylsilanExample 3b: Preparation of dimethylphenylsilane
Die Versuchsdurchführung erfolgt analog Beispiel 2 wobei Diphenylmethylchlorsilan (Ph2MeSiCl, 4 L; 19 mmol) mit einer Geschwindigkeit von 1.9'10-7 mol's""1 zu einer Lösung von Triethylamin (NEt3 6.0 mL; 43 mmol), Lithiumchlorid (0.5 mol'L" x) und Magnesiumchlorid (0.25 mol'L-1) in THF (88 mL) bei einer Temperatur von -4°C dosiert wird. Nach 42 Stunden (3 F) bei einer Spannung von 60 V wird die Reaktion abgebrochen. Nach Entfernen des Lösungsmittels wird der feste braune Rückstand mit Pentan/Wasser extrahiert. Nach Trocknen der Pentanphase und Abziehen des Lösungsmittels erhält man das Produkt 3.4 g (Ausbeute 86 %) .
29 Si-NMR : δ -17 . 98The experiment is carried out analogously to Example 2, with diphenylmethylchlorosilane (Ph 2 MeSiCl, 4 L; 19 mmol) at a rate of 1.9'10 -7 mol's "" 1 to a solution of triethylamine (NEt 3 6.0 mL; 43 mmol), lithium chloride (0.5 mol'L " x ) and magnesium chloride (0.25 mol'L -1 ) in THF (88 mL) at a temperature of -4 ° C. After 42 hours (3 F) at a voltage of 60 V, the reaction is stopped After removing the solvent, the solid brown residue is extracted with pentane / water, and after drying the pentane phase and stripping off the solvent, the product is obtained 3.4 g (yield 86%). 29 Si NMR: δ -17. 98
Beispiel 4 : Darstellung von (p- ethoxyphenyl) trimethylsilanExample 4: Preparation of (p-ethoxyphenyl) trimethylsilane
Die Versuchsdurchführung erfolgt analog Beispiel 1 mit einer Lösung von Trimethylchlorsilan (Me3SiCl, 4.5 g; 41 mmol) und p- Chloranisol (5.0 g; 35 mmol) in einer Leitsalzlösung von Lithiumchlorid (0.5 mol'L-1) und Magnesiumchlorid (0.25 mol'L-1) in THF (80 mL) . Weiters werden 15 g Amberlyst® A-21 zugegeben. Es wird eine Kathode aus Silber eingesetzt. Nach 2.0 F erhält man das Produkt in ca. 65% Ausbeute.The experiment is carried out analogously to Example 1 with a solution of trimethylchlorosilane (Me 3 SiCl, 4.5 g; 41 mmol) and p-chloroanisole (5.0 g; 35 mmol) in a conductive salt solution of lithium chloride (0.5 mol'L -1 ) and magnesium chloride (0.25 mol'L -1 ) in THF (80 mL). Furthermore, 15 g Amberlyst ® A-be added 21st A silver cathode is used. After 2.0 F, the product is obtained in about 65% yield.
Beispiel 5 : Darstellung von TetramethylsilanExample 5: Preparation of tetramethylsilane
Die Versuchsdurchführung erfolgt analog Beispiel 4 mit 15 g Amberlyst® A-21 und einer Lösung von Trimethylchlorsilan (Me3SiCl, 4.5 g; 41 mmol) und Methylchlorid (ca. 25 g; 0.5 mol) welches durch einen Rückflusskühler (-70°C) einkondensiert wird. Die Elektrolyse wird bei Raumtemperatur durchgeführt, das siedende Methylchlorid wird durch den Rückflusskühler in der Elektrolysenzelle gehalten. Nach 2.2 F erhält man das Produkt Tetramethylsilan in ca. 25 % Ausbeute.The experimental procedure is analogous to Example 4 with 15 g of Amberlyst ® A-21 and a solution of trimethylchlorosilane (Me 3 SiCl, 4.5 g; 41 mmol) and methylene chloride (about 25 g; 0.5 mol) obtained by a reflux condenser (-70 ° C ) is condensed. The electrolysis is carried out at room temperature, the boiling methyl chloride is kept in the electrolysis cell by the reflux condenser. After 2.2 F, the product tetramethylsilane is obtained in about 25% yield.
Beispiel 6: Darstellung von Methoxytrimethylsilan:Example 6: Preparation of methoxytrimethylsilane:
Die Versuchsdurchführung erfolgt analog Beispiel 5 mit 10 g Amberlyst® A-21 und einer Lösung von Dimethoxydimethylsilan ( (MeO)2SiMe2, 5.3 g; 44 mmol) und Methylchlorid (MeCl, ca. 25 g; 500 mmol) . Nach 2.2 F erhält man das Produkt Methoxytrimethylsilan mit ca. 10% Ausbeute. 29Si-NMR: δ +17.4 ppm
The experimental procedure is analogous to Example 5 with 10 g of Amberlyst ® A-21 and a solution of dimethoxydimethylsilane ((MeO) 2 SiMe 2, 5.3 g; 44 mmol) and methylene chloride (MeCl, ca. 25 g; 500 mmol). After 2.2 F, the product methoxytrimethylsilane is obtained in about 10% yield. 29 Si NMR: δ +17.4 ppm
Claims
1. Verfahren zur elektrochemischen Knüpfung von Silicium- Kohlenstoff- und Silicium-Wasserstoff-Bindungen, dadurch gekennzeichnet, dass als Anode eine Wasserstoffanode verwendetet wird.1. A method for the electrochemical formation of silicon-carbon and silicon-hydrogen bonds, characterized in that a hydrogen anode is used as the anode.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass ein substituiertes Silan der allgemeinen Formel (1)2. The method according to claim 1, characterized in that a substituted silane of the general formula (1)
[SiR1 (4-n)Xn] (1), wobei[SiR 1 (4 -n) Xn] (1), where
R1 unabhängig von einander einen Rest ausgewählt aus der Gruppe enthaltend Wasserstoff, substituierten oder unsubstituierten C6-Cι8-Aryl-, C3~Cι8- Heteroaryl-, C].-C3o-Alkyl-, C2-C3o-Alkenyl-, C3-C30- Alkinyl-, Cι-C30-Alkoxy-, C2-C3o-Alkenyloxy-, C3-C30- Alkinyloxy-, C6-Ci8-Aryl-Cι-C30-Alkyl-, C3-Cι8- Heteroaryl-Cι-C3o-Alkyl-, C6-Ci8-Aryl-C2-C3o-Alkenyl-, C3-Cι8-Heteroaryl-C2-C3o-Alkenyl-, Cι-Cι8-Alkoxy-Cι- C3o~Alkyl-, Cι-Cι8-Alkoxycarbonyl-, Cι-Cι8-Alkoxy-C2- C30-Alkenyl-, C6-Ci8-Aryloxy-Cι-C3o-Alkyl-, C6-Cι8- Aryloxy-C2-C3o-Alkenyl-, C3-C8-Cycloalkyl-, C3-C8- Cycloalkyloxy-, C3-C8-Cycloalkyl-Cι-C3o-Alkyl- oder C3-C8-Cycloalkyl-C2-C3o-Alkenylrest, Silyl- und Silyloxyrest, Oligomer und Polymer, organosilylfunktionalisiertes SiÜ2, organosilyl- funktionalisierte Harze und organosilylfunktionali- sierte Partikel, X unabhängig von einander einen Rest ausgewählt aus der Gruppe enthaltend Halogenatom und OR2, R2 einen Cι-Cιo-Alkylrest und n einen Wert 1, 2, 3 und 4R 1 independently of one another is a radical selected from the group consisting of hydrogen, substituted or unsubstituted C 6 -C 8 aryl, C 3 ~ C 8 heteroaryl, C] . -C 3 o-alkyl-, C 2 -C 3 o-alkenyl-, C 3 -C 30 - alkynyl-, Cι-C 30 -alkoxy-, C 2 -C 3 o-alkenyloxy-, C3-C 30 - alkynyloxy, C 6 -C 8 -aryl-Cι-C 30 alkyl, C 3 -Cι 8 - heteroaryl-Cι-C 3 o-alkyl, C 6 -C 8 -aryl-C 2 -C 3 o -alkenyl, C 3 -Cι 8 -heteroaryl-C 2 -C 3 O-alkenyl, Cι-Cι 8 -alkoxy-C 3 o Cι- ~ alkyl, Cι-Cι 8 alkoxycarbonyl, Cι-Cι 8 -Alkoxy-C2- C 30 alkenyl, C 6 -Ci 8 aryloxy -CC-C 3 o-alkyl-, C 6 -Cι 8 - aryloxy-C 2 -C 3 o-alkenyl-, C 3 -C 8 cycloalkyl, C 3 -C 8 - cycloalkyloxy, C 3 -C 8 cycloalkyl-Cι-C3-o-alkyl or C 3 -C 8 cycloalkyl-C 2 -C 3 O-alkenyl, silyl and silyloxy radical, oligomer and polymer, organosilyl-functionalized SiÜ 2 , organosilyl-functionalized resins and organosilyl-functionalized particles, X independently of one another is a radical selected from the group consisting of halogen atom and OR 2 , R 2 is a C 1 -C 10 -alkyl radical and n is 1, 2, 3 and 4
bedeuten,mean,
mit einer Verbindung der allgemeinen Formel (2)with a compound of general formula (2)
R3-Y (2) wobeiR 3 -Y (2) where
R3 unabhängig von einander einen Rest ausgewählt aus der Gruppe enthaltend Wasserstoff, substituierten oder unsubstituierten C6-Cι8-Aryl-, C3-C18- Heteroaryl-, Cι-C30-Alkyl-, C2-C3o-Alkenyl-, C3-C30- Alkinyl-, C5-Ci8-Aryl-Cι-C3o-Alkyl-, C3-C18- Heteroaryl-Cι-C3o-Alkyl-, C6-Cι8-Aryl-C2-C3o-Alkenyl-, C3-Ci8-Heteroaryl-C2-C3o-Alkenyl-, Cι-Cι8-Alkoxy-Cι- C3o-Alkyl-, Ci-Cis-Alkoxycarbonyl-, Cι~Cι8-Alkoxy-C2- C30-Alkenyl-, C6-Cι8-Aryloxy-Cι-C3o-Alkyl-, C6-Cι8- Aryloxy-C2-C3o-Alkenyl-, C3-C8-Cycloalkyl-, C3~C8- Cycloalkyl-Cι-C3o-Alkyl- und C3-C8-Cycloalkyl-C2-C3o~ Alkenylrest, Silyl-, Silyloxy- und Silylalkylrest, Oligomer und Polymer undR 3, independently of one another, is a radical selected from the group consisting of hydrogen, substituted or unsubstituted C 6 -C 8 aryl, C3-C18 heteroaryl, C 1 -C 30 alkyl, C 2 -C 3 o-alkenyl , C 3 -C 30 - alkynyl, C 5 -Ci 8 -aryl -CC-C 3 o-alkyl-, C 3 -C 18 - heteroaryl -CC-C 3 o -alkyl-, C 6 -Cι 8 - Aryl-C 2 -C 3 o-alkenyl, C 3 -Ci 8 heteroaryl-C 2 -C 3 o-alkenyl, -Cι-Cι 8 -alkoxy-Cι- C 3 o-alkyl-, Ci-Cis- Alkoxycarbonyl-, -C ~ 8 -alkoxy-C 2 - C 30 -alkenyl-, C 6 -C 8 -Aryloxy-Cι-C 3 o-alkyl, C 6 -C 8 - aryloxy-C 2 -C 3 o -Alkenyl-, C 3 -C 8 -cycloalkyl-, C 3 ~ C 8 - cycloalkyl-Cι-C 3 o-alkyl and C 3 -C 8 cycloalkyl-C 2 -C3o ~ alkenyl residue, silyl, silyloxy- and silylalkyl, oligomer and polymer and
Y unabhängig von einander einen Rest ausgewählt aus der Gruppe enthaltend Wasserstoff und HalogenatomY independently of one another is a radical selected from the group containing hydrogen and halogen atom
bedeuten, unter Verwendung einer Wasserstoffanode elektrochemisch umgesetzt wird, so dass eine Verbindung der allgemeinen Formel (3)mean, is electrochemically reacted using a hydrogen anode, so that a compound of the general formula (3)
[ SiR (4-n) X (n-m) Yml ( 3 ) , wobei n, m Werte 1, 2, [SiR (4-n) X (n-m) Yml (3), where n, m values 1, 2,
3 oder 4 bedeuten, mit der Maßgabe, dass m kleiner oder gleich n sein kann,3 or 4 mean, with the proviso that m can be less than or equal to n,
erhalten wird.is obtained.
Verfahren entsprechend einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass der monomere, oligomere oder polymere Rest R1 aus der Gruppe enthaltend Methyl-, Ethyl-, n- Propyl-, iso-Propyl-, n-Butyl-, iso-Butyl-, tert.-Butyl- , n-Pentyl-, iso-Pentyl-, neo-Pentyl-, tert . -Pentyl-, n- Hexyl, n-Heptyl, n-Octyl, iso-Octyl, n-Decyl, n-Dodecyl, n- Octadecyl, Vinyl-, Allyl, Cyclopentyl-, Cyclohexyl-, Cycloheptyl-, Methylcyclohexyl-, Phenyl-, Naphthyl, Anthryl-, Phenanthryl-, o-Tolyl-, m-Tolyl-, p-Tolyl-, Xylyl- und Ethylphenyl-, Benzyl-, -Phenylethyl-, ß- Phenylethyl-, Methoxy-, Ethoxy-, n- Propyloxy-, iso- Propyloxy-, n-Butoxy-, iso-Butoxy-, tert . -Butoxy-, n- Pentyloxy-, iso-Pentyloxy-, neo-Pentyloxy-, tert.- Pentyloxy-, n-Hexyloxy-, n-Heptyloxy-, n-Octyloxy-, Silyl- und Siliyloxyrest, Polyvinylchlorid, Polyethylen, Polypropylen, Polyvinylacetat, Polycarbonat, Polyacrylat, Polymethacrylat, Polymethylmethacrylat, Polystyrol, Polyacrylnitril, Polyvinylidenchlorid (PVC) , Polyvinylfluorid, Polyvinylidenfluorid, Polyvinylidencyanid, Polybutadien, Polyisopren, Polyether, Polyester, Polyamid, Polyimid, Polyvinylalkohol, Polyvinylpyrrolidon, Polyacrylamid, Polyethylenglykol, Copolymere, Styrol-Acrylat Copolymere, Vinylacetat-Acrylat Copolymere, Ethylen-Vinylacetat Copolymere, Ethylen- Propylen-Terpolymere, Ethylen-Propylen-Kautschuk, Polybutadien, Poly-Isobuten-Isopren, Polyisopren, Styrol- Butadien-Kautschuk, Cellulose, Stärke, Casein, natürliches Gummi, halbsynthetische Oligomere und Polymere, Cellulosederivate, Methylcellulose, Hydroxymethylcellulose und Carboxymethylcellulose, Siliconpolymere und organo- silylfunktionalisierte Organopolysiloxanharze ausgewählt wird.Method according to one of claims 1 or 2, characterized in that the monomeric, oligomeric or polymeric radical R 1 from the group containing methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl -, tert-butyl, n-pentyl, isopentyl, neopentyl, tert. -Pentyl-, n-hexyl, n-heptyl, n-octyl, iso-octyl, n-decyl, n-dodecyl, n-octadecyl, vinyl, allyl, cyclopentyl, cyclohexyl, cycloheptyl, methylcyclohexyl, phenyl -, Naphthyl, anthryl, phenanthryl, o-tolyl, m-tolyl, p-tolyl, xylyl and ethylphenyl, benzyl, -phenylethyl, ß-phenylethyl, methoxy, ethoxy, n - Propyloxy, iso-propyloxy, n-butoxy, iso-butoxy, tert. -Butoxy-, n- pentyloxy, iso-pentyloxy, neo-pentyloxy, tert-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, silyl and siliyloxy, polyvinyl chloride, polyethylene, polypropylene , Polyvinyl acetate, polycarbonate, polyacrylate, polymethacrylate, polymethyl methacrylate, polystyrene, polyacrylonitrile, polyvinylidene chloride (PVC), polyvinyl fluoride, polyvinylidene fluoride, polyvinylidene cyanide, polybutadiene, polyisoprene, polyether, Polyester, polyamide, polyimide, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, polyethylene glycol, copolymers, styrene-acrylate copolymers, vinyl acetate-acrylate copolymers, ethylene-vinyl acetate copolymers, ethylene-propylene terpolymers, ethylene-propylene rubber, polybutadiene, poly-isobutene-isoprene , Polyisoprene, styrene-butadiene rubber, cellulose, starch, casein, natural rubber, semi-synthetic oligomers and polymers, cellulose derivatives, methyl cellulose, hydroxymethyl cellulose and carboxymethyl cellulose, silicone polymers and organosilyl-functionalized organopolysiloxane resins.
4. Verfahren entsprechend einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass der Rest R1 aus der Gruppe enthaltend Methyl-, Ethyl-, Phenyl-, Vinyl-, Cyclohexyl-, Methoxy- und Ethoxyrest, der Substituent X aus der Gruppe enthaltend Chlorid- und Alkoxyrest, der Rest R3 aus der Gruppe enthaltend Wasserstoff, Methyl-, Ethyl-, substituierter und unsubstituierter Phenyl-, substituierter Silylalkyl- und Polyvinylrest und der Substituent Y aus der Gruppe enthaltend Wasserstoff und Cloridrest ausgewählt wird.4. The method according to any one of claims 1 to 3, characterized in that the radical R 1 from the group containing methyl, ethyl, phenyl, vinyl, cyclohexyl, methoxy and ethoxy, containing the substituent X from the group Chloride and alkoxy, the radical R 3 is selected from the group consisting of hydrogen, methyl, ethyl, substituted and unsubstituted phenyl, substituted silylalkyl and polyvinyl and the substituent Y is selected from the group consisting of hydrogen and chloride.
5. Verfahren entsprechend einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Verbindungen der allgemeinen Formel (1) aus der Gruppe enthaltend SiCl4, Si(CH3)Cl3, Si(CH3)2Cl2, Si(CH3)3Cl, Si (CH3) 2 (C6H5) Cl, Si (CH3) (C6H5) Cl2, Si(OMe)4, Si(CH3) (OMe)3, Si (CH3) 2 (OMe) 2, Si (CH3) 3 (OMe) , Si(0Et)4, Si(CH3) (OEt) 3, Si (CH3) 2 (OEt) 2, Si (CH3) 3 (OEt) und die Verbindungen der allgemeinen Formel (2) aus der Gruppe enthaltend Wasserstoff (H2) , CH3C1, C6H5CI und p-Cl-C6H4 ausgewählt sind. 5. The method according to any one of claims 1 to 4, characterized in that the compounds of general formula (1) from the group containing SiCl 4 , Si (CH 3 ) Cl 3 , Si (CH 3 ) 2 Cl 2 , Si (CH 3 ) 3 Cl, Si (CH 3 ) 2 (C 6 H 5 ) Cl, Si (CH 3 ) (C 6 H 5 ) Cl 2 , Si (OMe) 4 , Si (CH 3 ) (OMe) 3 , Si (CH 3 ) 2 (OMe) 2 , Si (CH 3 ) 3 (OMe), Si (0Et) 4 , Si (CH 3 ) (OEt) 3 , Si (CH 3 ) 2 (OEt) 2 , Si (CH 3 ) 3 (OEt) and the compounds of the general formula (2) are selected from the group consisting of hydrogen (H 2 ), CH 3 C1, C 6 H 5 CI and p-Cl-C 6 H 4 .
6. Verfahren entsprechend einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass in Anwesenheit eines Komplexierungsmittels gearbeitet wird.6. The method according to any one of claims 1 to 5, characterized in that it is carried out in the presence of a complexing agent.
7. Verfahren entsprechend einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass in Abwesenheit eines Komplexierungsmittels gearbeitet wird.7. The method according to any one of claims 1 to 5, characterized in that it is carried out in the absence of a complexing agent.
8. Verfahren entsprechend einem der Ansprüche 1 - 7, dadurch gekennzeichnet, dass in Anwesenheit einer Base gearbeitet wird.8. The method according to any one of claims 1-7, characterized in that it is carried out in the presence of a base.
9. Verfahren entsprechend Anspruch 8 bei dem Triethylamin oder Pyridin als Base verwendet wird.9. The method according to claim 8 in which triethylamine or pyridine is used as the base.
10. Verfahren entsprechend einem der Ansprüche 1 - 7, dadurch gekennzeichnet, dass in Abwesenheit einer Base gearbeitet wird.10. The method according to any one of claims 1-7, characterized in that one works in the absence of a base.
11. Verfahren entsprechend einem der Ansprüche 1 - 10, dadurch gekennzeichnet, dass in Anwesenheit eines Leitsalzes gearbeitet wird.11. The method according to any one of claims 1-10, characterized in that it is carried out in the presence of a conductive salt.
12. Verfahren entsprechend Anspruch 11, dadurch gekennzeichnet, dass als Leitsalz Magnesiumchlorid, Lithiumchlorid oder Mischungen davon verwendet wird.12. The method according to claim 11, characterized in that magnesium chloride, lithium chloride or mixtures thereof is used as the conductive salt.
13. Verfahren entsprechend Anspruch 11, dadurch gekennzeichnet, dass als Leitsalz Tetraethylammoniumtetrafluoroborat, Tetrabutylammoniumtetrafluoroborat oder Tetrabutylammoniumbromid verwendet wird. 13. The method according to claim 11, characterized in that tetraethylammonium tetrafluoroborate, tetrabutylammonium tetrafluoroborate or tetrabutylammonium bromide is used as the conductive salt.
14. Verfahren entsprechend einem der Ansprüche 1 - 13, dadurch gekennzeichnet, dass unter Verwendung eines aprotischen Lösungsmittels gearbeitet wird.14. The method according to any one of claims 1-13, characterized in that it is carried out using an aprotic solvent.
15. Verfahren entsprechend Anspruch 14, dadurch gekennzeichnet, dass als aprotisches Lösungsmittel Tetrahydrofuran verwendet wird.15. The method according to claim 14, characterized in that tetrahydrofuran is used as the aprotic solvent.
16. Verfahren entsprechend einem der Ansprüche 1 bis 15, dadurch gekennzeichnet, dass unter Verwendung eines überkritischen Gases oder einer ionischen Flüssigkeit als Lösungsmittel gearbeitet wird.16. The method according to any one of claims 1 to 15, characterized in that using a supercritical gas or an ionic liquid as a solvent.
17. Verfahren entsprechend Anspruch 16, dadurch gekennzeichnet, dass die ionische Flüssigkeit gleichzeitig als Leitsalz dient .17. The method according to claim 16, characterized in that the ionic liquid also serves as a conductive salt.
18. Verfahren nach einem der Ansprüche 1 bis 17, dadurch gekennzeichnet, dass der Wasserstoff aus der Wasserstoffelektrode gleichzeitig als Reagens im Sinn der allgemeinen Formel (2) dient. 18. The method according to any one of claims 1 to 17, characterized in that the hydrogen from the hydrogen electrode simultaneously serves as a reagent in the sense of the general formula (2).
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| DE102004029258.2 | 2004-06-17 | ||
| DE102004029258A DE102004029258A1 (en) | 2004-06-17 | 2004-06-17 | Process for the electrochemical formation of silicon-carbon and silicon-hydrogen bonds using a hydrogen electrode |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103952716A (en) * | 2014-05-16 | 2014-07-30 | 罗凯 | Method for electrolytic synthesis of siloxane |
| CN108604678A (en) * | 2015-11-17 | 2018-09-28 | 奈克松有限公司 | Surface is modified |
| CN110734550A (en) * | 2018-07-20 | 2020-01-31 | 东莞市博君来胶粘材料科技有限公司 | Preparation method of methyl phenyl silicone oil |
| WO2023222245A1 (en) | 2022-05-20 | 2023-11-23 | Wacker Chemie Ag | Process for producing organosilicon compounds |
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|---|---|---|---|---|
| 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 |
| WO2003100134A1 (en) * | 2002-05-29 | 2003-12-04 | Consortium für elektrochemische Industrie GmbH | Electrochemical method for the production of organofunctional silanes |
-
2004
- 2004-06-17 DE DE102004029258A patent/DE102004029258A1/en not_active Ceased
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2005
- 2005-06-09 WO PCT/EP2005/006225 patent/WO2005123811A1/en active Application Filing
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| WO2003100134A1 (en) * | 2002-05-29 | 2003-12-04 | Consortium für elektrochemische Industrie GmbH | Electrochemical method for the production of organofunctional silanes |
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| SHONO T ET AL: "AN ELECTROREDUCTIVE SYNTHESIS OF ALLYLSILANES AND BENZYLSILANES", CHEMISTRY LETTERS, CHEMICAL SOCIETY OF JAPAN. TOKYO, JP, vol. 4, 1985, pages 463 - 466, XP001160737, ISSN: 0366-7022 * |
| YOSHIDA J-I ET AL: "Electrochemical synthesis of organosilicon compounds", JOURNAL OF ORGANIC CHEMISTRY, AMERICAN CHEMICAL SOCIETY. EASTON, US, vol. 51, 1986, pages 3996 - 4000, XP002248897, ISSN: 0022-3263 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103952716A (en) * | 2014-05-16 | 2014-07-30 | 罗凯 | Method for electrolytic synthesis of siloxane |
| CN108604678A (en) * | 2015-11-17 | 2018-09-28 | 奈克松有限公司 | Surface is modified |
| CN110734550A (en) * | 2018-07-20 | 2020-01-31 | 东莞市博君来胶粘材料科技有限公司 | Preparation method of methyl phenyl silicone oil |
| WO2023222245A1 (en) | 2022-05-20 | 2023-11-23 | Wacker Chemie Ag | Process for producing organosilicon compounds |
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| DE102004029258A1 (en) | 2006-01-12 |
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