JP5057301B2 - Dialkylsilanol compound and process for producing the same - Google Patents
Dialkylsilanol compound and process for producing the same Download PDFInfo
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- JP5057301B2 JP5057301B2 JP2006092200A JP2006092200A JP5057301B2 JP 5057301 B2 JP5057301 B2 JP 5057301B2 JP 2006092200 A JP2006092200 A JP 2006092200A JP 2006092200 A JP2006092200 A JP 2006092200A JP 5057301 B2 JP5057301 B2 JP 5057301B2
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- 150000001875 compounds Chemical class 0.000 title claims description 66
- 238000000034 method Methods 0.000 title description 16
- 125000004036 acetal group Chemical group 0.000 claims description 54
- -1 dialkylsilane compound Chemical class 0.000 claims description 41
- 239000003054 catalyst Substances 0.000 claims description 36
- 125000000217 alkyl group Chemical group 0.000 claims description 32
- 125000003545 alkoxy group Chemical group 0.000 claims description 29
- 125000004122 cyclic group Chemical group 0.000 claims description 28
- 125000002015 acyclic group Chemical group 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 description 45
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 26
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 21
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 20
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- 239000007788 liquid Substances 0.000 description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 150000002576 ketones Chemical class 0.000 description 14
- 239000002994 raw material Substances 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 12
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 12
- 239000003377 acid catalyst Substances 0.000 description 12
- 238000010992 reflux Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 239000012044 organic layer Substances 0.000 description 11
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 10
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 9
- 230000032683 aging Effects 0.000 description 9
- 238000009835 boiling Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000007818 Grignard reagent Substances 0.000 description 8
- 150000004795 grignard reagents Chemical class 0.000 description 8
- ZQCXQVUKJLRHMR-UHFFFAOYSA-N [4-(dimethoxymethyl)phenyl]-methoxy-dimethylsilane Chemical compound COC(OC)C1=CC=C([Si](C)(C)OC)C=C1 ZQCXQVUKJLRHMR-UHFFFAOYSA-N 0.000 description 7
- 150000002170 ethers Chemical class 0.000 description 7
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 239000004927 clay Substances 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 6
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- 0 *c(cc1)ccc1N(*)* Chemical compound *c(cc1)ccc1N(*)* 0.000 description 5
- LIBWNYSEEPZNCD-UHFFFAOYSA-N COC(C1=CC=C(C=C1)[SiH](C)C)OC Chemical compound COC(C1=CC=C(C=C1)[SiH](C)C)OC LIBWNYSEEPZNCD-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 238000004440 column chromatography Methods 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- VYMVPLXVLZQVDT-UHFFFAOYSA-N C[SiH](C1=CC=C(C=C1)C1OCCCO1)C Chemical compound C[SiH](C1=CC=C(C=C1)C1OCCCO1)C VYMVPLXVLZQVDT-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- YGHUUVGIRWMJGE-UHFFFAOYSA-N chlorodimethylsilane Chemical compound C[SiH](C)Cl YGHUUVGIRWMJGE-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000002825 nitriles Chemical class 0.000 description 4
- 150000003961 organosilicon compounds Chemical class 0.000 description 4
- 239000003507 refrigerant Substances 0.000 description 4
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- KEOUUJPRWKAXGM-UHFFFAOYSA-N 4-[methoxy(dimethyl)silyl]benzaldehyde Chemical compound C(=O)C1=CC=C(C=C1)[Si](OC)(C)C KEOUUJPRWKAXGM-UHFFFAOYSA-N 0.000 description 3
- PEVOTVIPDZCGND-UHFFFAOYSA-N 4-dimethylsilylbenzaldehyde Chemical compound C(=O)C1=CC=C(C=C1)[SiH](C)C PEVOTVIPDZCGND-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- ZAICYGHCHXXSDO-UHFFFAOYSA-M magnesium;2-phenyl-1,3-dioxane;bromide Chemical compound [Mg+2].[Br-].O1CCCOC1C1=CC=[C-]C=C1 ZAICYGHCHXXSDO-UHFFFAOYSA-M 0.000 description 3
- ZDYVRSLAEXCVBX-UHFFFAOYSA-N pyridinium p-toluenesulfonate Chemical compound C1=CC=[NH+]C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 ZDYVRSLAEXCVBX-UHFFFAOYSA-N 0.000 description 3
- TWFNGPDYMFEHOB-UHFFFAOYSA-N 1-bromo-4-(dimethoxymethyl)benzene Chemical compound COC(OC)C1=CC=C(Br)C=C1 TWFNGPDYMFEHOB-UHFFFAOYSA-N 0.000 description 2
- HMXWGZTXWOBGOC-UHFFFAOYSA-N 2-(4-bromophenyl)-1,3-dioxane Chemical compound C1=CC(Br)=CC=C1C1OCCCO1 HMXWGZTXWOBGOC-UHFFFAOYSA-N 0.000 description 2
- NDOPHXWIAZIXPR-UHFFFAOYSA-N 2-bromobenzaldehyde Chemical compound BrC1=CC=CC=C1C=O NDOPHXWIAZIXPR-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- IGERFAHWSHDDHX-UHFFFAOYSA-N 1,3-dioxanyl Chemical group [CH]1OCCCO1 IGERFAHWSHDDHX-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- ALLDMNKTZGXFNC-UHFFFAOYSA-N 4-[chloro(dimethyl)silyl]benzonitrile Chemical compound C[Si](C)(Cl)C1=CC=C(C#N)C=C1 ALLDMNKTZGXFNC-UHFFFAOYSA-N 0.000 description 1
- QNDGKGDRGMEOIX-UHFFFAOYSA-N 4-[hydroxy(dimethyl)silyl]benzaldehyde Chemical compound C(=O)C1=CC=C(C=C1)[Si](O)(C)C QNDGKGDRGMEOIX-UHFFFAOYSA-N 0.000 description 1
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 1
- RPNVCEJQKNSNMJ-UHFFFAOYSA-N CC(c(cc1)ccc1[SiH](C)C)OCCCO Chemical compound CC(c(cc1)ccc1[SiH](C)C)OCCCO RPNVCEJQKNSNMJ-UHFFFAOYSA-N 0.000 description 1
- BJYZOLZNCHIJKC-UHFFFAOYSA-N CC(c(cc1)ccc1[Si](C)(C)O)OCCCO Chemical compound CC(c(cc1)ccc1[Si](C)(C)O)OCCCO BJYZOLZNCHIJKC-UHFFFAOYSA-N 0.000 description 1
- ZOENLNONBYLOAZ-UHFFFAOYSA-N CC1(C(C=C(C=C1)C)[SiH2]O)C1OCCCO1 Chemical compound CC1(C(C=C(C=C1)C)[SiH2]O)C1OCCCO1 ZOENLNONBYLOAZ-UHFFFAOYSA-N 0.000 description 1
- PHUOLKUYOPGMDM-UHFFFAOYSA-N CCO[SiH2]C1=C(C=CC(=C1)C)C1OCCCO1 Chemical compound CCO[SiH2]C1=C(C=CC(=C1)C)C1OCCCO1 PHUOLKUYOPGMDM-UHFFFAOYSA-N 0.000 description 1
- DCCBWTNHOQAQMJ-UHFFFAOYSA-N Cc(cc1)ccc1[SiH+](C)C Chemical compound Cc(cc1)ccc1[SiH+](C)C DCCBWTNHOQAQMJ-UHFFFAOYSA-N 0.000 description 1
- IUPJYUHGZZWDQS-UHFFFAOYSA-N Cc(cc1)ccc1[Si](C)(C)CCO Chemical compound Cc(cc1)ccc1[Si](C)(C)CCO IUPJYUHGZZWDQS-UHFFFAOYSA-N 0.000 description 1
- GIQXGMLMIZAKLB-UHFFFAOYSA-N Cc(cc1)ccc1[Si](C)(C)OC Chemical compound Cc(cc1)ccc1[Si](C)(C)OC GIQXGMLMIZAKLB-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- SAMFMZLIACNVGJ-UHFFFAOYSA-N [4-(1,3-dioxolan-2-yl)phenyl]-dimethylsilane Chemical compound O1C(OCC1)C1=CC=C(C=C1)[SiH](C)C SAMFMZLIACNVGJ-UHFFFAOYSA-N 0.000 description 1
- FLUSWRHFOVJUNC-UHFFFAOYSA-N [4-(dimethoxymethyl)phenyl]-hydroxy-dimethylsilane Chemical compound COC(C1=CC=C(C=C1)[Si](O)(C)C)OC FLUSWRHFOVJUNC-UHFFFAOYSA-N 0.000 description 1
- XQPGBELXORESPW-UHFFFAOYSA-M [Br-].COC(OC)C1=CC=C([Mg+])C=C1 Chemical compound [Br-].COC(OC)C1=CC=C([Mg+])C=C1 XQPGBELXORESPW-UHFFFAOYSA-M 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- OIKHZBFJHONJJB-UHFFFAOYSA-N dimethyl(phenyl)silicon Chemical compound C[Si](C)C1=CC=CC=C1 OIKHZBFJHONJJB-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- FDTBETCIPGWBHK-UHFFFAOYSA-N hydroxy-dimethyl-phenylsilane Chemical compound C[Si](C)(O)C1=CC=CC=C1 FDTBETCIPGWBHK-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- REQXNMOSXYEQLM-UHFFFAOYSA-N methoxy-dimethyl-phenylsilane Chemical compound CO[Si](C)(C)C1=CC=CC=C1 REQXNMOSXYEQLM-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- UUEVFMOUBSLVJW-UHFFFAOYSA-N oxo-[[1-[2-[2-[2-[4-(oxoazaniumylmethylidene)pyridin-1-yl]ethoxy]ethoxy]ethyl]pyridin-4-ylidene]methyl]azanium;dibromide Chemical compound [Br-].[Br-].C1=CC(=C[NH+]=O)C=CN1CCOCCOCCN1C=CC(=C[NH+]=O)C=C1 UUEVFMOUBSLVJW-UHFFFAOYSA-N 0.000 description 1
- ANRQGKOBLBYXFM-UHFFFAOYSA-M phenylmagnesium bromide Chemical compound Br[Mg]C1=CC=CC=C1 ANRQGKOBLBYXFM-UHFFFAOYSA-M 0.000 description 1
- 229920002577 polybenzoxazole Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Description
本発明は、半導体用絶縁膜機能性樹脂や液晶化合物の原料として有用な化合物であるジアルキルシラノール化合物およびその製造方法に関する。 The present invention relates to a dialkylsilanol compound which is a useful compound as a raw material for an insulating film functional resin for semiconductors and a liquid crystal compound, and a method for producing the same.
ホルミルフェニル基を有するシロキサンは、高い官能基変換能を有しており、半導体関連分野においてポリベンゾオキサゾールの原料、又は液晶化合物の原料として有用である。当該シロキサンを合成する方法としては、テトラメチルジフェニルジシロキサン−４，４′−ジカルボン酸クロリドをトリ−ｔｅｒｔ−ブトキシリチウムアルミニウムハイドライドにより還元する方法が知られている〔非特許文献１〕。この方法は高価な還元剤を基質に対して２当量以上必要とし、また収率も４０％であり、工業的製法としてはとても満足いくものではない。 Siloxane having a formylphenyl group has a high functional group conversion ability and is useful as a raw material for polybenzoxazole or a raw material for liquid crystal compounds in the field of semiconductors. As a method for synthesizing the siloxane, a method of reducing tetramethyldiphenyldisiloxane-4,4′-dicarboxylic acid chloride with tri-tert-butoxylithium aluminum hydride is known [Non-patent Document 1]. This method requires 2 equivalents or more of an expensive reducing agent, and the yield is 40%, which is not very satisfactory as an industrial production method.
一方、ホルミルフェニル基を有するジアルキルシラノール化合物が合成できれば、脱水縮合反応により容易に当該シロキサンを合成することが可能と思われるが、それらの合成例はこれまで報告されていない。さらに、その前駆体となり得るアセタール置換フェニル基を有するジアルキルシラノール化合物の合成例もこれまで報告されていない。 On the other hand, if a dialkylsilanol compound having a formylphenyl group can be synthesized, the siloxane can be easily synthesized by a dehydration condensation reaction. However, synthesis examples thereof have not been reported so far. Furthermore, no synthesis examples of dialkylsilanol compounds having an acetal-substituted phenyl group that can be a precursor thereof have been reported so far.
また、ホルミルフェニル基又はアセタール置換フェニル基を有するジアルキルシラノール化合物の前駆体としては、ホルミルフェニル基又はアセタール置換フェニル基を有する、ジアルキルシラン化合物、ジアルキルオルガノオキシ化合物が考えられるが、そのような化合物のうち、４−ホルミルフェニルジメチルシラン〔非特許文献１〕、２−（４−ジメチルシリルフェニル）−１，３−ジオキソラン〔非特許文献２〕、〔４−（ジメトキシメチル）フェニル〕メトキシジメチルシラン〔非特許文献３〕が既に知られている。 Moreover, as a precursor of a dialkylsilanol compound having a formylphenyl group or an acetal-substituted phenyl group, a dialkylsilane compound or a dialkylorganooxy compound having a formylphenyl group or an acetal-substituted phenyl group can be considered. Among them, 4-formylphenyldimethylsilane [Non-patent document 1], 2- (4-dimethylsilylphenyl) -1,3-dioxolane [Non-patent document 2], [4- (dimethoxymethyl) phenyl] methoxydimethylsilane [ Non-Patent Document 3] is already known.
しかし、４−ホルミルフェニルジメチルシランは４−シアノフェニルジメチルクロロシランを２当量のジイソブチルアルミニウムハイドライドにより還元して得られるが、高価な還元剤を使用し、また収率は１１％と非常に低いものである。〔４−（ジメトキシメチル）フェニル〕メトキシジメチルシランは、４−（ジメトキシメチル）ブロモベンゼンを−７８℃にてリチオ化した後、ジメチルジメトキシシランと反応させて得られるが、極低温下の反応であり、また収率も５８％と低く、満足いくものではない。 However, 4-formylphenyldimethylsilane is obtained by reducing 4-cyanophenyldimethylchlorosilane with 2 equivalents of diisobutylaluminum hydride, but uses an expensive reducing agent, and the yield is very low at 11%. is there. [4- (Dimethoxymethyl) phenyl] methoxydimethylsilane is obtained by lithiation of 4- (dimethoxymethyl) bromobenzene at −78 ° C. and then reaction with dimethyldimethoxysilane. In addition, the yield is as low as 58%, which is not satisfactory.
本発明の目的は、ホルミルフェニル基又はアセタール置換フェニル基を有するジアルキルシラノール化合物およびその製造方法を提供することにある。 An object of the present invention is to provide a dialkylsilanol compound having a formylphenyl group or an acetal-substituted phenyl group and a method for producing the same.
本発明者らは、上記目的を達成するにあたり鋭意研究を重ねた結果、ホルミルフェニル基又はアセタール置換フェニル基を有するジアルキルシラノール化合物およびその製造方法を見出し、本発明をなすに至った。
すなわち、本発明の第１は、一般式（１）
で表されるジアルキルシラノール化合物に関する。
本発明の第２は、一般式（２）
で表されるジアルキルシラン化合物を、触媒の存在下に水と反応させることを特徴とする、一般式（１）
で表されるジアルキルシラノール化合物の製造方法に関する。
本発明の第３は、一般式（３）
で表されるジアルキルオルガノオキシシラン化合物を、水と反応させることを特徴とする、一般式（１）
で表されるジアルキルシラノール化合物の製造方法に関する。
As a result of intensive studies to achieve the above object, the present inventors have found a dialkylsilanol compound having a formylphenyl group or an acetal-substituted phenyl group and a method for producing the same, and have made the present invention.
That is, the first of the present invention is the general formula (1)
It is related with the dialkyl silanol compound represented by these.
The second of the present invention is the general formula (2)
A dialkylsilane compound represented by general formula (1) is reacted with water in the presence of a catalyst:
The manufacturing method of the dialkyl silanol compound represented by these.
The third of the present invention is the general formula (3)
A dialkylorganooxysilane compound represented by general formula (1) is reacted with water:
The manufacturing method of the dialkyl silanol compound represented by these.
以下、本発明につき更に詳しく説明するが、本発明は以下に限定されるものではない。本発明の化合物において、Ｒ１は、ホルミル基、ジメトキシメチル基、
まず、一般式（１）で表されるジアルキルシラノール化合物の製造方法を［イ−１］（請求項２に対応）及び［イ−２］（請求項３に対応）に記載する。 First, the production method of the dialkylsilanol compound represented by the general formula (1) is described in [A-1] (corresponding to claim 2) and [A-2] (corresponding to claim 3).
［イ−１］．一般式（１）
で表されるジアルキルシラノール化合物は、一般式（２）
で表されるジアルキルシラン化合物を、触媒（Ａ）の存在下に水と反応させることにより製造することができる。
[A-1]. General formula (1)
The dialkylsilanol compound represented by the general formula (2)
Can be produced by reacting with water in the presence of the catalyst (A).
触媒（Ａ）は、パラジウム、白金、ルテニウム、ロジウムなどの白金族元素を含有する白金族触媒、テトラブチルアンモニウムフルオリド、水酸化ナトリウムなどの塩基触媒が挙げられる。白金族触媒は、白金族元素を含有する触媒であれば特に制限されない。例えば、アルミナ、シリカ、活性炭などの担体に担持した白金族触媒が挙げられる。触媒（Ａ）として、好ましくはパラジウム炭素触媒である。触媒（Ａ）の使用量は一般式（２）で表される化合物に対して０．０１質量％以上（白金族触媒の場合は金属換算で５×１０−４質量％以上）であり、好ましくは０．０１〜１０質量％（白金族触媒の場合は金属換算で５×１０−４〜０．５質量％）である。
水の使用量は一般式（２）で表される化合物に対して１倍モル以上であり、好ましくは１〜５倍モルである。原料の仕込み手順は任意であるが、例えば、一般式（２）で表される化合物と触媒（Ａ）を仕込み、これに水を滴下してもよく、あるいは、水と触媒（Ａ）を仕込んだ後、一般式（２）で表される化合物を滴下してもよい。
反応において溶媒は必要としないが、必要に応じて使用してもよく、反応を阻害しないものであれば特に限定されない。そのような溶媒としては、ペンタン、ヘキサン、ヘプタン、オクタン、ベンゼン、トルエン、キシレンなどの炭化水素類、テトラヒドロフラン、ジオキサン、ジメトキシエタンなどのエーテル類、メチルエチルケトン、アセトンなどのケトン類、酢酸エチルなどのエステル類、ジメチルホルムアミドなどのアミド類、アセトニトリルなどのニトリル類が挙げられる。
反応時間は、反応物の種類及び量にもよるが、およそ１〜８時間以内で終了する。
また、反応は空気雰囲気下で行うことができるが、水素ガスが発生するため不活性ガス雰囲気下で行うのが好ましい。反応終了後、目的物を単離するには、蒸留、抽出、カラムクロマトグラフィーなどの方法が使用できる。
Examples of the catalyst (A) include platinum group catalysts containing platinum group elements such as palladium, platinum, ruthenium and rhodium, and base catalysts such as tetrabutylammonium fluoride and sodium hydroxide. The platinum group catalyst is not particularly limited as long as it is a catalyst containing a platinum group element. For example, a platinum group catalyst supported on a carrier such as alumina, silica, activated carbon or the like can be used. The catalyst (A) is preferably a palladium carbon catalyst. The amount of the catalyst (A) used is 0.01% by mass or more based on the compound represented by the general formula (2) (in the case of a platinum group catalyst, 5 × 10 −4 % by mass or more in terms of metal), preferably Is 0.01 to 10% by mass (in the case of a platinum group catalyst, 5 × 10 −4 to 0.5% by mass in terms of metal).
The usage-amount of water is 1 time mole or more with respect to the compound represented by General formula (2), Preferably it is 1-5 times mole. The raw material charging procedure is arbitrary. For example, the compound represented by the general formula (2) and the catalyst (A) may be charged, and water may be added dropwise thereto, or water and the catalyst (A) may be charged. Thereafter, the compound represented by the general formula (2) may be added dropwise.
Although a solvent is not required in the reaction, it may be used as necessary, and is not particularly limited as long as it does not inhibit the reaction. Examples of such solvents include hydrocarbons such as pentane, hexane, heptane, octane, benzene, toluene and xylene, ethers such as tetrahydrofuran, dioxane and dimethoxyethane, ketones such as methyl ethyl ketone and acetone, and esters such as ethyl acetate. Amides such as dimethylformamide, and nitriles such as acetonitrile.
Although the reaction time depends on the type and amount of the reactants, the reaction is completed within about 1 to 8 hours.
In addition, the reaction can be performed in an air atmosphere, but hydrogen gas is generated, so that the reaction is preferably performed in an inert gas atmosphere. In order to isolate the target product after completion of the reaction, methods such as distillation, extraction and column chromatography can be used.
［イ−２］また、一般式（１）で表されるジアルキルシラノール化合物は、一般式（３）
で表されるジアルキルオルガノオキシシラン化合物を、水と反応させることにより製造することができる。
[A-2] The dialkylsilanol compound represented by the general formula (1) is represented by the general formula (3).
The dialkylorganooxysilane compound represented by these can be manufactured by making it react with water.
水の使用量は一般式（３）で表される化合物に対して１倍モル以上であり、好ましくは１〜１０倍モルである。原料の仕込み手順は任意であるが、例えば、一般式（３）で表される化合物を仕込み、これに水を滴下してもよく、あるいは、水を仕込んだ後、一般式（３）で表される化合物を滴下してもよい。
反応において溶媒は必要としないが、必要に応じて使用しても良く、反応を阻害しないものであれば特に限定されない。そのような溶媒としては、ペンタン、ヘキサン、ヘプタン、オクタン、ベンゼン、トルエン、キシレンなどの炭化水素類、テトラヒドロフラン、ジオキサン、ジメトキシエタンなどのエーテル類が挙げられる。
反応温度は特に限定されないが、２０℃程度で反応は進行する。反応時間は、反応物の種類及び量にもよるが、およそ１〜８時間以内で終了する。また、反応は空気雰囲気下で行うことができるが、不活性ガス雰囲気下で行ってもよい。反応終了後、目的物を単離するには、蒸留、抽出、カラムクロマトグラフィーなどの方法が使用できる。
The usage-amount of water is 1 times mole or more with respect to the compound represented by General formula (3), Preferably it is 1-10 times mole. The raw material charging procedure is arbitrary. For example, the compound represented by the general formula (3) may be charged, and water may be added dropwise thereto, or after water is charged, the raw material may be represented by the general formula (3). The compound to be prepared may be added dropwise.
Although a solvent is not required in the reaction, it may be used as necessary and is not particularly limited as long as it does not inhibit the reaction. Examples of such a solvent include hydrocarbons such as pentane, hexane, heptane, octane, benzene, toluene and xylene, and ethers such as tetrahydrofuran, dioxane and dimethoxyethane.
The reaction temperature is not particularly limited, but the reaction proceeds at about 20 ° C. Although the reaction time depends on the type and amount of the reactants, the reaction is completed within about 1 to 8 hours. The reaction can be performed in an air atmosphere, but may be performed in an inert gas atmosphere. In order to isolate the target product after completion of the reaction, methods such as distillation, extraction and column chromatography can be used.
次に、一般式（１）で表されるジアルキルシラノール化合物の原料である一般式（２）で表されるジアルキルシラン化合物の製造方法を［ロ−１］及び［ロ−２］に記載する。 Next, the production method of the dialkylsilane compound represented by the general formula (2), which is a raw material of the dialkylsilanol compound represented by the general formula (1), will be described in [Ro-1] and [Ro-2].
［ロ−１］一般式（２）で表されるジアルキルシラン化合物において、Ｒ１が５〜６員環の環状アセタール基又は炭素数１〜２のアルコキシ基を有する非環状アセタール基の場合、すなわち、一般式（６）
で表される化合物は、一般式（７）
で表される芳香族ハロゲン化物とマグネシウムとから得られる一般式（８）
で表されるグリニヤール試薬に、一般式（９）
で表される有機ケイ素化合物を反応させることにより製造することができる。
なお、前記一般式（６）の化合物において、Ｒ７が炭素数１〜２のアルコキシ基を有する非環状アセタール基の場合、すなわち一般式（１０）
で表される化合物は新規化合物であるが、Ｒ７が５〜６員環の環状アセタール基やホルミル基の場合は公知化合物である。
[B-1] In the dialkylsilane compound represented by the general formula (2), when R 1 is a 5- to 6-membered cyclic acetal group or an acyclic acetal group having a C 1-2 alkoxy group , And general formula (6)
The compound represented by general formula (7)
General formula (8) obtained from an aromatic halide represented by formula (II) and magnesium
A Grignard reagent represented by general formula (9)
It can manufacture by making the organosilicon compound represented by these react.
In the compound of the general formula (6), when R 7 is an acyclic acetal group having an alkoxy group having 1 to 2 carbon atoms , that is, the general formula (10)
Is a new compound, but is a known compound when R 7 is a 5- to 6-membered cyclic acetal group or formyl group.
一般式（８）で表されるグリニヤール試薬は、一般式（７）で表される芳香族ハロゲン化物とマグネシウムとから通常の条件（溶媒としてエーテル類をマグネシウムに対し２当量以上使用し、−２０℃〜還流温度程度にて反応を行う。）により調製することができる。
一般式（６）で表される化合物の製造において、一般式（９）で表される有機ケイ素化合物の使用量は、一般式（８）で表されるグリニヤール試薬に対して０．８倍モル以上であり、好ましくは０．９５〜１．０倍モルである。
原料の仕込み手順は任意であるが、例えば、一般式（８）で表されるグリニヤール試薬を仕込み、これに一般式（９）で表される有機ケイ素化合物を滴下してもよく、あるいは、一般式（９）で表される有機ケイ素化合物を仕込んだ後、一般式（８）で表されるグリニヤール試薬を滴下してもよい。
反応において溶媒は必要としないが、必要に応じて使用してもよく、反応を阻害しないものであれば特に限定されない。そのような溶媒としては、ペンタン、ヘキサン、ヘプタン、オクタン、ベンゼン、トルエン、キシレンなどの炭化水素類、テトラヒドロフラン、ジオキサン、ジメトキシエタンなどのエーテル類が挙げられる。
反応温度は特に限定されないが、２０℃程度で反応は進行する。反応時間は、反応物の種類及び量にもよるが、およそ１〜８時間以内で終了する。また、反応はチッソ、アルゴンなどの不活性ガス雰囲気下で行うことが望ましい。
The Grignard reagent represented by the general formula (8) is prepared from the aromatic halide represented by the general formula (7) and magnesium under the usual conditions (2 equivalents or more of ethers with respect to magnesium as a solvent, −20 The reaction is carried out at a temperature of from about ° C to the reflux temperature.
In the production of the compound represented by the general formula (6), the amount of the organosilicon compound represented by the general formula (9) is 0.8 times the mol of the Grignard reagent represented by the general formula (8). It is above, Preferably it is 0.95-1.0 times mole.
The raw material charging procedure is arbitrary. For example, a Grignard reagent represented by the general formula (8) may be charged, and an organosilicon compound represented by the general formula (9) may be added dropwise thereto. After preparing the organosilicon compound represented by the formula (9), a Grignard reagent represented by the general formula (8) may be added dropwise.
Although a solvent is not required in the reaction, it may be used as necessary, and is not particularly limited as long as it does not inhibit the reaction. Examples of such a solvent include hydrocarbons such as pentane, hexane, heptane, octane, benzene, toluene and xylene, and ethers such as tetrahydrofuran, dioxane and dimethoxyethane.
The reaction temperature is not particularly limited, but the reaction proceeds at about 20 ° C. Although the reaction time depends on the type and amount of the reactants, the reaction is completed within about 1 to 8 hours. The reaction is desirably performed in an inert gas atmosphere such as nitrogen or argon.
［ロ−２］また、一般式（２）で表されるジアルキルシラン化合物において、Ｒ１がホルミル基の場合、すなわち、一般式（１１）
で表されるホルミルフェニルジアルキルシランは、一般式（６）
で表される化合物を、酸触媒（Ｂ）の存在下に加水分解させるか、又は酸触媒（Ｂ）の存在下にケトン類と反応させることにより製造することができる。
[B-2] In the dialkylsilane compound represented by the general formula (2), when R 1 is a formyl group, that is, the general formula (11)
The formylphenyldialkylsilane represented by the general formula (6)
Can be produced by hydrolysis in the presence of an acid catalyst (B) or by reacting with a ketone in the presence of an acid catalyst (B).
酸触媒（Ｂ）は特に限定されないが、例えば、塩酸、硫酸などの鉱酸、ｐ−トルエンスルホン酸、ピリジニウム−ｐ−トルエンスルホン酸などの有機酸、活性白土などの固体酸などが挙げられる。酸触媒（Ｂ）の使用量は一般式（６）で表される化合物に対して０．０１質量％以上であり、好ましくは０．０１〜１０質量％である。
水の使用量は一般式（６）で表される化合物に対して１倍モル以上、好ましくは１０〜５０倍モルである。
ケトン類は、シクロヘキサノン、メチルエチルケトン、アセトンなどが挙げられる。ケトン類の使用量は一般式（６）で表される化合物に対して１倍モル以上、好ましくは１０〜５０倍モルである。
原料の仕込み手順は任意であるが、例えば、一般式（６）で表される化合物と酸触媒（Ｂ）を仕込み、これに水又はケトン類を滴下してもよく、あるいは、酸触媒（Ｂ）と水、又は酸触媒（Ｂ）とケトン類を仕込んだ後、一般式（６）で表される化合物を滴下してもよい。
反応において溶媒は必要としないが、必要に応じて使用してもよく、反応を阻害しないものであれば特に限定されない。そのような溶媒としては、ペンタン、ヘキサン、ヘプタン、オクタン、ベンゼン、トルエン、キシレンなどの炭化水素類、テトラヒドロフラン、ジオキサン、ジメトキシエタンなどのエーテル類、メタノール、エタノールなどのアルコール類、メチルエチルケトン、アセトンなどのケトン類、酢酸エチルなどのエステル類、ジメチルホルムアミドなどのアミド類、アセトニトリルなどのニトリル類が挙げられる。
反応温度は特に限定されないが、２０℃程度で反応は進行する。反応時間は、反応物の種類及び量にもよるが、およそ１〜８時間以内で終了する。また、反応は空気雰囲気下で行うことができるが、不活性ガス雰囲気下で行ってもよい。反応終了後、目的物を単離するには、蒸留、抽出、カラムクロマトグラフィーなどの方法が使用できる。
The acid catalyst (B) is not particularly limited, and examples thereof include mineral acids such as hydrochloric acid and sulfuric acid, organic acids such as p-toluenesulfonic acid and pyridinium-p-toluenesulfonic acid, and solid acids such as activated clay. The usage-amount of an acid catalyst (B) is 0.01 mass% or more with respect to the compound represented by General formula (6), Preferably it is 0.01-10 mass%.
The usage-amount of water is 1 time mole or more with respect to the compound represented by General formula (6), Preferably it is 10-50 times mole.
Examples of ketones include cyclohexanone, methyl ethyl ketone, and acetone. The amount of the ketone used is 1 time mol or more, preferably 10 to 50 times mol for the compound represented by the general formula (6).
The raw material charging procedure is arbitrary. For example, the compound represented by the general formula (6) and the acid catalyst (B) may be charged, and water or ketones may be added dropwise thereto, or the acid catalyst (B ) And water, or acid catalyst (B) and ketones, and then the compound represented by general formula (6) may be added dropwise.
Although a solvent is not required in the reaction, it may be used as necessary, and is not particularly limited as long as it does not inhibit the reaction. Examples of such solvents include hydrocarbons such as pentane, hexane, heptane, octane, benzene, toluene, and xylene, ethers such as tetrahydrofuran, dioxane, and dimethoxyethane, alcohols such as methanol and ethanol, methyl ethyl ketone, and acetone. Examples include ketones, esters such as ethyl acetate, amides such as dimethylformamide, and nitriles such as acetonitrile.
The reaction temperature is not particularly limited, but the reaction proceeds at about 20 ° C. Although the reaction time depends on the type and amount of the reactants, the reaction is completed within about 1 to 8 hours. The reaction can be performed in an air atmosphere, but may be performed in an inert gas atmosphere. In order to isolate the target product after completion of the reaction, methods such as distillation, extraction and column chromatography can be used.
続いて、一般式（１）で表されるジアルキルシラノール化合物の原料である一般式（３）で表されるジアルキルオルガノオキシシラン化合物の製造方法を［ハ−１］及び［ハ−２］に記載する。 Then, the manufacturing method of the dialkyl organooxysilane compound represented by General formula (3) which is a raw material of the dialkylsilanol compound represented by General formula (1) is described in [ha-1] and [ha-2]. To do.
［ハ−１］一般式（３）
で表されるジアルキルオルガノオキシシラン化合物は、一般式（２）
で表されるジアルキルシラン化合物を、触媒（Ｃ）の存在下にアルコール類と反応させることにより製造することができる。
前記一般式（３）の化合物において、Ｒ１が炭素数１〜２のアルコキシ基を有する非環状アセタール基である場合の化合物は公知化合物であるが、Ｒ１がホルミル基又は５〜６員環の環状アセタール基である場合、すなわち一般式（１２）
で表される化合物は新規化合物である。
[C-1] General formula (3)
The dialkylorganooxysilane compound represented by the general formula (2)
The dialkylsilane compound represented by these can be manufactured by making it react with alcohol in presence of a catalyst (C).
In the compound of the general formula (3), the compound in the case where R 1 is an acyclic acetal group having an alkoxy group having 1 to 2 carbon atoms is a known compound, but R 1 is a formyl group or a 5- to 6-membered ring. A cyclic acetal group of the general formula (12)
Is a novel compound.
触媒（Ｃ）は、パラジウム、白金、ルテニウム、ロジウムなどの白金族元素を含有する白金族触媒、テトラブチルアンモニウムフルオリド、ナトリウムメトキシドなどの塩基触媒が挙げられる。白金族触媒は、白金族元素を含有する触媒であれば特に制限されない。例えば、活性炭、アルミナ、シリカなどの担体に担持した白金族触媒が挙げられる。触媒（Ｃ）として、好ましくはパラジウム炭素触媒である。触媒（Ｃ）の使用量は一般式（２）で表される化合物に対して０．０１質量％以上（白金族触媒の場合は金属換算で５×１０−４質量％以上）であり、好ましくは０．０１〜１０質量％（白金族触媒の場合は金属換算で５×１０−４〜０．５質量％）である。
アルコール類はメタノール、エタノールなどが、アリールアルコール類はフェノール、クレゾールなどが挙げられる。アルコール類又はアリールアルコール類の使用量は一般式（２）で表される化合物に対して１倍モル以上であり、好ましくは１〜１０倍モルである。
原料の仕込み手順は任意であるが、例えば、一般式（２）で表される化合物と触媒（Ｃ）を仕込み、これにアルコール類又はアリールアルコール類を滴下してもよく、あるいは、アルコール類又はアリールアルコール類と触媒（Ｃ）とを仕込んだ後、一般式（２）で表される化合物を滴下してもよい。
反応において溶媒は必要としないが、必要に応じて使用してもよく、反応を阻害しないものであれば特に限定されない。そのような溶媒としては、ペンタン、ヘキサン、ヘプタン、オクタン、ベンゼン、トルエン、キシレンなどの炭化水素類、テトラヒドロフラン、ジオキサン、ジメトキシエタンなどのエーテル類、メチルエチルケトン、アセトンなどのケトン類、酢酸エチルなどのエステル類、ジメチルホルムアミドなどのアミド類、アセトニトリルなどのニトリル類が挙げられる。
反応温度は特に限定されないが、２０℃程度で反応は進行する。反応時間は、反応物の種類及び量にもよるが、およそ１〜８時間以内で終了する。また、反応は空気雰囲気下で行うことができるが、水素ガスが発生するため不活性ガス雰囲気下で行うのが好ましい。反応終了後、目的物を単離するには、蒸留、抽出、カラムクロマトグラフィーなどの方法が使用できる。
Examples of the catalyst (C) include platinum group catalysts containing platinum group elements such as palladium, platinum, ruthenium and rhodium, and base catalysts such as tetrabutylammonium fluoride and sodium methoxide. The platinum group catalyst is not particularly limited as long as it is a catalyst containing a platinum group element. For example, a platinum group catalyst supported on a support such as activated carbon, alumina, or silica can be used. The catalyst (C) is preferably a palladium carbon catalyst. The amount of the catalyst (C) used is 0.01% by mass or more based on the compound represented by the general formula (2) (in the case of a platinum group catalyst, 5 × 10 −4 % by mass or more in terms of metal), preferably Is 0.01 to 10% by mass (in the case of a platinum group catalyst, 5 × 10 −4 to 0.5% by mass in terms of metal).
Examples of alcohols include methanol and ethanol, and examples of aryl alcohols include phenol and cresol. The usage-amount of alcohol or aryl alcohol is 1 time mole or more with respect to the compound represented by General formula (2), Preferably it is 1-10 times mole.
The raw material charging procedure is arbitrary. For example, the compound represented by the general formula (2) and the catalyst (C) may be charged, and alcohols or aryl alcohols may be added dropwise thereto. After charging the aryl alcohol and the catalyst (C), the compound represented by the general formula (2) may be added dropwise.
Although a solvent is not required in the reaction, it may be used as necessary, and is not particularly limited as long as it does not inhibit the reaction. Examples of such solvents include hydrocarbons such as pentane, hexane, heptane, octane, benzene, toluene and xylene, ethers such as tetrahydrofuran, dioxane and dimethoxyethane, ketones such as methyl ethyl ketone and acetone, and esters such as ethyl acetate. Amides such as dimethylformamide, and nitriles such as acetonitrile.
The reaction temperature is not particularly limited, but the reaction proceeds at about 20 ° C. Although the reaction time depends on the type and amount of the reactants, the reaction is completed within about 1 to 8 hours. In addition, the reaction can be performed in an air atmosphere, but hydrogen gas is generated, so that the reaction is preferably performed in an inert gas atmosphere. In order to isolate the target product after completion of the reaction, methods such as distillation, extraction and column chromatography can be used.
［ハ−２］一般式（３）で表されるジアルキルオルガノオキシシラン化合物においてＲ１がホルミル基の場合、すなわち、一般式（１３）
で表される化合物は、一般式（１４）
で表される化合物を、酸触媒（Ｄ）の存在下にケトン類と反応させることにより製造することができる。
[C-2] When R 1 is a formyl group in the dialkylorganooxysilane compound represented by the general formula (3), that is, the general formula (13)
The compound represented by general formula (14)
Can be produced by reacting with a ketone in the presence of an acid catalyst (D).
酸触媒（Ｄ）は特に限定されないが、例えば、塩酸、硫酸などの鉱酸、ｐ−トルエンスルホン酸、ピリジニウム−ｐ−トルエンスルホン酸などの有機酸、活性白土などの固体酸が挙げられる。酸触媒（Ｄ）の使用量は一般式（１４）で表される化合物に対して０．０１質量％以上であり、好ましくは０．０１〜１０質量％である。
ケトン類は、シクロヘキサノン、メチルエチルケトン、アセトンなどが挙げられる。ケトン類の使用量は一般式（１４）で表される化合物に対して１倍モル以上、好ましくは１０〜５０倍モルである。
原料の仕込み手順は任意であるが、例えば、一般式（１４）で表される化合物と酸触媒（Ｄ）を仕込み、これにケトン類を滴下してもよく、あるいは、酸触媒（Ｄ）とケトン類を仕込んだ後、一般式（１４）で表される化合物を滴下してもよい。
反応において溶媒は必要としないが、必要に応じて使用してもよく、反応を阻害しないものであれば特に限定されない。そのような溶媒としては、ペンタン、ヘキサン、ヘプタン、オクタン、ベンゼン、トルエン、キシレンなどの炭化水素類、テトラヒドロフラン、ジオキサン、ジメトキシエタンなどのエーテル類、メタノール、エタノールなどのアルコール類、メチルエチルケトン、アセトンなどのケトン類、酢酸エチルなどのエステル類、ジメチルホルムアミドなどのアミド類、アセトニトリルなどのニトリル類が挙げられる。
反応温度は特に限定されないが、２０℃程度で反応は進行する。反応時間は、反応物の種類及び量にもよるが、およそ１〜８時間以内で終了する。また、反応は空気雰囲気下で行うことができるが、不活性ガス雰囲気下で行ってもよい。反応終了後、目的物を単離するには、蒸留、抽出、カラムクロマトグラフィーなどの方法が使用できる。
The acid catalyst (D) is not particularly limited, and examples thereof include mineral acids such as hydrochloric acid and sulfuric acid, organic acids such as p-toluenesulfonic acid and pyridinium-p-toluenesulfonic acid, and solid acids such as activated clay. The usage-amount of an acid catalyst (D) is 0.01 mass% or more with respect to the compound represented by General formula (14), Preferably it is 0.01-10 mass%.
Examples of ketones include cyclohexanone, methyl ethyl ketone, and acetone. The amount of the ketone used is 1 time mol or more, preferably 10 to 50 times mol, of the compound represented by the general formula (14).
The raw material charging procedure is arbitrary. For example, the compound represented by the general formula (14) and the acid catalyst (D) may be charged, and ketones may be added dropwise thereto, or the acid catalyst (D) and After the ketones are charged, the compound represented by the general formula (14) may be added dropwise.
Although a solvent is not required in the reaction, it may be used as necessary, and is not particularly limited as long as it does not inhibit the reaction. Examples of such solvents include hydrocarbons such as pentane, hexane, heptane, octane, benzene, toluene, and xylene, ethers such as tetrahydrofuran, dioxane, and dimethoxyethane, alcohols such as methanol and ethanol, methyl ethyl ketone, and acetone. Examples include ketones, esters such as ethyl acetate, amides such as dimethylformamide, and nitriles such as acetonitrile.
The reaction temperature is not particularly limited, but the reaction proceeds at about 20 ° C. Although the reaction time depends on the type and amount of the reactants, the reaction is completed within about 1 to 8 hours. The reaction can be performed in an air atmosphere, but may be performed in an inert gas atmosphere. In order to isolate the target product after completion of the reaction, methods such as distillation, extraction and column chromatography can be used.
（１）本発明により、新規なジアルキルシラノール化合物およびそれらの製造方法を提供することができた。
（２）また、本発明は前記ジアルキルシラノール化合物を製造する原料として好適な化合物を提供することができた。
(1) According to the present invention, it was possible to provide novel dialkylsilanol compounds and production methods thereof.
(2) Moreover, this invention has provided the compound suitable as a raw material which manufactures the said dialkyl silanol compound.
以下、本発明を調製例及び実施例で具体的に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated concretely with a preparation example and an Example, this invention is not limited to these.
調製例１
（１）〈４−ジメトキシメチルフェニルマグネシウムブロミドの調製〉
３Ｌの４つ口フラスコに還流冷却器、温度計、滴下ロート、及び撹拌機を取り付け、内部を窒素置換した。このフラスコに、マグネシウム４４．１ｇ（１．８２モル）とテトラヒドロフラン１３０８ｇを仕込んだ。その後、冷媒にて内温を０〜５℃に冷却した後、滴下ロートより４−ブロモベンズアルデヒドジメチルアセタール（アルドリッチ社製）４００ｇ（１．７３モル）を内温が２０℃を越えないように３時間かけて滴下した。その後、内温を２０〜３０℃に保ち１５時間熟成を行い、下記式で示すグリニヤール試薬（４−ジメトキシメチルフェニルマグネシウムブロミド）を調製した。
次いで、冷媒にて内温を０〜５℃に冷却した後、滴下ロートよりクロロジメチルシラン１５７ｇ（１．６６モル）を、内温が２０℃を越えないように３時間かけて滴下した。その後、内温を２０〜３０℃に保ち１時間熟成を行った。続いて、５Ｌの４つ口フラスコに還流冷却器、温度計、滴下ロート、及び撹拌機を取り付けた。このフラスコに、水８００ｇ及びトルエン８００ｇを仕込み、冷媒にて内温を０〜５℃に冷却した後、先ほどの反応で得られた混合物を滴下ロートより、内温が３０℃を越えないように１０分かけて滴下した。その後得られた溶液を５Ｌの分液ロートに移し、有機層と水層に分けた。さらに得られた有機層を水８００ｇにて２回洗浄し、有機層２１０６ｇを得た。この溶液をロータリーエバポレーターにて減圧濃縮し、濃縮液４４１ｇを得た。次いで、この濃縮液を減圧蒸留（沸点９２℃／１５０Ｐａ）して、無色液体の４−ジメトキシメチルフェニルジメチルシラン３３３ｇ（１．５８モル）が得られた。収率は９５．１％（クロロジメチルシランに対して）であった。このもののＮＭＲスペクトル及びＧＣ−ＭＳスペクトルを測定した結果、上記化合物であることが確認された。以下にその結果を示す。
１３Ｃ−ＮＭＲ（１００ＭＨｚ，δ ｉｎ ＣＤＣｌ３）：−３．７０，５２．５７，１０２．８７，１２５．９３，１３３．６７，１３７．４３，１３８．７７
ＧＣ−ＭＳ ｍ／ｚ（ｒｅｌａｔｉｖｅ ｉｎｔｅｎｓｉｔｙ）：２１０（５．４，Ｍ＋），１９６（９．０），１８０（１００），１６４（８．１），１５１（２１），１３５（５．４），１２１（４１），１０５（１５），９１（１４），７５（３５），５９（１４）
Preparation Example 1
(1) <manufactured tone of 4-dimethoxy-methylphenyl magnesium bromide>
A reflux condenser, thermometer, dropping funnel, and stirrer were attached to a 3 L four-necked flask, and the interior was purged with nitrogen. This flask was charged with 44.1 g (1.82 mol) of magnesium and 1308 g of tetrahydrofuran. Thereafter, the internal temperature was cooled to 0 to 5 ° C. with a refrigerant, and then 400 g (1.73 mol) of 4-bromobenzaldehyde dimethyl acetal (manufactured by Aldrich) was added from the dropping funnel so that the internal temperature did not exceed 20 ° C. It was added dropwise over time. Thereafter, aging was performed for 15 hours while maintaining the internal temperature at 20 to 30 ° C. to prepare a Grignard reagent (4-dimethoxymethylphenylmagnesium bromide) represented by the following formula.
Next, after cooling the internal temperature to 0 to 5 ° C. with a refrigerant, 157 g (1.66 mol) of chlorodimethylsilane was added dropwise from a dropping funnel over 3 hours so that the internal temperature did not exceed 20 ° C. Thereafter, aging was carried out for 1 hour while maintaining the internal temperature at 20-30 ° C. Subsequently, a 5 L four-necked flask was equipped with a reflux condenser, a thermometer, a dropping funnel, and a stirrer. Into this flask, 800 g of water and 800 g of toluene were charged, and the internal temperature was cooled to 0 to 5 ° C. with a refrigerant. Then, the internal temperature of the mixture obtained in the previous reaction was kept from exceeding 30 ° C. from the dropping funnel. It was added dropwise over 10 minutes. Thereafter, the resulting solution was transferred to a 5 L separatory funnel and separated into an organic layer and an aqueous layer. Furthermore, the obtained organic layer was washed twice with 800 g of water to obtain 2106 g of an organic layer. This solution was concentrated under reduced pressure using a rotary evaporator to obtain 441 g of a concentrated solution. Subsequently, this concentrated liquid was distilled under reduced pressure (boiling point 92 ° C./150 Pa) to obtain 333 g (1.58 mol) of colorless liquid 4-dimethoxymethylphenyldimethylsilane. The yield was 95.1% (based on chlorodimethylsilane). As a result of measuring the NMR spectrum and GC-MS spectrum of this product, it was confirmed to be the above compound. The results are shown below.
13 C-NMR (100 MHz, δ in CDCl 3 ): −3.70, 52.57, 102.87, 125.93, 133.67, 137.43, 138.77
GC-MS m / z (relative intensity): 210 (5.4, M + ), 196 (9.0), 180 (100), 164 (8.1), 151 (21), 135 (5.4) ), 121 (41), 105 (15), 91 (14), 75 (35), 59 (14)
調製例２〈４−ホルミルフェニルジメチルシランの調製〉
２Ｌの４つ口フラスコに還流冷却器、温度計、滴下ロート、及び撹拌機を取り付けた。このフラスコに、ピリジニウム−ｐ−トルエンスルホン酸１２．０ｇ（０．０４７６モル）、水３４．２ｇ（１．９０モル）及びテトラヒドロフラン６００ｇを仕込んだ。その後、内温２０〜３０℃で撹拌下、調製例１で得られた４−ジメトキシメチルフェニルジメチルシラン２００ｇ（０．９５１モル）を添加し、そのままの温度で１時間熟成を行った。そして、トルエン５００ｇ、水５００ｇを添加した後、得られた溶液を３Ｌの分液ロートに移し有機層と水層に分けた。さらに得られた有機層を水５００ｇで２回洗浄し、有機層１０５５ｇを得た。この溶液をロータリーエバポレーターにて減圧濃縮し、濃縮液１９２ｇを得た。次いで、この濃縮液を減圧蒸留（沸点８４℃／６６５Ｐａ）して、無色液体の４−ホルミルフェニルジメチルシラン１２０ｇ（０．７３２モル）が得られた。収率は７６．９％（４−ジメトキシメチルフェニルジメチルシランに対して）であった。このもののＮＭＲスペクトル及びＧＣ−ＭＳスペクトルを測定した結果、上記化合物であることが確認された。
１３Ｃ−ＮＭＲ（１００ＭＨｚ，δ ｉｎ ＣＤＣｌ３）：−４．０３，１２８．４０，１３４．２４，１３６．４７，１４５．６６，１９１．９８
ＧＣ−ＭＳ ｍ／ｚ（ｒｅｌａｔｉｖｅ ｉｎｔｅｎｓｉｔｙ）：１６３（５８，Ｍ＋），１４９（１００），１３３（８．１），１１９（７．２），１０５（１７），８９（６．３），７７（９），５９（６．３）
Preparation Example 2 <4-formylphenyl made tone phenyl dimethylsilane>
A 2 L four-necked flask was equipped with a reflux condenser, a thermometer, a dropping funnel, and a stirrer. The flask was charged with 12.0 g (0.0476 mol) of pyridinium-p-toluenesulfonic acid, 34.2 g (1.90 mol) of water and 600 g of tetrahydrofuran. Thereafter, 200 g (0.951 mol) of 4-dimethoxymethylphenyldimethylsilane obtained in Preparation Example 1 was added with stirring at an internal temperature of 20 to 30 ° C., and aging was performed for 1 hour at the same temperature. Then, after adding 500 g of toluene and 500 g of water, the resulting solution was transferred to a 3 L separatory funnel and separated into an organic layer and an aqueous layer. Furthermore, the obtained organic layer was washed twice with 500 g of water to obtain 1055 g of an organic layer. This solution was concentrated under reduced pressure using a rotary evaporator to obtain 192 g of a concentrated solution. Subsequently, this concentrated liquid was distilled under reduced pressure (boiling point 84 ° C./665 Pa) to obtain 120 g (0.732 mol) of colorless liquid 4-formylphenyldimethylsilane. The yield was 76.9% (based on 4-dimethoxymethylphenyldimethylsilane). As a result of measuring the NMR spectrum and GC-MS spectrum of this product, it was confirmed to be the above compound.
13 C-NMR (100 MHz, δ in CDCl 3 ): −4.03, 128.40, 134.24, 136.47, 145.66, 191.98
GC-MS m / z (relative intensity): 163 (58, M + ), 149 (100), 133 (8.1), 119 (7.2), 105 (17), 89 (6.3), 77 (9), 59 (6.3)
調製例３〈４−ジメトキシメチルフェニルジメチルメトキシシランの調製〉
３００ｍＬの４つ口フラスコに還流冷却器、温度計、滴下ロート、及び撹拌機を取り付け、内部を窒素置換した。このフラスコに、５％パラジウム炭素触媒０．５０ｇ及びメタノール１００ｇ（３．１３モル）を仕込んだ。その後、内温２０〜３０℃で撹拌下、調製例１で得られた４−ジメトキシメチルフェニルジメチルシラン１００ｇ（０．４７５モル）を滴下し、さらにそのままの温度で１時間熟成を行った。触媒をろ過により除去後、得られたろ液をロータリーエバポレーターにて減圧濃縮し、濃縮液１１３ｇを得た。次いで、この濃縮液を減圧蒸留（沸点１１４℃／３９０Ｐａ）して、無色液体の４−ジメトキシメチルフェニルジメチルメトキシシラン７９．４ｇ（０．３３０モル）が得られた。収率は６９．５％（４−ジメトキシメチルフェニルジメチルシランに対して）であった。このもののＮＭＲスペクトル及びＧＣ−ＭＳスペクトルを測定した結果、上記化合物であることが確認された。以下にその結果を示す。
１３Ｃ−ＮＭＲ（１００ＭＨｚ，δ ｉｎ ＣＤＣｌ３）：−２．１８，５０．６５，５２．７６，１０３．０３，１２５．９７，１３３．２１，１３７．５１，１３９．２３
ＧＣ−ＭＳ ｍ／ｚ（ｒｅｌａｔｉｖｅ ｉｎｔｅｎｓｉｔｙ）：２４０（１．０，Ｍ＋），２２６（３４），２１０（１００），１９５（１０），１７９（１２），１６３（２．７），１４９（１１），１３５（１３），１１９（６．３），１０５（８．１），８９（９．０），７５（１２），５９（１６）
Preparation Example 3 <made tone of 4-dimethoxy-methylphenyl dimethylmethoxysilane>
A 300 mL four-necked flask was equipped with a reflux condenser, a thermometer, a dropping funnel, and a stirrer, and the interior was purged with nitrogen. The flask was charged with 0.50 g of 5% palladium on carbon catalyst and 100 g (3.13 mol) of methanol. Thereafter, 100 g (0.475 mol) of 4-dimethoxymethylphenyldimethylsilane obtained in Preparation Example 1 was added dropwise with stirring at an internal temperature of 20 to 30 ° C., and further aging was performed for 1 hour at the same temperature. After removing the catalyst by filtration, the obtained filtrate was concentrated under reduced pressure using a rotary evaporator to obtain 113 g of a concentrated solution. Subsequently, this concentrated liquid was distilled under reduced pressure (boiling point 114 ° C./390 Pa) to obtain 79.4 g (0.330 mol) of colorless liquid 4-dimethoxymethylphenyldimethylmethoxysilane. The yield was 69.5% (based on 4-dimethoxymethylphenyldimethylsilane). As a result of measuring the NMR spectrum and GC-MS spectrum of this product, it was confirmed to be the above compound. The results are shown below.
13 C-NMR (100 MHz, δ in CDCl 3 ): -2.18, 50.65, 52.76, 103.03, 125.97, 133.21, 137.51, 139.23
GC-MS m / z (relative intensity): 240 (1.0, M + ), 226 (34), 210 (100), 195 (10), 179 (12), 163 (2.7), 149 ( 11), 135 (13), 119 (6.3), 105 (8.1), 89 (9.0), 75 (12), 59 (16)
実施例１〈４−ジメトキシメチルフェニルジメチルシラノールの調製〉
２０ｍＬの３つ口フラスコに還流冷却器、温度計、滴下ロート、及び撹拌子を取り付け、このフラスコに、水３．０ｇ（０．１６７モル）、テトラヒドロフラン１０ｇを仕込んだ。その後、内温２０〜３０℃で撹拌下、調製例３で得られた４−ジメトキシメチルフェニルジメチルメトキシシラン６．００ｇ（０．０２５モル）を滴下し、さらにそのままの温度で１時間熟成を行った。トルエン２０ｇを添加後、分液ロートにて有機層と水層に分液し、得られた有機層をロータリーエバポレーターにて減圧濃縮し、濃縮液４．９３ｇを得た。次いで、この濃縮液を減圧蒸留（沸点１２５℃／２００Ｐａ）して、無色液体の４−ジメトキシメチルフェニルジメチルシラノール１．１０ｇ（４．８６ミリモル）が得られた。収率は１９．４％（４−ジメトキシメチルフェニルジメチルメトキシシランに対して）であった。このもののＮＭＲスペクトル及びＧＣ−ＭＳスペクトルを測定した結果、上記化合物であることが確認された。以下にその結果を示す。
１３Ｃ−ＮＭＲ（１００ＭＨｚ，δ ｉｎ ＣＤＣｌ３）：０．１３，５２．６５，１０２．９１，１２５．９１，１３２．８１，１３８．８６，１３９．４３
ＧＣ−ＭＳ ｍ／ｚ（ｒｅｌａｔｉｖｅ ｉｎｔｅｎｓｉｔｙ）：２２６（１．０，Ｍ＋），１９６（１００），１８０（２．７），１６５（１４），１５１（２．０），１３５（９．０），１１９（４．４），１０５（５．４），９１（１０），７５（３３），５９（３．６）
Example 1 <made tone of 4-dimethoxy-methylphenyl dimethylsilanol>
A 20 mL three-necked flask was equipped with a reflux condenser, a thermometer, a dropping funnel, and a stirring bar, and 3.0 g (0.167 mol) of water and 10 g of tetrahydrofuran were charged into the flask. Thereafter, 6.00 g (0.025 mol) of 4-dimethoxymethylphenyldimethylmethoxysilane obtained in Preparation Example 3 was added dropwise with stirring at an internal temperature of 20 to 30 ° C., and further aged for 1 hour at the same temperature. It was. After adding 20 g of toluene, the organic layer and the aqueous layer were separated with a separatory funnel, and the obtained organic layer was concentrated under reduced pressure with a rotary evaporator to obtain 4.93 g of a concentrated solution. Subsequently, this concentrated liquid was distilled under reduced pressure (boiling point 125 ° C./200 Pa) to obtain 1.10 g (4.86 mmol) of 4-dimethoxymethylphenyldimethylsilanol as a colorless liquid. The yield was 19.4% (based on 4-dimethoxymethylphenyldimethylmethoxysilane). As a result of measuring the NMR spectrum and GC-MS spectrum of this product, it was confirmed to be the above compound. The results are shown below.
13 C-NMR (100 MHz, δ in CDCl 3 ): 0.13, 52.65, 102.91, 125.91, 132.81, 138.86, 139.43
GC-MS m / z (relative intensity): 226 (1.0, M + ), 196 (100), 180 (2.7), 165 (14), 151 (2.0), 135 (9.0) ), 119 (4.4), 105 (5.4), 91 (10), 75 (33), 59 (3.6)
調製例４〈４−ホルミルフェニルジメチルメトキシシランの調製〉
５００ｍＬの４つ口フラスコに還流冷却器、温度計、滴下ロート、及び撹拌機を取り付け、内部を窒素置換した。このフラスコに、活性白土５．０ｇ、アセトン３００ｇ（５．１７モル）を仕込んだ。その後、内温２０〜３０℃で撹拌下、調製例３で得られた４−ジメトキシメチルフェニルジメチルメトキシシラン５０．０ｇ（０．２０８モル）を滴下し、さらにそのままの温度で３０分熟成を行った。活性白土をろ過により除去後、得られたろ液をロータリーエバポレーターにて減圧濃縮し、濃縮液４８．７ｇを得た。次いで、この濃縮液を減圧蒸留（沸点９８℃／３６０Ｐａ）して、無色液体の４−ホルミルフェニルジメチルメトキシシラン１７．７ｇ（０．０９１１モル）が得られた。収率は４３．８％（４−ジメトキシメチルフェニルジメチルメトキシシランに対して）であった。このもののＮＭＲスペクトル及びＧＣ−ＭＳスペクトルを測定した結果、上記化合物であることが確認された。以下にその結果を示す。
１３Ｃ−ＮＭＲ（１００ＭＨｚ，δ ｉｎ ＣＤＣｌ３）：−２．３８，５０．５５，１２８．４２，１３３．６１，１３６．７１，１４５．４１，１９１．９４
ＧＣ−ＭＳ ｍ／ｚ（ｒｅｌａｔｉｖｅ ｉｎｔｅｎｓｉｔｙ）：１９４（６．３，Ｍ＋），１８０（１００），１６３（２．０），１４９（５１），１３３（４．０），１１９（１０），１０５（７．２），８９（１７），７７（４．６），５９（２８）
Preparation Example 4 <4-formylphenyl made tone phenyl dimethyl methoxysilane>
A 500 mL four-necked flask was equipped with a reflux condenser, a thermometer, a dropping funnel, and a stirrer, and the interior was purged with nitrogen. This flask was charged with 5.0 g of activated clay and 300 g (5.17 mol) of acetone. Thereafter, 50.0 g (0.208 mol) of 4-dimethoxymethylphenyldimethylmethoxysilane obtained in Preparation Example 3 was added dropwise with stirring at an internal temperature of 20 to 30 ° C., and further aged for 30 minutes at the same temperature. It was. After removing the activated clay by filtration, the obtained filtrate was concentrated under reduced pressure using a rotary evaporator to obtain 48.7 g of a concentrated solution. Subsequently, this concentrated liquid was distilled under reduced pressure (boiling point 98 ° C./360 Pa) to obtain 17.7 g (0.0911 mol) of colorless liquid 4-formylphenyldimethylmethoxysilane. The yield was 43.8% (based on 4-dimethoxymethylphenyldimethylmethoxysilane). As a result of measuring the NMR spectrum and GC-MS spectrum of this product, it was confirmed to be the above compound. The results are shown below.
13 C-NMR (100 MHz, δ in CDCl 3 ): -2.38, 50.55, 128.42, 133.61, 136.71, 145.41, 191.94
GC-MS m / z (relative intensity): 194 (6.3, M + ), 180 (100), 163 (2.0), 149 (51), 133 (4.0), 119 (10), 105 (7.2), 89 (17), 77 (4.6), 59 (28)
実施例２〈４−ホルミルフェニルジメチルシラノールの調製〉
５０ｍＬの４つ口フラスコに還流冷却器、温度計、滴下ロート、及び撹拌機を取り付け、内部を窒素置換した。このフラスコに、水５．０ｇ（０．２７８モル）、テトラヒドロフラン４０．０ｇを仕込んだ。その後、内温２０〜３０℃で撹拌下、調製例４で得られた４−ホルミルフェニルジメチルメトキシシラン１６．１ｇ（０．０８２９モル）を滴下し、さらにそのままの温度で１時間熟成を行った。得られた溶液をロータリーエバポレーターにて減圧濃縮し、濃縮液１５．４ｇを得た。次いで、この濃縮液を減圧蒸留（沸点１２８℃／２８０Ｐａ）して、無色液体の４−ホルミルフェニルジメチルシラノール６．４０ｇ（０．０３５５モル）が得られた。収率は４２．８％（４−ホルミルフェニルジメチルメトキシシランに対して）であった。このもののＮＭＲスペクトル及びＧＣ−ＭＳスペクトルを測定した結果、上記化合物であることが確認された。以下にその結果を示す。
１３Ｃ−ＮＭＲ（１００ＭＨｚ，δ ｉｎ ＣＤＣｌ３）：０．００，１２８．５４，１３３．３６，１３６．３８，１４７．５８，１９２．６８
ＧＣ−ＭＳ ｍ／ｚ（ｒｅｌａｔｉｖｅ ｉｎｔｅｎｓｉｔｙ）：１８０（１１，Ｍ＋），１６５（１００），１３７（３．６），１２１（４．５），１０５（３．６），９１（１０），７５（１５），６１（２．７）
Example 2 <4-formyl-made adjustment of the mill phenyl dimethylsilanol>
A 50 mL four-necked flask was equipped with a reflux condenser, a thermometer, a dropping funnel, and a stirrer, and the interior was purged with nitrogen. The flask was charged with 5.0 g (0.278 mol) of water and 40.0 g of tetrahydrofuran. Thereafter, 16.1 g (0.0829 mol) of 4-formylphenyldimethylmethoxysilane obtained in Preparation Example 4 was added dropwise with stirring at an internal temperature of 20 to 30 ° C., and further aging was performed for 1 hour at the same temperature. . The resulting solution was concentrated under reduced pressure using a rotary evaporator to obtain 15.4 g of a concentrated solution. Subsequently, this concentrated liquid was distilled under reduced pressure (boiling point 128 ° C./280 Pa) to obtain 6.40 g (0.0355 mol) of colorless liquid 4-formylphenyldimethylsilanol. The yield was 42.8% (based on 4-formylphenyldimethylmethoxysilane). As a result of measuring the NMR spectrum and GC-MS spectrum of this product, it was confirmed to be the above compound. The results are shown below.
13 C-NMR (100 MHz, δ in CDCl 3 ): 0.00, 128.54, 133.36, 136.38, 147.58, 192.68
GC-MS m / z (relative intensity): 180 (11, M + ), 165 (100), 137 (3.6), 121 (4.5), 105 (3.6), 91 (10), 75 (15), 61 (2.7)
調製例５〈２−（ｐ−ブロモフェニル）−１，３−ジオキサンの調製〉
２００ｍＬの４つ口フラスコにＤｅａｎ−Ｓｔａｒｋ装置、温度計、及び撹拌子を取り付け、内部を窒素置換した。このフラスコに、ブロモベンズアルデヒド１００ｇ（０．５４０モル）及び１，３−プロパンジオール４１．１ｇ（０．５４０モル）、活性白土５ｇ、トルエン２００ｇを仕込んだ。その後、加熱還流することにより系外へ生成した水を留去した。活性白土をろ過により除去後、得られたろ液をロータリーエバポレーターにて減圧濃縮・乾固し、濃縮残１３３ｇを得た。次いで、この濃縮残をヘキサン２００ｇにて再結晶・減圧乾燥して、白色結晶の２−（ｐ−ブロモフェニル）−１，３−ジオキサン１０５ｇ（０．４３２モル）が得られた。収率は７９．９％（ブロモベンズアルデヒドに対して）であった。このもののＮＭＲスペクトル及びＧＣ−ＭＳスペクトルを測定した結果、上記化合物であることが確認された。以下にその結果を示す。
ＧＣ−ＭＳ ｍ／ｚ（ｒｅｌａｔｉｖｅ ｉｎｔｅｎｓｉｔｙ）：２４３（１００，Ｍ＋），１８５（９０），１６３（２０），１０５（５５），８７（７６），７７（７８），５９（１２）
Preparation Example 5 <2- (p- bromophenyl) -1,3-made adjustment of dioxane>
A 200 mL four-necked flask was equipped with a Dean-Stark apparatus, a thermometer, and a stirring bar, and the inside was purged with nitrogen. This flask was charged with 100 g (0.540 mol) of bromobenzaldehyde, 41.1 g (0.540 mol) of 1,3-propanediol, 5 g of activated clay, and 200 g of toluene. Then, the water produced | generated out of the system by heating and refluxing was distilled off. After the activated clay was removed by filtration, the obtained filtrate was concentrated under reduced pressure using a rotary evaporator and dried to obtain 133 g of concentrated residue. Subsequently, this concentrated residue was recrystallized with 200 g of hexane and dried under reduced pressure to obtain 105 g (0.432 mol) of 2- (p-bromophenyl) -1,3-dioxane as white crystals. The yield was 79.9% (based on bromobenzaldehyde). As a result of measuring the NMR spectrum and GC-MS spectrum of this product, it was confirmed to be the above compound. The results are shown below.
GC-MS m / z (relative intensity): 243 (100, M + ), 185 (90), 163 (20), 105 (55), 87 (76), 77 (78), 59 (12)
調製例６
（１）〈４−（１，３−ジオキサン−２−イル）フェニルマグネシウムブロミドの調製〉
１Ｌの４つ口フラスコに還流冷却器、温度計、滴下ロート、及び撹拌子を取り付け、内部を窒素置換した。このフラスコに、マグネシウム１０．５ｇ（０．４３２モル）及びテトラヒドロフラン１６ｇ（０．２２２モル）を仕込んだ。その後、内温２０〜３０℃で撹拌下、調製例５で得られた２−（ｐ−ブロモフェニル）−１，３−ジオキサン１００ｇ（０．４１１モル）のテトラヒドロフラン２８０ｇ（３．８８モル）を滴下ロートより内温が２０℃を越えないように、１時間かけて滴下した。その後、そのままの温度で２時間熟成を行い、グリニヤール試薬〔４−（１，３−ジオキサン−２−イル）フェニルマグネシウムブロミド〕を調製した。
次に、前記（１）で得られたグリニヤール試薬含有溶液に内温が２０℃を越えないように、滴下ロートよりクロロジメチルシラン３６．９ｇ（０．３９０モル）を１５分かけて滴下した。その後、内温を２０〜３０℃に保ち１時間熟成を行った。続いて、トルエン２００ｇを添加した後、冷媒にて冷却下内温が２０℃を越えないように、滴下ロートより水２００ｇを滴下した。その後得られた溶液を１Ｌの分液ロートに移し、有機層と水層に分けた。さらに得られた有機層を水２００ｇにて２回洗浄し、有機層５４６ｇを得た。この溶液をロータリーエバポレーターにて減圧濃縮し、濃縮液１０２ｇを得た。次いで、この濃縮液を減圧蒸留（沸点１４４℃／３９０Ｐａ）して、無色液体の２−（ｐ−ジメチルシリルフェニル）−１，３−ジオキサン５６．９ｇ（０．２５６モル）が得られた。収率は６５．６％（クロロジメチルシランに対して）であった。このもののＮＭＲスペクトル及びＧＣ−ＭＳスペクトルを測定した結果、上記化合物であることが確認された。以下にその結果を示す。
１３Ｃ−ＮＭＲ（１００ＭＨｚ，δ ｉｎ ＣＤＣｌ３）：−３．７３，２５．７４，６７．１８，１０１．２６，１２５．１５，１３３．６３，１３７．７６，１３９．３５１
ＧＣ−ＭＳ ｍ／ｚ（ｒｅｌａｔｉｖｅ ｉｎｔｅｎｓｉｔｙ）：２２２（５８，Ｍ＋），２０８（１４），１７９（５．０），１６３（１００），１４９（３７），１３５（２２），１２１（３４），１０５（５０），８７（４５），７７（１２），５９（２０）
Preparation Example 6
(1) <4- (1,3-dioxan-2-yl) made tone phenyl magnesium bromide>
A 1 L four-necked flask was equipped with a reflux condenser, a thermometer, a dropping funnel, and a stirring bar, and the inside was purged with nitrogen. This flask was charged with 10.5 g (0.432 mol) of magnesium and 16 g (0.222 mol) of tetrahydrofuran. Thereafter, 280 g (3.88 mol) of tetrahydrofuran of 100 g (0.411 mol) of 2- (p-bromophenyl) -1,3-dioxane obtained in Preparation Example 5 was stirred at an internal temperature of 20 to 30 ° C. It dropped over 1 hour so that internal temperature might not exceed 20 degreeC from a dropping funnel. Thereafter, aging was carried out at the same temperature for 2 hours to prepare a Grignard reagent [4- (1,3-dioxan-2-yl) phenylmagnesium bromide].
Next, 36.9 g (0.390 mol) of chlorodimethylsilane was added dropwise to the Grignard reagent-containing solution obtained in (1) from the dropping funnel over 15 minutes so that the internal temperature did not exceed 20 ° C. Thereafter, aging was carried out for 1 hour while maintaining the internal temperature at 20-30 ° C. Subsequently, 200 g of toluene was added, and then 200 g of water was dropped from a dropping funnel so that the internal temperature under cooling did not exceed 20 ° C. with a refrigerant. Thereafter, the obtained solution was transferred to a 1 L separatory funnel and separated into an organic layer and an aqueous layer. Furthermore, the obtained organic layer was washed twice with 200 g of water to obtain 546 g of an organic layer. This solution was concentrated under reduced pressure using a rotary evaporator to obtain 102 g of a concentrated solution. Subsequently, this concentrated liquid was distilled under reduced pressure (boiling point 144 ° C./390 Pa) to obtain 56.9 g (0.256 mol) of colorless liquid 2- (p-dimethylsilylphenyl) -1,3-dioxane. The yield was 65.6% (based on chlorodimethylsilane). As a result of measuring the NMR spectrum and GC-MS spectrum of this product, it was confirmed to be the above compound. The results are shown below.
13 C-NMR (100 MHz, δ in CDCl 3 ): −3.73, 25.74, 67.18, 101.26, 125.15, 133.63, 137.76, 139.351
GC-MS m / z (relative intensity): 222 (58, M + ), 208 (14), 179 (5.0), 163 (100), 149 (37), 135 (22), 121 (34) , 105 (50), 87 (45), 77 (12), 59 (20)
調製例７〈２−（ｐ−ジメチルメトキシシリルフェニル）−１，３−ジオキサンの調製〉
５０ｍＬの４つ口フラスコに還流冷却器、温度計、滴下ロート、及び撹拌子を取り付け、内部を窒素置換した。このフラスコに、メタノール１５．０ｇ（０．４６９モル）及び５％パラジウム炭素触媒０．０７５ｇを仕込んだ。その後、内温２０〜３０℃で撹拌下、調製例６で得られた２−（ｐ−ジメチルシリルフェニル）−１，３−ジオキサン１５．０ｇ（０．０６７５モル）を滴下し、さらにそのままの温度で１０分間熟成を行った。触媒をろ過により除去後、得られたろ液をロータリーエバポレーターにて減圧濃縮し、濃縮液１６．７ｇを得た。次いで、この濃縮液を減圧蒸留（沸点１３８℃／１８０Ｐａ）して、無色液体の２−（ｐ−ジメチルメトキシシリルフェニル）−１，３−ジオキサン９．３５ｇ（０．０３７０モル）が得られた。収率は５４．９％〔２−（ｐ−ジメチルシリルフェニル）−１，３−ジオキサンに対して〕であった。このもののＮＭＲスペクトル及びＧＣ−ＭＳスペクトルを測定した結果、上記化合物であることが確認された。以下にその結果を示す。
１３Ｃ−ＮＭＲ（１００ＭＨｚ，δ ｉｎ ＣＤＣｌ３）：−２．３２，２５．６８，５０．４２，６７．１２，１０１．１６，１２５．１４，１３３．０８，１３７．６６，１３９．７１
ＧＣ−ＭＳ ｍ／ｚ（ｒｅｌａｔｉｖｅ ｉｎｔｅｎｓｉｔｙ）：２５２（４８，Ｍ＋），２３８（１００），２０８（６．０），１９４（１７），１７９（３４），１６３（８０），１５１（２５），１３５（９．０），１２１（２２），１０５（３３），８９（３６），７７（６．０），５９（４０）
Preparation Example 7 <2- (p- dimethylmethoxysilyl) -1,3-made adjustment of dioxane>
A 50 mL four-necked flask was equipped with a reflux condenser, a thermometer, a dropping funnel, and a stirring bar, and the inside was purged with nitrogen. This flask was charged with 15.0 g (0.469 mol) of methanol and 0.075 g of 5% palladium on carbon catalyst. Thereafter, 15.0 g (0.0675 mol) of 2- (p-dimethylsilylphenyl) -1,3-dioxane obtained in Preparation Example 6 was added dropwise with stirring at an internal temperature of 20 to 30 ° C. Aging was carried out at temperature for 10 minutes. After removing the catalyst by filtration, the obtained filtrate was concentrated under reduced pressure using a rotary evaporator to obtain 16.7 g of a concentrated solution. Then, this concentrated liquid was distilled under reduced pressure (boiling point 138 ° C./180 Pa) to obtain 9.35 g (0.0370 mol) of colorless liquid 2- (p-dimethylmethoxysilylphenyl) -1,3-dioxane. . The yield was 54.9% [based on 2- (p-dimethylsilylphenyl) -1,3-dioxane]. As a result of measuring the NMR spectrum and GC-MS spectrum of this product, it was confirmed to be the above compound. The results are shown below.
13 C-NMR (100 MHz, δ in CDCl 3 ): -2.32, 25.68, 50.42, 67.12, 101.16, 125.14, 133.08, 137.66, 139.71
GC-MS m / z (relative intensity): 252 (48, M + ), 238 (100), 208 (6.0), 194 (17), 179 (34), 163 (80), 151 (25) , 135 (9.0), 121 (22), 105 (33), 89 (36), 77 (6.0), 59 (40)
実施例３〈２−（ｐ−ジメチルヒドロキシシリルフェニル）−１，３−ジオキサンの調製〉
５０ｍＬの４つ口フラスコに還流冷却器、温度計、滴下ロート、及び撹拌子を取り付け、内部を窒素置換した。このフラスコに、水５．０ｇ（０．２７８モル）、テトラヒドロフラン１０ｇ及び５％パラジウム炭素触媒０．０７５ｇを仕込んだ。その後、内温２０〜３０℃で撹拌下、調製例６で得られた２−（ｐ−ジメチルシリルフェニル）−１，３−ジオキサン１５．０ｇ（０．０６７５モル）を滴下し、さらにそのままの温度で１０分間熟成を行った。触媒をろ過により除去後、得られたろ液をロータリーエバポレーターにて減圧濃縮し、濃縮液１８．２ｇを得た。次いで、この濃縮液を減圧蒸留（沸点１６８℃／１８０Ｐａ）して、無色液体の２−（ｐ−ジメチルヒドロキシシリルフェニル）−１，３−ジオキサン１０．２ｇ（０．０４２８モル）が得られた。収率は６３．４％（２−（ｐ−ジメチルシリルフェニル）−１，３−ジオキサンに対して）であった。このもののＮＭＲスペクトル及びＧＣ−ＭＳスペクトルを測定した結果、上記化合物であることが確認された。以下にその結果を示す。
１３Ｃ−ＮＭＲ（１００ＭＨｚ，δ ｉｎ ＣＤＣｌ３）：０．０６，２５．７３，６７．２７，１０１．４３，１２５．１６，１３２．７６，１３９．３４，１３９．８５
ＧＣ−ＭＳ ｍ／ｚ（ｒｅｌａｔｉｖｅ ｉｎｔｅｎｓｉｔｙ）：２３８（５８，Ｍ＋），２２４（４６），１７９（２９），１６３（１００），１５１（４．０），１３７（４８），１２１（９．０），１０５（５０），８７（５７），７５（４７），５９（１７）
Example 3 <2- (p- dimethylhydroxysilyl) -1,3-made adjustment of dioxane>
A 50 mL four-necked flask was equipped with a reflux condenser, a thermometer, a dropping funnel, and a stirring bar, and the inside was purged with nitrogen. The flask was charged with 5.0 g (0.278 mol) of water, 10 g of tetrahydrofuran and 0.075 g of 5% palladium on carbon catalyst. Thereafter, 15.0 g (0.0675 mol) of 2- (p-dimethylsilylphenyl) -1,3-dioxane obtained in Preparation Example 6 was added dropwise with stirring at an internal temperature of 20 to 30 ° C. Aging was carried out at temperature for 10 minutes. After removing the catalyst by filtration, the obtained filtrate was concentrated under reduced pressure using a rotary evaporator to obtain 18.2 g of a concentrated solution. Subsequently, this concentrated liquid was distilled under reduced pressure (boiling point 168 ° C./180 Pa) to obtain 10.2 g (0.0428 mol) of colorless liquid 2- (p-dimethylhydroxysilylphenyl) -1,3-dioxane. . The yield was 63.4% (based on 2- (p-dimethylsilylphenyl) -1,3-dioxane). As a result of measuring the NMR spectrum and GC-MS spectrum of this product, it was confirmed to be the above compound. The results are shown below.
13 C-NMR (100 MHz, δ in CDCl 3 ): 0.06, 25.73, 67.27, 101.43, 125.16, 132.76, 139.34, 139.85
GC-MS m / z (relative intensity): 238 (58, M + ), 224 (46), 179 (29), 163 (100), 151 (4.0), 137 (48), 121 (9. 0), 105 (50), 87 (57), 75 (47), 59 (17)
Claims (3)
で表されるジアルキルシラノール化合物。 General formula (1)
The dialkylsilanol compound represented by these.
で表されるジアルキルシラン化合物を、触媒の存在下に水と反応させることを特徴とする、一般式（１）
で表されるジアルキルシラノール化合物の製造方法。 General formula (2)
A dialkylsilane compound represented by general formula (1) is reacted with water in the presence of a catalyst:
The manufacturing method of the dialkyl silanol compound represented by these.
で表されるジアルキルオルガノオキシシラン化合物を、水と反応させることを特徴とする、一般式（１）
で表されるジアルキルシラノール化合物の製造方法。 General formula (3)
A dialkylorganooxysilane compound represented by general formula (1) is reacted with water:
The manufacturing method of the dialkyl silanol compound represented by these.
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