JP6355078B2 - Process for producing organosilane compound and catalyst composition for synthesis of organosilane compound - Google Patents
Process for producing organosilane compound and catalyst composition for synthesis of organosilane compound Download PDFInfo
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- JP6355078B2 JP6355078B2 JP2014001428A JP2014001428A JP6355078B2 JP 6355078 B2 JP6355078 B2 JP 6355078B2 JP 2014001428 A JP2014001428 A JP 2014001428A JP 2014001428 A JP2014001428 A JP 2014001428A JP 6355078 B2 JP6355078 B2 JP 6355078B2
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- organosilane compound
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- -1 organosilane compound Chemical class 0.000 title claims description 63
- 239000003054 catalyst Substances 0.000 title claims description 42
- 239000000203 mixture Substances 0.000 title description 20
- 238000000034 method Methods 0.000 title description 9
- 230000015572 biosynthetic process Effects 0.000 title description 4
- 238000003786 synthesis reaction Methods 0.000 title description 4
- 230000008569 process Effects 0.000 title description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 183
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 72
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 64
- 239000002105 nanoparticle Substances 0.000 claims description 50
- 239000002904 solvent Substances 0.000 claims description 44
- 238000004519 manufacturing process Methods 0.000 claims description 40
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- 150000002430 hydrocarbons Chemical group 0.000 claims description 32
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 32
- 150000001345 alkine derivatives Chemical class 0.000 claims description 28
- 150000001336 alkenes Chemical class 0.000 claims description 27
- 125000005843 halogen group Chemical group 0.000 claims description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 22
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 21
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 21
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical group [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 20
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 20
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 18
- 229910052710 silicon Inorganic materials 0.000 claims description 18
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 15
- 229910052717 sulfur Inorganic materials 0.000 claims description 15
- 125000004434 sulfur atom Chemical group 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- 125000004122 cyclic group Chemical group 0.000 claims description 9
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 6
- 230000001186 cumulative effect Effects 0.000 claims description 5
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 description 71
- 239000006185 dispersion Substances 0.000 description 59
- 238000006243 chemical reaction Methods 0.000 description 33
- 239000002245 particle Substances 0.000 description 20
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 19
- 229940031182 nanoparticles iron oxide Drugs 0.000 description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 14
- 229910052742 iron Inorganic materials 0.000 description 14
- 239000003921 oil Substances 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 10
- 239000012046 mixed solvent Substances 0.000 description 10
- 229910000077 silane Inorganic materials 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- 239000002798 polar solvent Substances 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000006459 hydrosilylation reaction Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 6
- 125000001309 chloro group Chemical group Cl* 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- 150000003961 organosilicon compounds Chemical class 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical group C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 description 3
- OIKHZBFJHONJJB-UHFFFAOYSA-N dimethyl(phenyl)silicon Chemical compound C[Si](C)C1=CC=CC=C1 OIKHZBFJHONJJB-UHFFFAOYSA-N 0.000 description 3
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 3
- 239000004210 ether based solvent Substances 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- AQBLLJNPHDIAPN-LNTINUHCSA-K iron(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Fe+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O AQBLLJNPHDIAPN-LNTINUHCSA-K 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 3
- SUJVAMIXNUAJEY-UHFFFAOYSA-N 4,4-dimethylhex-1-ene Chemical compound CCC(C)(C)CC=C SUJVAMIXNUAJEY-UHFFFAOYSA-N 0.000 description 2
- JUQRLACJJQXBDE-UHFFFAOYSA-N 6,6-dimethylhept-1-ene Chemical compound CC(C)(C)CCCC=C JUQRLACJJQXBDE-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- PBGVMIDTGGTBFS-UHFFFAOYSA-N but-3-enylbenzene Chemical compound C=CCCC1=CC=CC=C1 PBGVMIDTGGTBFS-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- NBBQQQJUOYRZCA-UHFFFAOYSA-N diethoxymethylsilane Chemical compound CCOC([SiH3])OCC NBBQQQJUOYRZCA-UHFFFAOYSA-N 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002003 electron diffraction Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000010813 internal standard method Methods 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- LAQFLZHBVPULPL-UHFFFAOYSA-N methyl(phenyl)silicon Chemical compound C[Si]C1=CC=CC=C1 LAQFLZHBVPULPL-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 150000001282 organosilanes Chemical class 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000003586 protic polar solvent Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 125000001981 tert-butyldimethylsilyl group Chemical group [H]C([H])([H])[Si]([H])(C([H])([H])[H])[*]C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- OGJCIAFFKGRGJC-UHFFFAOYSA-N 1,2-bis(chloranyl)ethane Chemical group ClCCCl.ClCCCl OGJCIAFFKGRGJC-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910021576 Iron(III) bromide Inorganic materials 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical group CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000006254 arylation reaction Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 description 1
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910001567 cementite Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000001162 cycloheptenyl group Chemical group C1(=CCCCCC1)* 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 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
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 150000004698 iron complex Chemical class 0.000 description 1
- 229910001337 iron nitride Inorganic materials 0.000 description 1
- QXYHCTRKUSRDPG-UHFFFAOYSA-L iron(2+);iron(3+);sulfate Chemical compound [Fe+2].[Fe+3].[O-]S([O-])(=O)=O QXYHCTRKUSRDPG-UHFFFAOYSA-L 0.000 description 1
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 1
- LNOZJRCUHSPCDZ-UHFFFAOYSA-L iron(ii) acetate Chemical compound [Fe+2].CC([O-])=O.CC([O-])=O LNOZJRCUHSPCDZ-UHFFFAOYSA-L 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 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 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- GZTNBKQTTZSQNS-UHFFFAOYSA-N oct-4-yne Chemical compound CCCC#CCCC GZTNBKQTTZSQNS-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004346 phenylpentyl group Chemical group C1(=CC=CC=C1)CCCCC* 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- GHUURDQYRGVEHX-UHFFFAOYSA-N prop-1-ynylbenzene Chemical compound CC#CC1=CC=CC=C1 GHUURDQYRGVEHX-UHFFFAOYSA-N 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Description
本発明は、有機シラン化合物の製造方法及び有機シラン化合物合成用触媒組成物に関し、より詳しくはアルケン類及び／又はアルキン類とヒドロシラン類とを、表面に溶媒が配位した鉄元素含有ナノ粒子存在下で反応させる有機シラン化合物の製造方法に関する。 The present invention relates to a method for producing an organic silane compound and a catalyst composition for synthesizing an organic silane compound, and more specifically, the presence of iron element-containing nanoparticles in which a alkene and / or an alkyne and a hydrosilane are coordinated on a surface thereof The present invention relates to a method for producing an organosilane compound to be reacted below.
アルケン類やアルキン類等の不飽和炭化水素化合物にヒドロシラン類を付加させるヒドロシリル化反応は、炭素−ケイ素結合を形成することができる有用な反応の１つであり、幅広い分野に利用されている。このようなヒドロシリル化反応においては、従来白金族触媒が主に用いられてきたが、鉄錯体等の貴金属を使用しない合成法も提案されている（非特許文献１及び２参照）。 The hydrosilylation reaction in which hydrosilanes are added to unsaturated hydrocarbon compounds such as alkenes and alkynes is one of useful reactions capable of forming a carbon-silicon bond, and is used in a wide range of fields. In such hydrosilylation reactions, platinum group catalysts have been mainly used in the past, but synthesis methods that do not use noble metals such as iron complexes have also been proposed (see Non-Patent Documents 1 and 2).
一方、金属塩化物等をジメチルホルムアミド（ＤＭＦ）中で還元することにより、粒子径が約２ｎｍ以下の金、白金、パラジウム等のナノ粒子を簡便かつ大量に合成することができることが報告されている。このようなナノ粒子は、分散剤等による表面処理を施すことなく各種媒体に均一に分散することができる優れた特性を有しており、これらのナノ粒子を有機合成反応の触媒として利用する検討が進められている。例えば、白金やパラジウムのナノ粒子を触媒として利用したクロスカップリング反応（特許文献１参照）、さらに鉄ナノ粒子を触媒として利用した酸化反応やアリール化反応が報告されている（特許文献２参照）。 On the other hand, it has been reported that nanoparticles such as gold, platinum and palladium having a particle diameter of about 2 nm or less can be synthesized easily and in large quantities by reducing metal chlorides or the like in dimethylformamide (DMF). . Such nanoparticles have excellent properties that can be uniformly dispersed in various media without being subjected to surface treatment with a dispersant or the like, and examination of using these nanoparticles as a catalyst for organic synthesis reactions. Is underway. For example, a cross-coupling reaction using platinum or palladium nanoparticles as a catalyst (see Patent Document 1), and an oxidation reaction or arylation reaction using iron nanoparticles as a catalyst have been reported (see Patent Document 2). .
前述のようにアルケン類やアルキン類のヒドロシリル化反応は、触媒として白金等の貴金属が用いられたり、特殊な配位子を含む錯体が用いられたりしていたため、コストの観点から改善の余地があった。優れた活性を示す触媒を簡便かつ安価に調製することができれば、ヒドロシリル化反応を利用した材料等の製造コスト低減に繋がる優れた技術となり得る。
即ち、本発明は、アルケン類やアルキン類のヒドロシリル化反応に使用する触媒を改良し、有機シラン化合物を効率良く、安価に製造することができる製造方法を提供することを課題とする。
As described above, in the hydrosilylation reaction of alkenes and alkynes, noble metals such as platinum are used as catalysts, or complexes containing special ligands are used, so there is room for improvement from the viewpoint of cost. there were. If a catalyst exhibiting excellent activity can be prepared easily and inexpensively, it can be an excellent technique that leads to a reduction in production cost of materials using hydrosilylation reaction.
That is, an object of the present invention is to provide a production method capable of improving the catalyst used for the hydrosilylation reaction of alkenes and alkynes and producing an organic silane compound efficiently and inexpensively.
本発明者らは、上記の課題を解決すべく鋭意検討を重ねた結果、アルケン類及び／又はアルキン類とヒドロシラン類とを触媒存在下で反応させる有機シラン化合物の製造方法において、表面に溶媒が配位した鉄含有ナノ粒子を触媒として用いることにより、有機シラ
ン化合物を効率良く、安価に製造することができることを見出し、本発明を完成させた。
As a result of intensive studies to solve the above problems, the inventors of the present invention have prepared a method for producing an organosilane compound in which an alkene and / or an alkyne and a hydrosilane are reacted in the presence of a catalyst. It has been found that by using coordinated iron-containing nanoparticles as a catalyst, an organosilane compound can be produced efficiently and inexpensively, and the present invention has been completed.
即ち、本発明は以下の通りである。
＜１＞ アルケン類及び／又はアルキン類と、ヒドロシラン類とを触媒存在下で反応させる有機シラン化合物の製造方法であって、前記触媒が、表面に溶媒が配位した鉄元素含有ナノ粒子であることを特徴とする、有機シラン化合物の製造方法。
＜２＞ 下記式（Ａ）、（Ａ’）、（Ｂ−１）、（Ｂ−２）、（Ｂ−３）、（Ｂ’−１）、（Ｂ’−２）、又は（Ｂ’−３）で表される化合物を製造する方法である、＜１＞に記載の有機シラン化合物の製造方法。
もよい。）
＜３＞ 前記溶媒が、トルエン、１，４−ジオキサン、テトラヒドロフラン（ＴＨＦ）、１，２−ジクロロエタン、ジメチルアセトアミド（ＤＭＡ）、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、及びＮ−メチルピロリドン（ＮＭＰ）からなる群より選択される少なくとも１種を含むものである、＜１＞又は＜２＞に記載の有機シラン化合物の製造方法。
＜４＞ 前記鉄元素含有ナノ粒子の累積中位径（Ｍｅｄｉａｎ径）が０．５〜４ｎｍである、＜１＞〜＜３＞の何れかに記載の有機シラン化合物の製造方法。
＜５＞ 前記鉄元素含有ナノ粒子が酸化鉄である、＜１＞〜＜４＞の何れかに記載の有機シラン化合物の製造方法。
＜６＞ アルケン類及び／又はアルキン類とヒドロシラン類から有機シラン化合物を合成するための有機シラン化合物の合成用触媒組成物であって、表面に溶媒が配位した鉄元素含有ナノ粒子を含むことを特徴とする、有機シラン化合物の合成用触媒組成物。
＜７＞ 前記溶媒が、トルエン、１，４−ジオキサン、テトラヒドロフラン（ＴＨＦ）、１，２−ジクロロエタン、ジメチルアセトアミド（ＤＭＡ）、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、及びＮ−メチルピロリドン（ＮＭＰ）からなる群より選択される少なくとも１種を含むものである、＜６＞に記載の有機シラン化合物の合成用触媒組成物。
That is, the present invention is as follows.
<1> A method for producing an organosilane compound in which an alkene and / or alkyne and hydrosilane are reacted in the presence of a catalyst, wherein the catalyst is an iron element-containing nanoparticle having a solvent coordinated on a surface thereof. A process for producing an organosilane compound, characterized in that
<2> The following formula (A), (A ′), (B-1), (B-2), (B-3), (B′-1), (B′-2), or (B ′) -3) The manufacturing method of the organosilane compound as described in <1> which is a method of manufacturing the compound represented.
<3> The solvent is toluene, 1,4-dioxane, tetrahydrofuran (THF), 1,2-dichloroethane, dimethylacetamide (DMA), N, N-dimethylformamide (DMF), and N-methylpyrrolidone (NMP). The method for producing an organosilane compound according to <1> or <2>, comprising at least one selected from the group consisting of:
<4> The method for producing an organosilane compound according to any one of <1> to <3>, wherein a cumulative median diameter (Median diameter) of the iron element-containing nanoparticles is 0.5 to 4 nm.
<5> The method for producing an organosilane compound according to any one of <1> to <4>, wherein the iron element-containing nanoparticles are iron oxide.
<6> A catalyst composition for synthesizing organosilane compounds for synthesizing organosilane compounds from alkenes and / or alkynes and hydrosilanes, comprising iron-element-containing nanoparticles coordinated with a solvent on the surface A catalyst composition for the synthesis of an organosilane compound, characterized in that
<7> The solvent is toluene, 1,4-dioxane, tetrahydrofuran (THF), 1,2-dichloroethane, dimethylacetamide (DMA), N, N-dimethylformamide (DMF), and N-methylpyrrolidone (NMP). it is intended to include at least one selected from the group consisting of, a catalyst for synthesizing the compositions of the organosilane compound according to <6>.
本発明によれば、有機シラン化合物を効率良く、安価に製造することができる。 According to the present invention, an organosilane compound can be produced efficiently and inexpensively.
本発明の有機シラン化合物の製造方法及び有機シラン化合物合成用触媒組成物の詳細を説明するに当たり、具体例を挙げて説明するが、本発明の趣旨を逸脱しない限り以下の内容に限定されるものではなく、適宜変更して実施することができる。 In describing the details of the method for producing an organic silane compound and the catalyst composition for synthesizing an organic silane compound of the present invention, specific examples will be described. However, the present invention is limited to the following contents without departing from the spirit of the present invention. Instead, it can be implemented with appropriate modifications.
＜有機シラン化合物の製造方法＞
本発明の一態様である有機シラン化合物の製造方法（以下、「本発明の製造方法」と略す場合がある。）は、「アルケン類及び／又はアルキン類」と「ヒドロシラン類」とを触媒存在下で反応させる方法であるが、触媒が表面に溶媒が配位した鉄元素含有ナノ粒子であることを特徴とする。
前述のようにアルケン類やアルキン類のヒドロシリル化反応は、触媒として白金等の貴金属が用いられたり、特殊な配位子を含む錯体が用いられたりしていたため、コストの観点から改善の余地があった。本発明者らは、優れた活性を示し、簡便かつ安価に調製することができる触媒材料を求め鋭意検討を重ねた結果、表面に溶媒が配位した鉄元素含有ナノ粒子がヒドロシリル化反応の触媒として好適であり、これを用いることによって有機シラン化合物を効率良く、安価に製造することができることを見出したのである。
表面に溶媒が配位した鉄元素含有ナノ粒子は、有機シラン化合物の製造に使用した後、回収して触媒として再利用することができる利点がある。例えば、鉄錯体を触媒として用いた場合、高い触媒活性が得られるものの、一般的に錯体触媒は反応終了後に失活してしまったり、分解してしまうため、再利用が困難となる。特に鉄元素含有ナノ粒子は、表面が溶媒に保護されているため、劣化しにくく、触媒活性を維持し易いと考えられる。また
、鉄元素は、原子番号の比較的小さい遷移金属で、イオン半径が小さいため、触媒反応において反応基質が中心金属の近くで作用し、高い触媒活性が得られるものと考えられる。
なお、「鉄元素含有ナノ粒子」とは、粒子径（累積中位径（Ｍｅｄｉａｎ径））が０．５〜１００ｎｍの範囲にあり、鉄元素を構成元素として含む粒子を意味するものとする。従って、鉄元素を含むものであれば具体的な組成は特に限定されず、金属鉄粒子のほか、鉄とその他の金属との合金粒子、金属鉄粒子に酸素原子や炭素原子等のその他の原子がドープされている粒子、或いは酸化鉄、窒化鉄、炭化鉄等の鉄元素を含む無機化合物粒子等も含まれることを意味する。
また、「表面に溶媒が配位した」とは、鉄元素含有ナノ粒子の表面に溶媒分子が配位していることを意味する。なお、鉄元素含有ナノ粒子に配位する「溶媒」は、具体的な種類は限定されず、置換可能であるため、目的の反応に合わせて適宜選択することができる。また、「溶媒」が鉄元素含有ナノ粒子に配位しているか否かについては、分散剤等による表面処理を施すことなく、「溶媒」に安定的に分散するか否かで判断することができる。即ち、例えばＮ，Ｎ−ジメチルホルムアミド（ＤＭＦ）を配位させた鉄元素含有ナノ粒子は、ＤＭＦと親和性のある「溶媒」に安定的に分散させることができる。
また、「アルケン類」とは炭素−炭素二重結合を少なくとも１つ有する有機化合物を、「アルキン類」とは炭素−炭素三重結合を少なくとも１つ有する有機化合物を、「ヒドロシラン類」とはケイ素−水素結合（Ｓｉ−Ｈ）を少なくとも１つ有する化合物を、「有機シラン化合物」とは炭素−ケイ素結合（Ｃ−Ｓｉ）を少なくとも１つ有する有機化合物を意味するものとする。従って、「アルケン類及び／又はアルキン類」と「ヒドロシラン類」の反応として、例えば下記の反応式で示されるような反応が挙げられる（「アルケン類」が「１−デセン」であり、「ヒドロシラン類」がフェニルシランである。）。
The method for producing an organic silane compound which is one embodiment of the present invention (hereinafter sometimes abbreviated as “the production method of the present invention”) includes “alkenes and / or alkynes” and “hydrosilanes” as catalysts. The catalyst is characterized in that the catalyst is iron element-containing nanoparticles with a solvent coordinated on the surface.
As described above, in the hydrosilylation reaction of alkenes and alkynes, noble metals such as platinum are used as catalysts, or complexes containing special ligands are used, so there is room for improvement from the viewpoint of cost. there were. The inventors of the present invention have intensively studied for a catalyst material that exhibits excellent activity and can be prepared easily and inexpensively. As a result, the iron element-containing nanoparticles having a coordinated solvent on the surface are catalysts for hydrosilylation reaction. It was found that the organosilane compound can be produced efficiently and inexpensively by using this.
The iron element-containing nanoparticles having a solvent coordinated on the surface have an advantage that they can be recovered and reused as a catalyst after being used for the production of an organosilane compound. For example, when an iron complex is used as a catalyst, although high catalytic activity is obtained, the complex catalyst is generally deactivated or decomposed after completion of the reaction, making it difficult to reuse. In particular, it is considered that the iron element-containing nanoparticles are hardly deteriorated because the surface is protected by a solvent, and the catalytic activity is easily maintained. In addition, iron element is a transition metal having a relatively small atomic number and has a small ionic radius. Therefore, it is considered that the reaction substrate acts near the central metal in the catalytic reaction and high catalytic activity can be obtained.
The “iron element-containing nanoparticle” means a particle having a particle diameter (cumulative median diameter (Median diameter)) in the range of 0.5 to 100 nm and containing an iron element as a constituent element. Therefore, the specific composition is not particularly limited as long as it contains an iron element, in addition to metallic iron particles, alloy particles of iron and other metals, and other atoms such as oxygen atoms and carbon atoms in the metallic iron particles. It is meant that inorganic particles containing iron elements such as iron oxide, iron nitride and iron carbide are also included.
Further, “the solvent is coordinated on the surface” means that solvent molecules are coordinated on the surface of the iron element-containing nanoparticles. The “solvent” coordinated to the iron element-containing nanoparticles is not limited to a specific type, and can be appropriately selected according to the target reaction because it can be substituted. Further, whether or not the “solvent” is coordinated to the iron element-containing nanoparticles can be determined by whether or not the “solvent” is stably dispersed without performing a surface treatment with a dispersant or the like. it can. That is, for example, iron element-containing nanoparticles coordinated with N, N-dimethylformamide (DMF) can be stably dispersed in a “solvent” having an affinity for DMF.
“Alkenes” means an organic compound having at least one carbon-carbon double bond, “alkynes” means an organic compound having at least one carbon-carbon triple bond, and “hydrosilanes” means silicon. -A compound having at least one hydrogen bond (Si-H) and an "organosilane compound" means an organic compound having at least one carbon-silicon bond (C-Si). Accordingly, examples of the reaction between “alkenes and / or alkynes” and “hydrosilanes” include reactions represented by the following reaction formulas (“alkenes” are “1-decene”, “hydrosilanes” Class "is phenylsilane).
（有機シラン化合物）
本発明の製造方法における有機シラン化合物は、前述のように炭素−ケイ素結合（Ｃ−Ｓｉ）を少なくとも１つ有する有機化合物であれば、具体的な構造は特に限定されず、幅広い有機シラン化合物に適用することができる。
具体的には、下記式（Ａ）、（Ａ’）、（Ｂ−１）、（Ｂ−２）、（Ｂ−３）、（Ｂ’−１）、（Ｂ’−２）、又は（Ｂ’−３）で表される化合物が挙げられる。
に水素原子、ハロゲン原子、シロキシ基、ケイ素数１〜５０のポリシロキシ基、又は窒素原子、酸素原子、ケイ素原子、硫黄原子、及びハロゲン原子からなる群より選択される少なくとも１種を含んでいてもよい炭素数１〜２０の炭化水素基を表す。但し、Ｒ1〜Ｒ4の２以上が炭化水素基である場合、２以上の炭化水素基が連結して環状構造を形成していてもよい。）
即ち、上記式（Ａ）及び（Ａ’）で表される化合物は、アルケン類とヒドロシラン類との反応によって得られる有機ケイ素化合物であり、上記式（Ｂ−１）〜（Ｂ−３）及び（Ｂ’−１）〜（Ｂ’〜３）で表される化合物は、アルキン類とヒドロシラン類との反応によって得られる有機ケイ素化合物である。また、ＳｉＲ5 3基が付加する位置は特に限定されず、さらにアルキン類とヒドロシラン類との反応によって得られる有機ケイ素化合物は、Ｚ体、Ｅ体、Ｚ体とＥ体の混合物の何れであってもよいことを意味する。
(Organic silane compound)
As long as the organosilane compound in the production method of the present invention is an organic compound having at least one carbon-silicon bond (C—Si) as described above, the specific structure is not particularly limited, and a wide variety of organosilane compounds can be used. Can be applied.
Specifically, the following formulas (A), (A ′), (B-1), (B-2), (B-3), (B′-1), (B′-2), or ( And a compound represented by B′-3).
That is, the compounds represented by the above formulas (A) and (A ′) are organosilicon compounds obtained by the reaction of alkenes and hydrosilanes, and the above formulas (B-1) to (B-3) and The compounds represented by (B′-1) to (B ′ to 3) are organosilicon compounds obtained by a reaction between alkynes and hydrosilanes. Further, the position to which the SiR 5 3 group is added is not particularly limited, and the organosilicon compound obtained by the reaction of alkynes and hydrosilanes is any of Z form, E form, and a mixture of Z form and E form. It means you may.
Ｒ1〜Ｒ4はそれぞれ独立に水素原子、ハロゲン原子、又は窒素原子、酸素原子、ケイ素原子、硫黄原子、及びハロゲン原子からなる群より選択される少なくとも１種を含んでいてもよい炭素数１〜２０の炭化水素基を表しているが、「窒素原子、酸素原子、ケイ素原子、硫黄原子、及びハロゲン原子からなる群より選択される少なくとも１種を含んでいてもよい」とは、クロロ基（−Ｃｌ）、フルオロ基（−Ｆ）、アミノ基（−ＮＨ2）、ニト
ロ基（−ＮＯ2）、エポキシ基、ヒドロキシル基（−ＯＨ）、カルボニル基（−Ｃ（＝Ｏ
）−）、ｔｅｒｔ−ブチルジメチルシリル基（−ＳｉＢｕＭｅ2）、アジ基（−Ｎ3）等の窒素原子、酸素原子、ケイ素原子、硫黄原子、又はハロゲン原子を含む官能基を含んでいてもよいことを意味するほか、エーテル基（−Ｏ−）、チオエーテル基（−Ｓ−）等の窒
素原子、酸素原子、ケイ素原子、硫黄原子、又はハロゲン原子を含む連結基を炭素骨格の内部又は末端に含んでいてもよいことを意味する。従って、「窒素原子、酸素原子、ケイ素原子、硫黄原子、及びハロゲン原子からなる群より選択される少なくとも１種を含んでいてもよい」としては、例えば−ＣＨ2−ＣＨ2−ＯＨのようなヒドロキシル基を含む炭素数２の炭化水素基、−ＣＨ2−Ｏ−ＣＨ3のようなエーテル基を炭素骨格の内部に含む炭素数２の炭化水素基、及び−Ｏ−ＣＨ2−ＣＨ3のようなエーテル基を炭素骨格の末端に含む炭素数２の炭化水素基等が含まれる。
Ｒ1〜Ｒ4が炭化水素基である場合の炭素数は、好ましくは２以上、より好ましくは３以上、さらに好ましくは４以上であり、好ましくは１９以下、より好ましくは１７以下、さらに好ましくは１５以下である。なお、Ｒ1〜Ｒ4の２以上が炭化水素基である場合、２以上の炭化水素基が連結して環状構造を形成していてもよいが、例えばＲ1とＲ2が連結してシクロヘプタン構造、シクロヘプテン構造、シクロヘキサン構造、シクロヘキセン構造等を形成していることが挙げられる。
Ｒ1〜Ｒ4が炭化水素基である場合の炭化水素基に含まれる官能基は、クロロ基（−Ｃｌ）、フルオロ基（−Ｆ）、アミノ基（−ＮＨ2）、ニトロ基（−ＮＯ2）、エポキシ基、ヒドロキシル基（−ＯＨ）、カルボニル基（−Ｃ（＝Ｏ）−）、ｔｅｒｔ−ブチルジメチルシリル基（−ＳｉＢｕＭｅ2）、アジ基（−Ｎ3）等が挙げられる。
また、Ｒ1〜Ｒ4が炭化水素基である場合、直鎖状の飽和炭化水素基に限られず、分岐構造、環状構造、炭素−炭素不飽和結合のそれぞれを有していてもよい（分岐構造、環状構造、及び炭素−炭素不飽和結合からなる群より選択される少なくとも１種を有していてもよい。）。
具体的なＲ1〜Ｒ4としては、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、ｎ−へキシル基、ｎ−ヘプチル基、ｎ−オクチル基、ｎ−ノニル基、メチルプロピル基、メチルブチル基、メチルペンチル基、メチルへキシル基、メチルヘプチル基、ジメチルプロピル基、ジメチルブチル基、ジメチルペンチル基、ジメチルへキシル基、ジメチルヘプチル基、フェニルエチル基、フェニルプロピル基、フェニルブチル基、フェニルペンチル基、フェニルへキシル基、フェニルヘプチル基等が挙げられる。
R 1 to R 4 may each independently contain at least one selected from the group consisting of a hydrogen atom, a halogen atom, or a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a halogen atom. Represents a hydrocarbon group of ˜20, but “may contain at least one selected from the group consisting of a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a halogen atom” means a chloro group (—Cl), fluoro group (—F), amino group (—NH 2 ), nitro group (—NO 2 ), epoxy group, hydroxyl group (—OH), carbonyl group (—C (═O
)-), A tert-butyldimethylsilyl group (—SiBuMe 2 ), an azido group (—N 3 ) and the like, and may contain a functional group containing a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, or a halogen atom. In addition, a linking group containing a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, or a halogen atom such as an ether group (—O—) or a thioether group (—S—) is formed inside or at the end of the carbon skeleton. It means that it may contain. Accordingly, “may contain at least one selected from the group consisting of a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a halogen atom” includes, for example, —CH 2 —CH 2 —OH. A hydrocarbon group having 2 carbon atoms including a hydroxyl group, a hydrocarbon group having 2 carbon atoms having an ether group such as —CH 2 —O—CH 3 inside the carbon skeleton, and —O—CH 2 —CH 3 A hydrocarbon group having 2 carbon atoms containing such an ether group at the end of the carbon skeleton is included.
The carbon number in the case where R 1 to R 4 are hydrocarbon groups is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, preferably 19 or less, more preferably 17 or less, and still more preferably 15 or less. In addition, when two or more of R 1 to R 4 are hydrocarbon groups, two or more hydrocarbon groups may be linked to form a cyclic structure. For example, R 1 and R 2 are linked to form a cyclo Examples include formation of a heptane structure, a cycloheptene structure, a cyclohexane structure, a cyclohexene structure, and the like.
The functional group contained in the hydrocarbon group when R 1 to R 4 are hydrocarbon groups is a chloro group (—Cl), a fluoro group (—F), an amino group (—NH 2 ), a nitro group (—NO 2 ), an epoxy group, a hydroxyl group (—OH), a carbonyl group (—C (═O) —), a tert-butyldimethylsilyl group (—SiBuMe 2 ), an azide group (—N 3 ) and the like.
Moreover, when R < 1 > -R < 4 > is a hydrocarbon group, it is not restricted to a linear saturated hydrocarbon group, You may have each of a branched structure, a cyclic structure, and a carbon-carbon unsaturated bond (branching) It may have at least one selected from the group consisting of a structure, a cyclic structure, and a carbon-carbon unsaturated bond.
Specific examples of R 1 to R 4 include a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and a methylpropyl group. , Methylbutyl group, methylpentyl group, methylhexyl group, methylheptyl group, dimethylpropyl group, dimethylbutyl group, dimethylpentyl group, dimethylhexyl group, dimethylheptyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, Examples thereof include a phenylpentyl group, a phenylhexyl group, and a phenylheptyl group.
Ｒ5はそれぞれ独立に水素原子、ハロゲン原子、シロキシ基、ケイ素数１〜５０のポリ
シロキシ基、又は窒素原子、酸素原子、ケイ素原子、硫黄原子、及びハロゲン原子からなる群より選択される少なくとも１種を含んでいてもよい炭素数１〜２０の炭化水素基を表しているが、「窒素原子、酸素原子、ケイ素原子、硫黄原子、及びハロゲン原子からなる群より選択される少なくとも１種を含んでいてもよい」については、Ｒ1〜Ｒ4と同義である。
Ｒ5が炭化水素基である場合の炭素数は、好ましくは２以上、より好ましくは３以上、
さらに好ましくは４以上であり、好ましくは１９以下、より好ましくは１７以下、さらに好ましくは１５以下である。
Ｒ5がポリシロキシ基である場合のケイ素数は、好ましくは２以上、より好ましくは３
以上、さらに好ましくは４以上であり、好ましくは４８以下、より好ましくは４６以下、さらに好ましくは４５以下である。
また、Ｒ5が炭化水素基である場合、直鎖状の飽和炭化水素基に限られず、分岐構造、
環状構造、炭素−炭素不飽和結合のそれぞれを有していてもよい（分岐構造、環状構造、及び炭素−炭素不飽和結合からなる群より選択される少なくとも１種を有していてもよい。）。
具体的なＲ5としては、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メ
チル基、エチル基、ｎ−プロピル基、イソプロピル基、フェニル基、メトキシ基、エトキシ基、ポリメチルシロキシ基等が挙げられる。この中でも、水素原子が好ましい。
Ｒ5はそれぞれ独立に水素原子等を表しているが、２つのＲ3が水素原子であることが特に好ましい。水素原子が２つ以上であると、より収率良く有機ケイ素化合物を製造することができる。
R 5 is independently at least one selected from the group consisting of a hydrogen atom, a halogen atom, a siloxy group, a polysiloxy group having 1 to 50 silicon atoms, or a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a halogen atom. Represents a hydrocarbon group having 1 to 20 carbon atoms, which may contain “at least one selected from the group consisting of a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a halogen atom. The term “may be present” has the same meaning as R 1 to R 4 .
The number of carbons in the case where R 5 is a hydrocarbon group is preferably 2 or more, more preferably 3 or more,
More preferably, it is 4 or more, preferably 19 or less, more preferably 17 or less, and further preferably 15 or less.
When R 5 is a polysiloxy group, the number of silicon is preferably 2 or more, more preferably 3
More preferably, it is 4 or more, preferably 48 or less, more preferably 46 or less, and still more preferably 45 or less.
In addition, when R 5 is a hydrocarbon group, it is not limited to a linear saturated hydrocarbon group, but a branched structure,
Each may have a cyclic structure and a carbon-carbon unsaturated bond (may have at least one selected from the group consisting of a branched structure, a cyclic structure, and a carbon-carbon unsaturated bond). ).
Specific examples of R 5 include a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a phenyl group, a methoxy group, an ethoxy group, and a polymethylsiloxy group. Etc. Among these, a hydrogen atom is preferable.
R 5 independently represents a hydrogen atom or the like, but it is particularly preferable that two R 3 are hydrogen atoms. When the number of hydrogen atoms is 2 or more, the organosilicon compound can be produced with higher yield.
（アルケン類・アルキン類）
本発明の製造方法は、アルケン類及び／又はアルキン類とヒドロシラン類とを触媒存在下で反応させる方法であるが、アルケン類及び／又はアルキン類の種類は特に限定されず、製造目的である有機シラン化合物に基づいて適宜選択されるべきである。
基本的に製造目的である有機シラン化合物と共通する構造を有するアルケン類やアルキン類を選択すべきであり、例えば式（Ａ）、（Ａ’）、（Ｂ−１）、（Ｂ−２）、（Ｂ−３）、（Ｂ’−１）、（Ｂ’−２）、又は（Ｂ’−３）で表される化合物を製造目的とする場合、アルケン類としては下記式（ａ）で表される化合物が、アルキン類としては（ｂ）で表される化合物が挙げられる。
具体的なアルケン類としては、１−デセン、４−フェニル−１−ブテン、６，６−ジメチル−１−ヘプテン、４，４−ジメチル−１−ヘキセン、１−オクテン、スチレン、シクロヘキセン等が挙げられる。
また、具体的なアルキン類としては、ジフェニルアセチレン、１−フェニル−１−プロピン、４−オクチン、フェニルアセチレン等が挙げられる。
(Alkenes and alkynes)
The production method of the present invention is a method in which alkenes and / or alkynes and hydrosilanes are reacted in the presence of a catalyst, but the type of alkenes and / or alkynes is not particularly limited, and is an organic target for production. It should be appropriately selected based on the silane compound.
Alkenes and alkynes having a structure in common with the organic silane compound that is basically the production purpose should be selected. For example, the formulas (A), (A ′), (B-1), (B-2) , (B-3), (B′-1), (B′-2), or (B′-3), the production of the compound represented by the following formula (a) Examples of the alkynes represented by the compound represented by (b) include compounds represented by (b).
Specific alkenes include 1-decene, 4-phenyl-1-butene, 6,6-dimethyl-1-heptene, 4,4-dimethyl-1-hexene, 1-octene, styrene, cyclohexene and the like. It is done.
Specific alkynes include diphenylacetylene, 1-phenyl-1-propyne, 4-octyne, phenylacetylene and the like.
（ヒドロシラン類）
本発明の製造方法は、アルケン類及び／又はアルキン類とヒドロシラン類とを触媒存在下で反応させる方法であるが、ヒドロシラン類の種類は特に限定されず、製造目的である有機シラン化合物に基づいて適宜選択されるべきである。
基本的に製造目的である有機シラン化合物と共通する構造を有するヒドロシラン類を選択すべきであり、例えば式（Ａ）、（Ａ’）、（Ｂ−１）、（Ｂ−２）、（Ｂ−３）、（Ｂ’−１）、（Ｂ’−２）、又は（Ｂ’−３）で表される化合物を製造目的とする場合、ヒドロシラン類としては下記式（Ｘ）で表される化合物が挙げられる。
〜５０のポリシロキシ基、又は窒素原子、酸素原子、ケイ素原子、硫黄原子、及びハロゲン原子からなる群より選択される少なくとも１種を含んでいてもよい炭素数１〜２０の炭化水素基を表す。）
具体的なヒドロシラン類としては、フェニルシラン、ジフェニルシラン、メチルフェニルシラン、ジメチルフェニルシラン、トリエトキシシラン、トリエチルシラン、ジエトキシメチルシラン等が挙げられる。
(Hydrosilanes)
The production method of the present invention is a method in which alkenes and / or alkynes and hydrosilanes are reacted in the presence of a catalyst, but the type of hydrosilanes is not particularly limited, and is based on the organosilane compound that is the production object. It should be selected as appropriate.
Basically, hydrosilanes having a structure in common with the organosilane compound that is the object of production should be selected. For example, the formulas (A), (A ′), (B-1), (B-2), (B -3) When the compound represented by (B′-1), (B′-2), or (B′-3) is intended for production, the hydrosilanes are represented by the following formula (X): Compounds.
Represents a polysiloxy group having ˜50 or a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one selected from the group consisting of a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a halogen atom. )
Specific hydrosilanes include phenylsilane, diphenylsilane, methylphenylsilane, dimethylphenylsilane, triethoxysilane, triethylsilane, diethoxymethylsilane, and the like.
本発明の製造方法におけるアルケン類及び／又はアルキン類とヒドロシラン類の使用量は、目的に応じて適宜することができるが、ヒドロシラン類の使用量は、アルケン類及び／又はアルキン類の使用量に対して、物質量（［ｍｏｌ］）で通常１倍以上、好ましくは２倍以上、より好ましくは３倍以上であり、通常５０倍以下、好ましくは２０倍以下、より好ましくは１０倍以下である。上記範囲内であると、有機シラン化合物をより収率良く製造することができる。 The amount of alkenes and / or alkynes and hydrosilanes used in the production method of the present invention can be appropriately determined according to the purpose, but the amount of hydrosilanes used is the amount of alkenes and / or alkynes used. In contrast, the amount ([mol]) of the substance is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 50 or less, preferably 20 or less, more preferably 10 or less. . Within the above range, the organosilane compound can be produced with higher yield.
（触媒）
本発明の製造方法は、触媒が表面に溶媒が配位した鉄元素含有ナノ粒子であることを特徴とする方法であるが、表面に溶媒が配位した鉄元素含有ナノ粒子は、前述した鉄元素含有ナノ粒子に該当するものであれば、溶媒の具体的な種類、鉄元素含有ナノ粒子の組成、物性等は特に限定されない。
鉄元素含有ナノ粒子に配位する溶媒は、前述のように目的の反応に合わせて適宜選択することができるが、具体的にはヘキサン、ベンゼン、トルエン等の炭化水素系溶媒、ジエチルエーテル、１，４−ジオキサン、テトラヒドロフラン（ＴＨＦ）等のエーテル系溶媒、１，２−ジクロロエタン、クロロホルム等のハロゲン系溶媒、エタノール、エチレングリコール、グリセリン等のプロトン性極性溶媒、アセトン、ジメチルアセトアミド（ＤＭＡ）、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、Ｎ−メチルピロリドン（ＮＭＰ）、ジメチルスルホキシド（ＤＭＳＯ）等の非プロトン性極性溶媒等が挙げられる。
なお、鉄元素含有ナノ粒子に配位する溶媒は、適宜置換することができる。例えばＤＭＦが配位した金属鉄ナノ粒子のＤＭＦ分散液からロータリーエバポレーター等を用いてＤＭＦを留去し、金属鉄ナノ粒子を固形物として得る。そして、固形物をＴＨＦ等のその他の溶媒に接触させ、撹拌等を行ってなじませることにより、ＴＨＦが配位した金属鉄ナノ粒子を得ることができる。また、接触させる溶媒は、１種類に限られず、２種類以上を混合した混合溶媒であってもよい。具体的な組み合わせとしては、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）と１，４−ジオキサン、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）とジメチルアセトアミド（ＤＭＡ）、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）とＮ−メチルピロリドン（ＮＭＰ）、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）とトルエン等が挙げられるが、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）と１，４−ジオキサンの混合溶媒であることが特に好ましい。
鉄元素含有ナノ粒子は、前述のように鉄元素を構成元素として含むものであれば具体的な組成は特に限定されないが、鉄元素のほかに酸素元素を含むことが好ましく、酸素原子がドープされている金属鉄粒子若しくは鉄合金粒子、又は酸化鉄粒子がより好ましく、α−Ｆｅ2Ｏ3粒子であることが特に好ましい。
鉄元素含有ナノ粒子の粒子径（累積中位径（Ｍｅｄｉａｎ径））は、前述のように１〜１００ｎｍの範囲であれば特に限定されないが、好ましくは１．５ｎｍ以上、より好ましくは２．０ｎｍ以上、さらに好ましくは３．０ｎｍ以上であり、好ましくは１００ｎｍ以下、より好ましくは５０ｎｍ以下、さらに好ましくは２０ｎｍ以下である。なお、累積中位径（Ｍｅｄｉａｎ径）は、透過型電子顕微鏡（ＴＥＭ）で測定することができる。
(catalyst)
The production method of the present invention is a method characterized in that the catalyst is an iron element-containing nanoparticle with a solvent coordinated on the surface, and the iron element-containing nanoparticle with a solvent coordinated on the surface is the above-mentioned iron If it corresponds to an element containing nanoparticle, the specific kind of solvent, the composition of an iron element containing nanoparticle, a physical property, etc. will not be specifically limited.
The solvent coordinated to the iron element-containing nanoparticles can be appropriately selected according to the target reaction as described above. Specifically, hydrocarbon solvents such as hexane, benzene and toluene, diethyl ether, 1 Ether solvents such as 1,4-dioxane and tetrahydrofuran (THF), halogen solvents such as 1,2-dichloroethane and chloroform, protic polar solvents such as ethanol, ethylene glycol and glycerol, acetone, dimethylacetamide (DMA), N , N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethylsulfoxide (DMSO) and the like aprotic polar solvents.
In addition, the solvent coordinated to the iron element-containing nanoparticles can be appropriately substituted. For example, DMF is distilled off from a DMF dispersion of metallic iron nanoparticles coordinated with DMF using a rotary evaporator or the like to obtain metallic iron nanoparticles as a solid. Then, the solid matter is brought into contact with another solvent such as THF, and the mixture is mixed by stirring, whereby metallic iron nanoparticles coordinated with THF can be obtained. Moreover, the solvent made to contact is not restricted to 1 type, The mixed solvent which mixed 2 or more types may be sufficient. Specific combinations include N, N-dimethylformamide (DMF) and 1,4-dioxane, N, N-dimethylformamide (DMF) and dimethylacetamide (DMA), N, N-dimethylformamide (DMF) and N -Methylpyrrolidone (NMP), N, N-dimethylformamide (DMF) and toluene are exemplified, and a mixed solvent of N, N-dimethylformamide (DMF) and 1,4-dioxane is particularly preferable.
The iron element-containing nanoparticle is not particularly limited as long as it contains an iron element as a constituent element as described above, but preferably contains an oxygen element in addition to the iron element, and is doped with oxygen atoms. More preferred are metallic iron particles, iron alloy particles, or iron oxide particles, and α-Fe 2 O 3 particles are particularly preferred.
The particle size (cumulative median diameter (Median diameter)) of the iron element-containing nanoparticles is not particularly limited as long as it is in the range of 1 to 100 nm as described above, but is preferably 1.5 nm or more, more preferably 2.0 nm. More preferably, the thickness is 3.0 nm or more, preferably 100 nm or less, more preferably 50 nm or less, and still more preferably 20 nm or less. The cumulative median diameter (Median diameter) can be measured with a transmission electron microscope (TEM).
表面に溶媒が配位した鉄元素含有ナノ粒子の調製方法は、特に限定されないが、鉄元素を含んだ前駆体を極性溶媒中で加熱還流する方法が挙げられる。
以下、鉄元素を含んだ前駆体を極性溶媒中で加熱還流する方法における条件等の詳細を説明する。
鉄元素を含んだ前駆体の種類は、特に限定されないが、塩化鉄（ＩＩＩ）（ＦｅＣｌ3
）、臭化鉄（ＩＩＩ）（ＦｅＢｒ3）、酢酸鉄（ＩＩ）（Ｆｅ（ＣＨ3ＣＯ2）2）、クエン酸鉄（ＩＩＩ）（ＦｅＣ6Ｈ5Ｏ7）、硫酸アンモニウム鉄（ＩＩＩ）（ＦｅＮＨ4（ＳＯ4
）2）、鉄（ＩＩＩ）アセチルアセトナート（Ｆｅ（ＣＨ3ＣＯＣＨＣＯＣＨ3）3）等が挙げられる。この中でも、鉄（ＩＩＩ）アセチルアセトナートが特に好ましい。鉄（ＩＩＩ
）アセチルアセトナートを使用することによって、触媒活性に優れる鉄元素含有ナノ粒子を調製し易くなる。
極性溶媒の種類は、特に限定されないが、エチレングリコール、ジメチルアセトアミド（ＤＭＡ）、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、Ｎ−メチルピロリドン（ＮＭＰ）、ジメチルスルホキシド（ＤＭＳＯ）等が挙げられる。この中でも、Ｎ，Ｎ−ジメチルホルムアミドが特に好ましい。Ｎ，Ｎ−ジメチルホルムアミドを使用することによって、触媒活性に優れる鉄元素含有ナノ粒子を調製し易くなる。
設定する温度条件は、使用する極性溶媒によって選択されるべきであり、特に限定されない。
還流は、撹拌子等を使用して撹拌しながら行うことが好ましい。撹拌子の回転数は、通常５００ｒｐｍ以上、好ましくは８００ｒｐｍ以上、より好ましくは１０００ｒｐｍ以上であり、通常２０００ｒｐｍ以下、好ましくは１８００ｒｐｍ以下、より好ましくは１７００ｒｐｍ以下である。上記範囲内であると触媒活性に優れる鉄元素含有ナノ粒子を調製し易くなる。
還流時間は、通常１時間以上、好ましくは３時間以上、より好ましくは６時間以上であり、通常２４時間以下、好ましくは１２時間以下、より好ましくは１０時間以下である。上記範囲内であると触媒活性に優れる鉄元素含有ナノ粒子を調製し易くなる。
還流は、窒素、アルゴン等の不活性雰囲気下で行っても、或いは空気雰囲気下で行ってもよい。酸素原子がドープされている金属鉄粒子又は鉄合金粒子、酸化鉄粒子等を調製する観点から、空気雰囲気下で行うことが好ましい。
Although the preparation method of the iron element containing nanoparticle which the solvent coordinated on the surface is not specifically limited, The method of heating and refluxing the precursor containing an iron element in a polar solvent is mentioned.
Hereinafter, details such as conditions in a method of heating and refluxing a precursor containing an iron element in a polar solvent will be described.
The type of the precursor containing iron element is not particularly limited, but iron (III) chloride (FeCl 3
), Iron (III) bromide (FeBr 3 ), iron (II) acetate (Fe (CH 3 CO 2 ) 2 ), iron (III) citrate (FeC 6 H 5 O 7 ), iron iron (III) sulfate (III) ( FeNH 4 (SO 4
2 ), iron (III) acetylacetonate (Fe (CH 3 COCHCOCH 3 ) 3 ) and the like. Among these, iron (III) acetylacetonate is particularly preferable. Iron (III
) By using acetylacetonate, it becomes easy to prepare iron element-containing nanoparticles having excellent catalytic activity.
Although the kind of polar solvent is not specifically limited, Ethylene glycol, dimethylacetamide (DMA), N, N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethylsulfoxide (DMSO), etc. are mentioned. Among these, N, N-dimethylformamide is particularly preferable. By using N, N-dimethylformamide, it becomes easy to prepare iron element-containing nanoparticles having excellent catalytic activity.
The temperature conditions to be set should be selected according to the polar solvent to be used, and are not particularly limited.
The refluxing is preferably performed while stirring using a stirrer or the like. The rotation speed of the stirrer is usually 500 rpm or more, preferably 800 rpm or more, more preferably 1000 rpm or more, and usually 2000 rpm or less, preferably 1800 rpm or less, more preferably 1700 rpm or less. Within the above range, it becomes easy to prepare iron element-containing nanoparticles having excellent catalytic activity.
The reflux time is usually 1 hour or longer, preferably 3 hours or longer, more preferably 6 hours or longer, and usually 24 hours or shorter, preferably 12 hours or shorter, more preferably 10 hours or shorter. Within the above range, it becomes easy to prepare iron element-containing nanoparticles having excellent catalytic activity.
The reflux may be performed under an inert atmosphere such as nitrogen or argon, or may be performed under an air atmosphere. From the viewpoint of preparing metal iron particles, iron alloy particles, iron oxide particles and the like doped with oxygen atoms, it is preferable to carry out in an air atmosphere.
本発明の製造方法における触媒（表面に溶媒が配位した鉄元素含有ナノ粒子）の使用量は、目的に応じて適宜選択することができるが、アルケン類及び／又はアルキン類の使用量に対して、物質量（［ｍｏｌ］）で通常０．５倍以下、好ましくは０．１倍以下、より好ましくは０．０１倍以下であり、通常０．０００１倍以上、好ましくは０．００５倍以上、より好ましくは０．００１倍以上である。上記範囲内であると、有機シラン化合物をより収率良く製造することができる。
なお、触媒は固形物として反応容器に投入してもよいが、溶媒に分散させた分散液として反応容器に投入してもよい。分散液として保存、使用することによって、触媒の劣化を抑制したり、操作を簡略化したりすることができる。
The amount of the catalyst (iron element-containing nanoparticles with a solvent coordinated on the surface) in the production method of the present invention can be appropriately selected according to the purpose, but the amount of alkene and / or alkyne used The amount of the substance ([mol]) is usually 0.5 times or less, preferably 0.1 times or less, more preferably 0.01 times or less, usually 0.0001 times or more, preferably 0.005 times or more. More preferably, it is 0.001 times or more. Within the above range, the organosilane compound can be produced with higher yield.
The catalyst may be charged into the reaction vessel as a solid substance, but may be charged into the reaction vessel as a dispersion liquid dispersed in a solvent. By storing and using it as a dispersion, it is possible to suppress the deterioration of the catalyst or to simplify the operation.
本発明の製造方法における溶媒の種類は特に限定されず、目的に応じて適宜することができるが、具体的にはヘキサン、ベンゼン、トルエン等の炭化水素系溶媒、ジエチルエーテル、１，４−ジオキサン、テトラヒドロフラン（ＴＨＦ）等のエーテル系溶媒、１，２−ジクロロエタン、クロロホルム等のハロゲン系溶媒、エタノール、エチレングリコール、グリセリン等のプロトン性極性溶媒、アセトン、ジメチルアセトアミド（ＤＭＡ）、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、Ｎ−メチルピロリドン（ＮＭＰ）、ジメチルスルホキシド（ＤＭＳＯ）等の非プロトン性極性溶媒等が挙げられる。また、溶媒は、１種類に限られず、２種類以上を混合した混合溶媒であってもよい。具体的な組み合わせとしては、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）と１，４−ジオキサン、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）とジメチルアセトアミド（ＤＭＡ）、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）とＮ−メチルピロリドン（ＮＭＰ）、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）とトルエン等が挙げられるが、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）と１，４−ジオキサンの混合溶媒であることが特に好ましい。 The kind of the solvent in the production method of the present invention is not particularly limited and may be appropriately selected according to the purpose. Specifically, hydrocarbon solvents such as hexane, benzene and toluene, diethyl ether, and 1,4-dioxane. , Ether solvents such as tetrahydrofuran (THF), halogen solvents such as 1,2-dichloroethane and chloroform, protic polar solvents such as ethanol, ethylene glycol and glycerin, acetone, dimethylacetamide (DMA), N, N-dimethyl Examples include aprotic polar solvents such as formamide (DMF), N-methylpyrrolidone (NMP), and dimethyl sulfoxide (DMSO). Moreover, the solvent is not limited to one type, and may be a mixed solvent in which two or more types are mixed. Specific combinations include N, N-dimethylformamide (DMF) and 1,4-dioxane, N, N-dimethylformamide (DMF) and dimethylacetamide (DMA), N, N-dimethylformamide (DMF) and N -Methylpyrrolidone (NMP), N, N-dimethylformamide (DMF) and toluene are exemplified, and a mixed solvent of N, N-dimethylformamide (DMF) and 1,4-dioxane is particularly preferable.
（反応条件）
本発明の製造方法は、アルケン類及び／又はアルキン類とヒドロシラン類とを触媒存在下で反応させる方法であるが、反応温度、反応時間等の反応条件は特に限定されない。
反応温度は、通常２５℃以上、好ましくは７０℃以上、より好ましくは１１０℃以上であり、通常２００℃以下、好ましくは１５０℃以下、より好ましくは１３０℃以下である
。上記範囲内であれば、有機シラン化合物をより収率良く製造することができる。
反応時間は、通常１時間以上、好ましくは２時間以上、より好ましくは１０時間以上であり、通常６０時間以下、好ましくは４８時間以下、より好ましくは２４時間以下である。
反応は、通常窒素、アルゴン等の不活性雰囲気下で行う。
(Reaction conditions)
The production method of the present invention is a method of reacting alkenes and / or alkynes with hydrosilanes in the presence of a catalyst, but the reaction conditions such as reaction temperature and reaction time are not particularly limited.
The reaction temperature is usually 25 ° C. or higher, preferably 70 ° C. or higher, more preferably 110 ° C. or higher, and is usually 200 ° C. or lower, preferably 150 ° C. or lower, more preferably 130 ° C. or lower. If it is in the said range, an organosilane compound can be manufactured with a sufficient yield.
The reaction time is usually 1 hour or longer, preferably 2 hours or longer, more preferably 10 hours or longer, and usually 60 hours or shorter, preferably 48 hours or shorter, more preferably 24 hours or shorter.
The reaction is usually carried out under an inert atmosphere such as nitrogen or argon.
＜有機シラン化合物の合成用触媒組成物＞
表面に溶媒が配位した鉄元素含有ナノ粒子を触媒として利用することにより、アルケン類及び／又はアルキン類とヒドロシラン類の反応によって、有機シラン化合物を製造することができることを前述したが、表面に溶媒が配位した鉄元素含有ナノ粒子を含み、有機シラン化合物を合成する触媒組成物も本発明の一態様である（以下、「本発明の触媒組成物」と略す場合がある。）。なお、本発明の触媒組成物は、有機シラン化合物を合成するためのものであれば、原料や反応条件等は特に限定されないが、アルケン類及び／又はアルキン類とヒドロシラン類から有機シラン化合物を合成するためのものであることが好ましい。
<Catalyst composition for synthesis of organosilane compound>
As described above, an organic silane compound can be produced by the reaction of alkenes and / or alkynes and hydrosilanes by using iron element-containing nanoparticles coordinated with a solvent on the surface as a catalyst. A catalyst composition that includes iron element-containing nanoparticles coordinated with a solvent and synthesizes an organosilane compound is also an embodiment of the present invention (hereinafter may be abbreviated as “the catalyst composition of the present invention”). The catalyst composition of the present invention is not particularly limited as long as it is for synthesizing an organosilane compound, but the organosilane compound is synthesized from alkenes and / or alkynes and hydrosilanes. It is preferable that
本発明の触媒組成物は、前述の表面に溶媒が配位した鉄元素含有ナノ粒子を含むものであればその他には特に限定されないが、溶媒を含むものであることが好ましく、溶媒に分散した分散液の状態にあるものが好ましい。具体的な溶媒としては、ヘキサン、ベンゼン、トルエン等の炭化水素系溶媒、ジエチルエーテル、１，４−ジオキサン、テトラヒドロフラン（ＴＨＦ）等のエーテル系溶媒、１，２−ジクロロエタン、クロロホルム等のハロゲン系溶媒、エタノール、エチレングリコール、グリセリン等のプロトン性極性溶媒、アセトン、ジメチルアセトアミド（ＤＭＡ）、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、Ｎ−メチルピロリドン（ＮＭＰ）、ジメチルスルホキシド（ＤＭＳＯ）等の非プロトン性極性溶媒等が挙げられる。 The catalyst composition of the present invention is not particularly limited as long as it contains iron element-containing nanoparticles in which a solvent is coordinated on the surface described above, but preferably contains a solvent, and a dispersion liquid dispersed in a solvent Those in the state are preferred. Specific solvents include hydrocarbon solvents such as hexane, benzene and toluene, ether solvents such as diethyl ether, 1,4-dioxane and tetrahydrofuran (THF), and halogen solvents such as 1,2-dichloroethane and chloroform. , Aprotic polar solvents such as ethanol, ethylene glycol and glycerin, aprotic such as acetone, dimethylacetamide (DMA), N, N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethylsulfoxide (DMSO) Examples include polar solvents.
以下に実施例及び比較例を挙げて本発明をさらに具体的に説明するが、本発明の趣旨を逸脱しない限り適宜変更することができる。従って、本発明の範囲は以下に示す具体例により限定的に解釈されるべきものではない。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but can be appropriately changed without departing from the gist of the present invention. Accordingly, the scope of the present invention should not be construed as being limited by the specific examples shown below.
［表面に溶媒が配位した酸化鉄ナノ粒子の調製］
（実施例１：ＤＭＦ配位酸化鉄ナノ粒子分散液１の調製）
ジムロート冷却器を連結した１００ｍＬの三口フラスコに、空気雰囲気下で１５ｍＬの脱水Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）を入れ、１４０℃に加熱したオイルバスに浸漬して、空気雰囲気下、撹拌子を１３００ｒｐｍで回転させながら還流条件で１０分程度予備加熱を行った。その後、空気雰囲気下で０．１モル濃度（０．１Ｍ）の鉄（ＩＩＩ）アセチルアセトナート（Ｆｅ（ＣＨ3ＣＯＣＨＣＯＣＨ3）3）水溶液１５０μｌをマイ
クロシリンジを使って加え、撹拌しながら１４０℃で８時間加熱還流を行った。なお、反応溶液は時間が経つごとに淡黄色が濃くなった。８時間後、室温まで冷却して、分散液１を得た。得られた分散液１の写真を図１に示す。
[Preparation of iron oxide nanoparticles with solvent coordinated on the surface]
(Example 1: Preparation of DMF coordination iron oxide nanoparticle dispersion 1)
A 100 mL three-necked flask connected with a Dimroth condenser is charged with 15 mL of dehydrated N, N-dimethylformamide (DMF) in an air atmosphere, immersed in an oil bath heated to 140 ° C., and a stirrer is placed in an air atmosphere. Preheating was performed for about 10 minutes under reflux conditions while rotating at 1300 rpm. Thereafter, 150 μl of a 0.1 molar (0.1 M) iron (III) acetylacetonate (Fe (CH 3 COCHCOCH 3 ) 3 ) aqueous solution was added using a microsyringe in an air atmosphere, and the mixture was stirred at 140 ° C. The mixture was heated to reflux for 8 hours. The reaction solution became light yellow with time. After 8 hours, the mixture was cooled to room temperature to obtain dispersion 1. A photograph of the resulting dispersion 1 is shown in FIG.
分散液１に波長３５０ｎｍのＵＶ照射を行ったところ、図２に示すように発光（蛍光）することが確認できた。また、分散液１を専用容器に充填して、日本分光社製蛍光分光光度計にて蛍光スペクトル（励起波長：３５０ｎｍ、０．１ｍＭ）を測定したところ、図３に示すスペクトル結果が得られた。 When the dispersion 1 was irradiated with UV light having a wavelength of 350 nm, it was confirmed that the dispersion 1 emitted light (fluorescence) as shown in FIG. Moreover, when the dispersion liquid 1 was filled in the exclusive container and the fluorescence spectrum (excitation wavelength: 350 nm, 0.1 mM) was measured with the fluorescence spectrophotometer by JASCO Corporation, the spectrum result shown in FIG. 3 was obtained. .
さらに、分散液１からロータリーエバポレーターを用いてＤＭＦを留去し（条件：１０ｈＰａ、４０℃）、十分に乾燥させた後、固形物を高分解能透過型電子顕微鏡（ＨＲＴＥＭ）によって観察した（エネルギー分散型Ｘ線分析（ＥＤＳ）による粒子の元素分析、制
限視野電子回折（ＳＡＥＤ）による結晶構造解析（電子線の入射方向：［０００１］方向）も行った。）。結果を図４（ａ）、（ｂ）、（ｃ）に示す。
これらの結果から、粒子径が数ｎｍでＤＭＦが配位したコランダム型のα−Ｆｅ2Ｏ3粒子が形成していることが確認できる（格子定数：ａ＝ｂ≒５．０４［Å］、ｃ≒１３．７７[Å]）。なお、このＤＭＦ配位酸化鉄ナノ粒子の溶媒への可溶性を確認したところ、ＤＭＦとＮ−メチルピロリドン（ＮＭＰ）には容易に溶解（分散）する一方、テトラヒドロフラン（ＴＨＦ）には難溶であることを確認した。
Furthermore, DMF was distilled off from the dispersion 1 using a rotary evaporator (conditions: 10 hPa, 40 ° C.), and after sufficient drying, the solid was observed with a high-resolution transmission electron microscope (HRTEM) (energy dispersion) Particle X-ray analysis (EDS) was used for elemental analysis of the particles, and crystal structure analysis was performed by limited-field electron diffraction (SAED) (electron beam incident direction: [0001] direction). The results are shown in FIGS. 4 (a), (b) and (c).
From these results, it can be confirmed that corundum type α-Fe 2 O 3 particles having a particle diameter of several nm and coordinated with DMF are formed (lattice constant: a = b≈5.04 [４], c≈13.77 [Å]). The solubility of the DMF-coordinated iron oxide nanoparticles in a solvent was confirmed. As a result, it was easily dissolved (dispersed) in DMF and N-methylpyrrolidone (NMP), but hardly soluble in tetrahydrofuran (THF). It was confirmed.
（実施例２：ＴＨＦ配位酸化鉄ナノ粒子分散液２の調製）
実施例１で得られたＤＭＦを留去したＤＭＦ配位酸化鉄ナノ粒子と、分散液１と同量のＴＨＦ（超脱水）をナス型フラスコに入れ、超音波洗浄機を用いて、壁面に付着した粒子を十分に落とし、分散液２を調製した。得られた分散液２の写真を図５に示す。ＴＨＦに容易に溶解（分散）することから、ＤＭＦがＴＨＦに置換された、ＴＨＦ配位酸化鉄ナノ粒子が形成しているものと考えられる。
(Example 2: Preparation of THF-coordinated iron oxide nanoparticle dispersion 2)
DMF coordinated iron oxide nanoparticles obtained by distilling off DMF obtained in Example 1 and the same amount of THF (ultra-dehydration) as dispersion 1 are placed in an eggplant-shaped flask, and are placed on the wall surface using an ultrasonic cleaner. The adhered particles were sufficiently dropped to prepare dispersion 2. A photograph of the resulting dispersion 2 is shown in FIG. Since it is easily dissolved (dispersed) in THF, it is considered that THF coordinated iron oxide nanoparticles in which DMF is substituted with THF are formed.
（実施例３：ＤＭＦ配位鉄ナノ粒子分散液３の調製）
ジムロート冷却器を連結した１００ｍＬの三口フラスコに、空気雰囲気下で１５ｍＬの脱水ＤＭＦを入れ、１４０℃に加熱したオイルバスに浸漬して、空気雰囲気下、撹拌子を１３００ｒｐｍで回転させながら還流条件で１０分程度予備加熱を行った。その後、空気雰囲気下で０．１モル濃度（０．１Ｍ）の塩化鉄（ＩＩＩ）（ＦｅＣｌ3）水溶液１５μ
ｌをマイクロシリンジを使って加え、撹拌しながら１４０℃で８時間加熱還流を行った。その後、室温まで冷却して、ＤＭＦ配位鉄ナノ粒子分散液３を調製した。なお、反応溶液は、時間が経つごとに淡黄色が濃くなった。８時間後、室温まで冷却して、分散液３を得た。
(Example 3: Preparation of DMF coordinated iron nanoparticle dispersion 3)
In a 100 mL three-necked flask connected with a Dimroth cooler, 15 mL of dehydrated DMF was placed in an air atmosphere, immersed in an oil bath heated to 140 ° C., and under a reflux condition while rotating the stir bar at 1300 rpm in an air atmosphere. Preheating was performed for about 10 minutes. Thereafter, a 0.1 molar (0.1 M) iron (III) chloride (FeCl 3 ) aqueous solution 15 μm in an air atmosphere.
1 was added using a microsyringe, and the mixture was refluxed with heating at 140 ° C. for 8 hours while stirring. Then, it cooled to room temperature and prepared DMF coordination iron nanoparticle dispersion liquid 3. The reaction solution became light yellow with time. After 8 hours, the mixture was cooled to room temperature to obtain dispersion 3.
実施例１と同様に、分散液２は発光（蛍光）の確認（図６参照）、蛍光スペクトル測定（図７参照）を行い、さらに乾燥させた固形物を高分解能透過型電子顕微鏡（ＨＲＴＥＭ）によって観察した（図８参照）。これらの結果から、実施例１と同様に、ＤＭＦ配位酸化鉄ナノ粒子が形成していることが確認できる。 As in Example 1, the dispersion 2 was subjected to confirmation of luminescence (fluorescence) (see FIG. 6), measurement of the fluorescence spectrum (see FIG. 7), and the dried solid was further analyzed with a high-resolution transmission electron microscope (HRTEM). (See FIG. 8). From these results, it can be confirmed that DMF coordinated iron oxide nanoparticles are formed as in Example 1.
［有機シラン化合物の製造１（アルケン類とヒドロシラン類の反応）］
＜溶媒の検討＞
（実施例４）
撹拌子を入れ、セプタムを取り付けて密閉したシュレンク管の管内をアルゴンで置換し、シリンジを使って１−デセン（１１２．２ｍｇ、１．０ｍｍｏｌ）、フェニルシラン（１０８．２ｍｇ、１．０ｍｍｏｌ）、及び実施例２で調製した分散液２（ＴＨＦ配位酸化鉄ナノ粒子が分散したＴＨＦ溶液（酸化鉄ナノ粒子濃度：１０-1ｍｏｌ％、ＴＨＦの量：１．０ｍＬ））をシュレンク管に投入した。次にアルゴンを入れた風船が取り付けられた二方コックを、アルゴンを流しながらシュレンク管に接続した。
シュレンク管を温度６０℃に設定したオイルバスに浸し、撹拌しながら２４時間反応させた。
反応終了後、二方コックを閉じ、シュレンク管をオイルバスから引き揚げた。次にパスツールピペットを用いて、内部基準物質であるトリデカンを入れ、酢酸エチル（１０ｍＬ）で希釈し、ガスクロマトグラフィーを用いた内部基準法によって、原料、生成物等を定量した。結果を表１に示す。
[Production of organosilane compound 1 (reaction of alkenes and hydrosilanes)]
<Study of solvent>
Example 4
A stir bar was inserted, and the inside of a Schlenk tube sealed with a septum was replaced with argon, and 1-decene (112.2 mg, 1.0 mmol), phenylsilane (108.2 mg, 1.0 mmol), And dispersion 2 prepared in Example 2 (THF solution in which THF-coordinated iron oxide nanoparticles are dispersed (iron oxide nanoparticle concentration: 10 −1 mol%, amount of THF: 1.0 mL)) is charged into a Schlenk tube. did. Next, a two-way cock equipped with a balloon containing argon was connected to a Schlenk tube while flowing argon.
The Schlenk tube was immersed in an oil bath set at a temperature of 60 ° C. and reacted for 24 hours with stirring.
After completion of the reaction, the two-way cock was closed and the Schlenk tube was lifted from the oil bath. Next, using a Pasteur pipette, tridecane as an internal standard substance was added, diluted with ethyl acetate (10 mL), and raw materials, products, and the like were quantified by an internal standard method using gas chromatography. The results are shown in Table 1.
（実施例５）
ＴＨＦを１，４−ジオキサン（１，４−Ｄｉｏｘａｎｅ、試薬特級）に置き換えた以外は、実施例２と同様の操作によって、分散液４（１，４−ジオキサン配位酸化鉄ナノ粒子が分散した１，４−ジオキサン溶液）を調製した。
次に分散液２を分散液４に置き換え、オイルバスの温度を８０℃（反応温度）に設定した以外は、実施例４と同様の操作によって原料を反応させた。原料、生成物等の定量結果を表１に示す。
(Example 5)
Dispersion 4 (1,4-dioxane-coordinated iron oxide nanoparticles) was dispersed by the same operation as in Example 2 except that THF was replaced with 1,4-dioxane (1,4-Dioxane, reagent grade). 1,4-dioxane solution) was prepared.
Next, the dispersion 2 was replaced with the dispersion 4, and the raw materials were reacted by the same operation as in Example 4 except that the temperature of the oil bath was set to 80 ° C. (reaction temperature). Table 1 shows quantitative results of raw materials, products, and the like.
（実施例６）
オイルバスの温度を１００℃（反応温度）に設定した以外は、実施例５と同様の操作によって原料を反応させた。原料、生成物等の定量結果を表１に示す。
(Example 6)
The raw materials were reacted by the same operation as in Example 5 except that the temperature of the oil bath was set to 100 ° C. (reaction temperature). Table 1 shows quantitative results of raw materials, products, and the like.
（実施例７）
ＴＨＦを１，２−ジクロロエタン（１，２−Ｄｉｃｈｌｏｒｏｅｔｈａｎｅ）に置き換えた以外は、実施例２と同様の操作によって、分散液５（１，２−ジクロロエタン配位酸化鉄ナノ粒子が分散した１，２−ジクロロエタン溶液）を調製した。
次に分散液２を分散液５に置き換え、オイルバスの温度を８０℃（反応温度）に設定した以外は、実施例４と同様の操作によって原料を反応させた。原料、生成物等の定量結果を表１に示す。
(Example 7)
The dispersion 5 (1,2-dichloroethane-coordinated iron oxide nanoparticles were dispersed in the same manner as in Example 2 except that THF was replaced with 1,2-dichloroethane (1,2-Dichloroethane). -Dichloroethane solution) was prepared.
Next, the dispersion liquid 2 was replaced with the dispersion liquid 5, and the raw materials were reacted by the same operation as in Example 4 except that the temperature of the oil bath was set to 80 ° C. (reaction temperature). Table 1 shows quantitative results of raw materials, products, and the like.
（実施例８）
ＴＨＦをトルエン（Ｔｏｌｕｅｎｅ）に置き換えた以外は、実施例２と同様の操作によって、分散液６（トルエン配位酸化鉄ナノ粒子が分散したトルエン溶液）を調製した。
次に分散液２を分散液６に置き換え、オイルバスの温度を１１０℃（反応温度）に設定した以外は、実施例４と同様の操作によって原料を反応させた。原料、生成物等の定量結果を表１に示す。
(Example 8)
A dispersion 6 (a toluene solution in which toluene-coordinated iron oxide nanoparticles are dispersed) was prepared in the same manner as in Example 2 except that THF was replaced with toluene (Toluene).
Next, the dispersion liquid 2 was replaced with the dispersion liquid 6, and the raw materials were reacted by the same operation as in Example 4 except that the oil bath temperature was set to 110 ° C. (reaction temperature). Table 1 shows quantitative results of raw materials, products, and the like.
＜ヒドロシラン類の使用量の検討＞
（実施例９）
投入するフェニルシランの量を１６２．３ｍｇ（１．５ｍｍｏｌ）とした以外は、実施例４と同様の操作によって原料を反応させた。原料、生成物等の定量結果を表２に示す。
<Examination of usage of hydrosilanes>
Example 9
The raw material was reacted by the same operation as in Example 4 except that the amount of phenylsilane to be added was 162.3 mg (1.5 mmol). Table 2 shows quantitative results of raw materials, products, and the like.
（実施例１０）
投入するフェニルシランの量を２１６．４ｍｇ（２．０ｍｍｏｌ）とした以外は、実施例４と同様の操作によって原料を反応させた。原料、生成物等の定量結果を表２に示す。
(Example 10)
The raw materials were reacted in the same manner as in Example 4 except that the amount of phenylsilane to be added was 216.4 mg (2.0 mmol). Table 2 shows quantitative results of raw materials, products, and the like.
（実施例１１）
投入するフェニルシランの量を２７０．５ｍｇ（２．５ｍｍｏｌ）とした以外は、実施例４と同様の操作によって原料を反応させた。原料、生成物等の定量結果を表２に示す。
(Example 11)
The raw materials were reacted in the same manner as in Example 4 except that the amount of phenylsilane to be added was 270.5 mg (2.5 mmol). Table 2 shows quantitative results of raw materials, products, and the like.
（実施例１２）
投入するフェニルシランの量を３２４．６ｍｇ（３．０ｍｍｏｌ）とした以外は、実施例４と同様の操作によって原料を反応させた。原料、生成物等の定量結果を表２に示す。
(Example 12)
The raw material was reacted by the same operation as in Example 4 except that the amount of phenylsilane to be added was 324.6 mg (3.0 mmol). Table 2 shows quantitative results of raw materials, products, and the like.
（実施例１３）
投入するフェニルシランの量を３７８．７ｍｇ（３．５ｍｍｏｌ）とした以外は、実施例４と同様の操作によって原料を反応させた。原料、生成物等の定量結果を表２に示す。
(Example 13)
The raw materials were reacted in the same manner as in Example 4 except that the amount of phenylsilane to be added was 378.7 mg (3.5 mmol). Table 2 shows quantitative results of raw materials, products, and the like.
（実施例１４）
投入するフェニルシランの量を４３２．８ｍｇ（４．０ｍｍｏｌ）とした以外は、実施例４と同様の操作によって原料を反応させた。原料、生成物等の定量結果を表２に示す。
(Example 14)
The raw materials were reacted in the same manner as in Example 4 except that the amount of phenylsilane to be added was changed to 432.8 mg (4.0 mmol). Table 2 shows quantitative results of raw materials, products, and the like.
＜アルカン類の種類の検討＞
（実施例１５）
１−デセンを１−オクテン３３６．６ｍｇ（３．０ｍｍｏｌ）に置き換えた以外は、実施例１２と同様の操作によって原料を反応させた。原料、生成物等の定量結果を表３に示す。
<Examination of types of alkanes>
(Example 15)
The raw materials were reacted in the same manner as in Example 12, except that 1-decene was replaced with 336.6 mg (3.0 mmol) of 1-octene. Table 3 shows quantitative results of raw materials, products and the like.
（実施例１６）
１−デセンを４−フェニル−１−ブテン３９６．６ｍｇ（３．０ｍｍｏｌ）に置き換えた以外は、実施例１２と同様の操作によって原料を反応させた。原料、生成物等の定量結果を表３に示す。
(Example 16)
The raw materials were reacted in the same manner as in Example 12 except that 1-decene was replaced with 396.6 mg (3.0 mmol) of 4-phenyl-1-butene. Table 3 shows quantitative results of raw materials, products and the like.
（実施例１７）
１−デセンを６，６−ジメチル−１−ヘプテン３７８．３ｍｇ（３．０ｍｍｏｌ）に置き換えた以外は、実施例１２と同様の操作によって原料を反応させた。原料、生成物等の定量結果を表３に示す。
(Example 17)
The raw materials were reacted in the same manner as in Example 12 except that 1-decene was replaced with 378.3 mg (3.0 mmol) of 6,6-dimethyl-1-heptene. Table 3 shows quantitative results of raw materials, products and the like.
（実施例１８）
１−デセンを４，４−ジメチル−１−ヘキセン３３６．６ｍｇ（３．０ｍｍｏｌ）に置き換えた以外は、実施例１２と同様の操作によって原料を反応させた。原料、生成物等の定量結果を表３に示す。
(Example 18)
The raw materials were reacted in the same manner as in Example 12 except that 1-decene was replaced with 336.6 mg (3.0 mmol) of 4,4-dimethyl-1-hexene. Table 3 shows quantitative results of raw materials, products and the like.
＜ヒドロシラン類の種類の検討＞
（実施例１９）
フェニルシランをジフェニルシラン５５２．９ｍｇ（３．０ｍｍｏｌ）に置き換えた以外は、実施例１２と同様の操作によって原料を反応させた。原料、生成物等の定量結果を
表４に示す。
<Examination of types of hydrosilanes>
(Example 19)
The raw materials were reacted in the same manner as in Example 12 except that phenylsilane was replaced with 552.9 mg (3.0 mmol) of diphenylsilane. Table 4 shows the results of quantification of the raw materials and products.
（実施例２０）
フェニルシランをジフェニルシラン５５２．９ｍｇ（３．０ｍｍｏｌ）に置き換え、オイルバスの温度を１００℃（反応温度）に設定した以外は、実施例５と同様の操作によって原料を反応させた。原料、生成物等の定量結果を表５に示す。
(Example 20)
The raw material was reacted in the same manner as in Example 5 except that phenylsilane was replaced with 552.9 mg (3.0 mmol) of diphenylsilane and the temperature of the oil bath was set to 100 ° C. (reaction temperature). Table 5 shows quantitative results of raw materials, products, and the like.
（実施例２１）
ジフェニルシランをメチルフェニルシラン３６６．７ｍｇ（３．０ｍｍｏｌ）に置き換えた以外は、実施例２０と同様の操作によって原料を反応させた。原料、生成物等の定量結果を表５に示す。
(Example 21)
The raw material was reacted by the same operation as in Example 20 except that 366.7 mg (3.0 mmol) of methylphenylsilane was replaced with diphenylsilane. Table 5 shows quantitative results of raw materials, products, and the like.
（実施例２２）
ジフェニルシランをジメチルフェニルシラン４０８．８ｍｇ（３．０ｍｍｏｌ）に置き換えた以外は、実施例２０と同様の操作によって原料を反応させた。原料、生成物等の定量結果を表５に示す。
(Example 22)
The raw materials were reacted in the same manner as in Example 20 except that diphenylsilane was replaced with 408.8 mg (3.0 mmol) of dimethylphenylsilane. Table 5 shows quantitative results of raw materials, products, and the like.
（実施例２３）
ジフェニルシランをトリエトキシシラン４９２．９ｍｇ（３．０ｍｍｏｌ）に置き換えた以外は、実施例２０と同様の操作によって原料を反応させた。原料、生成物等の定量結果を表５に示す。
(Example 23)
The raw materials were reacted in the same manner as in Example 20 except that diphenylsilane was replaced with 492.9 mg (3.0 mmol) of triethoxysilane. Table 5 shows quantitative results of raw materials, products, and the like.
（実施例２４）
ジフェニルシランをトリエチルシラン３４８．９ｍｇ（３．０ｍｍｏｌ）に置き換えた以外は、実施例２０と同様の操作によって原料を反応させた。原料、生成物等の定量結果を表５に示す。
(Example 24)
The raw materials were reacted in the same manner as in Example 20 except that diphenylsilane was replaced with 348.9 mg (3.0 mmol) of triethylsilane. Table 5 shows quantitative results of raw materials, products, and the like.
（実施例２５）
ジフェニルシランをジエトキシメチルシラン４０２．８ｍｇ（３．０ｍｍｏｌ）に置き換えた以外は、実施例２０と同様の操作によって原料を反応させた。原料、生成物等の定量結果を表５に示す。
(Example 25)
The raw materials were reacted in the same manner as in Example 20 except that diphenylsilane was replaced with 402.8 mg (3.0 mmol) of diethoxymethylsilane. Table 5 shows quantitative results of raw materials, products, and the like.
［有機シラン化合物の製造２（アルキン類とヒドロシラン類の反応）］
＜溶媒の検討＞
（実施例２６）
ＴＨＦを１，４−ジオキサン（１，４−Ｄｉｏｘａｎｅ、試薬特級）に置き換えた以外は、実施例２と同様の操作によって、分散液７（１，４−ジオキサン配位酸化鉄ナノ粒子が分散した１，４−ジオキサン溶液）を調製した。
次に撹拌子を入れ、セプタムを取り付けて密閉したシュレンク管の管内をアルゴンで置換し、シリンジを使ってジフェニルアセチレン（１７８．２ｍｇ、１．０ｍｍｏｌ）、フェニルシラン（１０８．２ｍｇ、１．０ｍｍｏｌ）、及び分散液７（１，４−ジオキサン配位酸化鉄ナノ粒子が分散した１，４−ジオキサン溶液（酸化鉄ナノ粒子濃度：１０-1ｍｏｌ％、ＴＨＦの量：１．０ｍＬ））をシュレンク管に投入した。次にアルゴンを入れた風船が取り付けられた二方コックを、アルゴンを流しながらシュレンク管に接続した。
シュレンク管を温度１００℃に設定したオイルバスに浸し、撹拌しながら２４時間反応させた。
反応終了後、二方コックを閉じ、シュレンク管をオイルバスから引き揚げた。次にパスツールピペットを用いて、内部基準物質であるトリデカンを入れ、酢酸エチル（１０ｍＬ）で希釈し、ガスクロマトグラフィーを用いた内部基準法によって、原料、生成物等を定量した。結果を表６に示す。
[Production of organosilane compound 2 (reaction of alkynes and hydrosilanes)]
<Study of solvent>
(Example 26)
Dispersion 7 (1,4-dioxane-coordinated iron oxide nanoparticles) was dispersed in the same manner as in Example 2 except that THF was replaced with 1,4-dioxane (1,4-Dioxane, reagent grade). 1,4-dioxane solution) was prepared.
Next, a stir bar was inserted, the inside of the Schlenk tube sealed with a septum was replaced with argon, and diphenylacetylene (178.2 mg, 1.0 mmol) and phenylsilane (108.2 mg, 1.0 mmol) were used using a syringe. And dispersion 7 (1,4-dioxane solution in which 1,4-dioxane-coordinated iron oxide nanoparticles are dispersed (iron oxide nanoparticle concentration: 10 −1 mol%, amount of THF: 1.0 mL)) I put it in the tube. Next, a two-way cock equipped with a balloon containing argon was connected to a Schlenk tube while flowing argon.
The Schlenk tube was immersed in an oil bath set at a temperature of 100 ° C. and reacted for 24 hours while stirring.
After completion of the reaction, the two-way cock was closed and the Schlenk tube was lifted from the oil bath. Next, using a Pasteur pipette, tridecane as an internal standard substance was added, diluted with ethyl acetate (10 mL), and raw materials, products, and the like were quantified by an internal standard method using gas chromatography. The results are shown in Table 6.
（実施例２７）
１，４−ジオキサンをジグライム（Ｄｉｇｌｙｍｅ、一級）に置き換えた以外は、実施例２５と同様の操作によって、分散液８（ジグライム配位酸化鉄ナノ粒子が分散したジグライム溶液）を調製した。
次に分散液７を分散液８に置き換え、オイルバスの温度を１２０℃（反応温度）に設定した以外は、実施例２６と同様の操作によって原料を反応させた。原料、生成物等の定量結果を表６に示す。
(Example 27)
Dispersion 8 (diglyme solution in which diglyme-coordinated iron oxide nanoparticles were dispersed) was prepared in the same manner as in Example 25 except that 1,4-dioxane was replaced with diglyme (primary).
Next, the raw material was reacted by the same operation as in Example 26 except that the dispersion 7 was replaced with the dispersion 8 and the temperature of the oil bath was set to 120 ° C. (reaction temperature). Table 6 shows quantitative results of raw materials, products and the like.
＜シラン類の種類の検討＞
（実施例２８）
１，４−ジオキサンをＤＭＦ／１，４−Ｄｉｏｘａｎｅの混合溶媒（０．５／２．０ｍＬ）に置き換えた以外は、実施例２と同様の操作によって、分散液９（溶媒配位酸化鉄ナノ粒子が分散した溶液）を調製した。
次に分散液７を分散液９に置き換え、投入するジフェニルアセチレンの量を８９．１ｍｇ、フェニルシランの量を５４．１ｍｇとし、オイルバスの温度を１２０℃（反応温度）に設定して、１６時間反応させた以外は、実施例２６と同様の操作によって原料を反応させた。原料、生成物等の定量結果を表７に示す。
<Examination of types of silanes>
(Example 28)
Dispersion 9 (solvent-coordinated iron oxide nanoparticle) was obtained in the same manner as in Example 2, except that 1,4-dioxane was replaced with a mixed solvent of DMF / 1,4-Dioxane (0.5 / 2.0 mL). A solution in which particles were dispersed was prepared.
Next, the dispersion 7 was replaced with the dispersion 9, the amount of diphenylacetylene charged was 89.1 mg, the amount of phenylsilane was 54.1 mg, and the oil bath temperature was set to 120 ° C. (reaction temperature). The raw materials were reacted by the same operation as in Example 26 except that the reaction was performed for a period of time. Table 7 shows quantitative results of raw materials, products, and the like.
（実施例２９）
フェニルシランをトリエトキシシラン１６４．３ｍｇ（１．０ｍｍｏｌ）に置き換えた以外は、実施例２８と同様の操作によって原料を反応させた。原料、生成物等の定量結果を表７に示す。
(Example 29)
The raw materials were reacted in the same manner as in Example 28 except that phenylsilane was replaced with 164.3 mg (1.0 mmol) of triethoxysilane. Table 7 shows quantitative results of raw materials, products, and the like.
（実施例３０）
フェニルシランをポリ（メチルヒドリドシラン）（ＰＭＨＳ）１．９ｇ（１．０ｍｍｏｌ,Ｍｎ＝１９００）に置き換えた以外は、実施例２８と同様の操作によって原料を反応
させた。原料、生成物等の定量結果を表７に示す。
(Example 30)
The raw materials were reacted in the same manner as in Example 28, except that phenylsilane was replaced with 1.9 g (1.0 mmol, Mn = 1900) of poly (methylhydridosilane) (PMHS). Table 7 shows quantitative results of raw materials, products, and the like.
（実施例３１）
フェニルシランをジフェニルシラン１８４．３ｇ（１．０ｍｍｏｌ）に置き換えた以外は、実施例２８と同様の操作によって原料を反応させた。原料、生成物等の定量結果を表７に示す。
(Example 31)
The raw materials were reacted in the same manner as in Example 28, except that phenylsilane was replaced with 184.3 g (1.0 mmol) of diphenylsilane. Table 7 shows quantitative results of raw materials, products, and the like.
（実施例３２）
フェニルシランをフェニルジメチルシラン１３６．３ｇ（１．０ｍｍｏｌ）に置き換えた以外は、実施例２８と同様の操作によって原料を反応させた。原料、生成物等の定量結果を表７に示す。
(Example 32)
The raw materials were reacted in the same manner as in Example 28 except that phenylsilane was replaced with 136.3 g (1.0 mmol) of phenyldimethylsilane. Table 7 shows quantitative results of raw materials, products, and the like.
（実施例３３）
フェニルシランをトリエチルシラン１１６．３ｇ（１．０ｍｍｏｌ）に置き換えた以外は、実施例２８と同様の操作によって原料を反応させた。原料、生成物等の定量結果を表７に示す。
(Example 33)
The raw materials were reacted in the same manner as in Example 28 except that 116.3 g (1.0 mmol) of triethylsilane was replaced with phenylsilane. Table 7 shows quantitative results of raw materials, products, and the like.
＜混合溶媒の検討＞
（実施例３４）
投入するフェニルシランの量を１０８．２ｍｇ（２．０ｍｍｏｌ）とした以外は、実施例２８と同様の操作によって原料を反応させた。原料、生成物等の定量結果を表８に示す。
<Examination of mixed solvent>
(Example 34)
The raw material was reacted by the same operation as in Example 28 except that the amount of phenylsilane to be added was 108.2 mg (2.0 mmol). Table 8 shows quantitative results of raw materials, products and the like.
（実施例３５）
ＴＨＦをＤＭＦ／１，４−Ｄｉｏｘａｎｅの混合溶媒（１．０／１．０ｍＬ）に置き換えた以外は、実施例２と同様の操作によって、分散液１０（溶媒配位酸化鉄ナノ粒子が分散した溶液）を調製した。
次に分散液９を分散液１０に置き換えた以外は、実施例３４と同様の操作によって原料を反応させた。原料、生成物等の定量結果を表８に示す。
(Example 35)
Dispersion 10 (solvent-coordinated iron oxide nanoparticles) was dispersed by the same operation as in Example 2 except that THF was replaced with a mixed solvent of DMF / 1,4-Dioxane (1.0 / 1.0 mL). Solution) was prepared.
Next, the raw materials were reacted in the same manner as in Example 34 except that the dispersion 9 was replaced with the dispersion 10. Table 8 shows quantitative results of raw materials, products and the like.
（実施例３６）
ＴＨＦをＤＭＦに置き換えた以外は、実施例２と同様の操作によって、分散液１１（ＤＭＦ配位酸化鉄ナノ粒子が分散したＤＭＦ溶液）を調製した。
次に分散液９を分散液１１に置き換えた以外は、実施例３４と同様の操作によって原料を反応させた。原料、生成物等の定量結果を表８に示す。
(Example 36)
A dispersion 11 (DMF solution in which DMF-coordinated iron oxide nanoparticles were dispersed) was prepared in the same manner as in Example 2 except that THF was replaced with DMF.
Next, the raw materials were reacted in the same manner as in Example 34 except that the dispersion 9 was replaced with the dispersion 11. Table 8 shows quantitative results of raw materials, products and the like.
（実施例３７）
ＴＨＦをＤＭＦ／ジメチルアセトアミド（ＤＭＡ）の混合溶媒（１．０／１．０ｍＬ）に置き換えた以外は、実施例２と同様の操作によって、分散液１２（溶媒配位酸化鉄ナノ粒子が分散した溶液）を調製した。
次に分散液９を分散液１２に置き換えた以外は、実施例３４と同様の操作によって原料を反応させた。原料、生成物等の定量結果を表８に示す。
(Example 37)
Dispersion 12 (solvent-coordinated iron oxide nanoparticles) was dispersed in the same manner as in Example 2 except that THF was replaced with a mixed solvent (1.0 / 1.0 mL) of DMF / dimethylacetamide (DMA). Solution) was prepared.
Next, the raw materials were reacted in the same manner as in Example 34 except that the dispersion 9 was replaced with the dispersion 12. Table 8 shows quantitative results of raw materials, products and the like.
（実施例３８）
ＴＨＦをＤＭＦ／ＮＭＰの混合溶媒（１．０／１．０ｍＬ）に置き換えた以外は、実施例２と同様の操作によって、分散液１３（溶媒配位酸化鉄ナノ粒子が分散した溶液）を調製した。
次に分散液９を分散液１３に置き換えた以外は、実施例３４と同様の操作によって原料を反応させた。原料、生成物等の定量結果を表８に示す。
(Example 38)
A dispersion 13 (solution in which solvent-coordinated iron oxide nanoparticles are dispersed) is prepared in the same manner as in Example 2 except that THF is replaced with a mixed solvent of DMF / NMP (1.0 / 1.0 mL). did.
Next, the raw materials were reacted in the same manner as in Example 34 except that the dispersion 9 was replaced with the dispersion 13. Table 8 shows quantitative results of raw materials, products and the like.
（実施例３９）
ＴＨＦをＤＭＦ／Ｔｏｌｕｅｎｅの混合溶媒（１．０／１．０ｍＬ）に置き換えた以外は、実施例２と同様の操作によって、分散液１４（溶媒配位酸化鉄ナノ粒子が分散した溶液）を調製した。
次に分散液９を分散液１４に置き換えた以外は、実施例３４と同様の操作によって原料を反応させた。原料、生成物等の定量結果を表８に示す。
(Example 39)
A dispersion 14 (a solution in which solvent-coordinated iron oxide nanoparticles are dispersed) is prepared in the same manner as in Example 2, except that THF is replaced with a mixed solvent of DMF / Toluene (1.0 / 1.0 mL). did.
Next, the raw materials were reacted in the same manner as in Example 34 except that the dispersion 9 was replaced with the dispersion 14. Table 8 shows quantitative results of raw materials, products and the like.
本発明の製造方法によって製造される有機シラン化合物は、例えば有機ケイ素化学工業における様々な原料として使用することができる。 The organosilane compound produced by the production method of the present invention can be used, for example, as various raw materials in the organosilicon chemical industry.
Claims (5)
前記触媒が、表面に溶媒が配位した鉄元素含有ナノ粒子であることを特徴とする、有機シラン化合物の製造方法。 A method for producing an organosilane compound, comprising reacting alkenes and / or alkynes with hydrosilanes in the presence of a catalyst,
The method for producing an organosilane compound, wherein the catalyst is iron element-containing nanoparticles having a solvent coordinated on a surface thereof.
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