JP3552139B2 - Method for producing silacyclohexane compound - Google Patents
Method for producing silacyclohexane compound Download PDFInfo
- Publication number
- JP3552139B2 JP3552139B2 JP00441397A JP441397A JP3552139B2 JP 3552139 B2 JP3552139 B2 JP 3552139B2 JP 00441397 A JP00441397 A JP 00441397A JP 441397 A JP441397 A JP 441397A JP 3552139 B2 JP3552139 B2 JP 3552139B2
- Authority
- JP
- Japan
- Prior art keywords
- carbon atoms
- group
- alkyl group
- reaction
- general formula
- 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
- 150000001875 compounds Chemical class 0.000 title claims description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- -1 silane compound Chemical class 0.000 claims description 51
- 125000004432 carbon atom Chemical group C* 0.000 claims description 47
- 125000000217 alkyl group Chemical group 0.000 claims description 36
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- 125000003944 tolyl group Chemical group 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 8
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 7
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 238000005859 coupling reaction Methods 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 125000002524 organometallic group Chemical group 0.000 claims description 4
- 239000005046 Chlorosilane Substances 0.000 claims description 3
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 3
- 238000005933 dealkoxycarbonylation reaction Methods 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 2
- 239000012433 hydrogen halide Substances 0.000 claims description 2
- 238000005580 one pot reaction Methods 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000004973 liquid crystal related substance Substances 0.000 description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 11
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 238000010898 silica gel chromatography Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 235000002639 sodium chloride Nutrition 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 239000005457 ice water Substances 0.000 description 6
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000001308 synthesis method Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 239000007818 Grignard reagent Substances 0.000 description 5
- 150000004795 grignard reagents Chemical class 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- PGJMHAWIYHJALG-UHFFFAOYSA-N 1-phenyl-1-propylsilinan-4-one Chemical compound C=1C=CC=CC=1[Si]1(CCC)CCC(=O)CC1 PGJMHAWIYHJALG-UHFFFAOYSA-N 0.000 description 4
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 4
- 125000005916 2-methylpentyl group Chemical group 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- LGVBRQGDHMPXIK-UHFFFAOYSA-N bis[2-(1,3-dioxolan-2-yl)ethyl]-phenyl-propylsilane Chemical compound O1CCOC1CC[Si](C=1C=CC=CC=1)(CCC)CCC1OCCO1 LGVBRQGDHMPXIK-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000012312 sodium hydride Substances 0.000 description 4
- 229910000104 sodium hydride Inorganic materials 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 0 *C(CCN)O* Chemical compound *C(CCN)O* 0.000 description 3
- 125000005917 3-methylpentyl group Chemical group 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- GGZQLTVZPOGLCC-UHFFFAOYSA-N 2-(2-bromoethyl)-1,3-dioxolane Chemical compound BrCCC1OCCO1 GGZQLTVZPOGLCC-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- GQTPAQRBJITTEQ-UHFFFAOYSA-N O1C(OCC1)CC[Si](CCCCC)(C1=CC=CC=C1)CCC1OCCO1 Chemical compound O1C(OCC1)CC[Si](CCCCC)(C1=CC=CC=C1)CCC1OCCO1 GQTPAQRBJITTEQ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- HFMYVQVKEFPRJV-UHFFFAOYSA-N dichloro-phenyl-propylsilane Chemical compound CCC[Si](Cl)(Cl)C1=CC=CC=C1 HFMYVQVKEFPRJV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 2
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000006197 hydroboration reaction Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 2
- FDHKZQQEVRSFET-UHFFFAOYSA-N methyl 4-oxo-1-phenyl-1-propylsilinane-3-carboxylate Chemical compound C=1C=CC=CC=1[Si]1(CCC)CCC(=O)C(C(=O)OC)C1 FDHKZQQEVRSFET-UHFFFAOYSA-N 0.000 description 2
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 125000005815 pentoxymethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 125000005767 propoxymethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])[#8]C([H])([H])* 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- XFGPSHWWPIFPNL-UHFFFAOYSA-N 1-bromo-4-(4-fluorophenyl)benzene Chemical group C1=CC(F)=CC=C1C1=CC=C(Br)C=C1 XFGPSHWWPIFPNL-UHFFFAOYSA-N 0.000 description 1
- 125000006219 1-ethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- RPTMRMFJCDEHMV-UHFFFAOYSA-N 1-pentyl-1-phenylsilinan-4-one Chemical compound C=1C=CC=CC=1[Si]1(CCCCC)CCC(=O)CC1 RPTMRMFJCDEHMV-UHFFFAOYSA-N 0.000 description 1
- GBKZPLIJKMRYTE-UHFFFAOYSA-N 2-(2-chloroethyl)-1,3-dioxolane Chemical compound ClCCC1OCCO1 GBKZPLIJKMRYTE-UHFFFAOYSA-N 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000003469 3-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 1
- ZLEPOJAOVMNBLT-UHFFFAOYSA-N 4-[4-(4-fluorophenyl)phenyl]-1-phenyl-1-propylsilinane Chemical group C1C[Si](CCC)(C=2C=CC=CC=2)CCC1C(C=C1)=CC=C1C1=CC=C(F)C=C1 ZLEPOJAOVMNBLT-UHFFFAOYSA-N 0.000 description 1
- NWGOEYGJBPOKPN-UHFFFAOYSA-N C(C)OC(=O)CC[SiH](CCC)C1=CC=CC=C1 Chemical compound C(C)OC(=O)CC[SiH](CCC)C1=CC=CC=C1 NWGOEYGJBPOKPN-UHFFFAOYSA-N 0.000 description 1
- FSCSWKFCOINTKT-XYWHTSSQSA-N C1C[Si@@H](CCC)CC[C@@H]1C1=CC=C(C=2C=CC(F)=CC=2)C=C1 Chemical group C1C[Si@@H](CCC)CC[C@@H]1C1=CC=C(C=2C=CC(F)=CC=2)C=C1 FSCSWKFCOINTKT-XYWHTSSQSA-N 0.000 description 1
- LOQLQXZFPJZATH-UHFFFAOYSA-N COC(=O)CC[Si](CCCCC)(C1=CC=CC=C1)CCC(=O)OC Chemical compound COC(=O)CC[Si](CCCCC)(C1=CC=CC=C1)CCC(=O)OC LOQLQXZFPJZATH-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000006228 Dieckmann condensation reaction Methods 0.000 description 1
- QZRGKCOWNLSUDK-UHFFFAOYSA-N Iodochlorine Chemical compound ICl QZRGKCOWNLSUDK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241000283907 Tragelaphus oryx Species 0.000 description 1
- 125000004036 acetal group Chemical group 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- CEWFCWAELJDQNC-UHFFFAOYSA-N dichloro-pentyl-phenylsilane Chemical compound CCCCC[Si](Cl)(Cl)C1=CC=CC=C1 CEWFCWAELJDQNC-UHFFFAOYSA-N 0.000 description 1
- 125000004786 difluoromethoxy group Chemical group [H]C(F)(F)O* 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 125000006232 ethoxy propyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- XVQSRLOZUKJFEU-UHFFFAOYSA-N ethyl 3-[(3-ethoxy-3-oxopropyl)-phenyl-propylsilyl]propanoate Chemical compound CCOC(=O)CC[Si](CCC)(CCC(=O)OCC)C1=CC=CC=C1 XVQSRLOZUKJFEU-UHFFFAOYSA-N 0.000 description 1
- JRJMLZZERTYTRS-UHFFFAOYSA-N ethyl 4-oxo-1-phenyl-1-propylsilinane-3-carboxylate Chemical compound C=1C=CC=CC=1[Si]1(CCC)CCC(=O)C(C(=O)OCC)C1 JRJMLZZERTYTRS-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- CNMZWTBBAMMUIV-UHFFFAOYSA-N methyl 3-[(3-methoxy-3-oxopropyl)-phenyl-propylsilyl]propanoate Chemical compound COC(=O)CC[Si](CCC)(CCC(=O)OC)C1=CC=CC=C1 CNMZWTBBAMMUIV-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 125000006233 propoxy propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])OC([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006225 propoxyethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Liquid Crystal Substances (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、シラシクロヘキサン型液晶化合物の有用な合成中間体となるシラシクロヘキサノン化合物を製造する方法、およびその製造方法における中間体となるケイ素化合物に関する。
【０００２】
【従来の技術】
液晶表示素子は、液晶物質が持つ光学異方性、および誘電異方性を利用したものであり、その表示様式によって、ＴＮ型（ねじれネマチック型）、ＳＴＮ型（超ねじれネマチック型）、ＳＢＥ型（超複屈折型）、ＤＳ型（動的散乱型）、ゲスト・ホスト型、ＤＡＰ型（整列相の変形型）、ＰＤ型（ポリマー分散型）、およびＯＭＩ型（光学的にモード干渉型）など各種の方式がある。最も一般的なディスプレイデバイスは、シャット−ヘルフリッヒ効果に基づき、ねじれネマチック構造を有するものである。これらの液晶表示に用いられる液晶物質に要求される性質は、その表示方式によって若干異なるが、液晶温度範囲が広いこと、水分、空気、光、熱、電界等に対して、安定であること等は、いずれの表示方式においても、共通して要求される。さらに、液晶材料は、低粘度であり、かつセル中において短いアドレス時間、しきい値電圧および高いコントラストを与えることが望まれる。さらに近年、液晶ディスプレイの用途が拡大するにつれて、液晶材料に要求される特性も益々高度な厳しいものとなりつつある。特に、駆動電圧の低電圧化、車載用ニーズに対応した広域温度範囲化、低温性能の向上等、従来の液晶物質の特性を更に上回るものが望まれている。このような観点から、発明者らは、液晶物質の特性の向上を目的として、分子中にケイ素原子を含有する新規なシラシクロヘキサン型液晶化合物を開発し、先に出願した。これらのシラシクロヘキサン型液晶化合物を製造する際の有用な合成中間体として、シラシクロヘキノン化合物がある。
【０００３】
このシラシクロヘキサノン化合物の製造方法としては、主に次の三つの方法が知られている。
第一の合成方法は、次の様な反応経路である。
【化７】
また、第二の合成法は、次の様な反応経路である。
【化８】
また、第三の合成法は、次の様な反応経路である。
【化９】
【発明が解決しようとする課題】
先に示した三つの製造法について、第一、第二の反応経路の場合には、ヒドロボレーション反応を行わなければならず、原料の価格取扱いの点で問題があり、工業化には経済的に不利な方法である。更に、第二の方法は、製造工程がかなり長く、全工程を通しての収率が２５〜３０％と極めて低い。また、第三の合成法の場合には、第一段階の脱水素カップリング反応の収率が４０％程度とかなり低い。この様な観点から、本発明は、シラシクロヘキサン型液晶化合物の有用な合成中間体となるシラシクロヘキサノン化合物のより高収率で、単純かつ安価な工業的に有利な製造方法を提供することを目的とするものである。
【０００７】
【課題を解決するための手段】
即ち、本発明は、一般式（６）
【化１０】
で表されるシラシクロヘキサノン化合物を製造するために、以下の改良合成方法に関する。
【化１１】
【０００８】
本発明をさらに詳細に説明する。
本発明において、Ｒ１ は、以下のいずれかの基を表す。
（ａ）フェニル基、またはトリル基
（ｂ）炭素数１〜１０の直鎖状アルキル基、すなわち、メチル、エチル、ｎ−プロピル、ｎ−ブチル、ｎ−ペンチル、ｎ−ヘキシル、ｎ−ヘプチル、ｎ−オクチル、ｎ−ノニル、またはｎ−デジル。
（ｃ）炭素数３〜８の分枝鎖状アルキル基、すなわち、イソプロピル、ｓｅｃ−ブチル、イソブチル、１−メチルブチル、２−メチルブチル、３−メチルブチル、１−メチルペンチル、２−メチルペンチル、３−メチルペンチル、１−エチルペンチル、１−メチルヘキシル、２−メチルヘキシル、３−メチルヘキシル、２−エチルヘキシル、３−エチルヘキシル、１−メチルヘプチル、２−メチルヘプチル、または３−メチルヘプチル。
（ｄ）炭素数２〜７のアルコキシアルキル基、すなわち、メトキシメチル、エトキシメチル、プロポキシメチル、ブトキシメチル、ペントキシメチル、ヘキシロキシメチル、メトキシエチル、エトキシエチル、プロポキシエチル、ブトキシエチル、メトキシプロピル、エトキシプロピル、プロポキシプロピル、ブトキシプロピル、メトキシブチル、エトキシブチル、プロポキシブチル、メトキシペンチル、エトキシペンチル、またはメトキシヘキシル。
【０００９】
本発明において、Ｒ２ は、以下のいずれかの基を表す。
（ｅ）炭素数１〜５の直鎖状アルキル基、すなわち、メチル、エチル、ｎ−プロピル、ｎ−ブチル、またはｎ−ペンチル。
（ｆ）炭素数３〜６の分枝鎖状アルキル基、すなわち、イソプロピル、ｓｅｃ−ブチル、イソブチル、ｔ−ブチル、１−メチルブチル、２−メチルブチル、３−メチルブチル、１−メチルペンチル、２−メチルペンチル、３−メチルペンチル、または１−エチルブチル。
（ｇ）炭素数２〜３の環状アセタールを形成するメチレン鎖、すなわち、エチレン、メチルエチレン、プロピレン。
【００１０】
本発明において、Ｒ３ は、以下のいずれかの基を表す。
（ｈ）炭素数１〜５の直鎖状アルキル基、すなわち、メチル、エチル、ｎ−プロピル、ｎ−ブチル、またはｎ−ペンチル。
（ｉ）炭素数３〜６の分枝鎖状アルキル基、すなわち、イソプロピル、ｓｅｃ−ブチル、イソブチル、ｔ−ブチル、１−メチルブチル、２−メチルブチル、３−メチルブチル、１−メチルペンチル、２−メチルペンチル、３−メチルペンチル、または１−エチルブチル。
【００１１】
本発明において、Ｒ１ は、好ましくは、以下のいずれかの基を表す。
（ａ’）フェニル基、またはトリル基。
（ｂ’）炭素数２〜７の直鎖状アルキル基、すなわち、エチル、ｎ−プロピル、ｎ−ブチル、ｎ−ペンチル、ｎ−ヘキシル、またはｎ−ヘプチル。
（ｃ’）炭素数３〜８の分枝鎖状アルキル基のうち、すなわち、イソプロピル、ｓｅｃ−ブチル、イソブチル、１−メチルブチル、２−メチルブチル、３−メチルブチル、１−メチルペンチル、２−メチルペンチル、または２−エチルヘキシル。
（ｄ’）炭素数２〜６のアルコキシアルキル基、すなわち、メトキシメチル、エトキシメチル、プロポキシメチル、ペントキシメチル、メトキシエチル、エトキシエチル、メトキシプロピル、またはメトキシペンチル。
【００１２】
本発明において、Ｒ２ は、好ましくは、以下のいずれかの基である。
（ｅ’）炭素数１〜５の直鎖状アルキル基のうち、メチル、エチル、またはｎ−プロピル。
（ｆ’）炭素数３〜６の分枝鎖状アルキル基のうち、イソプロピル、またはイソブチル。
（ｇ’）炭素数２〜３の環状アセタールを形成するメチレン鎖のうち、エチレン、またはプロピレン。
【００１３】
本発明において、Ｒ３ は、好ましくは、以下のいずれかの基である。
（ｈ’）炭素数１〜５の直鎖状アルキル基のうち、メチル、エチル、またはｎ−プロピル。
（ｉ’）炭素数３〜６の分枝鎖状アルキル基のうち、イソプロピル、またはイソブチル。
【００１４】
次に、各合成反応について詳細に説明する。
まず、一般式（７）で表わされる対応するハロゲン化合物から、一般式（３）で表される有機金属試薬を調製する。
【化１２】
【化１３】
使用する溶媒としては、エーテル系溶媒、特にテトラヒドロフラン、ジエチルエーテル、ジ−ｎ−ブチルエーテルが好ましく例示できる。
【００１５】
この有機金属試薬と、一般式（２）
【化１４】
で表されるクロロシラン化合物を反応させることで、カップリング反応が進行し、
一般式（１）
【化１５】
で表されるシラン化合物を得る。カップリング反応においては、無触媒でもよいが、銅触媒、特に、ヨウ化銅、シアン化銅を０．０１〜０．１当量用いれば、より迅速に反応が進行する。なお、ここに示した一般式（１）で表されるシラン化合物は、新規化合物である。
【００１６】
次に、この化合物をアルコール溶媒中、ハロゲン化水素として、塩化水素、臭化水素、ヨウ化水素、好ましくは塩化水素（具体的には、１２Ｎ 塩化水素水）を６．０〜１２．０当量と、過酸化水素水（具体的には、３４％過酸化水素水）を用いて、酸化し、一般式（４）
【化１６】
で表されるエステル化合物が、直接に一段階の反応で得られる。また、溶媒として用いるアルコールは、一般式（８）
【化１７】
を用い、なかでもメタノール、エタノールが好ましく、得られる化合物のエステル基のアルコキシ部位は、溶媒のアルコール由来となる。酸化反応における反応温度は、室温から４０℃で行い、４０℃付近で行えば、より迅速に反応が進行する。なお、このような溶媒由来のアルコキシ基を持ったエステルが、アセタールを酸化して直接得ることができるのは、本反応が最初である。これについては、以下を参照できる。
Ｈｅｙｗｏｏｄ，Ｄ．； Ｐｉｌｌｉｐｓ，Ｂ． Ｊ．Ｏｒｇ．Ｃｈｅｍ．，１９６０，２５，１６９９．
Ｎｉｓｈｉｈａｒａ，Ａ．； Ｋｕｂｏｔａ，Ｉ． Ｊ．Ｏｒｇ．Ｃｈｅｍ．，１９６８，３３，２５２５．
Ｅｌａｎｄ，Ｄ．； Ｙｏｕｓｓｅｆｙｅｈ，Ｒ．Ｄ． Ｔｅｔｒａｈｅｄｒｏｎ Ｌｅｔｔ．，１９６３，２１８９．
Ｓｔｅｖｅｎｓ，Ｒ．Ｖ．； Ｃｈａｐｍａｎ，Ｋ．Ｔ． Ｔｅｔｒａｈｅｄｒｏｎ Ｌｅｔｔ．，１９８２，４６４７．
Ｄｅｓｌｏｎｇｃｈａｍｐｓ，Ｐ； Ａｔｌａｎｉ，Ａ． ＣＡＮ．Ｊ．Ｃｈｅｍ．，１９７４，５２，３６５１．
さらに、使用する酸化剤も、過酸化水素水と塩化水素水と非常に安価であることから、本合成経路におけるこの酸化反応は有用である。
【００１７】
この化合物に、溶媒中、塩基を作用させることにより、Ｄｉｅｃｋｍａｎｎ縮合反応を行えば、一般式（５）
【化１８】
用いる塩基として、水素化ナトリウム、水素化カリウム、水素化カルシウム等の水素化金属類、ナトリウムメトキシド、ナトリウムエトキシド、カリウムｔ−ブトキシド等の金属アルコキシド類、炭酸ナトリウム、炭酸カリウム、水酸化ナトリウム、水酸化カリウム、水酸化バリウム等のアルカリ性無機塩類を挙げることができる。
溶媒として、ベンゼン、トルエン、キシレン、クメン等の炭化水素類、テトラヒドロフラン、ｎ−ブチルエーテル、ジグライム等のエーテル系溶媒を単独または混合して用いる。
縮合による環化反応が完結した後、酸処理することで目的物（５）が得られる。
【００１８】
最後に、この化合物を金属塩存在下、高沸点溶媒中で加熱、好ましくは、１００℃〜溶媒の還流温度に加熱することにより、脱エトキシカルボニル化反応が進行し、一般式（６）
【化１９】
で表されるシラシクロヘキサノン化合物を得ることができる。
脱アルコキシカルボニル化反応に用いる金属塩としては、塩化ナトリウム、臭化ナトリウム、ヨウ化ナトリウム、塩化リチウム、臭化リチウム、ヨウ化リチウムが挙げられる。なかでも、塩化ナトリウムは安価で有用である。溶媒としては、ジメチルスルホキシド、ヘキサメチルホスホリックトリアミド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、１，３−ジメチル−２−イミダゾリジノン、１，３−ジメチル−３，４，５，６−テトラヒドロ−２（１Ｈ）−ピリミジノン等の非プロトン性極性溶媒が好ましい。
【００１９】
以上示した、本発明によるシラシクロヘキサノン化合物合成法は、先に示した既知の三つの合成法と比較して、ヒドロボレーション反応を使用しない点、反応経路が４段階と短く、いずれの段階の反応も高収率である点、さらには、アセタールを一段階の酸化反応で直接エステルに変換でき、しかも酸化剤が非常に安価な過酸化水素である優れた新反応を含んでいる点から、工業的に有利な製造方法である。
【００２０】
シラシクロヘキサノン化合物の使用用途について以下に示す。
【化２０】
このようにして、シラシクロヘキサノン化合物に有機金属試薬を付加させてアルコール化合物を得、続けて、脱水、水素添加反応、さらにハロデシリレーション反応によりケイ素上の置換基Ａｒをハロゲンに変えて得られるハロシラン化合物を還元することにより、最終生成物として、分子中にケイ素原子を含有する、有用な特性を持ったシラシクロヘキサン型液晶化合物が得られる。
【００２１】
【実施例】
以下に、具体的な実施例を挙げて本発明を更に詳しく説明する。
（実施例１） ４−ｎ−プロピル−４−フェニル−４−シラシクロヘキサノンの製造
マグネシウム９．５ｇ（０．２６ｍｏｌ）、ＴＨＦ１００ｍｌを３００ｍｌ反応容器に入れ、窒素雰囲気下、２−（２−ブロモエチル）−１，３−ジオキソラン４７．１ｇ（０．２６ｍｏｌ）を滴下ロートを使用して加え、グリニヤール試薬を調製した。この時、反応温度は、４０〜４５℃に調節するのが好ましい。また、反応の開始段階においては、短時間の加熱を行った。滴下終了時点で反応は終了しているので、室温付近まで温度が下がるのを待ち、フェニル−ｎ−プロピルジクロロシラン２１．９ｇ（０．１０ｍｏｌ）を滴下した。滴下終了後、さらに室温で１時間攪拌後、飽和塩化アンモニウム水溶液１００ｍｌ、酢酸エチル溶媒１００ｍｌを用いて抽出を行い、有機層をさらに飽和食塩水５０ｍｌを用いて洗浄、続いて硫酸マグネシウムで乾燥し、濃縮操作を行い、シリカゲルクロマトグラフィーで精製して、ジ（２−（２−１，３−ジオキソラニル）エチル）−フェニル−ｎ−プロピルシラン３０．５ｇ（収率９６％）を得た。
１Ｈ−ＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３ ）：δ ０．７０−１．７８（１５Ｈ，ｍ）、３．７９−３．９８（８Ｈ，ｍ）、４．８１（２Ｈ，ｔ）、７．２８−７．４４（５Ｈ，ｍ）ｐｐｍ
ＩＲ（ＫＢｒ ｄｉｓｃ）νｍａｘ：２８８０（ｓ）、２８４０（ｓ）、１４００（ｓ）、１１２４（ｓ）、１０４１（ｓ）、９６２（ｍ）、８４０（ｓ）、７４０（ｓ）、７００（ｓ）ｃｍ−１
【００２２】
ジ（２−（２−１，３−ジオキソラニル）エチル）−フェニル−ｎ−プロピルシラン６．４ｇ（０．０２ｍｏｌ）に、メタノール４０ｍｌを加え、この反応容器を、氷水バスを用いて５℃付近まで冷却し、１２Ｎ ＨＣｌ水１０ｍｌを滴下し、さらに３４％過酸化水素水６．０ｇ（０．０６ｍｏｌ）を滴下終了後、氷水バスをオイルバスに入れ替えて４０℃まで加熱し４時間攪拌を行った。この混合溶液を室温まで冷却した後、酢酸エチル５０ｍｌ、亜硫酸ナトリウム水溶液５０ｍｌを用いて抽出を行い、有機層を通常の洗浄濃縮操作の後、シリカゲルクロマトグラフィーで精製して、ジ（２−メトキシカルボニルエチレン）−フェニル−ｎ−プロピルシラン４．９ｇ（収率９１％）を得た。
１Ｈ−ＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３ ）：δ ０．７４−１．３７（１１Ｈ、ｍ）、２．１８−２．３７（４Ｈ、ｍ）、３．６１（６Ｈ、ｓ）、７．３０−７．４７（５Ｈ、ｍ）ｐｐｍ
ＩＲ（ＫＢｒ ｄｉｓｃ）νｍａｘ：２９５２（ｍ）、１７３９（ｓ）、１４３４（ｓ）、１２１１（ｓ）、１１１０（ｍ）、１０５１（ｍ）、７３７（ｍ）、７０２（ｓ）ｃｍ−１
【００２３】
ジ（２−メトキシカルボニルエチル）−フェニル−ｎ−プロピルシラン１７．６ｇを水素化ナトリウム１．８５ｇとトルエン８０ｍｌの懸濁溶液に加え、エタノールを留去しながら、１００℃で３時間攪拌した。この混合溶液を冷却したところに、２０％塩酸５０ｍｌを加えて中和にし、トルエン層を濃縮することにより、２−メトキシカルボニル−４−ｎ−プロピル−４−フェニル−４−シラシクロヘキサノン１４．１ｇを得た。
この粗生成物に、食塩４．０ｇ、水１．２ｇ、およびジメチルスルホキシド７０ｍｌを加え、１５時間還流した。反応混合物を冷却後、水を加えて塩化メチレン溶媒で抽出した。抽出液を、通常の洗浄、濃縮操作の後、シリカゲルクロマトグラフィーで精製した目的物１１．５ｇ（収率９１％）を得た。
１Ｈ−ＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３ ）：δ
０．７０−１．０６（５Ｈ、ｍ）、１．０６−１．６０（６Ｈ、ｍ）、２．５６（４Ｈ、ｔ）、７．２５−７．６６（５Ｈ、ｍ）ｐｐｍ
ＩＲ（薄膜）νｍａｘ：２９２５（ｓ）、１７０５（ｓ）、１４２５（ｍ）、１３１０（ｍ）、１１５５（ｍ）、１１１０（ｓ）、１０８５（ｓ）、１０６５（ｓ）、７３０（ｓ）、７００（ｓ）ｃｍ−１
【００２４】
（実施例２） ４−ｎ−プロピル−４−フェニル−４−シラシクロヘキサノンの製造
マグネシウム９．７ｇ（０．４０ｍｏｌ）、ＴＨＦ１００ｍｌを３００ｍｌ反応容器に入れ、窒素雰囲気下、２−（２−クロロエチル）−１，３−ジオキソラン２７．２ｇ（０．２０ｍｏｌ）、ジブロモエタン３７．６ｇ（０．２０ｍｏｌ）、フェニル−ｎ−プロピルジクロロシラン２１．９ｇ（０．１０ｍｏｌ）の三つの混合溶液を滴下ロートを使用して加え、グリニヤール試薬の調製、およびクロロシランとのカップリング反応を同時に行なった。この時、反応温度は、４０〜４５℃に調節するのが好ましい。また、反応の開始段階においては、短時間の加熱を行なった。滴下終了後、さらに室温で１時間攪拌後、飽和塩化アンモニウム水溶液１００ｍｌ、酢酸エチル溶媒１００ｍｌを用いて抽出を行い、有機層をさらに飽和食塩水５０ｍｌを用いて洗浄、続いて硫酸マグネシウムで乾燥し、濃縮操作を行い、シリカゲルクロマトグラフィーで精製して、ジ（２−（２−１，３−ジオキソラニル）エチル）−フェニル−ｎ−プロプルシラン２６．７ｇ（収率８４％）を得た。
以下、実施例１と同様の実験操作を行い、目的物１０．１ｇを得た。
【００２５】
（実施例３） ４−ｎ−プロピル−４−フェニル−４−シラシクロヘキサノンの製造
まず、実施例１と同様の実験操作を行い、ジ（２−（２−１，３−ジオキソラニル）エチル）−フェニル−ｎ−プロピルシラン６．４ｇ（０．０２ｍｏｌ）を得た。これにエタノール４０ｍｌを加え、この反応容器を氷水バスを用いて５℃付近まで冷却し、１２Ｎ ＨＣｌ水１０ｍｌを滴下し、さらに３４％過酸化水素水６．０ｇ（０．０６ｍｏｌ）を滴下終了後、氷水バスをオイルバスに入れ替えて４０℃まで加熱し４時間攪拌を行なった。この混合溶液を室温まで冷却した後、酢酸エチル５０ｍｌ、亜硫酸ナトリウム水溶液５０ｍｌを用いて抽出を行い、有機層を、通常の洗浄濃縮操作の後、シリカゲルクロマトグラフィーで精製して、ジ（２−（エトキシカルボニルエチレン）−フェニル−ｎ−プロピルシラン５．３ｇ（収率８９％）を得た。
１Ｈ−ＮＭＲ（１００ＭＨｚ、ＣＤＣｌ３ ）：δ
０．９０−１．３８（１７Ｈ、ｍ）、２．３３（４Ｈ、ｔ）、４．１８（４Ｈ、ｍ）、７．２２−７．５３（５Ｈ、ｍ）ｐｐｍ
ＩＲ（薄膜）νｍａｘ：２９６０（ｓ）、１７３５（ｓ）、１４２５（ｍ）、１３６５（ｍ）、１２０５（ｓ）、１１１０（ｓ）、１０５０（ｓ）ｃｍ−１
【００２６】
次に、ジ（２−エトキシカルボニルエチル）−フェニル−ｎ−プロピルシラン１９．４ｇを、水素化ナトリウム１．８５ｇとトルエン８０ｍｌの懸濁溶液に加え、エタノールを留去しながら、１００℃で３時間攪拌した。この混合溶液を冷却したところに、２０％塩酸５０ｍｌを加えて中性にし、トルエン層を濃縮することにより２−エトキシカルボニル−４−ｎ−プロピル−４−フェニル−４−シラシクロヘキサノン１４．８ｇを得た。
この粗生成物に、食塩４．０ｇ、水１．２ｇ、およびジメチルスルホキシド７０ｍｌを加え、１５時間還流した。反応混合物を冷却後、水を加えて塩化メチレン溶媒で抽出した。抽出液を、通常の洗浄、濃縮操作の後、シリカゲルクロマトグラフィーで精製して目的物１１．５ｇを得た。
【００２７】
（実施例４） ４−ｎ−ペンチル−４−フェニル−４−シラシクロヘキサノンの製造
マグネシウム９．５ｇ（０．２６ｍｏｌ）、ＴＨＦ１００ｍｌを３００ｍｌ反応容器に入れ、窒素雰囲気下、２−（２−ブロモエチル）−１，３−ジオキソラン４７．１ｇ（０．２６ｍｏｌ）を滴下ロートを使用して加え、グリニヤール試薬を調製した。この時、反応温℃は４０〜４５℃に調節するのが好ましい。また、反応の開始段階においては、短時間の加熱を行なった。滴下終了時点で反応は終了しているので、室温付近まで温℃が下がるのを待ち、フェニル−ｎ−ペンチルジクロロシラン２４．７ｇ（０．１０ｍｏｌ）を滴下した。滴下終了後、さらに室温で１時間攪拌後、飽和塩化アンモニウム水溶液１００ｍｌ、酢酸エチル溶媒１００ｍｌを用いて抽出を行い、有機層をさらに飽和食塩水５０ｍｌを用いて洗浄、続いて硫酸マグネシウムで乾燥し、濃縮操作を行い、シリカゲルクロマトグラフィーで精製して、ジ（２−（２−１，３−ジオキソラニル）エチル）−フェニル−ｎ−ペンチルシラン３２．５ｇ（収率９４％）を得た。
【００２８】
次に、ジ（２−（２−１，３−ジオキソラニル）エチル）−フェニル−ｎ−ペンチルシラン６．９ｇ（０．０２ｍｏｌ）に、メタノール４０ｍｌを加え、この反応容器を氷水バスを用いて５℃付近まで冷却し、１２Ｎ ＨＣｌ水１０ｍｌを滴下し、さらに３４％過酸化水素水６．０ｇ（０．０６ｍｏｌ）を滴下終了後、氷水バスをオイルバスに入れ替えて４０℃まで加熱し４時間攪拌を行った。この混合溶液を室温まで冷却した後、酢酸エチル５０ｍｌ、亜硫酸ナトリウム水溶液５０ｍｌを用いて抽出を行い、有機層を通常の洗浄濃縮操作の後、シリカゲルクロマトグラフィーで精製して、ジ（２−メトキシカルボニルエチレン）−フェニル−ｎ−プロピルシラン６．０ｇ（収率９２％）を得た。
【００２９】
次に、ジ（２−メトキシカルボニルエチル）−フェニル−ｎ−ペンチルシラン１９．２ｇを水素化ナトリウム１．８５ｇとトルエン８０ｍｌの懸濁溶液に加え、エタノールを留去しながら、１００℃で３時間攪拌した。この混合溶液を冷却したところに、２０％塩酸５０ｍｌを加えて中性にし、トルエン層を濃縮することにより、２−メトリキシカルボニル−４−ｎ−プロピル−４−フェニル−４−シラシクロヘキサノン１４．１ｇを得た。
この粗生成物に、食塩４．０ｇ、水１．２ｇおよび、ジメチルスルホキド７０ｍｌを加え、１５時間還流した。反応混合物を冷却後、水を加えて塩化メチレン溶媒で抽出した。抽出液を通常の洗浄、濃縮操作の後、シリカゲルクロマトグラフィーで精製して目的物１１．５ｇを得た。
１Ｈ−ＮＭＲ（１００ＭＨｚ、ＣＤＣｌ３ ）：δ
０．７０−１．００（５Ｈ、ｍ）、１．００−１．６０（１０Ｈ、ｍ）、２．５６（４Ｈ、ｔ）、７．１０−７．６５（５Ｈ、ｍ）ｐｐｍ
ＩＲ（薄膜）νｍａｘ：２９２５（ｓ）、１７０５（ｓ）、１４２５（ｍ）、１３１０（ｍ）、１１５５（ｍ）、１１１０（ｓ）、１０８０（ｓ）、７２５（ｓ）、７００（ｓ）ｃｍ−１
【００３０】
（利用例）
本発明による製造方法で得られるシラシクロヘキサノン化合物の実際の利用例として、シラシクロヘキサン型液晶化合物合成の具体的な実施例を挙げる。
４’−（ｔｒａｎｓ−４−ｎ−プロピル−４−シラシクロヘキシル）−４−フルオロビフェニルの製造
マグネシウム１０．２ｇの入ったテトラヒドロフラン溶液２００ｍｌに、４’−ブロモ−４−フルオロビフェニル１００．４ｇを、４０〜５０℃で滴下した。さらに５０℃まで１時間攪拌することでグリニヤール試薬を調製し、ここに５０〜６０℃に保ったまま、４−ｎ−プロピル−４−フェニル−４−シラシクロヘキサノン４６．４ｇを滴下し、続けて２時間攪拌後、飽和塩化アンモニウム水溶液にあけ、ベンゼンで抽出した。ベンゼン溶液に、ｐ−トルエンスルホン酸一水和物５．０ｇを加え、還流しながら生じた水を留去した。水の留出が止まったら、反応混合物を炭化水素ナトリウム水溶液で洗い、乾燥、濃縮することにより、４’−（４−フェニル−４−ｎ−プロピル−４−シラシクロヘキ−３−セン）−４−フルオロビフェニルを得た。このものをエタノール１００ｍｌに溶かし、パラジウムカーボン２．０ｇを触媒として水素添加し、触媒を濾別後濃縮して、４’−（４−フェニル−４−ｎ−プロピル−４−シラシクロヘキシル）−４−フルオロビフェニル６６．０ｇを得た。
このものに、室温で１．０Ｍ−塩化ヨウ素の四塩化炭素溶液２００ｍｌを加え、３０分間攪拌した後、濃縮した。残渣をテトラヒドロフラン４０ｍｌに溶かし、０℃で水素化アルミニウムリチウム８．０ｇとテトラヒドロフラン１００ｍｌの混合溶液へ滴下した。反応混合物を１時間攪拌した後、５％塩酸４００ｍｌにあけ、酢酸エチルで抽出した。通常の洗浄・乾燥・濃縮の後、シリカゲルクロマトグラフィーで精製して目的物５２．９ｇ（収率７７％）を得た。
このものは、シラシクロヘキサン環に関して、トランス体とシス体の混合物であるので、さらにクロマトグラフィーにより分離して、トランス体のみを得、その分析結果を以下に示した。
ＩＲ（薄膜）νｍａｘ：２９１８、２８５４、２０８７、１６０４、１４９７、１２３８、９８７、８８９、８１６ｃｍ−１
Ｃ−Ｎ転移温度：８０．２℃
Ｎ−Ｉ転移温度：１１９．３℃
【００３１】
【発明の効果】
以上示したように、本発明での液晶化合物を製造する際の有用な合成中間体シラシクロヘキサノン化合物の改良合成法は、従来法と比較して、まず、反応工程の四段階が、グリニヤール試薬とのカップリング反応、酸化反応、塩基による縮合反応、脱アルコキシカルボニル化反応と、工業化に有利な方法であり、しかも、全４工程の収率が、すべて９割以上である点から、経済的にも優れている。また、酸化反応に関しては、過酸化水素水という非常に安価な酸化剤を使用して、アセタール基を直接エステル基に酸化する新手法である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing a silacyclohexanone compound which is a useful synthetic intermediate for a silacyclohexane type liquid crystal compound, and a silicon compound which is an intermediate in the production method.
[0002]
[Prior art]
The liquid crystal display element utilizes the optical anisotropy and the dielectric anisotropy of a liquid crystal material, and depending on the display mode, a TN type (twisted nematic type), an STN type (super twisted nematic type), an SBE type. (Super-birefringence type), DS type (dynamic scattering type), guest-host type, DAP type (deformed type of aligned phase), PD type (polymer dispersion type), and OMI type (optically mode interference type) There are various methods. The most common display devices have a twisted nematic structure based on the Schadt-Helfrich effect. The properties required of the liquid crystal materials used in these liquid crystal displays vary slightly depending on the display system, but they must be wide in the liquid crystal temperature range, stable against moisture, air, light, heat, electric fields, etc. Are required in common in all display methods. Further, it is desired that the liquid crystal material has a low viscosity and provides a short address time, a threshold voltage and a high contrast in the cell. Further, in recent years, as the applications of liquid crystal displays have expanded, the characteristics required for liquid crystal materials have become increasingly severe. In particular, it is desired to further improve the characteristics of conventional liquid crystal materials, such as lowering the driving voltage, widening the temperature range corresponding to the needs for vehicles, and improving low-temperature performance. From such a viewpoint, the inventors have developed a novel silacyclohexane-type liquid crystal compound containing a silicon atom in a molecule for the purpose of improving the properties of a liquid crystal material, and have previously filed an application. A useful synthetic intermediate for producing these silacyclohexane-type liquid crystal compounds is a silacyclohexynone compound.
[0003]
As a method for producing the silacyclohexanone compound, the following three methods are mainly known.
The first synthesis method is the following reaction route.
Embedded image
The second synthesis method uses the following reaction route.
Embedded image
The third synthesis method uses the following reaction route.
Embedded image
[Problems to be solved by the invention]
Regarding the three production methods described above, in the case of the first and second reaction routes, a hydroboration reaction must be performed, and there is a problem in the handling of raw material prices, and economical Disadvantageous method. Furthermore, the second method has a considerably long production process and a very low yield of 25 to 30% throughout the entire process. In the case of the third synthesis method, the yield of the first-stage dehydrogenation coupling reaction is as low as about 40%. From such a viewpoint, an object of the present invention is to provide a simple and inexpensive industrially advantageous production method of a silacyclohexanone compound which is a useful synthetic intermediate of a silacyclohexane type liquid crystal compound in a higher yield. It is assumed that.
[0007]
[Means for Solving the Problems]
That is, the present invention provides a compound represented by general formula (6)
Embedded image
The present invention relates to the following improved synthesis method for producing the silacyclohexanone compound represented by the formula:
Embedded image
[0008]
The present invention will be described in more detail.
In the present invention, R1Represents any of the following groups.
(A) phenyl group or tolyl group
(B) a linear alkyl group having 1 to 10 carbon atoms, that is, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, or n-Desyl.
(C) a branched alkyl group having 3 to 8 carbon atoms, that is, isopropyl, sec-butyl, isobutyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-methylpentyl, 2-methylpentyl, 3- Methylpentyl, 1-ethylpentyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 2-ethylhexyl, 3-ethylhexyl, 1-methylheptyl, 2-methylheptyl, or 3-methylheptyl.
(D) an alkoxyalkyl group having 2 to 7 carbon atoms, that is, methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, pentoxymethyl, hexyloxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl, methoxypropyl, Ethoxypropyl, propoxypropyl, butoxypropyl, methoxybutyl, ethoxybutyl, propoxybutyl, methoxypentyl, ethoxypentyl, or methoxyhexyl.
[0009]
In the present invention, R2Represents any of the following groups.
(E) A linear alkyl group having 1 to 5 carbon atoms, that is, methyl, ethyl, n-propyl, n-butyl, or n-pentyl.
(F) A branched alkyl group having 3 to 6 carbon atoms, that is, isopropyl, sec-butyl, isobutyl, t-butyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-methylpentyl, 2-methyl Pentyl, 3-methylpentyl, or 1-ethylbutyl.
(G) A methylene chain forming a cyclic acetal having 2 to 3 carbon atoms, that is, ethylene, methylethylene, and propylene.
[0010]
In the present invention, R3Represents any of the following groups.
(H) a linear alkyl group having 1 to 5 carbon atoms, that is, methyl, ethyl, n-propyl, n-butyl, or n-pentyl.
(I) a branched alkyl group having 3 to 6 carbon atoms, that is, isopropyl, sec-butyl, isobutyl, t-butyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-methylpentyl, 2-methyl Pentyl, 3-methylpentyl, or 1-ethylbutyl.
[0011]
In the present invention, R1Preferably represents any of the following groups:
(A ') a phenyl group or a tolyl group.
(B ') a linear alkyl group having 2 to 7 carbon atoms, that is, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, or n-heptyl.
(C ′) Among the branched alkyl groups having 3 to 8 carbon atoms, namely, isopropyl, sec-butyl, isobutyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-methylpentyl, 2-methylpentyl Or 2-ethylhexyl.
(D ') an alkoxyalkyl group having 2 to 6 carbon atoms, that is, methoxymethyl, ethoxymethyl, propoxymethyl, pentoxymethyl, methoxyethyl, ethoxyethyl, methoxypropyl, or methoxypentyl.
[0012]
In the present invention, R2Is preferably any of the following groups:
(E ′) Among linear alkyl groups having 1 to 5 carbon atoms, methyl, ethyl, or n-propyl.
(F ') Among the branched alkyl groups having 3 to 6 carbon atoms, isopropyl or isobutyl.
(G ') Among the methylene chains forming a cyclic acetal having 2 to 3 carbon atoms, ethylene or propylene.
[0013]
In the present invention, R3Is preferably any of the following groups:
(H ′) Among linear alkyl groups having 1 to 5 carbon atoms, methyl, ethyl or n-propyl.
(I ') Among the branched alkyl groups having 3 to 6 carbon atoms, isopropyl or isobutyl.
[0014]
Next, each synthesis reaction will be described in detail.
First, an organometallic reagent represented by the general formula (3) is prepared from a corresponding halogen compound represented by the general formula (7).
Embedded image
Embedded image
Preferred examples of the solvent used include ether solvents, particularly tetrahydrofuran, diethyl ether and di-n-butyl ether.
[0015]
The organometallic reagent is represented by the general formula (2)
Embedded image
By reacting the chlorosilane compound represented by the coupling reaction proceeds,
General formula (1)
Embedded image
Is obtained. In the coupling reaction, no catalyst may be used, but the reaction proceeds more quickly when a copper catalyst, particularly, copper iodide or copper cyanide is used in an amount of 0.01 to 0.1 equivalent. Note that the silane compound represented by the general formula (1) shown here is a novel compound.
[0016]
Next, this compound is used as a hydrogen halide in an alcohol solvent, and 6.0 to 12.0 equivalents of hydrogen chloride, hydrogen bromide, and hydrogen iodide, preferably, hydrogen chloride (specifically, 12N aqueous hydrogen chloride) are used. And an aqueous solution of hydrogen peroxide (specifically, 34% aqueous hydrogen peroxide), and oxidized using the general formula (4)
Embedded image
Is directly obtained in a one-step reaction. The alcohol used as the solvent is represented by the general formula (8)
Embedded image
Among them, methanol and ethanol are preferable, and the alkoxy portion of the ester group of the obtained compound is derived from the alcohol of the solvent. The reaction temperature in the oxidation reaction is from room temperature to 40 ° C., and the reaction proceeds more rapidly when performed at around 40 ° C. This reaction is the first time that such an ester having an alkoxy group derived from a solvent can be directly obtained by oxidizing an acetal. In this regard, reference can be made to:
Heywood, D .; Pillips, B .; J. Org. Chem. , 1960, 25, 1699.
Nishihara, A .; Kubota, I .; J. Org. Chem. , 1968, 33, 2525.
Eland, D.C. Youssefyeh, R .; D. Tetrahedron Lett. , 1963, 2189.
Stevens, R.A. V. Chapman, K .; T. Tetrahedron Lett. , 1982, 4647.
Deslongchamps, P; Atlani, A .; CAN. J. Chem. , 1974, 52, 3651.
Furthermore, since the oxidizing agents used are very inexpensive with aqueous hydrogen peroxide and aqueous hydrogen chloride, this oxidation reaction in the present synthesis route is useful.
[0017]
When a Dieckmann condensation reaction is carried out by reacting this compound with a base in a solvent, the compound represented by the general formula (5)
Embedded image
As a base to be used, sodium hydride, potassium hydride, metal hydrides such as calcium hydride, sodium methoxide, sodium ethoxide, metal alkoxides such as potassium t-butoxide, sodium carbonate, potassium carbonate, sodium hydroxide, Examples thereof include alkaline inorganic salts such as potassium hydroxide and barium hydroxide.
As the solvent, hydrocarbons such as benzene, toluene, xylene and cumene, and ether solvents such as tetrahydrofuran, n-butyl ether and diglyme are used alone or in combination.
After the completion of the cyclization reaction by condensation, the desired product (5) is obtained by acid treatment.
[0018]
Finally, by heating this compound in the presence of a metal salt in a high-boiling solvent, preferably at 100 ° C. to the reflux temperature of the solvent, the deethoxycarbonylation reaction proceeds and the general formula (6)
Embedded image
Can be obtained.
Examples of the metal salt used in the dealkoxycarbonylation reaction include sodium chloride, sodium bromide, sodium iodide, lithium chloride, lithium bromide, and lithium iodide. Among them, sodium chloride is inexpensive and useful. As the solvent, dimethyl sulfoxide, hexamethylphosphoric triamide, N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,4 Aprotic polar solvents such as 5,6-tetrahydro-2 (1H) -pyrimidinone are preferred.
[0019]
The method for synthesizing the silacyclohexanone compound according to the present invention as described above has a point that no hydroboration reaction is used and the reaction route is as short as four steps as compared with the three known synthesis methods described above. From the point that the reaction is also high yield, furthermore, the acetal can be directly converted to an ester in a one-step oxidation reaction, and the oxidizing agent contains an excellent new reaction that is very inexpensive hydrogen peroxide. This is an industrially advantageous production method.
[0020]
The usage of the silacyclohexanone compound will be described below.
Embedded image
In this way, an organometallic reagent is added to the silacyclohexanone compound to obtain an alcohol compound, followed by dehydration, hydrogenation, and halodesilation to obtain a halosilane obtained by changing the substituent Ar on silicon to halogen. By reducing the compound, a silacyclohexane type liquid crystal compound having a useful property and containing a silicon atom in the molecule is obtained as a final product.
[0021]
【Example】
Hereinafter, the present invention will be described in more detail with reference to specific examples.
Example 1 Production of 4-n-propyl-4-phenyl-4-silacyclohexanone
9.5 g (0.26 mol) of magnesium and 100 ml of THF are put into a 300 ml reaction vessel, and 47.1 g (0.26 mol) of 2- (2-bromoethyl) -1,3-dioxolane is added under a nitrogen atmosphere using a dropping funnel. In addition, a Grignard reagent was prepared. At this time, the reaction temperature is preferably adjusted to 40 to 45 ° C. At the start of the reaction, heating was performed for a short time. Since the reaction was completed at the end of the dropwise addition, 21.9 g (0.10 mol) of phenyl-n-propyldichlorosilane was added dropwise until the temperature was lowered to around room temperature. After completion of the dropwise addition, the mixture was further stirred at room temperature for 1 hour, extracted with 100 ml of a saturated aqueous ammonium chloride solution and 100 ml of an ethyl acetate solvent, and the organic layer was further washed with 50 ml of a saturated saline solution and subsequently dried over magnesium sulfate. The mixture was concentrated and purified by silica gel chromatography to obtain 30.5 g (96% yield) of di (2- (2-1,3-dioxolanyl) ethyl) -phenyl-n-propylsilane.
1H-NMR (100 MHz, CDCl3): Δ 0.70-1.78 (15H, m), 3.79-3.98 (8H, m), 4.81 (2H, t), 7.28-7.44 (5H, m) ppm
IR (KBr disc) νmax: 2880 (s), 2840 (s), 1400 (s), 1124 (s), 1041 (s), 962 (m), 840 (s), 740 (s), 700 (s) ) Cm-1
[0022]
40 ml of methanol is added to 6.4 g (0.02 mol) of di (2- (2-1,3-dioxolanyl) ethyl) -phenyl-n-propylsilane, and the reaction vessel is cooled to about 5 ° C. using an ice water bath. Then, 10 ml of 12N HCl aqueous solution was added dropwise, and further, 6.0 g (0.06 mol) of 34% hydrogen peroxide aqueous solution was added dropwise. After that, the ice water bath was replaced with an oil bath, heated to 40 ° C., and stirred for 4 hours. Was. After cooling the mixed solution to room temperature, extraction was performed using 50 ml of ethyl acetate and 50 ml of an aqueous solution of sodium sulfite. The organic layer was subjected to a usual washing and concentration operation, and then purified by silica gel chromatography to obtain di (2-methoxycarbonyl). 4.9 g (91% yield) of ethylene) -phenyl-n-propylsilane were obtained.
1H-NMR (100 MHz, CDCl3): Δ 0.74-1.37 (11H, m), 2.18-2.37 (4H, m), 3.61 (6H, s), 7.30-7.47 (5H, m) ppm
IR (KBr disc) νmax: 2952 (m), 1739 (s), 1434 (s), 1211 (s), 1110 (m), 1051 (m), 737 (m), 702 (s) cm-1
[0023]
17.6 g of di (2-methoxycarbonylethyl) -phenyl-n-propylsilane was added to a suspension of 1.85 g of sodium hydride and 80 ml of toluene, and the mixture was stirred at 100 ° C. for 3 hours while distilling off ethanol. When the mixed solution was cooled, 50 ml of 20% hydrochloric acid was added for neutralization, and the toluene layer was concentrated, thereby obtaining 14.1 g of 2-methoxycarbonyl-4-n-propyl-4-phenyl-4-silacyclohexanone. Got.
4.0 g of common salt, 1.2 g of water and 70 ml of dimethyl sulfoxide were added to the crude product, and the mixture was refluxed for 15 hours. After cooling the reaction mixture, water was added and extracted with a methylene chloride solvent. The extract was subjected to ordinary washing and concentration operations, and then purified by silica gel chromatography to obtain 11.5 g (yield: 91%) of the desired product.
1H-NMR (100 MHz, CDCl3): Δ
0.70-1.06 (5H, m), 1.06-1.60 (6H, m), 2.56 (4H, t), 7.25-7.66 (5H, m) ppm
IR (thin film) νmax: 2925 (s), 1705 (s), 1425 (m), 1310 (m), 1155 (m), 1110 (s), 1085 (s), 1065 (s), 730 (s) , 700 (s) cm-1
[0024]
Example 2 Production of 4-n-propyl-4-phenyl-4-silacyclohexanone
9.7 g (0.40 mol) of magnesium and 100 ml of THF were placed in a 300 ml reaction vessel, and under a nitrogen atmosphere, 27.2 g (0.20 mol) of 2- (2-chloroethyl) -1,3-dioxolane and 37.6 g of dibromoethane ( 0.20 mol) and 31.9 g (0.10 mol) of phenyl-n-propyldichlorosilane were added using a dropping funnel to simultaneously prepare a Grignard reagent and perform a coupling reaction with chlorosilane. . At this time, the reaction temperature is preferably adjusted to 40 to 45 ° C. At the start of the reaction, heating was performed for a short time. After completion of the dropwise addition, the mixture was further stirred at room temperature for 1 hour, extracted with 100 ml of a saturated aqueous ammonium chloride solution and 100 ml of an ethyl acetate solvent, and the organic layer was further washed with 50 ml of a saturated saline solution and subsequently dried over magnesium sulfate. The mixture was concentrated and purified by silica gel chromatography to obtain 26.7 g of di (2- (2-1,3-dioxolanyl) ethyl) -phenyl-n-propylsilane (yield 84%).
Hereinafter, the same experimental operation as in Example 1 was performed to obtain 10.1 g of the target product.
[0025]
Example 3 Production of 4-n-propyl-4-phenyl-4-silacyclohexanone
First, the same experimental operation as in Example 1 was performed to obtain 6.4 g (0.02 mol) of di (2- (2-1,3-dioxolanyl) ethyl) -phenyl-n-propylsilane. 40 ml of ethanol was added thereto, and the reaction vessel was cooled to around 5 ° C. using an ice water bath, 10 ml of 12N HCl was added dropwise, and further 6.0 g (0.06 mol) of 34% aqueous hydrogen peroxide was added. The ice water bath was replaced with an oil bath, heated to 40 ° C., and stirred for 4 hours. After cooling this mixed solution to room temperature, extraction was carried out using 50 ml of ethyl acetate and 50 ml of an aqueous solution of sodium sulfite, and the organic layer was purified by silica gel chromatography after a usual washing and concentration operation to obtain di (2- ( 5.3 g (89% yield) of (ethoxycarbonylethylene) -phenyl-n-propylsilane were obtained.
1H-NMR (100 MHz, CDCl3): Δ
0.90-1.38 (17H, m), 2.33 (4H, t), 4.18 (4H, m), 7.22-7.53 (5H, m) ppm
IR (thin film) νmax: 2960 (s), 1735 (s), 1425 (m), 1365 (m), 1205 (s), 1110 (s), 1050 (s) cm-1
[0026]
Next, 19.4 g of di (2-ethoxycarbonylethyl) -phenyl-n-propylsilane was added to a suspension of 1.85 g of sodium hydride and 80 ml of toluene. Stirred for hours. When the mixed solution was cooled, 50 ml of 20% hydrochloric acid was added to make the mixture neutral, and the toluene layer was concentrated to give 14.8 g of 2-ethoxycarbonyl-4-n-propyl-4-phenyl-4-silacyclohexanone. Obtained.
4.0 g of common salt, 1.2 g of water and 70 ml of dimethyl sulfoxide were added to the crude product, and the mixture was refluxed for 15 hours. After cooling the reaction mixture, water was added and extracted with a methylene chloride solvent. After the usual washing and concentration operations, the extract was purified by silica gel chromatography to obtain 11.5 g of the desired product.
[0027]
Example 4 Production of 4-n-pentyl-4-phenyl-4-silacyclohexanone
9.5 g (0.26 mol) of magnesium and 100 ml of THF are put into a 300 ml reaction vessel, and 47.1 g (0.26 mol) of 2- (2-bromoethyl) -1,3-dioxolane is added under a nitrogen atmosphere using a dropping funnel. In addition, a Grignard reagent was prepared. At this time, the reaction temperature is preferably adjusted to 40 to 45 ° C. At the start of the reaction, heating was performed for a short time. Since the reaction was completed at the end of the dropwise addition, 24.7 g (0.10 mol) of phenyl-n-pentyldichlorosilane was added dropwise while waiting for the temperature to drop to around room temperature. After completion of the dropwise addition, the mixture was further stirred at room temperature for 1 hour, extracted with 100 ml of a saturated aqueous ammonium chloride solution and 100 ml of an ethyl acetate solvent, and the organic layer was further washed with 50 ml of a saturated saline solution and subsequently dried over magnesium sulfate. The mixture was concentrated and purified by silica gel chromatography to obtain 32.5 g (yield 94%) of di (2- (2-1,3-dioxolanyl) ethyl) -phenyl-n-pentylsilane.
[0028]
Next, 40 ml of methanol was added to 6.9 g (0.02 mol) of di (2- (2-1,3-dioxolanyl) ethyl) -phenyl-n-pentylsilane, and the reaction vessel was placed in an ice water bath for 5 minutes. After cooling to around 0 ° C., 10 ml of 12N HCl water was added dropwise, and further 6.0 g (0.06 mol) of 34% hydrogen peroxide solution was added dropwise. The ice water bath was replaced with an oil bath, heated to 40 ° C., and stirred for 4 hours. Was done. After cooling the mixed solution to room temperature, extraction was performed using 50 ml of ethyl acetate and 50 ml of an aqueous solution of sodium sulfite. The organic layer was subjected to a usual washing and concentration operation, and then purified by silica gel chromatography to obtain di (2-methoxycarbonyl). 6.0 g (yield 92%) of ethylene) -phenyl-n-propylsilane was obtained.
[0029]
Next, 19.2 g of di (2-methoxycarbonylethyl) -phenyl-n-pentylsilane was added to a suspension of 1.85 g of sodium hydride and 80 ml of toluene, and ethanol was distilled off at 100 ° C. for 3 hours. Stirred. When the mixed solution was cooled, 50 ml of 20% hydrochloric acid was added to make it neutral, and the toluene layer was concentrated to give 2-methoxycarbonyl-4-n-propyl-4-phenyl-4-silacyclohexanone. 1 g was obtained.
4.0 g of sodium chloride, 1.2 g of water and 70 ml of dimethyl sulfoxide were added to the crude product, and the mixture was refluxed for 15 hours. After cooling the reaction mixture, water was added and extracted with a methylene chloride solvent. After the usual washing and concentration operations, the extract was purified by silica gel chromatography to obtain 11.5 g of the desired product.
1H-NMR (100 MHz, CDCl3): Δ
0.70-1.00 (5H, m), 1.00-1.60 (10H, m), 2.56 (4H, t), 7.10-7.65 (5H, m) ppm
IR (thin film) νmax: 2925 (s), 1705 (s), 1425 (m), 1310 (m), 1155 (m), 1110 (s), 1080 (s), 725 (s), 700 (s) cm-1
[0030]
(Application example)
As a practical application example of the silacyclohexanone compound obtained by the production method according to the present invention, a specific example of synthesizing a silacyclohexane type liquid crystal compound will be described.
Production of 4 '-(trans-4-n-propyl-4-silacyclohexyl) -4-fluorobiphenyl
To 200 ml of a tetrahydrofuran solution containing 10.2 g of magnesium, 100.4 g of 4'-bromo-4-fluorobiphenyl was added dropwise at 40 to 50C. A Grignard reagent was prepared by further stirring at 50 ° C. for 1 hour, and 46.4 g of 4-n-propyl-4-phenyl-4-silacyclohexanone was added dropwise while maintaining the temperature at 50 to 60 ° C. After stirring for 2 hours, the mixture was poured into a saturated aqueous solution of ammonium chloride and extracted with benzene. 5.0 g of p-toluenesulfonic acid monohydrate was added to the benzene solution, and the generated water was distilled off while refluxing. When the distillation of water stops, the reaction mixture is washed with an aqueous sodium hydrocarbon solution, dried and concentrated to give 4 ′-(4-phenyl-4-n-propyl-4-silacyclohex-3-cene) -4. -Fluorobiphenyl was obtained. This was dissolved in 100 ml of ethanol, hydrogenated using 2.0 g of palladium carbon as a catalyst, the catalyst was filtered off and concentrated, and 4 ′-(4-phenyl-4-n-propyl-4-silacyclohexyl) -4 -Fluorobiphenyl 66.0 g was obtained.
At room temperature, 200 ml of 1.0 M iodine chloride in carbon tetrachloride was added thereto, stirred for 30 minutes, and then concentrated. The residue was dissolved in 40 ml of tetrahydrofuran and added dropwise at 0 ° C. to a mixed solution of 8.0 g of lithium aluminum hydride and 100 ml of tetrahydrofuran. After stirring the reaction mixture for 1 hour, it was poured into 400 ml of 5% hydrochloric acid and extracted with ethyl acetate. After ordinary washing, drying and concentration, the residue was purified by silica gel chromatography to obtain 52.9 g (yield 77%) of the desired product.
Since this is a mixture of a trans form and a cis form with respect to the silacyclohexane ring, it was further separated by chromatography to obtain only the trans form, and the analysis results are shown below.
IR (thin film) νmax: 2918, 2854, 2087, 1604, 1497, 1238, 987, 889, 816 cm-1
CN transition temperature: 80.2 ° C
NI transition temperature: 119.3 ° C
[0031]
【The invention's effect】
As described above, the improved synthetic method of the useful synthetic intermediate silacyclohexanone compound for producing the liquid crystal compound according to the present invention, compared with the conventional method, first, the four steps of the reaction process, Grignard reagent Is a method advantageous for industrialization, such as a coupling reaction, an oxidation reaction, a condensation reaction with a base, and a dealkoxycarbonylation reaction. In addition, the yield of all four steps is 90% or more. Is also excellent. The oxidation reaction is a new method of directly oxidizing an acetal group to an ester group using a very inexpensive oxidizing agent such as aqueous hydrogen peroxide.
Claims (3)
で表されるクロロシラン化合物に、一般式（３）
で表される有機金属試薬とをカップリング反応させて得られる請求項１の一般式（１）で表される化合物の製造方法。General formula (2)
The chlorosilane compound represented by the general formula (3)
The method for producing a compound represented by the general formula (1) according to claim 1, which is obtained by performing a coupling reaction with an organometallic reagent represented by the following formula:
で表されるエステル化合物を直接に一段階の反応で得て、次に、この化合物に塩基を作用させ縮合反応を行うことで、一般式（５）
で表されるシラシクロヘキサノン化合物を得る製造方法。 The compound represented by the general formula (1) according to claim 1, a hydrogen halide and an aqueous solution of hydrogen peroxide are allowed to act in an alcohol solvent to oxidize an acetal moiety, and the general formula (4)
Is directly obtained in a one-step reaction, and then a base is allowed to act on this compound to carry out a condensation reaction, whereby a general formula (5)
A process for obtaining a silacyclohexanone compound represented by the formula:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00441397A JP3552139B2 (en) | 1997-01-14 | 1997-01-14 | Method for producing silacyclohexane compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00441397A JP3552139B2 (en) | 1997-01-14 | 1997-01-14 | Method for producing silacyclohexane compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10195079A JPH10195079A (en) | 1998-07-28 |
| JP3552139B2 true JP3552139B2 (en) | 2004-08-11 |
Family
ID=11583630
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP00441397A Expired - Fee Related JP3552139B2 (en) | 1997-01-14 | 1997-01-14 | Method for producing silacyclohexane compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3552139B2 (en) |
-
1997
- 1997-01-14 JP JP00441397A patent/JP3552139B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10195079A (en) | 1998-07-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI462993B (en) | Liquid crystal compound and liquid crystal mixture | |
| KR100821844B1 (en) | Liquid crystal composition comprising novel silicon containing compounds and liquid crystal display device using the same | |
| JP5476421B2 (en) | Liquid crystal compound | |
| KR101113901B1 (en) | Novel pyran derivative, its preparation method, liquid crystal composition and liquid crystal display device comprising the same | |
| KR100812067B1 (en) | Liquid crystal composition comprising novel silicon containing compounds and liquid crystal display device using the same | |
| JP3552139B2 (en) | Method for producing silacyclohexane compound | |
| US5560866A (en) | Process for preparing silacyclohexane compounds | |
| KR100196657B1 (en) | Process for preparing silacyclohexane compounds | |
| JP2750436B2 (en) | Alkenyl ether compound and liquid crystal composition containing the same | |
| CN103788039B (en) | Liquid-crystal compounds containing oxinane difluoromethylenedioconnecting linking group and preparation method and application | |
| TWI495710B (en) | Liquid crystal compound having hexahydro-cyclopenta(1,3)dioxinyl-based structure and liquid crystal composition | |
| TWI417368B (en) | Liquid crystal compound and liquid crystal mixture | |
| JPH08133996A (en) | Diacetylene compound, its production, liquid crystal composition containing the same as active component and liquid crystal element using the same | |
| JP2646262B2 (en) | Difluoroalkylcyclohexylbenzonitrile derivative | |
| JPH0316959B2 (en) | ||
| JPH0316958B2 (en) | ||
| JP4887591B2 (en) | Method for producing alkene derivative | |
| JP4501388B2 (en) | Liquid crystal composition and liquid crystalline compound containing difluorotetrahydronaphthalene derivative | |
| JP4115002B2 (en) | Liquid crystal compound | |
| JP3646739B2 (en) | Aromatic compound and process for producing the same | |
| JP2004352931A (en) | Liquid crystal composition containing difluorotetrahydronaphthalene derivative and liquid crystalline compound | |
| JPH03123750A (en) | Optically active liquid crystal compound | |
| JPH1072472A (en) | Silacyclohexane compound, liquid crystal composition and liquid crystal display element comprising the same | |
| JPH10251173A (en) | Production of fluoroalkenyl compound | |
| JPH0820588A (en) | Silaspiro compound, liquid crystal composition containing the same and liquid crystal display element |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20040203 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20040324 |
|
| 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: 20040409 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20040422 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130514 Year of fee payment: 9 |
|
| LAPS | Cancellation because of no payment of annual fees |