JP5627483B2 - Method for producing allylsilanes - Google Patents
Method for producing allylsilanes Download PDFInfo
- Publication number
- JP5627483B2 JP5627483B2 JP2011015146A JP2011015146A JP5627483B2 JP 5627483 B2 JP5627483 B2 JP 5627483B2 JP 2011015146 A JP2011015146 A JP 2011015146A JP 2011015146 A JP2011015146 A JP 2011015146A JP 5627483 B2 JP5627483 B2 JP 5627483B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- unsubstituted
- formula
- mmol
- substituted
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 34
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 46
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 34
- 239000003054 catalyst Substances 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 27
- PBDBXAQKXCXZCJ-UHFFFAOYSA-L palladium(2+);2,2,2-trifluoroacetate Chemical compound [Pd+2].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F PBDBXAQKXCXZCJ-UHFFFAOYSA-L 0.000 claims description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 22
- 229910052760 oxygen Inorganic materials 0.000 claims description 22
- 239000001301 oxygen Substances 0.000 claims description 22
- 239000012298 atmosphere Substances 0.000 claims description 19
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 125000001072 heteroaryl group Chemical group 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 239000007800 oxidant agent Substances 0.000 claims description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 6
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 6
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 claims description 5
- 150000002576 ketones Chemical class 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000005017 substituted alkenyl group Chemical group 0.000 claims description 5
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 5
- 125000003107 substituted aryl group Chemical group 0.000 claims description 5
- 125000005346 substituted cycloalkyl group Chemical group 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- DNAJDTIOMGISDS-UHFFFAOYSA-N prop-2-enylsilane Chemical compound [SiH3]CC=C DNAJDTIOMGISDS-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 3
- 150000003462 sulfoxides Chemical class 0.000 claims description 3
- 239000002904 solvent Substances 0.000 description 52
- -1 allyl halide Chemical class 0.000 description 47
- 238000006243 chemical reaction Methods 0.000 description 32
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 30
- 239000000047 product Substances 0.000 description 27
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 26
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 26
- 239000000203 mixture Substances 0.000 description 20
- 239000000758 substrate Substances 0.000 description 16
- 239000006227 byproduct Substances 0.000 description 14
- NEXSMEBSBIABKL-UHFFFAOYSA-N hexamethyldisilane Chemical compound C[Si](C)(C)[Si](C)(C)C NEXSMEBSBIABKL-UHFFFAOYSA-N 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 239000000654 additive Substances 0.000 description 13
- 239000012044 organic layer Substances 0.000 description 13
- 239000000741 silica gel Substances 0.000 description 13
- 229910002027 silica gel Inorganic materials 0.000 description 13
- 230000000996 additive effect Effects 0.000 description 12
- 229910052763 palladium Inorganic materials 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 8
- 125000002619 bicyclic group Chemical group 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 6
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 6
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 6
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 241000894007 species Species 0.000 description 6
- 125000000753 cycloalkyl group Chemical group 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 229940069096 dodecene Drugs 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 125000003367 polycyclic group Chemical group 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- NLDGJRWPPOSWLC-UHFFFAOYSA-N deca-1,9-diene Chemical compound C=CCCCCCCC=C NLDGJRWPPOSWLC-UHFFFAOYSA-N 0.000 description 3
- 239000011964 heteropoly acid Substances 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000002950 monocyclic group Chemical group 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- AJKNNUJQFALRIK-UHFFFAOYSA-N 1,2,3-trifluorobenzene Chemical compound FC1=CC=CC(F)=C1F AJKNNUJQFALRIK-UHFFFAOYSA-N 0.000 description 2
- VQOXUMQBYILCKR-UHFFFAOYSA-N 1-Tridecene Chemical compound CCCCCCCCCCCC=C VQOXUMQBYILCKR-UHFFFAOYSA-N 0.000 description 2
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- PJLHTVIBELQURV-UHFFFAOYSA-N 1-pentadecene Chemical compound CCCCCCCCCCCCCC=C PJLHTVIBELQURV-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 125000006027 3-methyl-1-butenyl group Chemical group 0.000 description 2
- YIKYVFNFLHAUPA-UHFFFAOYSA-N 4-but-1-enylpyridine Chemical compound CCC=CC1=CC=NC=C1 YIKYVFNFLHAUPA-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 description 2
- 238000010813 internal standard method Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- VXXAPQAFRHIOBP-UHFFFAOYSA-N oct-7-enylcyclopentane Chemical compound C=CCCCCCCC1CCCC1 VXXAPQAFRHIOBP-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- VOSLXTGMYNYCPW-UHFFFAOYSA-N 1,10-Undecadiene Chemical compound C=CCCCCCCCC=C VOSLXTGMYNYCPW-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- CLTMQCGFHLPTBB-UHFFFAOYSA-N 1-but-3-enyl-4-methoxybenzene Chemical compound COC1=CC=C(CCC=C)C=C1 CLTMQCGFHLPTBB-UHFFFAOYSA-N 0.000 description 1
- FYUSTYDEUMSXRE-UHFFFAOYSA-N 1-but-3-enylpyrazolidine Chemical compound C=CCCN1CCCN1 FYUSTYDEUMSXRE-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000006039 1-hexenyl group Chemical group 0.000 description 1
- JQCSUVJDBHJKNG-UHFFFAOYSA-N 1-methoxy-ethyl Chemical group C[CH]OC JQCSUVJDBHJKNG-UHFFFAOYSA-N 0.000 description 1
- 125000006025 1-methyl-1-butenyl group Chemical group 0.000 description 1
- 125000006023 1-pentenyl group Chemical group 0.000 description 1
- RJFCFNWLPJRCLR-UHFFFAOYSA-N 1-prop-2-enylnaphthalene Chemical compound C1=CC=C2C(CC=C)=CC=CC2=C1 RJFCFNWLPJRCLR-UHFFFAOYSA-N 0.000 description 1
- YZBVIYJNUQVTTQ-UHFFFAOYSA-N 1-prop-2-enylpyrrolidine Chemical compound C=CCN1CCCC1 YZBVIYJNUQVTTQ-UHFFFAOYSA-N 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- PAPJLMYEUQUVEZ-UHFFFAOYSA-N 2-but-3-enyl-4-methoxypyridine Chemical compound COC1=CC=NC(CCC=C)=C1 PAPJLMYEUQUVEZ-UHFFFAOYSA-N 0.000 description 1
- VTXWAVDGZZPPIO-UHFFFAOYSA-N 2-but-3-enylpyrazine Chemical compound C=CCCC1=CN=CC=N1 VTXWAVDGZZPPIO-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000006026 2-methyl-1-butenyl group Chemical group 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- BSULJZVYLWGJOF-UHFFFAOYSA-N 2-prop-2-enyl-1-azabicyclo[2.2.2]octane Chemical compound C1CN2C(CC=C)CC1CC2 BSULJZVYLWGJOF-UHFFFAOYSA-N 0.000 description 1
- DCSJOYUSHGVMFL-UHFFFAOYSA-N 2-prop-2-enyl-1h-pyrrole Chemical compound C=CCC1=CC=CN1 DCSJOYUSHGVMFL-UHFFFAOYSA-N 0.000 description 1
- SPOPFXRSBQPLLV-UHFFFAOYSA-N 2-prop-2-enylnaphthalene Chemical compound C1=CC=CC2=CC(CC=C)=CC=C21 SPOPFXRSBQPLLV-UHFFFAOYSA-N 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- SJLQYVZDSRERTN-UHFFFAOYSA-N 3-prop-1-enylpyridine Chemical compound CC=CC1=CC=CN=C1 SJLQYVZDSRERTN-UHFFFAOYSA-N 0.000 description 1
- KLCNJIQZXOQYTE-UHFFFAOYSA-N 4,4-dimethylpent-1-ene Chemical compound CC(C)(C)CC=C KLCNJIQZXOQYTE-UHFFFAOYSA-N 0.000 description 1
- VDTUJQCSPFYIKZ-UHFFFAOYSA-N 4-methoxybut-1-ene Chemical compound COCCC=C VDTUJQCSPFYIKZ-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 description 1
- SUWJESCICIOQHO-UHFFFAOYSA-N 4-methylhex-1-ene Chemical compound CCC(C)CC=C SUWJESCICIOQHO-UHFFFAOYSA-N 0.000 description 1
- JIUFYGIESXPUPL-UHFFFAOYSA-N 5-methylhex-1-ene Chemical compound CC(C)CCC=C JIUFYGIESXPUPL-UHFFFAOYSA-N 0.000 description 1
- XRYAVMDYXXEJGJ-UHFFFAOYSA-N C(C)OC1CCN(C1)CCC=C Chemical compound C(C)OC1CCN(C1)CCC=C XRYAVMDYXXEJGJ-UHFFFAOYSA-N 0.000 description 1
- GMGLDAXTRKXZRF-UHFFFAOYSA-N C1(=CC=CC=C1)C(CCCCCC=C)CC Chemical compound C1(=CC=CC=C1)C(CCCCCC=C)CC GMGLDAXTRKXZRF-UHFFFAOYSA-N 0.000 description 1
- OKTQSNFRVWILQJ-UHFFFAOYSA-N C1(=CC=CC=C1)C(CCCCCCCC=C)CC Chemical compound C1(=CC=CC=C1)C(CCCCCCCC=C)CC OKTQSNFRVWILQJ-UHFFFAOYSA-N 0.000 description 1
- QLNQRQAKPGIISC-UHFFFAOYSA-N COC1CCC(CC1)CCC=C Chemical compound COC1CCC(CC1)CCC=C QLNQRQAKPGIISC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000010485 C−C bond formation reaction Methods 0.000 description 1
- ZFMSMUAANRJZFM-UHFFFAOYSA-N Estragole Chemical compound COC1=CC=C(CC=C)C=C1 ZFMSMUAANRJZFM-UHFFFAOYSA-N 0.000 description 1
- 238000006960 Hosomi-Sakurai reaction Methods 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- PLKHHLLEQJKYKL-UHFFFAOYSA-N N1(CCCC1)C(CCCCCCCC=C)CC.N1(CCOCC1)C(CCCCCC=C)CC Chemical compound N1(CCCC1)C(CCCCCCCC=C)CC.N1(CCOCC1)C(CCCCCC=C)CC PLKHHLLEQJKYKL-UHFFFAOYSA-N 0.000 description 1
- YRYLYUIUEGKACP-UHFFFAOYSA-N N1=C(C=CC=C1)C(CCCCCCCC=C)CC Chemical compound N1=C(C=CC=C1)C(CCCCCCCC=C)CC YRYLYUIUEGKACP-UHFFFAOYSA-N 0.000 description 1
- NWLSTIJPBWFVGC-UHFFFAOYSA-N N1=C(N=CC=C1)CCCCCCC=C Chemical compound N1=C(N=CC=C1)CCCCCCC=C NWLSTIJPBWFVGC-UHFFFAOYSA-N 0.000 description 1
- JDGQNOURWDVEOM-UHFFFAOYSA-N N1CNCC1C=CCC Chemical compound N1CNCC1C=CCC JDGQNOURWDVEOM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 101710182846 Polyhedrin Proteins 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002009 alkene group Chemical group 0.000 description 1
- 125000002785 azepinyl group Chemical group 0.000 description 1
- 125000004604 benzisothiazolyl group Chemical group S1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 125000004603 benzisoxazolyl group Chemical group O1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 125000004602 benzodiazinyl group Chemical group N1=NC(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004619 benzopyranyl group Chemical group O1C(C=CC2=C1C=CC=C2)* 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004600 benzothiopyranyl group Chemical group S1C(C=CC2=C1C=CC=C2)* 0.000 description 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 1
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- PBGVMIDTGGTBFS-UHFFFAOYSA-N but-3-enylbenzene Chemical compound C=CCCC1=CC=CC=C1 PBGVMIDTGGTBFS-UHFFFAOYSA-N 0.000 description 1
- PKIGUSMKZWIRRZ-UHFFFAOYSA-N but-3-enylcyclobutane Chemical compound C=CCCC1CCC1 PKIGUSMKZWIRRZ-UHFFFAOYSA-N 0.000 description 1
- FPFLMFYIDYAPJW-UHFFFAOYSA-N but-3-enylcycloheptane Chemical compound C=CCCC1CCCCCC1 FPFLMFYIDYAPJW-UHFFFAOYSA-N 0.000 description 1
- LXAHJTLFCWQKCR-UHFFFAOYSA-N but-3-enylcyclohexane Chemical compound C=CCCC1CCCCC1 LXAHJTLFCWQKCR-UHFFFAOYSA-N 0.000 description 1
- AAAVTDCFEWFTIY-UHFFFAOYSA-N but-3-enylcyclopentane Chemical compound C=CCCC1CCCC1 AAAVTDCFEWFTIY-UHFFFAOYSA-N 0.000 description 1
- UBHRQZLRQKVRRD-UHFFFAOYSA-N but-3-enylcyclopropane Chemical compound C=CCCC1CC1 UBHRQZLRQKVRRD-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000000259 cinnolinyl group Chemical group N1=NC(=CC2=CC=CC=C12)* 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 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
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- NTQGILPNLZZOJH-UHFFFAOYSA-N disilicon Chemical compound [Si]#[Si] NTQGILPNLZZOJH-UHFFFAOYSA-N 0.000 description 1
- IYPLTVKTLDQUGG-UHFFFAOYSA-N dodeca-1,11-diene Chemical compound C=CCCCCCCCCC=C IYPLTVKTLDQUGG-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000012039 electrophile Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000004615 furo[2,3-b]pyridinyl group Chemical group O1C(=CC=2C1=NC=CC2)* 0.000 description 1
- 125000004613 furo[2,3-c]pyridinyl group Chemical group O1C(=CC=2C1=CN=CC2)* 0.000 description 1
- 125000004614 furo[3,1-b]pyridinyl group Chemical group 0.000 description 1
- 125000004612 furopyridinyl group Chemical group O1C(=CC2=C1C=CC=N2)* 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- GEAWFZNTIFJMHR-UHFFFAOYSA-N hepta-1,6-diene Chemical compound C=CCCCC=C GEAWFZNTIFJMHR-UHFFFAOYSA-N 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002632 imidazolidinyl group Chemical group 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000003406 indolizinyl group Chemical group C=1(C=CN2C=CC=CC12)* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical group C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [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
- 125000004593 naphthyridinyl group Chemical group N1=C(C=CC2=CC=CN=C12)* 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 125000001715 oxadiazolyl group Chemical group 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- CYCUXCSZQIHKAU-UHFFFAOYSA-N pent-4-enylcyclohexane Chemical compound C=CCCCC1CCCCC1 CYCUXCSZQIHKAU-UHFFFAOYSA-N 0.000 description 1
- IRNRMIXNPUTRHT-UHFFFAOYSA-N pent-4-enylcyclopentane Chemical compound C=CCCCC1CCCC1 IRNRMIXNPUTRHT-UHFFFAOYSA-N 0.000 description 1
- LZJIXEXUTQTLPF-UHFFFAOYSA-N pent-4-enylcyclopropane Chemical compound C=CCCCC1CC1 LZJIXEXUTQTLPF-UHFFFAOYSA-N 0.000 description 1
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000004934 phenanthridinyl group Chemical group C1(=CC=CC2=NC=C3C=CC=CC3=C12)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229930015698 phenylpropene Natural products 0.000 description 1
- 125000004592 phthalazinyl group Chemical group C1(=NN=CC2=CC=CC=C12)* 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003072 pyrazolidinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000004590 pyridopyridyl group Chemical group N1=C(C=CC2=C1C=CC=N2)* 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000006085 pyrrolopyridyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000004620 quinolinyl-N-oxide group Chemical group 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 125000004621 quinuclidinyl group Chemical group N12C(CC(CC1)CC2)* 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- CTDQAGUNKPRERK-UHFFFAOYSA-N spirodecane Chemical compound C1CCCC21CCCCC2 CTDQAGUNKPRERK-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000004589 thienofuryl group Chemical group O1C(=CC2=C1C=CS2)* 0.000 description 1
- 125000004588 thienopyridyl group Chemical group S1C(=CC2=C1C=CC=N2)* 0.000 description 1
- 125000004587 thienothienyl group Chemical group S1C(=CC2=C1C=CS2)* 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- BKUZFJFHKLLDQB-UHFFFAOYSA-N tri(propan-2-yl)-tri(propan-2-yl)silylsilane Chemical compound CC(C)[Si](C(C)C)(C(C)C)[Si](C(C)C)(C(C)C)C(C)C BKUZFJFHKLLDQB-UHFFFAOYSA-N 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- XEJUFRSVJVTIFW-UHFFFAOYSA-N triethyl(triethylsilyl)silane Chemical compound CC[Si](CC)(CC)[Si](CC)(CC)CC XEJUFRSVJVTIFW-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ZMHATUZXFSOVSC-UHFFFAOYSA-N triphenyl(triphenylsilyl)silane Chemical compound C1=CC=CC=C1[Si]([Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 ZMHATUZXFSOVSC-UHFFFAOYSA-N 0.000 description 1
- RZLUWWOHMSPJOC-UHFFFAOYSA-N tritert-butyl(tritert-butylsilyl)silane Chemical compound CC(C)(C)[Si](C(C)(C)C)(C(C)(C)C)[Si](C(C)(C)C)(C(C)(C)C)C(C)(C)C RZLUWWOHMSPJOC-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本願発明は、アルケンとジシランからのアリルシランの新規な製造方法に関する。具体的には、単純アルケンである１−アルケンをアリル化剤として用いて、該１−アルケンとジシランから、トリフルオロ酢酸パラジウム触媒の存在下、高い位置選択性でアリルシラン類を得る、新規な製造方法に関する。 The present invention relates to a novel method for producing allylsilane from alkene and disilane. Specifically, a novel production in which allylsilanes are obtained with high regioselectivity in the presence of a palladium trifluoroacetate catalyst from 1-alkene and disilane using 1-alkene, which is a simple alkene, as an allylating agent. Regarding the method.
近年医薬等を指向した高付加価値の精密化学品の合成に関するファインケミカルズに対する関心が益々高まっている。特に、安価かつ入手可能な化学産業資源（フィードストック）を原料として用いて、有機合成上有用なビルディングブロックを簡便に得る方法が求められている。 In recent years, interest in fine chemicals relating to the synthesis of high-value-added fine chemicals oriented to pharmaceuticals and the like has been increasing. In particular, there is a demand for a method for easily obtaining a building block useful for organic synthesis using cheap and available chemical industrial resources (feedstock) as a raw material.
アリルシラン類は、様々な化学変換が可能な官能基であるアリル基とシリル基とを有する分子であり、そのため天然物化合物の合成をはじめとした有機合成反応に利用されている。例えば、ルイス酸の存在のもと、アリルシラン類を、ケトン、アセタール等の種々の求電子剤と反応させることにより、位置選択的な炭素−炭素結合生成反応が生起する細見−櫻井反応が知られている（非特許文献１を参照）。従って、アリルシラン類は、炭素骨格上にアリル部位を導入する有機合成上有用なビルディングブロックである。 Allylsilanes are molecules having an allyl group and a silyl group, which are functional groups capable of various chemical transformations, and are therefore used in organic synthesis reactions including the synthesis of natural product compounds. For example, the Hosomi-Sakurai reaction is known in which regioselective carbon-carbon bond formation reaction occurs by reacting allylsilanes with various electrophiles such as ketones and acetals in the presence of Lewis acids. (See Non-Patent Document 1). Accordingly, allylsilanes are useful building blocks in organic synthesis that introduce an allyl moiety on the carbon skeleton.
これまでに、種々のアリルシランの製造方法が報告されている。しかしながら、従来の製法では、例えばハロゲン化アリルをマグネシウムまたはリチウムなどの化学両論量の金属試薬と反応させ、続いて得られる有機金属アリル化合物をハロシランと反応させてアリルシラン類を製造する方法であり、そのため多量の金属塩が副生するという問題点があった（非特許文献２および特許文献１を参照）。また、別製法として、シリル供給源として天然物の石油などに含まれるジシランを用いた製造法も報告されているが、アリル供給源がアリル酢酸エステルに代表されるエステル基やハロゲンなどの電子吸引性で反応性の高い脱離基を有するアリル化合物に制限されており（非特許文献３を参照）、別途それらアリル化合物を調製する必要があった。よって、アリル供給源として単純アルケンを用いたアリルシラン類の製法が求められていた。
さらに、パラジウム触媒を用いたこれまでの反応では、ゼロ価のパラジウム種（Pd(0)）と活性な二価のパラジウム種（Pd(II)）との間のリサイクルに必要な酸化剤として、ヘテロポリ酸などの固体酸を要していた（非特許文献４を参照）。 Furthermore, in the previous reactions using a palladium catalyst, as an oxidant necessary for recycling between a zero-valent palladium species (Pd (0)) and an active divalent palladium species (Pd (II)), A solid acid such as a heteropoly acid was required (see Non-Patent Document 4).
本願発明は、従来反応性が低いと考えられていた単純アルケンである１−アルケンとジシランから、アリルシラン類を製造する方法を提供することにある。 The present invention is to provide a method for producing allylsilanes from 1-alkene and disilane, which are simple alkenes that are conventionally considered to have low reactivity.
本願発明者が鋭意研究した結果、トリフルオロ酢酸パラジウム（Ｐｄ(ＯＣ(＝Ｏ)ＣＦ３)２を触媒として使用することにより、単純アルケンである１−アルケンを用いて、酸素雰囲気下でジシランと反応させることにより、高い位置選択性で酸化的アリル位シリル化されたアリルシラン類が得られることを見出した。すなわち、本願発明は以下の通りである。 As a result of intensive studies by the present inventors, by using palladium trifluoroacetate (Pd (OC (═O) CF 3 ) 2 as a catalyst, 1-alkene, which is a simple alkene, is used in an oxygen atmosphere and disilane. It has been found that allylsilanes that are oxidatively allylically silylated with high regioselectivity can be obtained by the reaction, that is, the present invention is as follows.
［１］ 式（Ｉ）：
Ｒ１は、無置換または置換のアルキル基、無置換または置換のシクロアルキル基、無置換または置換の飽和へテロシクロアルキル基、無置換または置換のアルケニル基、無置換または置換のアリール基、および無置換または置換のヘテロアリール基からなる群から選ばれ；そして、
ｎは、１〜１５の整数である）
で表される１−アルケン、および
式（II）：
Ｒ２は、無置換のアルキル基または無置換のアリール基からなる群から選ばれる）
で表されるジシランを、トリフルオロ酢酸パラジウム（Ｐｄ(ＯＣ(＝Ｏ)ＣＦ３)２）触媒の存在下、酸素雰囲気下で反応させることによる、
式（III）：
で表されるアリルシラン類の製造方法。
[1] Formula (I):
R 1 is an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted saturated heterocycloalkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group, and Selected from the group consisting of unsubstituted or substituted heteroaryl groups; and
n is an integer of 1 to 15)
A 1-alkene represented by formula (II):
R 2 is selected from the group consisting of an unsubstituted alkyl group or an unsubstituted aryl group)
By reacting a disilane represented by the following formula in the presence of a palladium trifluoroacetate (Pd (OC (═O) CF 3 ) 2 ) catalyst in an oxygen atmosphere:
Formula (III):
The manufacturing method of allylsilane represented by these.
［２］ Ｒ１がｎ−ヘプチルであって、ｎが１である、［１］記載の製造方法。 [2] The production method according to [1], wherein R 1 is n-heptyl and n is 1.
［３］ Ｒ２がメチルである、［１］または［２］記載の製造方法。 [3] The production method of [1] or [2], wherein R 2 is methyl.
［４］ 式（III）−Ａの化合物と式（III）−Ｂの化合物の生成比率が、約９０：１０以上である、［１］乃至［３］のいずれか１項記載の製造方法。 [4] The production method according to any one of [1] to [3], wherein the production ratio of the compound of formula (III) -A and the compound of formula (III) -B is about 90:10 or more.
［５］ 触媒量のさらなる酸化剤の存在下で行う、［１］乃至［４］のいずれか１項記載の製造方法。 [5] The production method according to any one of [1] to [4], which is carried out in the presence of a catalytic amount of an additional oxidizing agent.
［６］ 前記さらなる酸化剤がモリブドバナドリン酸塩である、［５］記載の製造方法。 [6] The production method according to [5], wherein the further oxidizing agent is molybdovanadophosphate.
［７］ さらに、触媒量の、ケトン、ホスフィンおよびスルホキシドからなる群から選ばれる配位子性化合物の存在下で行う、［１］乃至［６］のいずれか１項記載の製造方法。 [7] The production method according to any one of [1] to [6], further performed in the presence of a catalytic amount of a ligand compound selected from the group consisting of ketone, phosphine and sulfoxide.
［８］ 前記配位子性化合物が、アセチルアセトンおよびジベンジリデンアセトンからなる群から選ばれる化合物である、［７］記載の製造方法。 [8] The production method according to [7], wherein the ligand compound is a compound selected from the group consisting of acetylacetone and dibenzylideneacetone.
［９］ 式（Ｉ）で表される１−アルケンの配合量が、式（II）で表されるジシランの配合量基準で５〜１００モル％当量である、［１］乃至［８］のいずれか１項記載の製造方法。 [9] The amount of 1-alkene represented by formula (I) is 5 to 100 mol% equivalent based on the amount of disilane represented by formula (II). The manufacturing method of any one of Claims.
本願発明は、さらに下記の態様の発明を提供するものである。 The present invention further provides the following aspects of the invention.
［１０］ トリフルオロ酢酸パラジウム触媒の使用量が、ジシランの配合量基準で約０．１〜０．５モル％当量である、［１］乃至［９］のいずれか１項記載の製造方法。 [10] The production method according to any one of [1] to [9], wherein the amount of the palladium trifluoroacetate catalyst used is about 0.1 to 0.5 mol% equivalent based on the amount of disilane.
［１１］ 反応を、室温から使用する反応溶媒の沸点で行う、［１］乃至［１０］のいずれか１項記載の製造方法。 [11] The production method according to any one of [1] to [10], wherein the reaction is performed from room temperature to the boiling point of the reaction solvent used.
本願発明により、従来、反応性が低いため反応基質として用いることが困難であった単純アルケンを用いて有機合成上有用なアリルシラン類を高い位置選択性で製造することができる。 According to the present invention, allylsilanes useful for organic synthesis can be produced with high regioselectivity using simple alkenes that have been difficult to use as a reaction substrate because of their low reactivity.
以下に、本願発明をさらに詳細に説明する。
（定義）
以下に、本明細書および特許請求の範囲中で使用する用語の定義を示す。特に断らなければ、本明細書中の基または用語について示す最初の定義を、個別にまたは別の基の一部として本明細書中の基または用語に適用する。
Below, this invention is demonstrated in detail.
(Definition)
The definitions of terms used in the present specification and claims are shown below. Unless otherwise indicated, the first definition given for a group or term herein applies to the group or term herein individually or as part of another group.
用語「１−アルケン」とは、式（Ｉ）：
ここで、Ｒ１は、以下に定義する、無置換または置換のアルキル基、無置換または置換のシクロアルキル基、無置換または置換の飽和へテロシクロアルキル基、無置換または置換のアルケニル基、無置換または置換のアリール基、および無置換または置換のヘテロアリール基からなる群から選ばれる基である。好ましくは、無置換アルキル基または無置換アルケン基が挙げられる。
また、ｎは、メチレン炭素部分の数を表すものであって、１〜１５の整数を意味し、例えば１〜１２の整数、２〜１２の整数、１〜１０の整数、３〜１０の整数が挙げられる。
The term “1-alkene” refers to the formula (I):
Here, R 1 is an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted saturated heterocycloalkyl group, an unsubstituted or substituted alkenyl group, It is a group selected from the group consisting of a substituted or substituted aryl group and an unsubstituted or substituted heteroaryl group. Preferably, an unsubstituted alkyl group or an unsubstituted alkene group is used.
N represents the number of methylene carbon moieties and means an integer of 1 to 15, for example, an integer of 1 to 12, an integer of 2 to 12, an integer of 1 to 10, an integer of 3 to 10 Is mentioned.
１−アルケンの具体的な例としては、１−ブテン、１−ペンテン、４−メチル−１−ペンテン、４,４−ジメチル−１−ペンテン、１−ヘキセン、５−メチル−１−ヘキセン、４−メチル−１−ヘキセン、１−ヘプテン、１−オクテン、１−ノネン、１−デセン、１−ウンデセン、１−ドデセン、１−トリデセン、１−テトラデセン、１−ペンタデセン、１−ヘキサデセン、４−メトキシ−１−ブテン；４−シクロプロピル−１−ブテン、５−シクロプロピル−１−ペンテン、４−シクロブチル−１−ブテン、４−シクロペンチル−１−ブテン、５−シクロペンチル−１−ペンテン、８−シクロペンチル−１−オクテン、４−シクロヘキシル−１−ブテン、５−シクロヘキシル−１−ペンテン、８−シクロペンチル−１−オクテン、４−シクロヘプチル−１−ブテン、４−（４−メトキシシクロヘキシル）−１−ブテン；３−ピロリジニル−１−プロペン、４−ピラゾリジニル−１−ブテン、５−イミダゾリジニル−１−ブテン、８−モルホリニル−１−デセン、１０−ピロリジニル−１−ドデセン、３−キヌクリジニル−１−プロペン、４−（４−エトキシピロリジニル）−１−ブテン；１,４−ペンタジエン、１,５−ヘキサジエン、１,６−ヘプタジエン、１,９−デカジエン、１,１０−ウンデカジエン、１,１１−ドデカジエン；３−フェニル−１−プロペン、４−フェニル−１−ブテン、５−フェニル−１−ブテン、８−フェニル−１−デセン、１０−フェニル−１−ドデセン、３−（１−ナフチル）−１−プロペン、３−（２−ナフチル）−１−プロペン、１０−（１−ナフチル）−１−ドデセン、４−（４−メトキシフェニル）−１−ブテン（４−アリルアニソール）；３−ピリジル−１−プロペン、４−ピリジル−１−ブテン、１０−ピリジル−１−ドデセン、３−ピロリル−１−プロペン、４−ピリジル−１−ブテン、４−ピラジニル−１−ブテン、８−ピリミジニル−１−オクテン、４−（４−メトキシピリジル）−１−ブテンなどを挙げられるが、これらに限定されない。１−デセン、１−オクテン、１−ヘキセン、１−ヘプテン、１−ドデセン、１−テトラデセン、１−ヘキサデセン、１，９−デカジエンなどが好ましい。 Specific examples of 1-alkene include 1-butene, 1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 1-hexene, 5-methyl-1-hexene, 4 -Methyl-1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 4-methoxy -1-butene; 4-cyclopropyl-1-butene, 5-cyclopropyl-1-pentene, 4-cyclobutyl-1-butene, 4-cyclopentyl-1-butene, 5-cyclopentyl-1-pentene, 8-cyclopentyl -1-octene, 4-cyclohexyl-1-butene, 5-cyclohexyl-1-pentene, 8-cyclopentyl-1-octene, 4-cyclo Heptyl-1-butene, 4- (4-methoxycyclohexyl) -1-butene; 3-pyrrolidinyl-1-propene, 4-pyrazolidinyl-1-butene, 5-imidazolidinyl-1-butene, 8-morpholinyl-1-decene 10-pyrrolidinyl-1-dodecene, 3-quinuclidinyl-1-propene, 4- (4-ethoxypyrrolidinyl) -1-butene; 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene; 3-phenyl-1-propene, 4-phenyl-1-butene, 5-phenyl-1-butene, 8-phenyl-1-decene, 10-phenyl-1-dodecene, 3- (1-naphthyl) -1-propene, 3- (2-naphthyl) -1-propene, 10- (1-naphthyl) ) -1-dodecene, 4- (4-methoxyphenyl) -1-butene (4-allyl anisole); 3-pyridyl-1-propene, 4-pyridyl-1-butene, 10-pyridyl-1-dodecene, 3 -Pyrrolyl-1-propene, 4-pyridyl-1-butene, 4-pyrazinyl-1-butene, 8-pyrimidinyl-1-octene, 4- (4-methoxypyridyl) -1-butene, and the like. It is not limited to. 1-decene, 1-octene, 1-hexene, 1-heptene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1,9-decadiene and the like are preferable.
用語「ジシラン」とは、式（II）：
ここで、Ｒ２は、以下に定義する無置換アルキル基または無置換アリール基からなる群から選ばれる。好ましくは、無置換アルキル基である。
The term “disilane” refers to the formula (II):
Here, R 2 is selected from the group consisting of an unsubstituted alkyl group or an unsubstituted aryl group defined below. An unsubstituted alkyl group is preferable.
ジシランの具体的な例としては、ヘキサメチルジシラン、ヘキサエチルジシラン、ヘキサイソプロピルジシラン、ヘキサｔ−ブチルジシラン、ヘキサフェニルジシランを挙げられ、ヘキサメチルジシランが好ましい。 Specific examples of disilane include hexamethyldisilane, hexaethyldisilane, hexaisopropyldisilane, hexa-t-butyldisilane, and hexaphenyldisilane, with hexamethyldisilane being preferred.
用語「アリルシラン類」とは、式（III）：
ここで、式（III）の化合物は、α−付加物としての式（III）−Ａで表される化合物及びγ−付加物としての式（III）−Ｂで表される化合物を含む。
The term “allylsilanes” refers to the formula (III):
Here, the compound of the formula (III) includes a compound represented by the formula (III) -A as an α-adduct and a compound represented by the formula (III) -B as a γ-adduct.
式（III）−Ａで表される化合物が優先的に生成する。式（III）−Ａの化合物と式（III）−Ｂの化合物の生成比率は、例えば約９０：１０以上であって、約９５：５以上が好ましい。 A compound represented by the formula (III) -A is preferentially produced. The production ratio of the compound of formula (III) -A and the compound of formula (III) -B is, for example, about 90:10 or more, preferably about 95: 5 or more.
用語「無置換または置換のアルキル基」とは、炭素数が１〜１６個である、直鎖または分枝鎖の炭化水素基を意味する。例えば、炭素数が１〜１６個、１〜１３個、１〜１２個、１〜８個、１〜７個、１〜６個のアルキル基を挙げられる。具体例としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔ−ブチル基、ペンチル基、イソペンチル基、ネオペンチル基、ｎ−ヘキシル基、ｎ−ヘプチル基、ｎ−オクチル基、ｎ−ノニル基、ｎ−デシル基、ｎ−ウンデシル基、ｎ−ドデシル基、ｎ−トリデシル基、ｎ−テトラデシル基、ｎ−ペンタデシル基、ｎ−ヘキサデシル基などが挙げられるが、これらに限定されない。 The term “unsubstituted or substituted alkyl group” means a linear or branched hydrocarbon group having 1 to 16 carbon atoms. For example, a C1-C16, 1-13, 1-12, 1-8, 1-7, 1-6 alkyl group is mentioned. Specific examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group, neopentyl group, n-hexyl group, and n-heptyl group. N-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group and the like. However, it is not limited to these.
用語「無置換または置換のシクロアルキル基」とは、炭素数が３〜８個である、環状炭化水素基を意味する。炭素数が５〜８個、５〜７個、５〜６個のシクロアルキル基を挙げられる。具体例としては、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、およびシクロオクチル基が挙げられるが、これらに限定されない。炭素数が１〜３個の炭素架橋、縮合環（これは、シクロアルキル、飽和へテロシクロ、アリール、ヘテロアリールから選ばれる）、またはスピロ環様式で結合した多環式基（例えば、二環式基）、をも本定義に含む。 The term “unsubstituted or substituted cycloalkyl group” means a cyclic hydrocarbon group having 3 to 8 carbon atoms. Examples include cycloalkyl groups having 5 to 8 carbon atoms, 5 to 7 carbon atoms, and 5 to 6 carbon atoms. Specific examples include, but are not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. C1-C3 carbon bridges, fused rings (which are selected from cycloalkyl, saturated heterocyclo, aryl, heteroaryl), or polycyclic groups attached in a spirocyclic manner (eg, bicyclic Group) is also included in this definition.
用語「無置換または置換の飽和へテロシクロアルキル基」とは、少なくとも１つの環内に、窒素原子、酸素原子、または硫黄原子から選ばれる少なくとも１つのヘテロ原子を有する、飽和の環式基を意味する。炭素数が１〜３個の炭素架橋、縮合環（これは、シクロアルキル、飽和へテロシクロ、アリール、ヘテロアリールから選ばれる）またはスピロ環様式、で結合した多環式基（例えば、二環式基）をも本定義に含む。具体例としては、ピロリジニル基、イミダゾリジニル基、ピラゾリジニル基、ピペリジニル基、ピペラジニル基、モルホリニル基等の単環式ヘテロシクロ基；キヌクリジニル基、２−クロマニル基、２−インドリニル基等の二環式ヘテロシクロ；１−アザ[４.５]スピロデカン等のスピロ環などが挙げられるが、これらに限定されない。 The term “unsubstituted or substituted saturated heterocycloalkyl group” means a saturated cyclic group having at least one heteroatom selected from a nitrogen atom, an oxygen atom, or a sulfur atom in at least one ring. means. A polycyclic group (eg, bicyclic) bonded in a carbon bridge of 1 to 3 carbon atoms, fused ring (which is selected from cycloalkyl, saturated heterocyclo, aryl, heteroaryl) or spiro ring mode Group) is also included in this definition. Specific examples include monocyclic heterocyclo groups such as pyrrolidinyl group, imidazolidinyl group, pyrazolidinyl group, piperidinyl group, piperazinyl group and morpholinyl group; bicyclic heterocyclo groups such as quinuclidinyl group, 2-chromanyl group and 2-indolinyl group; 1 -Spiro rings such as aza [4.5] spirodecane, but are not limited to these.
用語「無置換または置換のアルケニル基」とは、１個の二重結合を有する炭素数が２〜１６個である、直鎖または分枝鎖の炭化水素基を意味する。例えば、炭素数が１〜１６個、１〜１３個、１〜１２個、１〜８個、１〜７個、１〜６個のアルケニル基を挙げられる。末端位に二重結合を有する１−アルケニルが好ましい。具体例としては、エテニル、１−プロペニル、１−ブテニル、２−ブテニル、３−ブテニル、２−メチル−１−ブテニル、３−メチル−１−ブテニル、１−ペンテニル、１−ヘキセニル、１−ヘプテニル、１−オクテニル、１−ノネニル、１−デセニル、１−ウンデセニル、１−ドデセニル、１−トリデセニル、１−テトラデセニル、１−ペンタデセニル、１−ヘキサデセニルなどが挙げられるが、これらに限定されない。 The term “unsubstituted or substituted alkenyl group” means a linear or branched hydrocarbon group having 2 to 16 carbon atoms having one double bond. Examples thereof include alkenyl groups having 1 to 16, 1 to 13, 1 to 12, 1 to 8, 1 to 7, and 1 to 6 carbon atoms. 1-alkenyl having a double bond at the terminal position is preferred. Specific examples include ethenyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-pentenyl, 1-hexenyl, 1-heptenyl. , 1-octenyl, 1-nonenyl, 1-decenyl, 1-undecenyl, 1-dodecenyl, 1-tridecenyl, 1-tetradecenyl, 1-pentadecenyl, 1-hexadecenyl and the like.
用語「無置換または置換のアリール基」とは、芳香族性炭素環式を意味する。縮合環様式で結合した多環式基（例えば、二環式基）をも本定義に含む。具体例としては、フェニル基、１−ナフチル基、２−ナフチル基等の単環式アリール基；フェナントリジニル基、６−クロマニル基、５−イソインドリル基等の二環式アリール基等が挙げられるが、これらに限定されない。 The term “unsubstituted or substituted aryl group” means an aromatic carbocyclic group. Also included in this definition are polycyclic groups (eg, bicyclic groups) linked in a fused ring fashion. Specific examples include monocyclic aryl groups such as phenyl group, 1-naphthyl group and 2-naphthyl group; bicyclic aryl groups such as phenanthridinyl group, 6-chromanyl group and 5-isoindolyl group. However, it is not limited to these.
用語「無置換または置換のヘテロアリール基」とは、適宜１〜５個の置換基を有する、少なくとも１つの環内に、窒素原子、酸素原子、または硫黄原子から選ばれる少なくとも１つのヘテロ原子を有する、芳香族性の環式基を意味する。縮合環様式で結合した多環式基（例えば、二環式基）をも本定義に含む。具体例としては、ピロリル基、ピラゾリル基、イミダゾリル基、オキサゾリル基、イソキサゾリル基、チアゾリル基、チアジアゾリル基、イソチアゾリル基、ピリジル基、フリル基、チエニル基、オキサジアゾリル基、２−オキサアゼピニル基、アゼピニル基、ピラジニル基、ピリミジニル基、ピリダジニル基、トリアジニル基、トリアゾリル基などの単環式へテロアリール基；および、ベンゾチアゾリル基、ベンゾキサゾリル基、ベンゾチエニル基、ベンゾフリル基、キノリニル基、キノリニル−Ｎ−オキシド基、イソキノリニル基、ベンゾイミダゾリル基、ベンゾピラニル基、インドリジニル基、シンノリニル基、キノキサリニル基、インダゾリル基、ピロロピリジル基、フロピリジニル基（例えば、フロ[２,３−ｃ]ピリジニル基、フロ[３,１−ｂ]ピリジニル基、またはフロ[２,３−ｂ]ピリジニル基）、ベンジイソチアゾリル基、ベンゾイソキサゾリル基、ベンゾジアジニル基、ベンゾチオピラニル基、ベンゾトリアゾリル基、ベンゾピラゾリル基、ナフチリジニル基、フタラジニル基、プリニル基、ピリドピリジル基、キナゾリニル基、チエノフリル基、チエノピリジル基、チエノチエニル基などの二環式ヘテロアリール基等の二環式アリール基等が挙げられるが、これらに限定されない。 The term “unsubstituted or substituted heteroaryl group” refers to at least one heteroatom selected from a nitrogen atom, an oxygen atom, or a sulfur atom in at least one ring, optionally having 1 to 5 substituents. Means an aromatic cyclic group. Also included in this definition are polycyclic groups (eg, bicyclic groups) linked in a fused ring fashion. Specific examples include pyrrolyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, thiadiazolyl, isothiazolyl, pyridyl, furyl, thienyl, oxadiazolyl, 2-oxaazepinyl, azepinyl, pyrazinyl A monocyclic heteroaryl group such as a group, pyrimidinyl group, pyridazinyl group, triazinyl group, triazolyl group; and benzothiazolyl group, benzoxazolyl group, benzothienyl group, benzofuryl group, quinolinyl group, quinolinyl-N-oxide group, isoquinolinyl group, Benzoimidazolyl group, benzopyranyl group, indolizinyl group, cinnolinyl group, quinoxalinyl group, indazolyl group, pyrrolopyridyl group, furopyridinyl group (for example, furo [2,3-c] pyridinyl group, furo [ 3,1-b] pyridinyl group or furo [2,3-b] pyridinyl group), benzisothiazolyl group, benzisoxazolyl group, benzodiazinyl group, benzothiopyranyl group, benzotriazolyl group, Bicyclic aryl groups such as bicyclic heteroaryl groups such as benzopyrazolyl group, naphthyridinyl group, phthalazinyl group, purinyl group, pyridopyridyl group, quinazolinyl group, thienofuryl group, thienopyridyl group, thienothienyl group, etc. are mentioned. It is not limited.
用語「アルコキシ基」とは、上記直鎖もしくは分枝鎖のアルキル基が酸素原子に連結した基を意味する。具体的には、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等が挙げられるが、これらに限定されない。 The term “alkoxy group” means a group in which the linear or branched alkyl group is linked to an oxygen atom. Specific examples include, but are not limited to, methoxy group, ethoxy group, propoxy group, butoxy group and the like.
前記用語「置換（の）アルキル基」、「置換（の）シクロアルキル基」、「置換（の）飽和へテロシクロアルキル基」、「置換（の）アルケニル基」、「置換（の）アリール基」および「置換（の）ヘテロアリール基」における置換基とは、有機化学分野において電子供与性基として知られる基が挙げられる。例えばアミノ基（これは、アルキル基、アリール基、またはヘテロアリール基でモノ−、ジ−、トリ−置換されたアミノ基を含む）、ヒドロキシ基、アルキル基、およびアルコキシ基からなる群から選ばれる１個以上の基が挙げられるが、これらに限定されない。アルキル基、アルコキシ基が好ましい。具体例としては、前記アルキル基（例えば、炭素数が１〜６個のアルキル基（例えば、メチル基、エチル基））、前記アルコキシ基（例えば、メトキシ基、エトキシ基）などを挙げられる。 The terms “substituted (of) alkyl group”, “substituted (of) cycloalkyl group”, “substituted (of) saturated heterocycloalkyl group”, “substituted (of) alkenyl group”, “substituted (of) aryl group” Examples of the substituent in the “substituted heteroaryl group” include groups known as electron donating groups in the field of organic chemistry. For example, an amino group (which includes an amino group mono-, di-, or tri-substituted with an alkyl group, an aryl group, or a heteroaryl group), a hydroxy group, an alkyl group, and an alkoxy group. One or more groups may be mentioned, but are not limited to these. An alkyl group and an alkoxy group are preferred. Specific examples include the alkyl group (for example, an alkyl group having 1 to 6 carbon atoms (for example, a methyl group and an ethyl group)), the alkoxy group (for example, a methoxy group and an ethoxy group), and the like.
「置換（の）アルキル基」の具体例としては例えば、１−メトキシエチル、１−エトキシ−ｎ−ブチル、１−ジメチルアミノエチルなどが挙げられる。「置換（の）シクロアルキル基」の具体例としては例えば、４−メチル−１−シクロヘキシル、４−メトキシ−１−シクロヘキシルなどが挙げられる。「置換（の）飽和へテロシクロアルキル基」の具体例としては例えば、４−メチル−１−ピペリジル、２−エチル−４−ピペリジル、４−メトキシ−１−ピペリジル、２−メトキシ−４−ピペリジル、４−ジメチルアミノ−１−ピペリジルなどが挙げられる。「置換（の）アルケニル基」の具体例としては例えば、１−メチル−１−ブテニル、３−メチル−１−ブテニル、１−メトキシ−１−ブテニル、３−メトキシ−１−ブテニル、１−ジメチルアミノ−１−ブテニルなどが挙げられる。「置換（の）アリール基」の具体例としては例えば、２−，３−，４−トリル、３，４−キシリル、メシチル、２−，３−，４−メトキシフェニル、３−メチル−４−メトキシフェニルなどが挙げられる。「置換（の）ヘテロアリール基」の具体例としては例えば、４−メチル−１−ピリジル、４−メチル−２−ピリジル、４−メトキシ−２−ピリジル、４−エトキシ−２−ピリジル、４−ジメチルアミノ−２−ピリジルなどが挙げられる。 Specific examples of the “substituted alkyl group” include 1-methoxyethyl, 1-ethoxy-n-butyl, 1-dimethylaminoethyl and the like. Specific examples of the “substituted cycloalkyl group” include 4-methyl-1-cyclohexyl, 4-methoxy-1-cyclohexyl and the like. Specific examples of the “substituted (saturated) heterocycloalkyl group” include, for example, 4-methyl-1-piperidyl, 2-ethyl-4-piperidyl, 4-methoxy-1-piperidyl, 2-methoxy-4-piperidyl , 4-dimethylamino-1-piperidyl and the like. Specific examples of the “substituted alkenyl group” include, for example, 1-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methoxy-1-butenyl, 3-methoxy-1-butenyl, 1-dimethyl. Amino-1-butenyl and the like can be mentioned. Specific examples of the “substituted aryl group” include, for example, 2-, 3-, 4-tolyl, 3,4-xylyl, mesityl, 2-, 3-, 4-methoxyphenyl, 3-methyl-4- And methoxyphenyl. Specific examples of the “substituted heteroaryl group” include, for example, 4-methyl-1-pyridyl, 4-methyl-2-pyridyl, 4-methoxy-2-pyridyl, 4-ethoxy-2-pyridyl, 4- And dimethylamino-2-pyridyl.
用語「トリフルオロ酢酸パラジウム」とは、化学式：Ｐｄ(ＯＣＯＣＦ３)２で示される二価のパラジウム（Ｐｄ(II））の化合物を意味する。当該化合物は、本願発明の製法において触媒として作用する。 The term “palladium trifluoroacetate” means a compound of divalent palladium (Pd (II)) represented by the chemical formula: Pd (OCOCF 3 ) 2 . The compound acts as a catalyst in the production method of the present invention.
本願の製法は、酸素雰囲気下で行う。ここで、酸素は、上記のトリフルオロ酢酸パラジウム触媒由来のゼロ価のパラジウム（Ｐｄ(０)）種を活性種である二価のパラジウム種に戻す（再酸化する）ために作用する。「酸素雰囲気下」とは、常圧（１ａｔｍ）または加圧条件下（約２〜５０ａｔｍ、約５〜１０ａｔｍ）であることを意味する。 The production method of the present application is performed in an oxygen atmosphere. Here, the oxygen acts to return (reoxidize) the zero-valent palladium (Pd (0)) species derived from the palladium trifluoroacetate catalyst to the active divalent palladium species. “Under an oxygen atmosphere” means normal pressure (1 atm) or pressurized conditions (about 2 to 50 atm, about 5 to 10 atm).
「さらなる酸化剤」とは、他の物質を酸化するための物質をいい、具体的には、上記のトリフルオロ酢酸パラジウム触媒由来のゼロ価のパラジウム（Ｐｄ(０)）種を活性種である二価のパラジウム種に戻す（再酸化する）ための、酸素以外の物質を意味する。具体例としては、塩化銅、酸化銀、ヘテロポリ酸などが挙げられるが、これらに限定されない。ヘテロポリ酸が好ましい。ここで、ヘテロポリ酸とは、モリブドバナドリン酸（ＨＰＭｏＶと略す（Ｈ３＋ｘＰＭｏ１２−ｘＶｘＯ４０・ｎＨ２Ｏ（ｘは０〜４の整数であり、ｎは１０〜３０の整数である）））またはその塩（例えば、ＮＰＭｏＶと略す（(ＮＨ４)６Ｈ３ＰＭｏ６Ｖ６Ｏ４０・ｎＨ２Ｏ（ｎは１０〜３０の整数である）））を意味し、具体例としては、ＮＰＭｏＶ、ＨＰＭｏＶ１、ＨＰＭｏＶ２、ＨＰＭｏＶ３などを含む。 “Further oxidizing agent” refers to a substance for oxidizing other substances. Specifically, the zero-valent palladium (Pd (0)) species derived from the palladium trifluoroacetate catalyst is an active species. It means a substance other than oxygen for returning (reoxidizing) to a divalent palladium species. Specific examples include, but are not limited to, copper chloride, silver oxide, heteropolyacid and the like. Heteropoly acids are preferred. Here, the heteropoly acid, is an integer of molybdenum de banner abbreviated as polyhedrin acid (HPMoV (H 3 + x PMo 12-x V x O 40 · nH 2 O (x is 0 to 4, n is 10 to 30 integer Or a salt thereof (for example, abbreviated as NPMoV ((NH 4 ) 6 H 3 PMo 6 V 6 O 40 · nH 2 O (n is an integer of 10 to 30))) Examples include NPMoV, HPMoV 1 , HPMoV 2 , HPMoV 3 and the like.
用語「配位性化合物」とは、遷移金属であるパラジウムと配位することが可能な化合物を意味し、ケトン、ホスフィン、およびスルホキシドからなる群から選ばれる化合物、またはそれらの混合物を意味する。ケトンが好ましい。具体例としては、アセチルアセトン、ジベンジリデンアセトン（ＤＢＡ）、トリフェニルホスフィン、およびジメチルスルホキシド（ＤＭＳＯ）等を挙げられ、アセチルアセトン、ジベンジリデンアセトンが好ましい。 The term “coordinating compound” means a compound capable of coordinating with palladium as a transition metal, and means a compound selected from the group consisting of ketone, phosphine, and sulfoxide, or a mixture thereof. Ketones are preferred. Specific examples include acetylacetone, dibenzylideneacetone (DBA), triphenylphosphine, and dimethylsulfoxide (DMSO), and acetylacetone and dibenzylideneacetone are preferred.
本願発明の製造方法を以下に詳しく説明する。
（反応式１）
(Reaction Formula 1)
本願発明の製造方法は、上記の反応式１に従って、１−アルケン（Ｉ）およびジシラン（II）を、トリフルオロ酢酸パラジウム（Ｐｄ(Ｏ(Ｃ(＝Ｏ)ＣＦ３)２）触媒の存在下、酸素雰囲気下で反応させることにより、アリルシラン類（（III）−Ａおよび（III）−Ｂ）を製造することができる。 According to the production method of the present invention, 1-alkene (I) and disilane (II) are converted into palladium trifluoroacetate (Pd (O (C (═O) CF 3 ) 2 ) catalyst according to the above reaction formula 1. Allylsilanes ((III) -A and (III) -B) can be produced by reacting in an oxygen atmosphere.
反応基質である、１−アルケン（Ｉ）、およびジシラン（II）はいずれも市販されているか、または当該有機化学の分野において知られる方法、或いはこれらに準じた方法により製造することができる。 The reaction substrates 1-alkene (I) and disilane (II) are both commercially available, or can be produced by methods known in the field of organic chemistry, or methods analogous thereto.
トリフルオロ酢酸パラジウムは、市販されているか、または当該有機金属化学の分野において知られる方法、或いはこれらに準じた方法により製造することができる。 Palladium trifluoroacetate is commercially available, or can be produced by a method known in the field of the organometallic chemistry or a method analogous thereto.
１−アルケンの配合量は、ジシランの配合量基準で５〜１００モル％当量で使用することができる。例えば、約１０〜８０モル％当量、約１０〜５０モル％当量、約２０〜約５０モル％当量、約２０〜約４０モル％当量を挙げられる。約４０モル％当量が好ましい。 The compounding quantity of 1-alkene can be used by 5-100 mol% equivalent on the compounding quantity basis of disilane. For example, about 10 to 80 mol% equivalent, about 10 to 50 mol% equivalent, about 20 to about 50 mol% equivalent, about 20 to about 40 mol% equivalent can be mentioned. About 40 mol% equivalent is preferred.
トリフルオロ酢酸パラジウム触媒の使用量は、ジシランの配合量基準で約０．０１〜０．５モル％当量であり、例えば約０．０１〜０．２モル％当量、約０．０５〜０．２モル％当量、約０．１〜０．２モル％当量が挙げられ、約０．１モル％当量が好ましい。 The amount of the palladium trifluoroacetate catalyst used is about 0.01 to 0.5 mol% equivalent, for example, about 0.01 to 0.2 mol% equivalent, about 0.05 to 0.00. 2 mol% equivalent, about 0.1-0.2 mol% equivalent is mentioned, and about 0.1 mol% equivalent is preferable.
該さらなる酸化剤の使用量は、ジシランの配合量基準で約０．００５〜０．２モル％当量であり、例えば約０．０１〜０．２モル％当量、約０．０１〜０．１モル％当量、約０．０２〜０．０５モル％当量が挙げられ、約０．０２モル％当量が好ましい。あるいは、当該使用量は、トリフルオロ酢酸パラジウム触媒の配合量基準で約０．０５〜２．０モル％当量であり、例えば約０．１〜２．０モル％当量、約０．１〜１．０モル％当量、約０．２〜０．５モル％当量が挙げられ、約０．２モル％当量が好ましい。 The amount of the additional oxidizing agent used is about 0.005 to 0.2 mol% equivalent based on the amount of disilane added, such as about 0.01 to 0.2 mol% equivalent, about 0.01 to 0.1. A mol% equivalent, about 0.02-0.05 mol% equivalent is mentioned, About 0.02 mol% equivalent is preferable. Or the said usage-amount is about 0.05-2.0 mol% equivalent on the basis of the compounding quantity of a trifluoroacetate palladium catalyst, for example, about 0.1-2.0 mol% equivalent, about 0.1-1 0.0 mol% equivalent, about 0.2-0.5 mol% equivalent is mentioned, and about 0.2 mol% equivalent is preferable.
該配位性化合物の使用量は、ジシランの配合量基準で約０．０１〜０．５モル％当量であり、例えば約０．０１〜０．２モル％当量、約０．０５〜０．２モル％当量、約０．１〜０．２モル％当量が挙げられ、約０．１モル％当量が好ましい。あるいは、当該使用量は、トリフルオロ酢酸パラジウム触媒の配合量基準で約０．５〜２．０モル％当量であり、例えば約１．０〜１．５モル％当量、約１．０〜１．２モル％当量が挙げられ、約１．０モル％当量が好ましい。 The amount of the coordination compound used is about 0.01 to 0.5 mol% equivalent based on the amount of disilane added, for example about 0.01 to 0.2 mol% equivalent, about 0.05 to about 0.00. 2 mol% equivalent, about 0.1-0.2 mol% equivalent is mentioned, and about 0.1 mol% equivalent is preferable. Alternatively, the amount used is about 0.5 to 2.0 mol% equivalent, for example, about 1.0 to 1.5 mol% equivalent, about 1.0 to 1 based on the blending amount of the palladium trifluoroacetate catalyst. .2 mol% equivalent is mentioned, and about 1.0 mol% equivalent is preferred.
本願発明の反応は有機溶媒中で行なうことが好ましい。反応有機溶媒は特に限定されず、飽和炭化水素（例えば、ペンタン、ヘキサン）、芳香族炭化水素（例えば、ベンゼン、トルエン、キシレン）、ハロゲン化炭化水素（例えば、ジクロロメタン、クロロホルム、１,２−ジクロロエタン）等が挙げられるが、それぞれ単独でまたは２種以上を混合して用いることができる。芳香族炭化水素が好ましく、例えば、トリフルオロベンゼン、トルエン、メシチレンを挙げられ、トリフルオロベンゼンが好ましい。 The reaction of the present invention is preferably carried out in an organic solvent. The reaction organic solvent is not particularly limited, and is a saturated hydrocarbon (for example, pentane, hexane), aromatic hydrocarbon (for example, benzene, toluene, xylene), halogenated hydrocarbon (for example, dichloromethane, chloroform, 1,2-dichloroethane). ), Etc., may be used alone or in admixture of two or more. Aromatic hydrocarbons are preferable, and examples thereof include trifluorobenzene, toluene, and mesitylene, and trifluorobenzene is preferable.
本願発明の反応は、室温（例えば、約２０℃）から高温（例えば、１００℃以上）で行なうことができ、通常室温から使用する反応溶媒の沸点であり、室温〜約４０℃が好ましい。 The reaction of the present invention can be carried out from room temperature (for example, about 20 ° C.) to high temperature (for example, 100 ° C. or more), and is usually the boiling point of the reaction solvent used from room temperature, preferably room temperature to about 40 ° C.
本願発明の反応は、酸素雰囲気下で行い、常圧（１ａｔｍ）または加圧容器（例えば、市販のステンレス加圧容器）中での加圧条件（約２〜５０ａｔｍ、約５〜１０ａｔｍ）下で行なうことができ、通常常圧で行なう。 The reaction of the present invention is carried out in an oxygen atmosphere, under normal pressure (1 atm) or under pressurized conditions (about 2 to 50 atm, about 5 to 10 atm) in a pressurized container (for example, a commercially available stainless steel pressurized container). Can be performed, usually at normal pressure.
また、本願発明の反応時間は、使用する溶媒、反応温度などの反応条件に依存して変わり得るが、数時間〜数日間で完結し、通常６時間〜約２４時間で完結し、約１２時間〜２４時間が好ましい。 The reaction time of the present invention can vary depending on the reaction conditions such as the solvent used and the reaction temperature, but it can be completed in several hours to several days, usually 6 hours to 24 hours, and about 12 hours. ~ 24 hours is preferred.
以下に実施例を挙げて本願発明を更に具体的に説明するが、本願発明はこれら実施例に限定されるものではない。化合物の確認は、各種分光学的分析の解析により行なった。具体的には、一次元プロトン、炭素１３核磁気共鳴スペクトル（１Ｈ ＮＭＲ、１３Ｃ ＮＭＲ）およびＤＥＰＴ(Distorsionless Enhancement by Polarization Transfer)、質量スペクトル（ＭＳ）（例えば、ガスクロマトグラフィー質量スペクトル（ＧＣ−ＭＳ））、赤外線吸収スペクトル(ＩＲ）の解析により行った。核磁気共鳴スペクトルには、テトラメチルシランを内部標準として用いた。また、生成物が公知化合物の場合は適宜文献名もあわせて記す。 The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples. The compound was confirmed by analysis of various spectroscopic analyses. Specifically, one-dimensional proton, carbon-13 nuclear magnetic resonance spectrum ( 1 H NMR, 13 C NMR), DEPT (Distorsionless Enhancement by Polarization Transfer), mass spectrum (MS) (for example, gas chromatography mass spectrum (GC− MS)), and infrared absorption spectrum (IR) analysis. Tetramethylsilane was used as an internal standard for the nuclear magnetic resonance spectrum. In addition, when the product is a known compound, the name of the document is also described as appropriate.
実施例中に用いた以下の略号を説明する。
Ｍｅはメチル基を、ＳｉＭｅ３はトリメチルシリル基を意味する。１−アルケン、ジシラン、トリフルオロ酢酸パラジウム、モリブドバナドリン酸またはその塩などの試薬は商業主から入手可能であり、あるいは通常の有機合成により製造可能である。
The following abbreviations used in the examples will be described.
Me represents a methyl group, and SiMe 3 represents a trimethylsilyl group. Reagents such as 1-alkene, disilane, palladium trifluoroacetate, molybdovanadolinic acid or a salt thereof can be obtained from a commercial owner, or can be produced by ordinary organic synthesis.
生成物の収率：定量的(GC 収率58%、選択比 α:γ=95:5)
GC-MS: 212(4%)[M]+,127(1),113(1),99(2),73(100),71(4),43(15)
参考文献：Y Tsuji, et al, Journal of Organic Chemistry, 1993, 58(14), 3607-8.
Product yield: quantitative (GC yield 58%, selectivity α: γ = 95: 5)
GC-MS: 212 (4%) [M] +, 127 (1), 113 (1), 99 (2), 73 (100), 71 (4), 43 (15)
Reference: Y Tsuji, et al, Journal of Organic Chemistry, 1993, 58 (14), 3607-8.
生成物の収率：定量的(GC 収率65%、選択比 α:γ=95:5)
GC-MS: 212(4%)[M]+,127(1),113(1),99(2),73(100),71(4),43(15)
参考文献：Y Tsuji, et al, Journal of Organic Chemistry, 1993, 58(14), 3607-8.
Product yield: quantitative (GC yield 65%, selectivity α: γ = 95: 5)
GC-MS: 212 (4%) [M] +, 127 (1), 113 (1), 99 (2), 73 (100), 71 (4), 43 (15)
Reference: Y Tsuji, et al, Journal of Organic Chemistry, 1993, 58 (14), 3607-8.
生成物の収率：定量的(GC 収率43%、選択比 α:γ=95:5)
GC-MS: 156(8%)[M]+,113(2),73(100),43(4),29(1)
参考文献：D. A. Evans, et al, Organic Letters, 2006, 8(10), 2071-2073.
Product yield: quantitative (GC yield 43%, selectivity α: γ = 95: 5)
GC-MS: 156 (8%) [M] +, 113 (2), 73 (100), 43 (4), 29 (1)
References: DA Evans, et al, Organic Letters, 2006, 8 (10), 2071-2073.
生成物の収率：定量的(GC 収率41%、選択比 α:γ=95:5)
GC-MS: 170(6.5%)[M]+,127(1),97(1),87(1),73(100),43(4)
参考文献：N. G. Bhat et al, Tetrahedron Letters, 2007, 48(24), 4267-4269.
Product yield: quantitative (GC yield 41%, selectivity α: γ = 95: 5)
GC-MS: 170 (6.5%) [M] +, 127 (1), 97 (1), 87 (1), 73 (100), 43 (4)
References: NG Bhat et al, Tetrahedron Letters, 2007, 48 (24), 4267-4269.
生成物の収率：定量的(GC 収率46%、選択比 α:γ=96:4)
GC-MS: 184(4.7%)[M]+,169(2),113(1),97(1),73(100),43(2),29(2)
参考文献：S. Okamoto, et al, Tetrahedron Letters, 1993, 34(15), 2509-12.
Product yield: quantitative (GC yield 46%, selectivity α: γ = 96: 4)
GC-MS: 184 (4.7%) [M] +, 169 (2), 113 (1), 97 (1), 73 (100), 43 (2), 29 (2)
References: S. Okamoto, et al, Tetrahedron Letters, 1993, 34 (15), 2509-12.
生成物の収率：定量的(GC 収率44%、選択比 α:γ=94:6)
GC-MS: 240(3.5%)[M]+,224(1),127(1),73(100),43(2),29(1)
参考文献：K. Itami, et al, Journal of the American Chemical Society, 2003, 125(20), 6058-6059.
Product yield: quantitative (GC yield 44%, selectivity α: γ = 94: 6)
GC-MS: 240 (3.5%) [M] +, 224 (1), 127 (1), 73 (100), 43 (2), 29 (1)
Reference: K. Itami, et al, Journal of the American Chemical Society, 2003, 125 (20), 6058-6059.
生成物の収率：定量的(GC 収率43%、選択比 α:γ=95:5)
GC-MS: 268(3%)[M]+,253(2),127(1),99(1),73(100),57(1),43(3),29(1)
参考文献：T. K. Sarkar, et al, Tetrahedron, 46(6), 1990, 1885-98.
Product yield: quantitative (GC yield 43%, selectivity α: γ = 95: 5)
GC-MS: 268 (3%) [M] +, 253 (2), 127 (1), 99 (1), 73 (100), 57 (1), 43 (3), 29 (1)
Reference: TK Sarkar, et al, Tetrahedron, 46 (6), 1990, 1885-98.
生成物の収率：定量的(GC 収率46%、選択比 α:γ=94:6)
GC-MS: 296(2%)[M]+,281(2),127(1),73(100),57(1),43(4),29(1)
Product yield: quantitative (GC yield 46%, selectivity α: γ = 94: 6)
GC-MS: 296 (2%) [M] +, 281 (2), 127 (1), 73 (100), 57 (1), 43 (4), 29 (1)
生成物の収率：定量的(GC 収率54%、選択比 α:γ=92:8)
GC-MS: 210(1%)[M]+,137(3),73(100),55(1),41(3),27(1)
Product yield: quantitative (GC yield 54%, selectivity α: γ = 92: 8)
GC-MS: 210 (1%) [M] +, 137 (3), 73 (100), 55 (1), 41 (3), 27 (1)
生成物の収率：定量的(GC 収率34.6%、選択比 α:γ=89:11)
GC-MS: 238(1%)[M]+,113(1),73(100),55(2),41(4),
参考文献：Ｊ．M. Concellon, et al, Synlett, 2007, (1), 75-78.
Product yield: quantitative (GC yield 34.6%, selectivity α: γ = 89: 11)
GC-MS: 238 (1%) [M] +, 113 (1), 73 (100), 55 (2), 41 (4),
References: J.M. M. Concellon, et al, Synlett, 2007, (1), 75-78.
生成物の収率：定量的(GC 収率50.8%、選択比 α:γ=>99:-)
GC-MS: 190(12%)[M]+,117(2),73(100),
参考文献：N. Selander, et al., Angewandte Chemie, International Edition, 2010, 49(24), 4051-4053.
Product yield: quantitative (GC yield 50.8%, selectivity α: γ => 99 :-)
GC-MS: 190 (12%) [M] +, 117 (2), 73 (100),
References: N. Selander, et al., Angewandte Chemie, International Edition, 2010, 49 (24), 4051-4053.
生成物の収率：定量的(GC 収率44.6%、選択比 α:γ=92:8)
GC-MS: 204(8%)[M]+,131(3),77(1),73(100),
参考文献：J. M. Concellon, et al., Synlett, 2007, (1) 75-78.
Product yield: quantitative (GC yield 44.6%, selectivity α: γ = 92: 8)
GC-MS: 204 (8%) [M] +, 131 (3), 77 (1), 73 (100),
Reference: JM Concellon, et al., Synlett, 2007, (1) 75-78.
生成物の収率：定量的(GC 収率42.2%、選択比 α:γ=>99:-)
GC-MS: 220(20%)[M]+,189(6),147(5),133(1),107(1),73(100),
参考文献：D. A. Evans,Organic Letters, 2006, 8(10), 2071-2073.
Product yield: quantitative (GC yield 42.2%, selectivity α: γ => 99 :-)
GC-MS: 220 (20%) [M] +, 189 (6), 147 (5), 133 (1), 107 (1), 73 (100),
References: DA Evans, Organic Letters, 2006, 8 (10), 2071-2073.
以下に、本願反応の種々の反応条件を変えた場合の結果を示す。
反応条件の検討結果を示す。
The examination result of reaction conditions is shown.
同様に、Ｐｄ触媒および配位性化合物の条件を変えた場合の結果を示す。
本願発明により、安価かつ入手安価な化学産業資源（フィードストック）である単純アルケンである１−アルケンを原料として用いて、パラジウム触媒存在下、酸素雰囲気下、ジシランとから、アリルシラン類を高い位置選択性で製造することができる。本願発明の製造方法は、金属塩、ハロゲン等の副生成物の発生を伴なわず、また酸化剤として酸素を利用できることから、低環境負荷型反応として有用であり、工業的に利用価値が高い。 According to the present invention, 1-alkene, a simple alkene, which is a cheap and inexpensive chemical industry resource (feedstock), is used as a raw material, and allylsilanes are highly selected from disilane in the presence of a palladium catalyst in an oxygen atmosphere. It can be manufactured with sex. The production method of the present invention is useful as a low environmental load reaction because it does not involve the generation of by-products such as metal salts and halogens, and can use oxygen as an oxidizing agent, and has high industrial utility value. .
Claims (9)
Ｒ１は、無置換または置換のアルキル基、無置換または置換のシクロアルキル基、無置換または置換の飽和へテロシクロアルキル基、無置換または置換のアルケニル基、無置換または置換のアリール基、および無置換または置換のヘテロアリール基からなる群から選ばれ；そして、
ｎは、１〜１５の整数である）
で表される１−アルケン、および
式（II）：
Ｒ２は、無置換のアルキル基または無置換のアリール基からなる群から選ばれる）
で表されるジシランを、トリフルオロ酢酸パラジウム（Ｐｄ(ＯＣ(＝Ｏ)ＣＦ３)２）触媒の存在下、酸素雰囲気下で反応させることによる、
式（III）：
で表されるアリルシラン類の製造方法。 Formula (I):
R 1 is an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted saturated heterocycloalkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group, and Selected from the group consisting of unsubstituted or substituted heteroaryl groups; and
n is an integer of 1 to 15)
A 1-alkene represented by formula (II):
R 2 is selected from the group consisting of an unsubstituted alkyl group or an unsubstituted aryl group)
By reacting a disilane represented by the following formula in the presence of a palladium trifluoroacetate (Pd (OC (═O) CF 3 ) 2 ) catalyst in an oxygen atmosphere:
Formula (III):
The manufacturing method of allylsilane represented by these.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011015146A JP5627483B2 (en) | 2011-01-27 | 2011-01-27 | Method for producing allylsilanes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011015146A JP5627483B2 (en) | 2011-01-27 | 2011-01-27 | Method for producing allylsilanes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2012153663A JP2012153663A (en) | 2012-08-16 |
| JP5627483B2 true JP5627483B2 (en) | 2014-11-19 |
Family
ID=46835800
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2011015146A Expired - Fee Related JP5627483B2 (en) | 2011-01-27 | 2011-01-27 | Method for producing allylsilanes |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5627483B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6635257B2 (en) * | 2015-11-04 | 2020-01-22 | 国立研究開発法人産業技術総合研究所 | Method for producing nitrogen-containing silicon-containing compound having both amino and silyl groups |
| JP7303502B2 (en) * | 2019-02-18 | 2023-07-05 | 学校法人 関西大学 | Method for producing allylsilane compound using palladium nanoparticle catalyst |
| JP7756360B2 (en) * | 2022-02-08 | 2025-10-20 | 学校法人 関西大学 | Method for producing 4-silyl-2-butenyl carboxylic acid ester compounds |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3104326A1 (en) * | 1981-02-07 | 1982-08-19 | Basf Ag, 6700 Ludwigshafen | "METHOD FOR PRODUCING AROMATIC SILANES" |
| JPH0680677A (en) * | 1992-09-04 | 1994-03-22 | Mitsubishi Petrochem Co Ltd | Method for producing bis (allylsilane) compound |
-
2011
- 2011-01-27 JP JP2011015146A patent/JP5627483B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2012153663A (en) | 2012-08-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Oh et al. | Nucleophile-assisted Pt-catalyzed cyclization of enynones: an access to synthesis of highly substituted furans | |
| Qiu et al. | Direct synthesis of arylboronic pinacol esters from arylamines | |
| Young et al. | A general approach to medium ring alkynes by using metathesis of cobalt hexacarbonyl containing dienes | |
| Koreeda et al. | Ruthenium-catalyzed reductive deamination and tandem alkylation of aniline derivatives | |
| Nicolaou et al. | Total synthesis of marinomycins A–C | |
| Wakabayashi et al. | Practical conversion of chlorosilanes into alkoxysilanes without generating HCl | |
| Faller et al. | Ruthenium catalyzed enyne cycloisomerizations and hydroxycyclizations with skeletal rearrangement | |
| Żak et al. | Efficient Functionalisation of Cubic Monovinylsilsesquioxanes via Cross‐Metathesis and Silylative Coupling with Olefins in the Presence of Ruthenium Complexes | |
| Hanada et al. | Hydrosilanes Are Not Always Reducing Agents for Carbonyl Compounds but Can Also Induce Dehydration: A Ruthenium‐Catalyzed Conversion of Primary Amides to Nitriles | |
| Lesbani et al. | Facile synthesis of hypersilylated aromatic compounds by palladium-mediated arylation reaction | |
| JP5627483B2 (en) | Method for producing allylsilanes | |
| Iwasaki et al. | Synthesis of Multisubstituted Olefins through Regio‐and Stereoselective Addition of Interelement Compounds Having B–Si, B–B, and Cl–S Bonds to Alkynes, and Subsequent Cross‐Couplings | |
| Li et al. | Haloamidation of alkynes and related reactions using zirconacycles and isocyanates | |
| Crandall et al. | Cis reduction of acetylenes by organocopper reagents | |
| Miyoshi et al. | One-pot method for α-phenylation of ketones using isoxazolidine and triphenylaluminum | |
| Zirngast et al. | Group 4 metallocene complexes of tris (trimethylsilyl) silylacetylene and related alkynes | |
| Li et al. | Metal-free defluorinative silylation of α-CF3-styrenes with silyl carboxylic acid by photo-redox catalysis | |
| Yanagisawa et al. | Dibutyltin dimethoxide-catalyzed aldol reaction of enol trichloroacetates | |
| Deng et al. | Peroxide-mediated efficient addition of cycloalkanes to imines | |
| CN102791661B (en) | The manufacture method of difluoro cyclopropane compound | |
| Oukessou et al. | The triazolyl analogue of the trityl cation | |
| Cordier et al. | An efficient method for synthesising unsymmetrical silaketals: substrates for ring-closing, including macrocycle-closing, metathesis | |
| Kinoshita et al. | Syntheses of substituted benzosiloles and siloles by diisobutylaluminium hydride-promoted cyclization of 1-silyl-2-(2-silylethynyl) benzenes and 1, 4-disilylalk-3-en-1-ynes | |
| Hafner et al. | Building blocks for oligomeric siloxanes–selective chlorination of hydrido-siloxanes | |
| Rost et al. | Methylrhenium oxides |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20131002 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20140723 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20140729 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140827 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20140924 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20140930 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5627483 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20140723 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |