US20060211876A1 - (organothiomethyl)chlorosilanes and their preparation methods - Google Patents
(organothiomethyl)chlorosilanes and their preparation methods Download PDFInfo
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- US20060211876A1 US20060211876A1 US11/245,786 US24578605A US2006211876A1 US 20060211876 A1 US20060211876 A1 US 20060211876A1 US 24578605 A US24578605 A US 24578605A US 2006211876 A1 US2006211876 A1 US 2006211876A1
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- organothiomethyl
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- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000005046 Chlorosilane Substances 0.000 title abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 150000003839 salts Chemical class 0.000 claims abstract description 32
- 238000005859 coupling reaction Methods 0.000 claims abstract description 25
- 150000004820 halides Chemical class 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 21
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 150000002367 halogens Chemical group 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 150000007530 organic bases Chemical class 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- 150000004714 phosphonium salts Chemical group 0.000 claims description 5
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 2
- 239000007810 chemical reaction solvent Substances 0.000 claims 1
- 229920000620 organic polymer Polymers 0.000 claims 1
- 239000011347 resin Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 29
- 239000011541 reaction mixture Substances 0.000 abstract description 13
- 229910018540 Si C Inorganic materials 0.000 abstract description 12
- 229910010271 silicon carbide Inorganic materials 0.000 abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 abstract description 8
- 125000004434 sulfur atom Chemical group 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000007796 conventional method Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- JWMLCCRPDOIBAV-UHFFFAOYSA-N chloro(methylsulfanyl)methane Chemical compound CSCCl JWMLCCRPDOIBAV-UHFFFAOYSA-N 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 8
- 150000003961 organosilicon compounds Chemical class 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 5
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 description 5
- XICIWDLSLRRFQO-UHFFFAOYSA-N trichloro(methylsulfanylmethyl)silane Chemical compound CSC[Si](Cl)(Cl)Cl XICIWDLSLRRFQO-UHFFFAOYSA-N 0.000 description 5
- 239000005052 trichlorosilane Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 0 [1*][Si](Cl)(Cl)CS[2*] Chemical compound [1*][Si](Cl)(Cl)CS[2*] 0.000 description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 4
- 229910004721 HSiCl3 Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- LLSMWLJPWFSMCP-UHFFFAOYSA-N chloromethylsulfanylbenzene Chemical compound ClCSC1=CC=CC=C1 LLSMWLJPWFSMCP-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- -1 sodium halide Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- ZALZKJRGLFDUNR-UHFFFAOYSA-N chloro(triphenyl)phosphanium Chemical compound C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 ZALZKJRGLFDUNR-UHFFFAOYSA-N 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 2
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 description 2
- RWVHGTLCKLCLBP-UHFFFAOYSA-N dichloro-methyl-(methylsulfanylmethyl)silane Chemical compound CSC[Si](C)(Cl)Cl RWVHGTLCKLCLBP-UHFFFAOYSA-N 0.000 description 2
- ZIXMNXZVPXWUJM-UHFFFAOYSA-N dichloro-methyl-(phenylsulfanylmethyl)silane Chemical compound C[Si](Cl)(Cl)CSC1=CC=CC=C1 ZIXMNXZVPXWUJM-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000005048 methyldichlorosilane Substances 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 125000005497 tetraalkylphosphonium group Chemical group 0.000 description 2
- NMFCBOHZCKLAAG-UHFFFAOYSA-N trichloro(phenylsulfanylmethyl)silane Chemical compound Cl[Si](Cl)(Cl)CSC1=CC=CC=C1 NMFCBOHZCKLAAG-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- DALDUXIBIKGWTK-UHFFFAOYSA-N benzene;toluene Chemical compound C1=CC=CC=C1.CC1=CC=CC=C1 DALDUXIBIKGWTK-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical class Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BBFLFLISKBFBEU-UHFFFAOYSA-M hexyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCCCC)C1=CC=CC=C1 BBFLFLISKBFBEU-UHFFFAOYSA-M 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000006198 methoxylation reaction Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000013464 silicone adhesive Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000003375 sulfoxide group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 1
- CCIYPTIBRAUPLQ-UHFFFAOYSA-M tetrabutylphosphanium;iodide Chemical compound [I-].CCCC[P+](CCCC)(CCCC)CCCC CCIYPTIBRAUPLQ-UHFFFAOYSA-M 0.000 description 1
- FBOJNMRAZJRCNS-UHFFFAOYSA-M tetraethylphosphanium;chloride Chemical compound [Cl-].CC[P+](CC)(CC)CC FBOJNMRAZJRCNS-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ZTXFOCMYRCGSMU-UHFFFAOYSA-M tetramethylphosphanium;bromide Chemical compound [Br-].C[P+](C)(C)C ZTXFOCMYRCGSMU-UHFFFAOYSA-M 0.000 description 1
- WAGFXJQAIZNSEQ-UHFFFAOYSA-M tetraphenylphosphonium chloride Chemical compound [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WAGFXJQAIZNSEQ-UHFFFAOYSA-M 0.000 description 1
- JQLOJTZPFXKUIM-UHFFFAOYSA-M tributyl(methyl)phosphanium;chloride Chemical compound [Cl-].CCCC[P+](C)(CCCC)CCCC JQLOJTZPFXKUIM-UHFFFAOYSA-M 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 238000007039 two-step reaction Methods 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60N—SEATS SPECIALLY ADAPTED FOR VEHICLES; VEHICLE PASSENGER ACCOMMODATION NOT OTHERWISE PROVIDED FOR
- B60N3/00—Arrangements or adaptations of other passenger fittings, not otherwise provided for
- B60N3/04—Arrangements or adaptations of other passenger fittings, not otherwise provided for of floor mats or carpets
- B60N3/044—Arrangements or adaptations of other passenger fittings, not otherwise provided for of floor mats or carpets of removable mats
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2471/00—Floor coverings
- B32B2471/04—Mats
Definitions
- This invention relates to (organothiomethyl)chlorosilanes and methods for their preparation by the dehydrohalogenation Si—C coupling reaction of organothiomethyl halides with Si—H containing chlorosilanes (hydrosilanes), wherein a mixture of organothiomethyl halide and hydrosilane is heated in the presence of tertiary amine or organic salts (quaternary organoammonium and organophosphonium halides to give (organothiomethyl)chlorosilanes, which is existing a sulfur atom in alkyl chain, (formula::: R 2 SCH 2 SiCl 2 R 1 ) in good yield, wherein R 1 represents a hydrogen atom, halogen, or C 1 -C 6 alkyl; R2 is selected from the group consisting of C 1 -C 6 alkyl or an aryl group.
- this reaction using organic salt as a catalyst provide better economical matter and yield compared with conventional methods, because only a catalytic amount of organic salt is required and the catalyst can be separated from the reaction mixture and recycled easily.
- the (organothiomethyl)chlorosilane compounds can be widely used for the synthesis of various silane monomers, silicone polymers, and surfactants.
- Organosilicon compounds are important starting materials for organosilicon polymers. Especially, sulfur atom containing organosilicon compounds are interesting and potential monomer precursors in synthesizing functional inorganic polymers.
- Voronkov and co-workers reported that sodium alkylthiolate reacted with haloalkylalkoxysilane to give the corresponding alkylthio-substituted products through the C—S coupling reaction, eliminating sodium halide [Voronkov, M. G.; Sorokin, M.S.; D'yakov, V.M.; Sigalov, M.V. Zhurnal Obshchei Khimii, 1975, 45(8), 1807-11].
- 1,1,1-trimethoxy-3-thio-1-silabutane was synthesized by the reaction of methyl iodide with sodium trimethylsilylmethylthiolate [NaSCH 2 Si(OMe) 3 ].
- the inventors have obtained a patent on a method of preparing a variety of organosilicon compounds by the dehydrohalogenation of alkyl halide and chlorosilane in the presence of the tertiary phosphine [U.S. Pat. No. 6,251,057, Korean Patent No. 306574].
- the inventors also prepared organosilicon compounds with Si—Cl bonds from the Si—C coupling reaction of chloromethyl-substituted organosiliocn compounds with chlorosilane containing Si—H bond in better yield using tetraalkylphosphonium salt catalyst instead of tertiary phosphine or amine compound.
- This tetraalkylphosphonium salt catalyzed reaction provide a better yield compared with phosphine compound-catalyzed reaction, because the catalyst can be separated from the reaction mixture and recycled easily [Jung, I.; Yoo, B.; Han, J.; Kang, S. U.S. Pat. NO, 6,392,077 ].
- the present inventors have discovered that a coupling reaction of organothiomethyl halides and hydrochlorosilanes in the presence of tertiary phosphines, quaternary ammonium salt, or quaternary phosphonium salt as a catalyst proceeded to give the corresponding coupled products, (organothiomethyl)chlorosilicon compounds containing a sulfur atom in organic group, in good yields.
- the present invention relates to (organothiomethyl)chlorosilanes and methods for their preparation by the dehydrohalogenative Si—C coupling reaction of oranothiomethyl halides with hydrosilanes expressed by the following Formula 1 in the presence of quaternary organophosphonium salt catalyst, wherein R 1 represents a hydrogen atom, halogen, or C 1 -C 6 alkyl; R 2 is selected from the group consisting of C 1 -C 6 alkyl or an aryl group.
- the present invention relates to (organothiomethyl)chlorosilanes expressed by the following Formula 1 and methods for their preparation by the dehydrohalogenative Si—C coupling reaction of oranothiomethyl halides expressed by the following Formula 3 with hydrosilanes expressed by the following Formula 2 in the presence of quaternary organophosphonium salt, quaternary organoammonium salt, tertiary amine as a catalyst.
- R, R 2 , and X are the same as defined above.
- the present invention relates to preparing new organosilicon compounds having Si—Cl bonds and organic group with a sulfur atom, which can be widely used for the synthesis of various functional organosilicon compounds and silicone monomer, polymers, binders, etc.
- hydrochlorosilanes expressed by formula II in this invention can be used instead of (haloalkyl)alkoxysilanes used in conventional methods and the reaction is carried out at a lower temperature from 70 to 150 ° C., preferably 100 to 120 ° C. than that in the dehydrogenative Si—C coupling of alkyl halide, and further can be applied for a continuous process.
- the reaction can be carried out using a small amount of quaternary organophosphonium salt or quaternary organoammonium salt as a catalyst. Additionally, the catalyst can be easily recovered from the reaction product and has good catalytic activity for reuse.
- the amount of organothiomethyl halides of formula III is equivalent or more, preferably 1 to 5 folds, relative to the amount of the hydrochlorosilane compounds of formula II.
- Organic salt or organic base is used as a catalyst in an amount sufficient to catalyze the reaction, generally, 1 to 100 mol %, preferably 3 to 15 mol %, relative to the mole of the hydrochlorosilane compounds of formula II.
- the coupling reaction can be carried out in most aliphatic or aromatic hydrocarbon solvents such as hexane, benzene toluene, etc, but also proceeds in neat condition.
- the reaction is carried out at a temperature from 70 to 150 ° C., preferably 100 to 120 ° C.
- the heating and stirring of a reaction mixture may be applied for a certain period of time, generally 1 hr to about 48 hours to complete the reaction.
- the target compound can be obtained by distilling the reaction mixture under normal or reduced pressure.
- the organic salt catalysts such as quaternary organophosphonium salt and quaternary organoammonium salt can be easily recovered from the reaction mixture by two following methods: first, the products are distilled out under atmospheric pressure and vacuum and the remaining catalyst can be washed with aliphatic hydrocarbon solvents and purified by recrystallization. The recovery ratio can be as high as 90%. Second hydrocarbon solvents are added to the product mixture to precipitate out the catalyst and the catalyst is filtered and recovered for recycling. When recovered catalyst is reused for the Si—C coupling reaction, the similar activity is shown in the repeated five runs of coupling reactions.
- hydrochlorosilanes with Si—H bond expressed by formula 2 used in this invention may be dichlorosilane, trichlorosilane, and alkyldichlorosilane.
- Organothiomethyl halide raw material of this invention, expressed by the following Formula 3 may be alkylthiomethyl halide and arylthiomethyl halide
- organothiomethyl halide expressed by Formula 2 examples are methylthiomethyl chloride and phenylthiomethyl chloride, etc.
- the catalyst of this invention expressed by the following Formulae 4, 5 and 6 may be quaternary phosphonium salt, quaternary ammonium salts and tertiary amine. (R′′) 3 N (6)
- Quaternary organic salt in this invention can be expressed by the following Formula 4 and 5, E(R′′) 4 X (4) wherein E represents a phosphorus or a nitrogen atom; X may be chloro, bromo or iodo; and R′′ may be identical or different and is a C 1 -C 12 alkyl, phenyl group or —CnH 2n+1 —C 6 H 5 (n is an integer of 0-6); and two of the R′′ functional groups may be covalently bonded to form a C 4 -C 8 ring.
- the organic, salt of the following formula 4 used in this invention may be quaternary organophosphonium halide or quaternary organoammonium halide.
- Specific examples of the quaternary organophosphonium salt are tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide, methyltributylphosphonium chloride, tetramethylphosphonium bromide, tetraethylphosphonium chloride, hexyltriphenylphosphonium chloride, and tetraphenylphosphonium chloride, etc.
- quaternary organoammonium halide are the same except that nitrogen atom is replaced instead of phosphorous atom of quaternary organophosphonium halide.
- Specific examples of quaternary organophosphonium salt of the following formula 5 used in this invention may be bis(chlorotrialkylphosphonium)alkylene, bis(chlorotrialkylphosphonium)phenylene, bis(chlorotriphenylphosphonium)alkylene, bis(chlorotriphenylphosphonium)phenylene, and etc.
- Specific examples of quaternary organoammonium halide of the following formula 5 used in this invention are the same except that nitrogen atom is replaced instead of phosphorous atom of quaternary organophosphonium halide.
- Tertiary amine in this invention can be expressed by the following Formula 6 (R′′) 3 N (6) wherein R′′ is same as defined above.
- the organic base of the following formula 5 used in this invention may be tertiary organic amines.
- tertiary amine compounds are trimethylamine, triethylamine, tributylamine, etc.
- organic salt or organic base is used for the Si—C coupling reaction in this invention
- organic salt or organic base immobilized on silicone resins, silica, or zeolite can be easier recovery and more convenient for recycling.
- this method uses a small amount of catalyst, which can be easily recovered for reuse and has good catalytic activity even at low temperature.
- the present invention is a very economical and effective method, which can be used for the preparation of new and various organothiomethylsilicon compounds. Furthermore, its process is very simple and the production cost is relatively low.
- organosilicon compounds, expressed by formula 1, prepared by this invention can be widely used for the synthesis of various polymers and silicone surfactants, because organothiomethyl group of silane can be converted to sulfoxide group applicable to hydrophilic silicones.
- These compounds are new type hydrophilic silicone different from modified polyethylene- or propyleneoxide-silicones.
- dialkyl sulfide can be converted to dialkyl sulfonoxide or sulfone by the oxidation reaction with hydrogen peroxide (A. Kh. Sharipov, Russian Journal of Applied Chemistry, 2003, 76, 108-113).
- oragnothiomethylchlorosilanes may be chemically bonded to inorganic substrate and oxidized to make surface to be hydrophilic.
- reaction chamber (a 250 mL stainless steel tube) dried in an oven was cooled to room temperature under dry nitrogen gas methylthiomethyl chloride (138.1 g, 1.02 mol), trichlorosilane (138.1 g, 1.02 mol) and tetrabutylphosphonium chloride (5.01 g, 0.0169 mol) were put in the chamber under nitrogen atmosphere.
- the opening of the reaction chamber was closed with a cover and the reaction was carried out at 100 ° C. for 12 hours.
- This reaction mixture was distilled under normal pressure to give (methylthiomethyl)trichlorosilane (52.2 g, yield: 73.8%).
- methylthiomethyl chloride 49.2 g, 0.428 mol
- methyldichlorosilane 49.2 g, 0.428 mol
- tetrabutylphosphonium chloride 2.10 g, 0.00713 mol
- phenylthiomethyl chloride (3.31 g, 0.0209 mol), methyldichlorosilane (7.23 g, 0.0628 mol) and tetrabutylphosphonium chloride (0.615 g, 0.00209 mol) were put in a 50 mL stainless steel tube under nitrogen atmosphere.
- the reaction chamber was closed with a cover and the reaction was carried out at 120 ° C. for 12 hours.
- This reaction mixture was distilled under low pressure to give 1.82 g of methyl(phenylthiomethyl)dichlorosilane in 36.9% yield.
- methylthiomethyl chloride (1.16 g, 0.0120 mol), trichlorosilane (8.13 g, 0.0600 mol) and triethylamine (1.21 g, 0.0120 mol) were put in a 50 mL stainless steel tube under nitrogen atmosphere.
- the reaction chamber was closed with a cover and the reaction was carried out at 100 ° C. for 12 hours.
- This reaction mixture was distilled under low pressure to give 1.12 g of (methylthiomethyl)trichlorosilane in 47.8% yield.
- methylthiomethyl chloride (1.04 g, 0.0108 mol), trichlorosilane (4.39 g, 0.0324 mol) and tetrabutylammonium chloride (0.301 g, 0.00108 mol) were put in a 50 mL stainless steel tube under nitrogen atmosphere.
- the reaction chamber was closed with a cover and the reaction was carried out at 100 ° C. for 12 hours.
- This reaction mixture was distilled under low pressure to give 1.08 g of (methylthiomethyl)trichlorosilane in 51 % yield.
- the present invention relates to (organothiomethyl)chlorosilanes with a sulfur-containing alkyl group and their preparation expressed by Formulas 1 by the Si—C coupling reaction of Si—H containing chlorosilanes with organothiomethyl halide in the presence of quaternary organic salt catalyst or amines.
- this reaction using organic salt as a catalyst provide better economical matter and yield compared with conventional methods, because only catalytic amount of organic salt is required and the catalyst can be separated from the reaction mixture and recycled easily.
- Si—H containing silanes used in this invention are an easily available material in the industry. Therefore, this invention is effective for industrial mass production of (organothiomethyl)chlorosilane compounds, which are widely used for raw material of silicon polymers, silicone adhesives, etc.
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Abstract
Description
- This application is based on, and claims priority from Korean Application No. 2005-0023276, filed on Mar. 21, 2005, the disclosure of which is hereby incorporated by reference.
- This invention relates to (organothiomethyl)chlorosilanes and methods for their preparation by the dehydrohalogenation Si—C coupling reaction of organothiomethyl halides with Si—H containing chlorosilanes (hydrosilanes), wherein a mixture of organothiomethyl halide and hydrosilane is heated in the presence of tertiary amine or organic salts (quaternary organoammonium and organophosphonium halides to give (organothiomethyl)chlorosilanes, which is existing a sulfur atom in alkyl chain, (formula:: R2SCH2SiCl2R1) in good yield, wherein R1 represents a hydrogen atom, halogen, or C1-C6 alkyl; R2 is selected from the group consisting of C1-C6 alkyl or an aryl group. Especially, this reaction using organic salt as a catalyst provide better economical matter and yield compared with conventional methods, because only a catalytic amount of organic salt is required and the catalyst can be separated from the reaction mixture and recycled easily. The (organothiomethyl)chlorosilane compounds can be widely used for the synthesis of various silane monomers, silicone polymers, and surfactants.
- Organosilicon compounds are important starting materials for organosilicon polymers. Especially, sulfur atom containing organosilicon compounds are interesting and potential monomer precursors in synthesizing functional inorganic polymers. In 1975, Voronkov and co-workers reported that sodium alkylthiolate reacted with haloalkylalkoxysilane to give the corresponding alkylthio-substituted products through the C—S coupling reaction, eliminating sodium halide [Voronkov, M. G.; Sorokin, M.S.; D'yakov, V.M.; Sigalov, M.V. Zhurnal Obshchei Khimii, 1975, 45(8), 1807-11]. Here, 1,1,1-trimethoxy-3-thio-1-silabutane was synthesized by the reaction of methyl iodide with sodium trimethylsilylmethylthiolate [NaSCH2Si(OMe)3].
- In 2001, Sorokin; Voronkov reported that a sulfur atom-containing alkylalkoxysilane could be prepared by a Si—C coupling reaction of haloalkylalkoxysilane with RSMgX in tetrahydrofuran in situ [Sorokin, M. S.; Voronkov, M. G. Russian Journal of General Chemistry, 2001, 71(12), 1883-90].
- As explained above, the current known methods for preparing sulfur atom-containing organosilanes are limitedly synthesizing alkoxysilanes by S—C coupling of haloalkylalkoxysilane with organometal reagents. However, these methods are not applied for chlorosilane compounds containing Si—Cl bond(s), which can be modified by alcohol, amine, organometal reagents, etc. and haloalkylalkoxysilane should be prepared by two step reactions: hydrosilylation and methoxylations. The former reaction requires a very expensive platinum catalyst and the latter evolves HCl gas in the reaction of Si—Cl with methanol and thus needs a trapping process of HCl.
-
- The inventors also prepared organosilicon compounds with Si—Cl bonds from the Si—C coupling reaction of chloromethyl-substituted organosiliocn compounds with chlorosilane containing Si—H bond in better yield using tetraalkylphosphonium salt catalyst instead of tertiary phosphine or amine compound. This tetraalkylphosphonium salt catalyzed reaction provide a better yield compared with phosphine compound-catalyzed reaction, because the catalyst can be separated from the reaction mixture and recycled easily [Jung, I.; Yoo, B.; Han, J.; Kang, S. U.S. Pat. NO, 6,392,077 ].
- However, a Si—C coupling reaction of hydrochlorosilane containing Si—H bond with organothiomthyl halide in the presence of organic amine, phosphine, or organic salt have never been reported
- As above-mentioned, the present inventors have discovered that a coupling reaction of organothiomethyl halides and hydrochlorosilanes in the presence of tertiary phosphines, quaternary ammonium salt, or quaternary phosphonium salt as a catalyst proceeded to give the corresponding coupled products, (organothiomethyl)chlorosilicon compounds containing a sulfur atom in organic group, in good yields.
- Accordingly, it is an object of the present invention to provide new (organothiomethyl)chlorosilane and methods for their preparation.
- The present invention relates to (organothiomethyl)chlorosilanes and methods for their preparation by the dehydrohalogenative Si—C coupling reaction of oranothiomethyl halides with hydrosilanes expressed by the following Formula 1 in the presence of quaternary organophosphonium salt catalyst,
wherein R1 represents a hydrogen atom, halogen, or C1-C6 alkyl; R2 is selected from the group consisting of C1-C6 alkyl or an aryl group. - The present invention relates to (organothiomethyl)chlorosilanes expressed by the following Formula 1 and methods for their preparation by the dehydrohalogenative Si—C coupling reaction of oranothiomethyl halides expressed by the following Formula 3 with hydrosilanes expressed by the following Formula 2 in the presence of quaternary organophosphonium salt, quaternary organoammonium salt, tertiary amine as a catalyst.
wherein R, R2, and X are the same as defined above. - The details of the present invention are described as follows.
- The present invention relates to preparing new organosilicon compounds having Si—Cl bonds and organic group with a sulfur atom, which can be widely used for the synthesis of various functional organosilicon compounds and silicone monomer, polymers, binders, etc.
- In a typical preparation, hydrochlorosilanes expressed by formula II in this invention can be used instead of (haloalkyl)alkoxysilanes used in conventional methods and the reaction is carried out at a lower temperature from 70 to 150 ° C., preferably 100 to 120 ° C. than that in the dehydrogenative Si—C coupling of alkyl halide, and further can be applied for a continuous process. The reaction can be carried out using a small amount of quaternary organophosphonium salt or quaternary organoammonium salt as a catalyst. Additionally, the catalyst can be easily recovered from the reaction product and has good catalytic activity for reuse.
- The coupling reaction of hydrochlorosilanes expressed by formula II with organothiomethyl halides expressed by formula III in the present invention in the presence of a catalyst of which one among quaternary organophosphonium salt, quaternary organoammonium salt, or organic base can afford organothiomethylchlorosilanes compounds in good yields. In a typical preparation, hydrochlorosilanes of the following formula II, organothiomethyl halides of formula III, and a catalyst are placed all together into a sealed stainless steel tube under inert atmosphere after sealing the reaction tube with a stainless steel stopper. The reaction is carried out at high temperature and under high pressure.
- In the coupling reaction explained above, the amount of organothiomethyl halides of formula III is equivalent or more, preferably 1 to 5 folds, relative to the amount of the hydrochlorosilane compounds of formula II. Organic salt or organic base is used as a catalyst in an amount sufficient to catalyze the reaction, generally, 1 to 100 mol %, preferably 3 to 15 mol %, relative to the mole of the hydrochlorosilane compounds of formula II.
- In the coupling reaction explained above, the coupling reaction can be carried out in most aliphatic or aromatic hydrocarbon solvents such as hexane, benzene toluene, etc, but also proceeds in neat condition.
- In the coupling reaction explained above, the reaction is carried out at a temperature from 70 to 150 ° C., preferably 100 to 120 ° C.
- In the coupling reaction explained above, the heating and stirring of a reaction mixture may be applied for a certain period of time, generally 1 hr to about 48 hours to complete the reaction. When the reaction is completed, the target compound can be obtained by distilling the reaction mixture under normal or reduced pressure.
- The organic salt catalysts such as quaternary organophosphonium salt and quaternary organoammonium salt can be easily recovered from the reaction mixture by two following methods: first, the products are distilled out under atmospheric pressure and vacuum and the remaining catalyst can be washed with aliphatic hydrocarbon solvents and purified by recrystallization. The recovery ratio can be as high as 90%. Second hydrocarbon solvents are added to the product mixture to precipitate out the catalyst and the catalyst is filtered and recovered for recycling. When recovered catalyst is reused for the Si—C coupling reaction, the similar activity is shown in the repeated five runs of coupling reactions.
- As mentioned above, even though the recovery ratio can be as high as 90%, when organic phophonium salt immobilized on silicone resins, silica, or zeolite is used the recovery of the catalyst is more convenient and easier for recycling as previously reported (Jung, I. N.; Cho, K. D.; Lim, J, C; Yoo, B. R., U.S. Pat. No. 4,613,491).
- The details of starting materials and catalysts used in the Si—C coupling reaction in the present invention are described as follows.
- As explained above, hydrochlorosilanes with Si—H bond expressed by formula 2 used in this invention may be dichlorosilane, trichlorosilane, and alkyldichlorosilane.
- Organothiomethyl halide, raw material of this invention, expressed by the following Formula 3 may be alkylthiomethyl halide and arylthiomethyl halide
- Examples of the organothiomethyl halide expressed by Formula 2 are methylthiomethyl chloride and phenylthiomethyl chloride, etc.
- The catalyst of this invention expressed by the following Formulae 4, 5 and 6 may be quaternary phosphonium salt, quaternary ammonium salts and tertiary amine.
(R″)3N (6) - Quaternary organic salt in this invention can be expressed by the following Formula 4 and 5,
E(R″)4X (4)
wherein E represents a phosphorus or a nitrogen atom; X may be chloro, bromo or iodo; and R″ may be identical or different and is a C1-C12 alkyl, phenyl group or —CnH2n+1—C6H5 (n is an integer of 0-6); and two of the R″ functional groups may be covalently bonded to form a C4-C8 ring.
X(R″)3E-Y-E(R″)3X (5)
wherein E, X and R″ are defined as above; and Y can be C1-12 alkylene or aromatic group optionally containing alkyls. - The organic, salt of the following formula 4 used in this invention may be quaternary organophosphonium halide or quaternary organoammonium halide. Specific examples of the quaternary organophosphonium salt are tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide, methyltributylphosphonium chloride, tetramethylphosphonium bromide, tetraethylphosphonium chloride, hexyltriphenylphosphonium chloride, and tetraphenylphosphonium chloride, etc. Specific examples of quaternary organoammonium halide are the same except that nitrogen atom is replaced instead of phosphorous atom of quaternary organophosphonium halide. Specific examples of quaternary organophosphonium salt of the following formula 5 used in this invention may be bis(chlorotrialkylphosphonium)alkylene, bis(chlorotrialkylphosphonium)phenylene, bis(chlorotriphenylphosphonium)alkylene, bis(chlorotriphenylphosphonium)phenylene, and etc. Specific examples of quaternary organoammonium halide of the following formula 5 used in this invention are the same except that nitrogen atom is replaced instead of phosphorous atom of quaternary organophosphonium halide.
- Tertiary amine in this invention can be expressed by the following Formula 6
(R″)3N (6)
wherein R″ is same as defined above. - The organic base of the following formula 5 used in this invention may be tertiary organic amines.
- Specific examples of tertiary amine compounds are trimethylamine, triethylamine, tributylamine, etc.
- As explained above, even though organic salt or organic base is used for the Si—C coupling reaction in this invention, organic salt or organic base immobilized on silicone resins, silica, or zeolite can be easier recovery and more convenient for recycling.
- As explained above, this method uses a small amount of catalyst, which can be easily recovered for reuse and has good catalytic activity even at low temperature. Considering these advantages, the present invention is a very economical and effective method, which can be used for the preparation of new and various organothiomethylsilicon compounds. Furthermore, its process is very simple and the production cost is relatively low.
- Also, the organosilicon compounds, expressed by formula 1, prepared by this invention can be widely used for the synthesis of various polymers and silicone surfactants, because organothiomethyl group of silane can be converted to sulfoxide group applicable to hydrophilic silicones. These compounds are new type hydrophilic silicone different from modified polyethylene- or propyleneoxide-silicones. Generally dialkyl sulfide can be converted to dialkyl sulfonoxide or sulfone by the oxidation reaction with hydrogen peroxide (A. Kh. Sharipov, Russian Journal of Applied Chemistry, 2003, 76, 108-113). Thus oragnothiomethylchlorosilanes may be chemically bonded to inorganic substrate and oxidized to make surface to be hydrophilic.
- The invention will be further illustrated by the following examples. However, they should not construed as limiting the scope of the present invention.
-
HSiCl3+CH3SCH2Cl→CH3SCH2SiCl3 - A reaction chamber (a 250 mL stainless steel tube) dried in an oven was cooled to room temperature under dry nitrogen gas methylthiomethyl chloride (138.1 g, 1.02 mol), trichlorosilane (138.1 g, 1.02 mol) and tetrabutylphosphonium chloride (5.01 g, 0.0169 mol) were put in the chamber under nitrogen atmosphere. The opening of the reaction chamber was closed with a cover and the reaction was carried out at 100 ° C. for 12 hours. This reaction mixture was distilled under normal pressure to give (methylthiomethyl)trichlorosilane (52.2 g, yield: 73.8%).
- 1H-NMR(CDCl3,ppm) δ2.26(s, 3H, CH3), 2.41(s, 2H, CH2)
-
CH3SiHCl2+CH3SCH2Cl→CH3SCH2SiCH3Cl2 - As in Example 1, methylthiomethyl chloride (49.2 g, 0.428 mol), methyldichlorosilane (49.2 g, 0.428 mol) and tetrabutylphosphonium chloride (2.10 g, 0.00713 mol) were put in a 250 mL stainless steel tube under nitrogen atmosphere. The reaction chamber was closed with a cover and the reaction was carried out at 100 ° C. for 12 hours. This reaction mixture was distilled to give 25.04 g of methyl(methylthiomethyl)dichlorosilane in 20.2% yield.
- 1H-NMR(CDCl3,ppm) δ0.87(s, 3H, SiCH3), 2.27(s, 3H, SCH3), 2.28(s, 2H, CH2)
-
HSiCl3+C6H5SCH2Cl→C6H5SCH2SiCl3 - As in Example 1, phenylthiomethyl chloride (2.97 g, 0.0187 mol)), trichlorosilane (7.61 g, 0.0562 mol) and tetrabutylphosphonium chloride (2.97 g, 0.0187 mol) were put in a 50 mL stainless steel tube under nitrogen atmosphere. The reaction chamber was closed with a cover and the reaction was carried out at 120 ° C. for 12 hours. This reaction mixture was distilled under low pressure to give 2.15 g of (phenylthiomethyl)trichlorosilane in 44.5% yield.
- 1H-NMR(CDCl3, ppm) δ2.91 (s, 3H, CH2), 7.21-7.42 (m, 5H, ArH)
-
CH3SiHCl2+C6H5SCH2Cl→C6H5SCH2SiCH3Cl2 - As in Example 1, phenylthiomethyl chloride (3.31 g, 0.0209 mol), methyldichlorosilane (7.23 g, 0.0628 mol) and tetrabutylphosphonium chloride (0.615 g, 0.00209 mol) were put in a 50 mL stainless steel tube under nitrogen atmosphere. The reaction chamber was closed with a cover and the reaction was carried out at 120 ° C. for 12 hours. This reaction mixture was distilled under low pressure to give 1.82 g of methyl(phenylthiomethyl)dichlorosilane in 36.9% yield.
- 1H NMR(CDCl3,ppm) δ0.84(s, 3H, SiCH3 ), 2.71(s, 2H, CH2), 7.19-7.37(m, 5H, ArH)
-
HSiCl3+CH3SCH2Cl→CH3SCH2SiCl3
1) Reaction in the presence of triethylamine - As in Example 1, methylthiomethyl chloride (1.16 g, 0.0120 mol), trichlorosilane (8.13 g, 0.0600 mol) and triethylamine (1.21 g, 0.0120 mol) were put in a 50 mL stainless steel tube under nitrogen atmosphere. The reaction chamber was closed with a cover and the reaction was carried out at 100 ° C. for 12 hours. This reaction mixture was distilled under low pressure to give 1.12 g of (methylthiomethyl)trichlorosilane in 47.8% yield.
- 2) Reaction in the presence of tetrabutylammonium chloride
- As in Example 1, methylthiomethyl chloride (1.04 g, 0.0108 mol), trichlorosilane (4.39 g, 0.0324 mol) and tetrabutylammonium chloride (0.301 g, 0.00108 mol) were put in a 50 mL stainless steel tube under nitrogen atmosphere. The reaction chamber was closed with a cover and the reaction was carried out at 100 ° C. for 12 hours. This reaction mixture was distilled under low pressure to give 1.08 g of (methylthiomethyl)trichlorosilane in 51 % yield.
- Having now fully described the present invention, it will be apparent to one of ordinary skill in the art that many changes and modifications can be made thereto without departing from the spirit of scope of the invention as set forth herein.
- As explained above, the present invention relates to (organothiomethyl)chlorosilanes with a sulfur-containing alkyl group and their preparation expressed by Formulas 1 by the Si—C coupling reaction of Si—H containing chlorosilanes with organothiomethyl halide in the presence of quaternary organic salt catalyst or amines. Especially, this reaction using organic salt as a catalyst provide better economical matter and yield compared with conventional methods, because only catalytic amount of organic salt is required and the catalyst can be separated from the reaction mixture and recycled easily. Si—H containing silanes used in this invention are an easily available material in the industry. Therefore, this invention is effective for industrial mass production of (organothiomethyl)chlorosilane compounds, which are widely used for raw material of silicon polymers, silicone adhesives, etc.
Claims (10)
(R″)4EX (4)
X(R″)3E-Y-E(R″)3X (5)
(R″)3N (6)
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US20100323530A1 (en) * | 2007-02-06 | 2010-12-23 | Central Glass Company, Limited | Modifier for low dielectric constant film, and method for production thereof |
CN112638921A (en) * | 2018-09-06 | 2021-04-09 | 瓦克化学股份公司 | Method for the dehydrogenation of dichlorosilanes |
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KR101144497B1 (en) * | 2007-02-06 | 2012-05-11 | 샌트랄 글래스 컴퍼니 리미티드 | Modifier for low dielectric constant film, and method for production thereof |
KR101161134B1 (en) | 2009-09-14 | 2012-07-02 | 제이에스아이실리콘주식회사 | Organochlorosilylacene and Bisorganochlorosilylacene derivatives and Their Preparation method |
CN114258396A (en) | 2019-08-22 | 2022-03-29 | 美国陶氏有机硅公司 | Method for purifying silicon compounds |
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JP3501008B2 (en) * | 1998-04-10 | 2004-02-23 | ダイソー株式会社 | Method for producing sulfur-containing organosilicon compound and method for producing intermediate thereof |
KR100306574B1 (en) | 1999-04-13 | 2001-09-13 | 박호군 | Dehydrohalogenative coupling reaction of alkyl halides with silane |
US6211345B1 (en) * | 1999-12-22 | 2001-04-03 | Witco Corporation | Synthesis of cyclic sulfur silanes |
KR20050023276A (en) | 2002-05-28 | 2005-03-09 | 사타케 유에스에이 인코포레이티드 | Illumination source for sorting machine |
US6740767B1 (en) * | 2002-11-12 | 2004-05-25 | Dow Corning Corporation | Method of making sulfur containing organosilicon compounds |
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US4613491A (en) * | 1984-05-17 | 1986-09-23 | Korea Advanced Institute Of Science And Technology | Redistribution catalyst and methods for its preparation and use to convert chlorosilicon hydrides to silane |
US6251057B1 (en) * | 1999-04-13 | 2001-06-26 | Korea Institute Of Science And Technology | Dehydrohalogenative coupling reaction of organic halides with silanes |
US6392077B1 (en) * | 2000-11-01 | 2002-05-21 | Korea Institute Of Science And Technology | Process for preparing organochlorosilanes by dehydrohalogenative coupling reaction of alkyl halides with chlorosilanes |
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US20100323530A1 (en) * | 2007-02-06 | 2010-12-23 | Central Glass Company, Limited | Modifier for low dielectric constant film, and method for production thereof |
US7973390B2 (en) | 2007-02-06 | 2011-07-05 | Central Glass Company, Limited | Modifier for low dielectric constant film, and method for production thereof |
CN112638921A (en) * | 2018-09-06 | 2021-04-09 | 瓦克化学股份公司 | Method for the dehydrogenation of dichlorosilanes |
CN112638921B (en) * | 2018-09-06 | 2024-05-14 | 瓦克化学股份公司 | Method for the dehydrogenation of dichlorosilane |
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