JPH08119974A - Silaspiro compound, its production and liquid crystal composition containing the same compound - Google Patents
Silaspiro compound, its production and liquid crystal composition containing the same compoundInfo
- Publication number
- JPH08119974A JPH08119974A JP6282741A JP28274194A JPH08119974A JP H08119974 A JPH08119974 A JP H08119974A JP 6282741 A JP6282741 A JP 6282741A JP 28274194 A JP28274194 A JP 28274194A JP H08119974 A JPH08119974 A JP H08119974A
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- group
- compound
- compound represented
- 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.)
- Pending
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 115
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 36
- 239000000203 mixture Substances 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- -1 3-n-pentyl-3-phenyl-3-silaspiro[5,5]undecane-9-one Chemical compound 0.000 claims abstract description 200
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 24
- 150000002367 halogens Chemical class 0.000 claims abstract description 22
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 20
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 15
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 12
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 11
- 125000002524 organometallic group Chemical group 0.000 claims abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 8
- 230000018044 dehydration Effects 0.000 claims abstract description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- 125000003944 tolyl group Chemical group 0.000 claims abstract description 4
- 230000007062 hydrolysis Effects 0.000 claims abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000007327 hydrogenolysis reaction Methods 0.000 claims description 9
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 7
- 238000005882 aldol condensation reaction Methods 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 230000007704 transition Effects 0.000 claims description 4
- 238000006845 Michael addition reaction Methods 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims 2
- 239000000126 substance Substances 0.000 abstract description 91
- 238000005828 desilylation reaction Methods 0.000 abstract description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 23
- 239000000047 product Substances 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000000460 chlorine Substances 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 6
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 6
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 4
- QZRGKCOWNLSUDK-UHFFFAOYSA-N Iodochlorine Chemical compound ICl QZRGKCOWNLSUDK-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000012280 lithium aluminium hydride Substances 0.000 description 4
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 4
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 3
- 239000012039 electrophile Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 150000002816 nickel compounds Chemical class 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 150000003335 secondary amines Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 125000006226 butoxyethyl group Chemical group 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 2
- 229940106681 chloroacetic acid Drugs 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- ZBQUMMFUJLOTQC-UHFFFAOYSA-L dichloronickel;3-diphenylphosphanylpropyl(diphenyl)phosphane Chemical compound Cl[Ni]Cl.C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 ZBQUMMFUJLOTQC-UHFFFAOYSA-L 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 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 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- RPNNPZHFJPXFQS-UHFFFAOYSA-N methane;rhodium Chemical compound C.[Rh] RPNNPZHFJPXFQS-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 2
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 2
- 150000002941 palladium compounds Chemical class 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 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
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910003446 platinum oxide Inorganic materials 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000006225 propoxyethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 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
- 238000011403 purification operation Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 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
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- SDTYFWAQLSIEBH-UHFFFAOYSA-N undec-3-ene Chemical compound CCCCCCCC=CCC SDTYFWAQLSIEBH-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- SYTBZMRGLBWNTM-SNVBAGLBSA-N (R)-flurbiprofen Chemical compound FC1=CC([C@H](C(O)=O)C)=CC=C1C1=CC=CC=C1 SYTBZMRGLBWNTM-SNVBAGLBSA-N 0.000 description 1
- 125000006002 1,1-difluoroethyl group Chemical group 0.000 description 1
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-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
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-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
- 125000004776 1-fluoroethyl group Chemical group [H]C([H])([H])C([H])(F)* 0.000 description 1
- HNEGJTWNOOWEMH-UHFFFAOYSA-N 1-fluoropropane Chemical group [CH2]CCF HNEGJTWNOOWEMH-UHFFFAOYSA-N 0.000 description 1
- 125000006039 1-hexenyl group Chemical group 0.000 description 1
- 125000006023 1-pentenyl group Chemical group 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- 125000004778 2,2-difluoroethyl group Chemical group [H]C([H])(*)C([H])(F)F 0.000 description 1
- 125000004777 2-fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 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
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000006041 3-hexenyl group Chemical group 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
- 125000005917 3-methylpentyl group Chemical group 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
- 125000006043 5-hexenyl group Chemical group 0.000 description 1
- UISZWYORHKBZTP-UHFFFAOYSA-N 7-methoxy-n,n-dimethyl-1h-indazole-3-carboxamide Chemical compound COC1=CC=CC2=C1NN=C2C(=O)N(C)C UISZWYORHKBZTP-UHFFFAOYSA-N 0.000 description 1
- PIVQQUNOTICCSA-UHFFFAOYSA-N ANTU Chemical compound C1=CC=C2C(NC(=S)N)=CC=CC2=C1 PIVQQUNOTICCSA-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000012448 Lithium borohydride Substances 0.000 description 1
- 238000006957 Michael reaction Methods 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004983 Polymer Dispersed Liquid Crystal Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- IZFMMUBPBGYYCI-UHFFFAOYSA-N [Mg]C1=CC=C(Cl)C=C1 Chemical compound [Mg]C1=CC=C(Cl)C=C1 IZFMMUBPBGYYCI-UHFFFAOYSA-N 0.000 description 1
- JEDZLBFUGJTJGQ-UHFFFAOYSA-N [Na].COCCO[AlH]OCCOC Chemical compound [Na].COCCO[AlH]OCCOC JEDZLBFUGJTJGQ-UHFFFAOYSA-N 0.000 description 1
- QWQONZVLXJGXHV-UHFFFAOYSA-N [chlorosulfonyloxy(dimethyl)silyl]methane Chemical compound C[Si](C)(C)OS(Cl)(=O)=O QWQONZVLXJGXHV-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- FXXACINHVKSMDR-UHFFFAOYSA-N acetyl bromide Chemical compound CC(Br)=O FXXACINHVKSMDR-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- XXECWTBMGGXMKP-UHFFFAOYSA-L dichloronickel;2-diphenylphosphanylethyl(diphenyl)phosphane Chemical compound Cl[Ni]Cl.C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 XXECWTBMGGXMKP-UHFFFAOYSA-L 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 125000000532 dioxanyl group Chemical group 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 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
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide 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
- 239000004615 ingredient Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- TWXDDNPPQUTEOV-FVGYRXGTSA-N methamphetamine hydrochloride Chemical compound Cl.CN[C@@H](C)CC1=CC=CC=C1 TWXDDNPPQUTEOV-FVGYRXGTSA-N 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000006610 n-decyloxy group Chemical group 0.000 description 1
- 125000001298 n-hexoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000006609 n-nonyloxy group Chemical group 0.000 description 1
- 125000006608 n-octyloxy group Chemical group 0.000 description 1
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 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 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- KFBKRCXOTTUAFS-UHFFFAOYSA-N nickel;triphenylphosphane Chemical compound [Ni].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 KFBKRCXOTTUAFS-UHFFFAOYSA-N 0.000 description 1
- UYLRKRLDQUXYKB-UHFFFAOYSA-N nickel;triphenylphosphane Chemical compound [Ni].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UYLRKRLDQUXYKB-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- ANRQGKOBLBYXFM-UHFFFAOYSA-M phenylmagnesium bromide Chemical compound Br[Mg]C1=CC=CC=C1 ANRQGKOBLBYXFM-UHFFFAOYSA-M 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229960003975 potassium Drugs 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 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
- 239000003586 protic polar solvent Substances 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 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 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- BEOOHQFXGBMRKU-UHFFFAOYSA-N sodium cyanoborohydride Chemical compound [Na+].[B-]C#N BEOOHQFXGBMRKU-UHFFFAOYSA-N 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 1
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-O tributylazanium Chemical compound CCCC[NH+](CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-O 0.000 description 1
- GGKBDRBGBRHDBH-UHFFFAOYSA-N undec-4-en-3-one Chemical compound CCCCCCC=CC(=O)CC GGKBDRBGBRHDBH-UHFFFAOYSA-N 0.000 description 1
- YNMZZHPSYMOGCI-UHFFFAOYSA-N undecan-3-one Chemical compound CCCCCCCCC(=O)CC YNMZZHPSYMOGCI-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Liquid Crystal Substances (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、液晶組成物の成分とし
て用いられる新規なシラスピロ化合物、その製造方法、
これを含有する液晶組成物及び該液晶組成物を含有する
液晶表示素子に関する。TECHNICAL FIELD The present invention relates to a novel silaspiro compound used as a component of a liquid crystal composition, a method for producing the same,
The present invention relates to a liquid crystal composition containing the same and a liquid crystal display device containing the liquid crystal composition.
【０００２】[0002]
【従来の技術】液晶表示素子は、液晶物質が持つ光学異
方性及び誘電異電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）、ＯＭＩ型（光学的モード干渉
型）、ＰＤＬＣ型（高分子分散型）、ＦＬＣＧ型（強誘
電液晶型）等、各種の方式がある。最も一般的なディス
プレーデバイスは、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。2. Description of the Related Art A liquid crystal display device utilizes an optical anisotropy and a dielectric heteroelectric property of a liquid crystal material. Depending on the display mode, a TN type (twisted nematic type) and an STN type (super twisted nematic type) are used. ), SBE type (super birefringent type),
DS type (dynamic scattering type), guest-host type, DAP type (aligned phase deformation type), OMI type (optical mode interference type), PDLC type (polymer dispersion type), FLCG type (ferroelectric liquid crystal type) ) Etc., there are various methods. The most common display devices are those that have a twisted nematic structure based on the Schatt-Helfrich effect.
【０００３】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、且つセル中において短いアドレス時間、低
い閾値電圧及び高いコントラストを与えることが望まれ
る。The properties required of the liquid crystal material used in these liquid crystal displays slightly vary depending on the display system, but the liquid crystal temperature range is wide, and the liquid crystal material is stable against moisture, air, light, heat, an electric field, and the like. This is commonly required in any of the display methods. Furthermore, it is desired that the liquid crystal material has a low viscosity and provides a short addressing time, a low threshold voltage and a high contrast in the cell.
【０００４】現在、単一の化合物でこれらの要求をすべ
て満たす物質はなく、実際には数種〜１０数種の液晶化
合物・潜在液晶化合物を混合して得られる液晶性混合物
が使用されている。それ故、構成成分が互いに容易に混
和できることが重要ともなる。At present, there is no substance that satisfies all of these requirements with a single compound. In practice, a liquid crystal mixture obtained by mixing several to several tens of liquid crystal compounds and latent liquid crystal compounds is used. . Therefore, it is also important that the components be easily miscible with each other.
【０００５】これらの液晶化合物として従来から知られ
ている化合物として、その分子構造中にベンゼン環、シ
クロヘキサン環、ピリミジン環、ジオキサン環、ピリジ
ン環等を含むものが数多く知られている。As the conventionally known compounds as these liquid crystal compounds, there are many known compounds containing a benzene ring, a cyclohexane ring, a pyrimidine ring, a dioxane ring, a pyridine ring, etc. in the molecular structure.
【０００６】一方、上記以外の環構造を含む化合物とし
て、以下のスピロ環構造を含む化合物が挙げられる。On the other hand, examples of compounds containing a ring structure other than those mentioned above include the following compounds containing a spiro ring structure.
【０００７】[0007]
【化２１】 （特開昭５９−１５２３４３号公報参照）[Chemical 21] (See JP-A-59-152343)
【０００８】[0008]
【化２２】Ｒ1−Ａ1−Ｚ1−Ａ2−［Ｚ2−Ａ3］n−Ｒ2 （Ｒ1、Ｒ2、Ａ1、Ａ2又はＡ3は、[Chemical formula 22] R1-A1-Z1-A2-[Z2-A3]n-R2 (R1, R2, A1, A2Or A3Is
【化２３】 又は[Chemical formula 23] Or
【化２４】 構造を含む。）（特表平１−５０３３８７号公報参照）[Chemical formula 24] Including structure. ) (See Japanese Patent Publication No. 1-503387)
【化２５】 （Ｍｏｌ．Ｃｒｙｓｔ．Ｌｉｑ．Ｃｒｙｓｔ．，１９８
９，Ｖｏｌ．１６８，ｐ．２３４）[Chemical 25] (Mol. Cryst. Liq. Cryst., 198.
9, Vol. 168, p. 234)
【０００９】[0009]
【発明が解決しようとする課題】近年、液晶ディスプレ
ーの用途が拡大するにつれて、液晶材料に要求される特
性も益々高度なものになりつつあり、また、駆動方式、
動作モードに関しても多様化が進みつつある。これに伴
って、従来の液晶化合物だけでは満足し得る液晶組成物
を構成することが難しくなってきており、成分選択幅の
拡大が求められてきた。With the recent widespread use of liquid crystal displays, the characteristics required of liquid crystal materials are becoming more and more sophisticated, and the driving method,
The operation modes are also diversifying. Along with this, it has become difficult to form a satisfactory liquid crystal composition only with conventional liquid crystal compounds, and there has been a demand for wider selection of components.
【００１０】本発明者らは、分子構造中にケイ素原子を
含んだネマチック液晶化合物としてシラシクロヘキサン
化合物について先に出願したが、成分選択幅の拡大が求
められるに従い、シラシクロヘキサン化合物以外の液晶
組成物の成分となり得る化合物の要望が高まっている。The present inventors have previously filed an application for a silacyclohexane compound as a nematic liquid crystal compound containing a silicon atom in its molecular structure. However, as the selection range of the components has been expanded, liquid crystal compositions other than the silacyclohexane compound have been filed. There is an increasing demand for compounds that can be used as ingredients.
【００１１】また、シクロヘキサン環又はシラシクロヘ
キサン環を有する液晶化合物は、その環の置換基の立体
配置に関してシス体及びトランス体の２種類の立体異性
体が存在する。このうち、液晶性を示すものはトランス
体のみであり、製造した化合物がシス体とトランス体の
混合物である場合は、トランス体を高純度に分離精製し
なければならず、これが液晶化合物が高価であることの
原因の一つとなっていた。The liquid crystal compound having a cyclohexane ring or a silacyclohexane ring has two stereoisomers of a cis isomer and a trans isomer with respect to the configuration of substituents on the ring. Of these, only the trans isomer exhibits liquid crystallinity, and if the produced compound is a mixture of cis isomer and trans isomer, the trans isomer must be separated and purified to a high purity, which makes the liquid crystal compound expensive. Was one of the causes of being.
【００１２】この様な観点から、本発明は、従来知られ
ていなかった新規な構造を有し、且つ製造時においてシ
ラシクロヘキサン化合物におけるトランス体とシス体の
分離操作のようなコストアップ要因となる精製操作が不
要である液晶化合物を提供することを目的とする。From this point of view, the present invention has a novel structure which has not been heretofore known, and causes a cost increase such as an operation for separating a trans form and a cis form in a silacyclohexane compound at the time of production. An object of the present invention is to provide a liquid crystal compound that does not require a purification operation.
【００１３】[0013]
【課題を解決するための手段】本発明者らは、分子構造
中にケイ素原子を３−シラスピロ［５．５］ウンデカン
環として含有するシラスピロ化合物がシラシクロヘキサ
ン化合物よりも更に安定であり、液晶組成物を構成する
成分についての選択肢を広げるものであることを見出
し、本発明に至った。DISCLOSURE OF THE INVENTION The inventors of the present invention have found that a silaspiro compound containing a silicon atom as a 3-silaspiro [5.5] undecane ring in its molecular structure is more stable than a silacyclohexane compound, and has a liquid crystal composition. The present invention has been completed by discovering that the choices of the components that compose a product are expanded.
【００１４】すなわち本発明は、下記一般式（Ｉ）で表
されるシラスピロ化合物である。That is, the present invention is a silaspiro compound represented by the following general formula (I).
【化２６】 但し、Ｒは炭素数１〜１０の直鎖状アルキル基、モノ又
はジフルオロアルキル基、炭素数３〜８の分枝鎖状アル
キル基、炭素数２〜７のアルコキシアルキル基又は炭素
数２〜８のアルケニル基、ＸはＣＮ、Ｆ、Ｃｌ、Ｂｒ、
ＣＦ3、ＯＣＦ3、ＯＣＨＦ2、ＯＣＨＦＣｌ、ＯＣＦ2Ｃ
ｌ、ＣＦ2Ｃｌ、Ｒ又はＯＲ基、Ｙ及びＺそれぞれ相互
に独立してハロゲン又はＣＨ3、ｉ及びｊはそれぞれ相
互に独立して０から３の整数、ｎは０又は１を表す。[Chemical formula 26] However, R is a C1-C10 linear alkyl group, a mono- or difluoroalkyl group, a C3-C8 branched alkyl group, a C2-C7 alkoxyalkyl group, or a C2-C8. Alkenyl group, X is CN, F, Cl, Br,
CF 3 , OCF 3 , OCHF 2 , OCHFCl, OCF 2 C
1, CF 2 Cl, R or OR group, Y and Z each independently of each other halogen or CH 3 , i and j each independently of each other represent an integer from 0 to 3, and n represents 0 or 1.
【００１５】また本発明は、上記一般式（Ｉ）で表され
るシラスピロ化合物の製造のための有用な合成中間体で
ある下記一般式（II）で表されるシラスピロケトン化合
物である。Further, the present invention is a silaspiroketone compound represented by the following general formula (II) which is a useful synthetic intermediate for the production of the silaspiro compound represented by the above general formula (I).
【化２７】 但し、Ａｒはフェニル基又はトリル基、ＲはＡｒ、炭素
数１〜１０の直鎖状アルキル基、モノ又はジフルオロア
ルキル基、炭素数３〜８の分枝鎖状アルキル基又は炭素
数２〜７のアルコキシアルキル基を表す。[Chemical 27] However, Ar is a phenyl group or a tolyl group, R is Ar, a linear alkyl group having 1 to 10 carbon atoms, a mono- or difluoroalkyl group, a branched chain alkyl group having 3 to 8 carbon atoms or 2 to 7 carbon atoms. Represents an alkoxyalkyl group.
【００１６】また本発明は、前記一般式（II）で表され
るシラスピロケトン化合物と、一般式The present invention also provides a silaspyroketone compound represented by the general formula (II)
【化２８】 （式中において、ＭはＭｇＰ（Ｐはハロゲンを表
す。）、ＺｎＰ又はＬｉ、ＸはＣＮ、Ｆ、Ｃｌ、Ｂｒ、
ＣＦ３、ＯＣＦ３、ＯＣＨＦ２、ＯＣＨＦＣｌ、ＯＣＦ
２Ｃｌ、ＣＦ２Ｃｌ、Ｒ又はＯＲ基、Ｙはハロゲン又は
ＣＨ３、ｉは０から２の整数を表す。）で表される有機
金属試薬とを反応させ、一般式[Chemical 28] (In the formula, M is MgP (P represents halogen), ZnP or Li, X is CN, F, Cl, Br,
CF 3 , OCF 3 , OCHF 2 , OCHFCl, OCF
2 Cl, CF 2 Cl, R or OR group, Y represents halogen or CH 3 , and i represents an integer of 0 to 2. ) With an organometallic reagent represented by the general formula
【化２９】 で表される化合物を得、次いで加水素分解又は脱水後に
水素添加することにより、一般式[Chemical 29] The compound represented by the general formula is prepared by hydrogenolysis or dehydration followed by hydrogenation.
【化３０】 で表される化合物を得、次にデシリレーションした後、
還元することにより、一般式Embedded image After obtaining the compound represented by
By reduction, the general formula
【化３１】 で表されるシラスピロ化合物を得ることを特徴とするシ
ラスピロ化合物の製造方法である。[Chemical 31] A method for producing a silaspiro compound, comprising obtaining a silaspiro compound represented by:
【００１７】また本発明は、一般式（II）で表されるシ
ラスピロケトン化合物と、一般式The present invention also relates to a silaspyroketone compound represented by the general formula (II)
【化３２】 （式中において、ＭはＭｇＵ（Ｕはハロゲンを表
す。）、ＺｎＵ又はＬｉ、ＸはＣＮ、Ｆ、Ｃｌ、Ｂｒ、
ＣＦ３、ＯＣＦ３、ＯＣＨＦ２、ＯＣＨＦＣｌ、ＯＣＦ
２Ｃｌ、ＣＦ２Ｃｌ、Ｒ又はＯＲ基、Ｙ及びＺはそれぞ
れ独立してハロゲン又はＣＨ３、ｉ及びｊはそれぞれ独
立して０から２の整数を表す。）で表される有機金属試
薬とを反応させ、一般式Embedded image (In the formula, M is MgU (U represents halogen), ZnU or Li, X is CN, F, Cl, Br,
CF 3 , OCF 3 , OCHF 2 , OCHFCl, OCF
2 Cl, CF 2 Cl, R or OR group, Y and Z each independently represent halogen or CH 3 , and i and j each independently represent an integer of 0 to 2. ) With an organometallic reagent represented by the general formula
【化３３】 で表される化合物を得、次いで加水素分解又は脱水後に
水素添加することにより、一般式[Chemical 33] The compound represented by the general formula is prepared by hydrogenolysis or dehydration followed by hydrogenation.
【化３４】 で表される化合物を得、次にデシリレーションした後、
還元することにより、一般式Embedded image After obtaining the compound represented by
By reduction, the general formula
【化３５】 で表されるシラスピロ化合物を得ることを特徴とするシ
ラスピロ化合物の製造方法である。Embedded image A method for producing a silaspiro compound, comprising obtaining a silaspiro compound represented by:
【００１８】また本発明は、一般式（II）で表されるシ
ラスピロケトン化合物と、一般式The present invention also relates to a silaspyroketone compound represented by the general formula (II)
【化３６】 （式中において、ＭはＭｇＵ（Ｕはハロゲンを表
す。）、ＺｎＵ又はＬｉ、Ｘ’はハロゲン、Ｙはハロゲ
ン又はＣＨ３、ｉは０から２の整数を表す。）で表され
る有機金属試薬とを反応させ、一般式Embedded image (In the formula, M is MgU (U represents halogen), ZnU or Li, X ′ is halogen, Y is halogen or CH 3 , and i is an integer of 0 to 2.) Reacts with reagents to give the general formula
【化３７】 で表される化合物を得、次いで加水素分解又は脱水後に
水素添加することにより、一般式Embedded image The compound represented by the general formula is prepared by hydrogenolysis or dehydration followed by hydrogenation.
【化３８】 で表される化合物を得、次いでこの化合物と、一般式[Chemical 38] A compound of the general formula
【化３９】 （式中において、Ｍ’はＭｇＵ（Ｕはハロゲンを表
す。）、ＺｎＵ又はＢ（ＯＶ）2（ＶはＨ又はアルキル
基を表す。）を表す。）で表される有機金属試薬とを遷
移金属触媒の存在下に反応させ、一般式[Chemical Formula 39] (In the formula, M ′ represents MgU (U represents halogen), ZnU or B (OV) 2 (V represents H or an alkyl group), and transition with an organometallic reagent. Reaction in the presence of a metal catalyst, the general formula
【化４０】 で表される化合物を得、次にデシリレーションした後、
還元することにより、一般式[Chemical 40] After obtaining the compound represented by
By reduction, the general formula
【化４１】 で表されるシラスピロ化合物を得ることを特徴とするシ
ラスピロ化合物の製造方法である。Embedded image A method for producing a silaspiro compound, comprising obtaining a silaspiro compound represented by:
【００１９】また本発明は、一般式The present invention also has the general formula
【化４２】 （式中において、Ｒ1 及びＲ2はそれぞれ炭素数１〜４の
アルキル基又はＲ1とＲ2とで環状をなす−（ＣＨ2）
4−、−（ＣＨ2）5−及び−（ＣＨ2） Ｏ（ＣＨ2）2−の
いずれかを表す。）で表されるエナミン化合物とメチル
ビニルケトンとをマイケル付加反応させ、次いで加水分
解して、一般式[Chemical 42](In the formula, R1 And R2Each has 1 to 4 carbon atoms
Alkyl group or R1And R2Form a ring with-(CH2)
Four-,-(CH2)Five-And- (CH2) O (CH2)2− Of
Represents either. ) Enamine compound and methyl
Michael addition reaction with vinyl ketone, followed by hydrolysis
By solving, the general formula
【化４３】 で表されるケトアルデヒド化合物を得、次にこのケトア
ルデヒド化合物を分子内アルドール縮合させることによ
り、一般式[Chemical 43] To obtain a ketoaldehyde compound, and then subject the ketoaldehyde compound to intramolecular aldol condensation to give a compound of the general formula
【化４４】 で表される不飽和ケトン化合物を得、次いでこの化合物
を水素添加することにより、一般式（II）[Chemical 44] An unsaturated ketone compound represented by the formula (II) is obtained by hydrogenating this compound.
【化４５】 で表されるシラスピロケトン化合物を製造することを特
徴とするシラスピロケトン化合物の製造方法である。Embedded image A method for producing a silaspyroketone compound, which comprises producing a silaspyroketone compound represented by:
【００２０】さらに本発明は、一般式（Ｉ）で表される
シラスピロ化合物を含有することを特徴とする液晶組成
物及びこの液晶組成物を含有することを特徴とする液晶
表示素子である。Further, the present invention is a liquid crystal composition characterized by containing a silaspiro compound represented by the general formula (I), and a liquid crystal display device characterized by containing the liquid crystal composition.
【００２１】次に、本発明をさらに詳細に説明する。Next, the present invention will be described in more detail.
【００２２】本発明の一般式（Ｉ）The general formula (I) of the present invention
【化４６】 で表されるシラスピロ化合物は、このように３−シラス
ピロ［５．５］ウンデカン環を含む構造で表される。こ
の化合物は軸性キラリティーを有しており、前記一般式
（Ｉ）で示したものは、鏡像体（エナンチオマ−）対、
すなわちＲ体とＳ体の混合物であるラセミ体を表すもの
である。Embedded image The silaspiro compound represented by is thus represented by a structure containing a 3-silaspiro [5.5] undecane ring. This compound has axial chirality, and the compound represented by the above general formula (I) is an enantiomer (enantiomer) pair,
That is, it represents a racemic body which is a mixture of R-form and S-form.
【００２３】Ｒは、以下のいずれかを表す。 （ａ）炭素数１〜１０の直鎖状アルキル基、即ち、メチ
ル基、エチル基、ｎ−プロピル基、ｎ−ブチル基、ｎ−
ペンチル基、ｎ−ヘキシル基、ｎ−ヘプチル基、ｎ−オ
クチル基、ｎ−ノニル基又はｎ−デシル基。 （ｂ）炭素数１〜１０のモノ又はジフロロアルキル基、
即ち、フロロメチル、１−フロロエチル、１−フロロプ
ロピル、１−フロロブチル、１−フロロペンチル、１−
フロロヘキシル、１−フロロヘプチル、１−フロロオク
チル、１−フロロノニル、１−フロロデシル、２−フロ
ロエチル、２−フロロプロピル、２−フロロブチル、２
−フロロペンチル、２−フロロヘキシル、２−フロロヘ
プチル、２−フロロオクチル、２−フロロノニル、２−
フロロデシル、３−フロロプロピル、３−フロロブチ
ル、３−フロロペンチル、３−フロロヘキシル、３−フ
ロロヘプチル、３−フロロオクチル、３−フロロノニ
ル、３−フロロデシル、４−フロロブチル、４−フロロ
ペンチル、４−フロロヘキシル、４−フロロヘプチル、
４−フロロオクチル、４−フロロノニル、４−フロロデ
シル、５−フロロペンチル、５−フロロヘキシル、５−
フロロヘプチル、５−フロロオクチル、５−フロロノニ
ル、５−フロロデシル、６−フロロヘキシル、６−フロ
ロヘプチル、６−フロロオクチル、６−フロロノニル、
６−フロロデシル、７−フロロヘプチル、７−フロロオ
クチル、７−フロロノニル、７−フロロデシル、８−フ
ロロオクチル、８−フロロノニル、８−フロロデシル、
９−フロロノニル、９−フロロデシル、１０−フロロデ
シル、ジフロロメチル、１，１−ジフロロエチル、１，
１−ジフロロプロピル、１，１−ジフロロブチル、１，
１−ジフロロペンチル、１，１−ジフロロヘキシル、
１，１−ジフロロヘプチル、１，１−ジフロロオクチ
ル、１，１−ジフロロノニル、１，１−ジフロロデシ
ル、２，２−ジフロロエチル、２，２−ジフロロプロピ
ル、２，２−ジフロロブチル、２，２−ジフロロペンチ
ル、２，２−ジフロロヘキシル、２，２−ジフロロヘプ
チル、２，２−ジフロロオクチル、２，２−ジフロロノ
ニル、２，２−ジフロロデシル、３，３−ジフロロプロ
ピル、３，３−ジフロロブチル、３，３−ジフロロペン
チル、３，３−ジフロロヘキシル、３，３−ジフロロヘ
プチル、３，３−ジフロロオクチル、３，３−ジフロロ
ノニル、３，３−ジフロロデシル、４，４−ジフロロブ
チル、４，４−ジフロロペンチル、４，４−ジフロロヘ
キシル、４，４−ジフロロヘプチル、４，４−ジフロロ
オクチル、４，４−ジフロロノニル、４，４−ジフロロ
デシル、５，５−ジフロロペンチル、５，５−ジフロロ
ヘキシル、５，５−ジフロロヘプチル、５，５−ジフロ
ロオクチル、５，５−ジフロロノニル、５，５−ジフロ
ロデシル、６，６−ジフロロヘキシル、６，６−ジフロ
ロヘプチル、６，６−ジフロロオクチル、６，６−ジフ
ロロノニル、６，６−ジフロロデシル、７，７−ジフロ
ロヘプチル、７，７−ジフロロオクチル、７，７−ジフ
ロロノニル、７，７−ジフロロデシル、８，８−ジフロ
ロオクチル、８，８−ジフロロノニル、８，８−ジフロ
ロデシル、９，９−ジフロロノニル、９，９−ジフロロ
デシル又は１０，１０−ジフロロデシル。 （ｃ）炭素数３〜８の分枝鎖状アルキル基、即ち、イソ
プロピル基、ｓｅｃ−ブチル基、イソブチル基、１−メ
チルブチル基、２−メチルブチル基、３−メチルブチル
基、１−メチルペンチル基、２−メチルペンチル基、３
−メチルペンチル基、１−エチルペンチル基、１−メチ
ルヘキシル基、２−メチルヘキシル基、３−メチルヘキ
シル基、２−エチルヘキシル基、３−エチルヘキシル
基、１−メチルヘプチル基、２−メチルヘプチル基又は
３−メチルヘプチル基。 （ｄ）炭素数２〜７のアルコキシアルキル基、即ち、メ
トキシメチル基、エトキシメチル基、プロポキシメチル
基、ブトキシメチル基、ペントキシメチル基、ヘキシロ
キシメチル基、メトキシエチル基、エトキシエチル基、
プロポキシエチル基、ブトキシエチル基、ペントキシエ
チル基、メトキシプロピル基、エトキシプロピル基、プ
ロポキシプロピル基、ブトキシプロピル基、メトキシブ
チル基、エトキシブチル基、プロポキシブチル基、メト
キシペンチル基、エトキシペンチル基又はメトキシヘキ
シル基。 （ｅ）炭素類２〜８のアルケニル基、即ち、ビニル基、
１−プロペニル基、アリル基、１−ブテニル基、イソプ
レニル基、１−ペンテニル基、３−ペンテニル基、４−
ペンテニル基、ジメチルアリル基、１−ヘキセニル基、
３−ヘキセニル基、５−ヘキセニル基、１−ヘプテニル
基、３−ヘプテニル基、６−ヘプテニル基又は７−オク
テニル基。R represents any of the following: (A) A linear alkyl group having 1 to 10 carbon atoms, that is, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-
Pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group or n-decyl group. (B) a mono- or difluoroalkyl group having 1 to 10 carbon atoms,
That is, fluoromethyl, 1-fluoroethyl, 1-fluoropropyl, 1-fluorobutyl, 1-fluoropentyl, 1-
Fluorohexyl, 1-fluoroheptyl, 1-fluorooctyl, 1-fluorononyl, 1-fluorodecyl, 2-fluoroethyl, 2-fluoropropyl, 2-fluorobutyl, 2
-Fluoropentyl, 2-fluorohexyl, 2-fluoroheptyl, 2-fluorooctyl, 2-fluorononyl, 2-
Fluorodecyl, 3-fluoropropyl, 3-fluorobutyl, 3-fluoropentyl, 3-fluorohexyl, 3-fluoroheptyl, 3-fluorooctyl, 3-fluorononyl, 3-fluorodecyl, 4-fluorobutyl, 4-fluoropentyl, 4- Fluorohexyl, 4-fluoroheptyl,
4-fluorooctyl, 4-fluorononyl, 4-fluorodecyl, 5-fluoropentyl, 5-fluorohexyl, 5-
Fluoroheptyl, 5-fluorooctyl, 5-fluorononyl, 5-fluorodecyl, 6-fluorohexyl, 6-fluoroheptyl, 6-fluorooctyl, 6-fluororonyl,
6-fluorodecyl, 7-fluoroheptyl, 7-fluorooctyl, 7-fluororonyl, 7-fluorodecyl, 8-fluorooctyl, 8-fluororonyl, 8-fluorodecyl,
9-Fluorononyl, 9-fluorodecyl, 10-fluorodecyl, difluoromethyl, 1,1-difluoroethyl, 1,
1-difluoropropyl, 1,1-difluorobutyl, 1,
1-difluoropentyl, 1,1-difluorohexyl,
1,1-difluoroheptyl, 1,1-difluorooctyl, 1,1-difluorononyl, 1,1-difluorodecyl, 2,2-difluoroethyl, 2,2-difluoropropyl, 2,2-difluorobutyl, 2, 2-difluoropentyl, 2,2-difluorohexyl, 2,2-difluoroheptyl, 2,2-difluorooctyl, 2,2-difluororonyl, 2,2-difluorodecyl, 3,3-difluoropropyl, 3,3-difluorobutyl, 3,3-difluoropentyl, 3,3-difluorohexyl, 3,3-difluoroheptyl, 3,3-difluorooctyl, 3,3-difluorononyl, 3,3-difluorodecyl, 4,4-difluorobutyl, 4,4-difluoropentyl, 4,4-difluorohexyl, 4,4-difluoroheptyl, 4,4-difluorooctyl, 4,4-di Rorononyl, 4,4-difluorodecyl, 5,5-difluoropentyl, 5,5-difluorohexyl, 5,5-difluoroheptyl, 5,5-difluorooctyl, 5,5-difluororonyl, 5,5- Difluorodecyl, 6,6-difluorohexyl, 6,6-difluoroheptyl, 6,6-difluorooctyl, 6,6-difluororonyl, 6,6-difluorodecyl, 7,7-difluoroheptyl, 7,7- Difluorooctyl, 7,7-difluororonyl, 7,7-difluorodecyl, 8,8-difluorooctyl, 8,8-difluororonyl, 8,8-difluorodecyl, 9,9-difluorononyl, 9,9-difluorodecyl or 10, 10-difluorodecyl. (C) a branched alkyl group having 3 to 8 carbon atoms, i.e., isopropyl, sec-butyl, isobutyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-methylpentyl, 2-methylpentyl group, 3
-Methylpentyl group, 1-ethylpentyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 1-methylheptyl group, 2-methylheptyl group Or a 3-methylheptyl group. (D) an alkoxyalkyl group having 2 to 7 carbon atoms, that is, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, a pentoxymethyl group, a hexyloxymethyl group, a methoxyethyl group, an ethoxyethyl group,
Propoxyethyl group, butoxyethyl group, pentoxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, butoxypropyl group, methoxybutyl group, ethoxybutyl group, propoxybutyl group, methoxypentyl group, ethoxypentyl group or methoxy Hexyl group. (E) an alkenyl group having 2 to 8 carbon atoms, that is, a vinyl group,
1-propenyl group, allyl group, 1-butenyl group, isoprenyl group, 1-pentenyl group, 3-pentenyl group, 4-
Pentenyl group, dimethylallyl group, 1-hexenyl group,
3-hexenyl group, 5-hexenyl group, 1-heptenyl group, 3-heptenyl group, 6-heptenyl group or 7-octenyl group.
【００２４】ＸはＣＮ、Ｆ、Ｃｌ、Ｂｒ、ＣＦ3、ＯＣ
Ｆ 3、ＯＣＨＦ 2、ＯＣＨＦＣｌ、ＯＣＦ 2Ｃｌ、ＣＦ 2Ｃ
ｌ又は以下のいずれかを表す。 （ｆ）炭素数１〜１０の直鎖状アルキル基、即ち、メチ
ル基、エチル基、ｎ−プロピル基、ｎ−ブチル基、ｎ−
ヘキシル基、ｎ−ヘプチル基、ｎ−オクチル基、ｎ−ノ
ニル基又はｎ−デシル基。 （ｇ）炭素数１〜１０の直鎖状アルコキシ基、即ち、メ
トキシ基、エトキシ基、ｎ−プロポキシ基、ｎ−ブトキ
シ基、ｎ−ペントキシ基、ｎ−ヘキシロキシ基、ｎ−ヘ
プチロキシ基、ｎ−オクチロキシ基、ｎ−ノニロキシ基
又はｎ−デシロキシ基。 （ｈ）炭素数２〜７のアルコキシアルキル基、即ち、メ
トキシメチル基、エトキシメチル基、プロポキシメチル
基、ブトキシメチル基、ペントキシメチル基、ヘキシロ
キシメチル基、メトキシエチル基、エトキシエチル基、
プロポキシエチル基、ブトキシエチル基、ペントキシエ
チル基、メトキシプロピル基、エトキシプロピル基、プ
ロポキシプロピル基、ブトキシプロピル基、メトキシブ
チル基、エトキシブチル基、プロポキシブチル基、メト
キシペンチル基、エトキシペンチル基又はメトキシヘキ
シル基。X is CN, F, Cl, Br, CF3, OC
F 3, OCHF 2, OCHFCl, OCF 2Cl, CF 2C
represents either 1 or the following: (F) a linear alkyl group having 1 to 10 carbon atoms, that is, a methyl group
Group, ethyl group, n-propyl group, n-butyl group, n-
Hexyl group, n-heptyl group, n-octyl group, n-no
Nyl group or n-decyl group. (G) a straight-chain alkoxy group having 1 to 10 carbon atoms, that is,
Toxy group, ethoxy group, n-propoxy group, n-butoxy group
Si group, n-pentoxy group, n-hexyloxy group, n-hexyl group
Butyloxy group, n-octyloxy group, n-nonyloxy group
Or an n-decyloxy group. (H) an alkoxyalkyl group having 2 to 7 carbon atoms, that is,
Toxymethyl group, ethoxymethyl group, propoxymethyl group
Group, butoxymethyl group, pentoxymethyl group, hexyl
Xymethyl group, methoxyethyl group, ethoxyethyl group,
Propoxyethyl group, butoxyethyl group, pentoxye
Chill group, methoxypropyl group, ethoxypropyl group,
Ropoxypropyl group, butoxypropyl group, methoxybu
Cyl group, ethoxybutyl group, propoxybutyl group, meth
Xypentyl group, ethoxypentyl group or methoxyhexyl group
Sil group.
【００２５】Ｙ及びＺはそれぞれ相互に独立してハロゲ
ン又はＣＨ3を表す。Y and Z each independently represent halogen or CH 3 .
【００２６】次に、前記一般式（Ｉ）で表されるシラス
ピロ化合物の部分構造であるNext, it is a partial structure of the silaspiro compound represented by the general formula (I).
【化４７】 としては、以下のものが挙げられる。[Chemical 47] The following may be mentioned as examples.
【００２７】[0027]
【化４８】 Embedded image
【００２８】[0028]
【化４９】 [Chemical 49]
【００２９】[0029]
【化５０】 Embedded image
【００３０】[0030]
【化５１】 [Chemical 51]
【００３１】[0031]
【化５２】 Embedded image
【００３２】[0032]
【化５３】 Embedded image
【００３３】[0033]
【化５４】 [Chemical 54]
【００３４】[0034]
【化５５】 [Chemical 55]
【００３５】[0035]
【化５６】 [Chemical 56]
【００３６】[0036]
【化５７】 [Chemical 57]
【００３７】[0037]
【化５８】 Embedded image
【００３８】[0038]
【化５９】 Embedded image
【００３９】[0039]
【化６０】 Embedded image
【００４０】[0040]
【化６１】 [Chemical formula 61]
【００４１】[0041]
【化６２】 Embedded image
【００４２】[0042]
【化６３】 [Chemical formula 63]
【００４３】[0043]
【化６４】 [Chemical 64]
【００４４】[0044]
【化６５】 Embedded image
【００４５】[0045]
【化６６】 [Chemical formula 66]
【００４６】[0046]
【化６７】 Embedded image
【００４７】[0047]
【化６８】 [Chemical 68]
【００４８】[0048]
【化６９】 [Chemical 69]
【００４９】[0049]
【化７０】 Embedded image
【００５０】[0050]
【化７１】 Embedded image
【００５１】[0051]
【化７２】 Embedded image
【００５２】[0052]
【化７３】 Embedded image
【００５３】[0053]
【化７４】 [Chemical 74]
【００５４】[0054]
【化７５】 [Chemical 75]
【００５５】[0055]
【化７６】 [Chemical 76]
【００５６】[0056]
【化７７】 Embedded image
【００５７】[0057]
【化７８】 Embedded image
【００５８】[0058]
【化７９】 Embedded image
【００５９】[0059]
【化８０】 Embedded image
【００６０】[0060]
【化８１】 [Chemical 81]
【００６１】[0061]
【化８２】 [Chemical formula 82]
【００６２】[0062]
【化８３】 [Chemical 83]
【００６３】[0063]
【化８４】 [Chemical 84]
【００６４】[0064]
【化８５】 Embedded image
【００６５】[0065]
【化８６】 [Chemical 86]
【００６６】[0066]
【化８７】 [Chemical 87]
【００６７】[0067]
【化８８】 Embedded image
【００６８】[0068]
【化８９】 [Chemical 89]
【００６９】[0069]
【化９０】 [Chemical 90]
【００７０】[0070]
【化９１】 Embedded image
【００７１】[0071]
【化９２】 Embedded image
【００７２】[0072]
【化９３】 Embedded image
【００７３】[0073]
【化９４】 Embedded image
【００７４】[0074]
【化９５】 Embedded image
【００７５】[0075]
【化９６】 [Chemical 96]
【００７６】[0076]
【化９７】 Embedded image
【００７７】[0077]
【化９８】 Embedded image
【００７８】[0078]
【化９９】 Embedded image
【００７９】[0079]
【化１００】 [Chemical 100]
【００８０】[0080]
【化１０１】 [Chemical 101]
【００８１】[0081]
【化１０２】 Embedded image
【００８２】[0082]
【化１０３】 Embedded image
【００８３】[0083]
【化１０４】 [Chemical 104]
【００８４】[0084]
【化１０５】 Embedded image
【００８５】[0085]
【化１０６】 [Chemical formula 106]
【００８６】[0086]
【化１０７】 [Chemical formula 107]
【００８７】[0087]
【化１０８】 [Chemical 108]
【００８８】[0088]
【化１０９】 [Chemical 109]
【００８９】[0089]
【化１１０】 [Chemical 110]
【００９０】[0090]
【化１１１】 [Chemical 111]
【００９１】[0091]
【化１１２】 [Chemical 112]
【００９２】[0092]
【化１１３】 [Chemical 113]
【００９３】[0093]
【化１１４】 [Chemical 114]
【００９４】[0094]
【化１１５】 [Chemical 115]
【００９５】[0095]
【化１１６】 [Chemical formula 116]
【００９６】[0096]
【化１１７】 [Chemical 117]
【００９７】[0097]
【化１１８】 [Chemical 118]
【００９８】[0098]
【化１１９】 [Chemical formula 119]
【００９９】[0099]
【化１２０】 [Chemical 120]
【０１００】[0100]
【化１２１】 [Chemical 121]
【０１０１】[0101]
【化１２２】 [Chemical formula 122]
【０１０２】[0102]
【化１２３】 [Chemical 123]
【０１０３】[0103]
【化１２４】 [Chemical formula 124]
【０１０４】[0104]
【化１２５】 Embedded image
【０１０５】[0105]
【化１２６】 [Chemical formula 126]
【０１０６】[0106]
【化１２７】 Embedded image
【０１０７】[0107]
【化１２８】 [Chemical 128]
【０１０８】[0108]
【化１２９】 [Chemical formula 129]
【０１０９】[0109]
【化１３０】 Embedded image
【０１１０】[0110]
【化１３１】 [Chemical 131]
【０１１１】[0111]
【化１３２】 [Chemical 132]
【０１１２】[0112]
【化１３３】 Embedded image
【０１１３】[0113]
【化１３４】 Embedded image
【０１１４】[0114]
【化１３５】 [Chemical 135]
【０１１５】[0115]
【化１３６】 [Chemical 136]
【０１１６】[0116]
【化１３７】 [Chemical 137]
【０１１７】[0117]
【化１３８】 [Chemical 138]
【０１１８】[0118]
【化１３９】 [Chemical 139]
【０１１９】[0119]
【化１４０】 [Chemical 140]
【０１２０】[0120]
【化１４１】 [Chemical 141]
【０１２１】次に、本発明の一般式（Ｉ）Next, the general formula (I) of the present invention:
【化１４２】 で表されるシラスピロ化合物の製造方法について説明す
る。この一般式（Ｉ）で表されるシラスピロ化合物は、
一般式(II)[Chemical 142] The method for producing the silaspiro compound represented by will be described. The silaspiro compound represented by the general formula (I) is
General formula (II)
【化１４３】 （式中において、Ａｒはフェニル基又はトリル基、Ｒは
Ａｒ、炭素数１〜１０の直鎖状アルキル基、モノ又はジ
フルオロアルキル基、炭素数３〜８の分枝鎖状アルキル
基又は炭素数２〜７のアルコキシアルキル基を表す。）
で表されるシラスピロケトン化合物から誘導される。[Chemical 143] (In the formula, Ar is a phenyl group or a tolyl group, R is Ar, a linear alkyl group having 1 to 10 carbon atoms, a mono- or difluoroalkyl group, a branched chain alkyl group having 3 to 8 carbon atoms, or the number of carbon atoms. It represents an alkoxyalkyl group of 2 to 7.)
It is derived from a silaspyroketone compound represented by
【０１２２】この一般式（II）で表されるシラスピロケ
トン化合物は、一般式The silaspiroketone compound represented by the general formula (II) has the general formula
【化１４４】 （式中において、Ｒ1 及びＲ2はそれぞれ炭素数１〜４の
アルキル基又はＲ1とＲ2とで環状をなす−（ＣＨ2）
4−、−（ＣＨ2）5及び−（ＣＨ2）2Ｏ（ＣＨ2）2−の
いずれかを表す。）で表されるエナミン化合物とメチル
ビニルケトンとから、以下に詳しく述べるようにＳｔｏ
ｒｋ法（Ｇ．Ｓｔｏｒｋら、Ｊ．Ａｍｅｒ．Ｃｈｅｍ．
Ｓｏｃ．，８５，２０７（１９６３））により製造され
る。[Chemical 144](In the formula, R1 And R2Each has 1 to 4 carbon atoms
Alkyl group or R1And R2Form a ring with-(CH2)
Four-,-(CH2)FiveAnd- (CH2)2O (CH2)2− Of
Represents either. ) Enamine compound and methyl
From vinyl ketone, as described in detail below, Sto
rk method (G. Stork et al.,J. Amer. Chem.
Soc.,85, 207 (1963))
You.
【０１２３】出発原料のエナミン化合物は、先に本発明
者等が出願したシラシクロヘキサンカルバルデヒド化合
物と２級アミンとの脱水反応を行うことによって得られ
る。The enamine compound as a starting material can be obtained by subjecting the silacyclohexanecarbaldehyde compound previously filed by the present inventors to a dehydration reaction with a secondary amine.
【０１２４】[0124]
【化１４５】 [Chemical 145]
【０１２５】この脱水反応は、ベンゼン、トルエン、キ
シレン、クメン、ｎ−ヘキサン、ｎ−ヘプタン、イソオ
クタン等の炭化水素溶媒を用いて生じる水を共沸（Ａｚ
ｅｏｔｒｏｐｅ）により系外に除去することにより反応
速度を高めることができる。この際、触媒としてｐ−ト
ルエンスルホン酸、ベンゼンスルホン酸、カンファース
ルホン酸等の酸類を添加してもよい。In this dehydration reaction, water produced by using a hydrocarbon solvent such as benzene, toluene, xylene, cumene, n-hexane, n-heptane and isooctane is azeotropically distilled (Az).
The reaction rate can be increased by removing it outside the system by eotrope). At this time, acids such as p-toluenesulfonic acid, benzenesulfonic acid and camphorsulfonic acid may be added as a catalyst.
【０１２６】また、無水炭酸カリウム、無視炭酸ナトリ
ウム等の無水塩類を加えておいて、生じる水を除く方法
も用いられる。Further, a method of adding anhydrous salts such as anhydrous potassium carbonate, neglected sodium carbonate and the like to remove water produced can also be used.
【０１２７】なお、２級アミンとしては、ジメチルアミ
ン、ジエチルアミン、ジ−ｎ−プロピルアミン、ピロリ
ジン、ピペリジン、モルホリン等を好ましく例示でき
る。Preferred examples of the secondary amine include dimethylamine, diethylamine, di-n-propylamine, pyrrolidine, piperidine and morpholine.
【０１２８】このようにして合成されたエナミン化合物
をメチルビニルケトンとマイケル付加反応させ、次いで
酸による加水分解を行い、ケトアルデヒド化合物を得
る。The enamine compound thus synthesized is subjected to a Michael addition reaction with methyl vinyl ketone and then hydrolyzed with an acid to obtain a ketoaldehyde compound.
【０１２９】[0129]
【化１４６】 [Chemical 146]
【０１３０】メチルビニルケトンを、エナミン化合物に
対し１〜５等量、好ましくは１〜１．５等量用いて溶媒
中で加熱する。反応溶媒として、ベンゼン、トルエン、
キシレン、クメン、ｎ−ヘキサン、ｎ−ヘプタン、イソ
オクタン、シクロヘキサン等の炭化水素類、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、１，４−ジオキサン等のエーテル類、メタノール、
エタノール、プロパノール、ブタノール等のアルコール
類、Ｎ，Ｎ−ジメチルホルムアミド、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、１，３−
ジメチル−２−イミダゾリジノン、Ｎ，Ｎ’−ジメチル
プロピレンウレア等の極性溶媒類を単独または混合して
用いる。この際、プロトン性溶媒を含むようにするとマ
イケル反応におけるプロトン移動が加速され、反応時間
を短縮できる場合がある。Methyl vinyl ketone is heated in a solvent in an amount of 1 to 5 equivalents, preferably 1 to 1.5 equivalents, based on the enamine compound. As a reaction solvent, benzene, toluene,
Hydrocarbons such as xylene, cumene, n-hexane, n-heptane, isooctane and cyclohexane, tetrahydrofuran, diethyl ether, di-n-butyl ether, ethers such as 1,4-dioxane, methanol,
Alcohols such as ethanol, propanol, butanol, N, N-dimethylformamide, dimethyl sulfoxide, hexamethylphosphoric triamide, 1,3-
Polar solvents such as dimethyl-2-imidazolidinone and N, N'-dimethylpropyleneurea are used alone or in combination. At this time, if a protic solvent is included, the proton transfer in the Michael reaction may be accelerated, and the reaction time may be shortened in some cases.
【０１３１】このマイケル付加物を、塩酸、硫酸等の無
機酸類、またはシュウ酸、トリフルオロ酢酸、クロロ酢
酸等の有機酸類を用いて加水分解することによりケトア
ルデヒド化合物を得る。The Michael adduct is hydrolyzed with an inorganic acid such as hydrochloric acid or sulfuric acid or an organic acid such as oxalic acid, trifluoroacetic acid or chloroacetic acid to obtain a ketoaldehyde compound.
【０１３２】次に、得られたケトアルデヒド化合物を分
子内アルドール縮合させることにより、反応式［化１４
７］で示すように不飽和ケトン化合物を得る。Then, the obtained ketoaldehyde compound is subjected to intramolecular aldol condensation to give a reaction formula
7] to obtain an unsaturated ketone compound.
【０１３３】[0133]
【化１４７】 [Chemical 147]
【０１３４】このアルドール縮合反応は、塩基又は酸に
よって触媒される。塩基触媒として、上記の２級アミ
ン、トリエチルアミン、トリ−ｎ−ブチルアミン、ジメ
チルアニリン等の有機塩基、炭酸ナトリウム、炭酸カリ
ウム、炭酸水素ナトリウム、炭酸水素カリウム等の無機
塩類、または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−ブトキシド等のアルコキシド類を挙
げることができる。酸触媒として、塩酸、硫酸等の無機
酸類、ｐ−トルエンスルホン酸、ベンゼンスルホン酸、
酢酸、プロピオン酸、シュウ酸、トリフルオロ酢酸、ク
ロロ酢酸等の有機酸類を挙げることができる。The aldol condensation reaction is catalyzed by base or acid. As the base catalyst, organic bases such as secondary amine, triethylamine, tri-n-butylamine and dimethylaniline, inorganic salts such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate, or sodium methoxide and sodium ethoxy as the base catalyst. And alkoxides such as potassium t-butoxide. As an acid catalyst, inorganic acids such as hydrochloric acid and sulfuric acid, p-toluenesulfonic acid, benzenesulfonic acid,
Organic acids such as acetic acid, propionic acid, oxalic acid, trifluoroacetic acid and chloroacetic acid can be mentioned.
【０１３５】塩基触媒アルドール縮合反応において、生
成した不飽和ケトン化合物が触媒のアミンと更に反応し
てそのエナミン化合物、例えば、一般式In the base-catalyzed aldol condensation reaction, the unsaturated ketone compound formed is further reacted with the amine of the catalyst to form its enamine compound, for example, a compound of the general formula
【化１４８】 で表される化合物になっている場合、または、アルドー
ル縮合反応がβ−ヒドロキシケトン化合物、すなわち、
一般式Embedded image Or a aldol condensation reaction is a β-hydroxyketone compound, that is,
General formula
【化１４９】 で表される化合物の段階で止まっている場合には、酸処
理によって上記不飽和ケトン化合物に導くことができ
る。[Chemical 149] When the compound represented by the formula (3) is stopped at the stage, it can be converted to the unsaturated ketone compound by acid treatment.
【０１３６】次に、反応式［化１５０］に示すように、
得られた不飽和ケトン化合物の二重結合を水素添加（接
触還元）して、一般式（II）で表されるシラスピロケト
ン化合物を得る。Next, as shown in the reaction formula [Chemical Formula 150],
The double bond of the obtained unsaturated ketone compound is hydrogenated (catalytic reduction) to obtain a silaspyroketone compound represented by the general formula (II).
【０１３７】[0137]
【化１５０】 [Chemical 150]
【０１３８】水素添加に用いられる触媒としては、パラ
ジウム、白金、ロジウム、ニッケル、ルテニウム等の金
属類が挙げられる。特に、パラジウム−炭素、パラジウ
ム−硫酸バリウム、パラジウム−ケイソウ土、酸化白
金、白金−炭素、ロジウム−炭素、ラネーニッケル等を
使用するとよい結果を与える。Examples of the catalyst used for hydrogenation include metals such as palladium, platinum, rhodium, nickel and ruthenium. In particular, palladium-carbon, palladium-barium sulfate, palladium-diatomaceous earth, platinum oxide, platinum-carbon, rhodium-carbon, Raney nickel and the like give good results.
【０１３９】以上のようにして得られた一般式（II）で
表されるシラスピロケトン化合物を、一般式（Ｉ）で表
されるシラスピロ化合物の製造に用いる。以下、この一
般式（Ｉ）で表されるシラスピロ化合物の製造方法につ
いて述べる。The silaspiroketone compound represented by the general formula (II) thus obtained is used for the production of the silaspiroke compound represented by the general formula (I). Hereinafter, a method for producing the silaspiro compound represented by the general formula (I) will be described.
【０１４０】まず、対応するハロゲン化物から容易に調
製される有機金属試薬を、一般式（II）で表されるシラ
スピロケトン化合物と反応させると、アルコール化合物
が得られる。First, an organometallic reagent, which is easily prepared from the corresponding halide, is reacted with a silaspiroketone compound represented by the general formula (II) to obtain an alcohol compound.
【０１４１】[0141]
【化１５１】 （式中において、ｎは０又は１を表す。）Embedded image (In the formula, n represents 0 or 1.)
【０１４２】有機金属試薬としては、Ｇｒｉｇｎａｒｄ
試薬、有機亜鉛試薬、有機リチウム試薬が挙げられ、い
ずれの場合も反応は高い収率で進行する。As the organometallic reagent, Grignard
Examples include reagents, organozinc reagents, and organolithium reagents. In any case, the reaction proceeds in high yield.
【０１４３】次に、得られたアルコール化合物を加水素
分解（Ｈｙｄｒｏｇｅｎｏｌｙｓｉｓ）するか、あるい
は、酸触媒によって脱水反応を行った後、生じた二重結
合を水素添加する。Next, the obtained alcohol compound is subjected to hydrogenolysis (hydrogenolysis) or dehydration reaction is performed with an acid catalyst, and then the resulting double bond is hydrogenated.
【０１４４】[0144]
【化１５２】 [Chemical 152]
【０１４５】加水素分解や水素添加に用いられる触媒と
して、パラジウム、白金、ロジウム、ニッケル、ルテニ
ウム等の金属類が挙げられる。特に、パラジウム−炭
素、パラジウム−硫酸バリウム、パラジウム−ケイソウ
土、酸化白金、白金−炭素、ロジウム−炭素、ラネーニ
ッケル等を使用するとよい結果を与える。Examples of catalysts used for hydrogenolysis and hydrogenation include metals such as palladium, platinum, rhodium, nickel and ruthenium. In particular, palladium-carbon, palladium-barium sulfate, palladium-diatomaceous earth, platinum oxide, platinum-carbon, rhodium-carbon, Raney nickel and the like give good results.
【０１４６】脱水反応に用いる酸としては、塩酸、硫
酸、硝酸等の無機酸類やその塩類、ｐ−トルエンスルホ
ン酸、カンファースルホン酸、トリフルオロ酢酸等の有
機酸類を挙げることができる。生じる水をすみやかに除
去するために、ベンゼン、トルエン、キシレン、クメ
ン、ヘキサン、イソオクタン等の炭化水素類を溶媒とし
て用いて、その共沸により反応の進行を加速することも
有用である。Examples of the acid used in the dehydration reaction include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid and salts thereof, and organic acids such as p-toluenesulfonic acid, camphorsulfonic acid and trifluoroacetic acid. In order to promptly remove the produced water, it is also effective to use hydrocarbons such as benzene, toluene, xylene, cumene, hexane and isooctane as a solvent and accelerate the progress of the reaction by azeotropic distillation thereof.
【０１４７】続いて、求電子試薬によるデシリレーショ
ン反応でハロシラシクロヘキサン化合物とし、更に還元
反応を行い、一般式（Ｉ）で表されるシラスピロ化合物
（Ｉ）を得る。Then, a halosilacyclohexane compound is obtained by a desilylation reaction with an electrophile, and a reduction reaction is further carried out to obtain a silaspiro compound (I) represented by the general formula (I).
【０１４８】[0148]
【化１５３】 （式中において、ＥＷは求電子試薬（Ｗはハロゲンを表
す。）を表す。）Embedded image (In the formula, EW represents an electrophile (W represents halogen).)
【０１４９】求電子試薬として、ハロゲン、ハロゲン化
水素、ハロゲン化金属、スルホン酸誘導体、酸ハロゲン
化物、ハロゲン化アルキル等を挙げることができる。特
に、ヨウ素、臭素、塩素、一塩化ヨウ素、塩化水素、臭
化水素、ヨウ化水素、塩化水銀（II）、クロロスルホン
酸トリメチルシリル、塩化アセチル、臭化アセチル、塩
化ベンゾイル、塩化ｔ−ブチル等を好ましく例示でき
る。なお、反応速度を高めるために、塩化アルミニウ
ム、塩化亜鉛、四塩化チタン、三フッ化ホウ素等のルイ
ス酸類の添加や、光の照射を行ってもよい。Examples of the electrophile include halogen, hydrogen halide, metal halide, sulfonic acid derivative, acid halide, alkyl halide and the like. In particular, iodine, bromine, chlorine, iodine monochloride, hydrogen chloride, hydrogen bromide, hydrogen iodide, mercury (II) chloride, trimethylsilyl chlorosulfonate, acetyl chloride, acetyl bromide, benzoyl chloride, t-butyl chloride, etc. It can be preferably exemplified. In addition, in order to increase the reaction rate, Lewis acids such as aluminum chloride, zinc chloride, titanium tetrachloride, and boron trifluoride may be added or light irradiation may be performed.
【０１５０】生じたハロシラシクロヘキサン化合物の還
元に用いられる試薬として、水素化ナトリウム、水素化
カルシウム、トリアルキルシラン類、ボラン類、ジアル
キルアルミニウム等の金属水素化物、水素化アルミニウ
ムリチウム、水素化ホウ素ナトリウム、水素化ホウ素リ
チウム、水素化ホウ素カリウム、水素化ホウ素トリブチ
ルアンモニウム等の錯水素化化合物（Ｃｏｍｐｌｅｘ
ｈｙｄｒｉｄｅ）やこれらの置換型ヒドリド化合物、す
なわち、リチウムトリアルコキシアルミニウムヒドリ
ド、ナトリウムジ（メトキシエトキシ）アルミニウムヒ
ドリド、リチウムトリエチルボロヒドリド、ナトリウム
シアノボロヒドリド等を挙げることができる。As a reagent used for the reduction of the produced halosilacyclohexane compound, sodium hydride, calcium hydride, trialkylsilanes, boranes, metal hydrides such as dialkylaluminum, lithium aluminum hydride, sodium borohydride, etc. , Complex hydride compounds such as lithium borohydride, potassium borohydride, tributylammonium borohydride (Complex
and a substituted hydride compound thereof, that is, lithium trialkoxyaluminum hydride, sodium di (methoxyethoxy) aluminum hydride, lithium triethylborohydride, sodium cyanoborohydride and the like.
【０１５１】また、反応式［化１５２］で得られた生成
物のうち、ｎ＝０に対応する、一般式Of the products obtained by the reaction formula [Chemical Formula 152], the general formula corresponding to n = 0
【化１５４】 （Ｘ’はハロゲンを表す。）で表される化合物から、ｎ
＝１に対応する、一般式Embedded image From the compound represented by (X ′ represents halogen), n
General formula corresponding to = 1
【化１５５】 で表される化合物に導くことも可能である。[Chemical 155] It is also possible to lead to a compound represented by.
【０１５２】この反応は次式に従う。This reaction follows the formula:
【０１５３】[0153]
【化１５６】 [Chemical 156]
【０１５４】この反応は遷移触媒の存在下に行われる。
遷移触媒として、特にパラジウムあるいはニッケル化合
物が好ましい。This reaction is carried out in the presence of a transition catalyst.
Palladium or nickel compounds are particularly preferable as the transition catalyst.
【０１５５】パラジウム触媒としては、例えばテトラキ
ス（トリフェニルホスフィン）パラジウム（０）、ジ
［１，２−ビス（ジフェニルホスフィノ）エタン］パラ
ジウム（０）等の０価のパラジウム化合物、あるいは酢
酸パラジウム、塩化パラジウム等の２価のパラジウム化
合物と配位子から成る化合物、またはこれらと還元剤の
組み合わせ等を用いることができる。Examples of the palladium catalyst include zero-valent palladium compounds such as tetrakis (triphenylphosphine) palladium (0) and di [1,2-bis (diphenylphosphino) ethane] palladium (0), or palladium acetate. A compound consisting of a divalent palladium compound such as palladium chloride and a ligand, or a combination of these with a reducing agent can be used.
【０１５６】ニッケル触媒としては、例えば１，３−ビ
ス（ジフェニルホスフィノ）プロパンニッケル（II）ク
ロリド、１，２−ビス（ジフェニルホスフィノ）エタン
ニッケル（II）クロリド、ビス（トリフェニルホスフィ
ン）ニッケル（II）クロリド等の２価のニッケル化合物
や、テトラキス（トリフェニルホスフィン）ニッケル
（０）等の０価のニッケル化合物を挙げることができ
る。Examples of the nickel catalyst include 1,3-bis (diphenylphosphino) propane nickel (II) chloride, 1,2-bis (diphenylphosphino) ethane nickel (II) chloride and bis (triphenylphosphine) nickel. (II) A divalent nickel compound such as chloride and a zero-valent nickel compound such as tetrakis (triphenylphosphine) nickel (0) can be mentioned.
【０１５７】以上によって製造された化合物は、再結晶
やクロマトグラフィー等の常法によって精製し、実用に
供される。The compound produced as described above is purified by a conventional method such as recrystallization or chromatography and put into practical use.
【０１５８】[0158]
【実施例】以下に具体的な実施例を挙げて本発明をさら
に詳しく説明する。EXAMPLES The present invention will be described in more detail with reference to specific examples.
【０１５９】［実施例１］ ３−ｎ−ペンチル−３−フェニル−３−シラスピロ
［５．５］ウンデカン−９−オンの製造 ４−ｎ−ペンチル−４−フェニル−４−シラシクロヘキ
サンカルバルデヒド１２０ｇとピペリジン３８．２ｇを
ベンゼン２５０ｍｌに溶かし、この溶液を還流しながら
生じた水を留去した。水の留出が止まったら、４０℃に
冷却し、メチルビニルケトン３６．８ｇとメタノール１
５０ｍｌの混合物を加え、この温度で８時間攪拌した。
このものに２０％塩酸２００ｍｌを加え、室温で３時間
攪拌後、有機層を分取した。水層はベンゼンで抽出して
有機層と合わせた。このベンゼン溶液にｐ−トルエンス
ルホン酸一水和物１．０ｇを加え、還流しながら生じた
水を留去した。この反応混合物を洗浄、乾燥、濃縮した
後、シリカゲルクロマトグラフィーで精製して、３−ｎ
−ペンチル−３−フェニル−３−シラスピロ［５．５］
ウンデカ−７−エン−９−オン１２７ｇ（収率８９％）
を得た。 ＩＲ（液膜） νｍａｘ：２９２０，２８５０，１６８
０，１１８０，１１０５，８１５ｃｍ-1 1 Ｈ−ＮＭＲ（ＣＤＣｌ3）δ：０．５５−２．１０（２
１Ｈ，ｍ），２．３０−２．５５（２Ｈ，ｍ），５．８
６（１Ｈ，ｄｄ），６．７２（１Ｈ，ｄｄ），７．２５
−７．７０（５Ｈ，ｍ）ｐｐｍExample 1 Preparation of 3-n-pentyl-3-phenyl-3-silaspiro [5.5] undecane-9-one 4-n-pentyl-4-phenyl-4-silacyclohexanecarbaldehyde 120 g And 38.2 g of piperidine were dissolved in 250 ml of benzene, and the resulting water was distilled off while the solution was refluxed. When the distillation of water stopped, the temperature was cooled to 40 ° C, and 36.8 g of methyl vinyl ketone and 1 part of methanol were added.
50 ml of the mixture was added and stirred at this temperature for 8 hours.
200 ml of 20% hydrochloric acid was added to this product, and the mixture was stirred at room temperature for 3 hours, and then the organic layer was separated. The aqueous layer was extracted with benzene and combined with the organic layer. 1.0 g of p-toluenesulfonic acid monohydrate was added to this benzene solution, and the water produced was distilled off under reflux. The reaction mixture is washed, dried, concentrated and then purified by silica gel chromatography to give 3-n
-Pentyl-3-phenyl-3-silaspiro [5.5]
127 g of undec-7-en-9-one (yield 89%)
I got IR (liquid film) νmax: 2920, 2850, 168
0,1180,1105,815cm -1 1 H-NMR (CDCl 3) δ: 0.55-2.10 (2
1H, m), 2.30-2.55 (2H, m), 5.8
6 (1H, dd), 6.72 (1H, dd), 7.25
-7.70 (5H, m) ppm
【０１６０】このもの１０２ｇをエタノール８００ｍｌ
に溶かし、パラジウム−炭素４ｇを触媒として１０ｋｇ
／ｃｍ2 の圧力下に接触還元した。理論量の水素が消費
されたら触媒を濾別し、濾液を濃縮して目的物１０２ｇ
（収率９９％）を得た。 ＩＲ（液膜） νｍａｘ：２９２０，２８５０，１７１
５，１１８０，１１１０，８１５ｃｍ-1 1 Ｈ−ＮＭＲ（ＣＤＣｌ3）δ：０．５５−１．９６（２
３Ｈ，ｍ），２．１５−２．４５（４Ｈ，ｍ），７．３
０−７．７０（５Ｈ，ｍ）ｐｐｍ102 g of this product was added to 800 ml of ethanol.
Dissolved in 10 kg of palladium-carbon 4 g as a catalyst
/ Cm2 Catalytic reduction under the pressure of. Consume theoretical amount of hydrogen
When this is done, the catalyst is filtered off and the filtrate is concentrated to 102 g of the desired product.
(Yield 99%) was obtained. IR (liquid film) νmax: 2920, 2850, 171
5,1180,1110,815cm-1 1 H-NMR (CDCl3) Δ: 0.55-1.96 (2
3H, m), 2.15-2.45 (4H, m), 7.3
0-7.70 (5H, m) ppm
【０１６１】実施例１と同様な方法で以下の化合物を得
た。The following compounds were obtained in the same manner as in Example 1.
【０１６２】［実施例２］ ３−フェニル−３−ｎ−プロピル−３−シラスピロ
［５．５］ウンデカン−９−オンExample 2 3-Phenyl-3-n-propyl-3-silaspiro [5.5] undecan-9-one
【０１６３】［実施例３］ ９−（４−クロロフェニル）−３−ｎ−ペンチル−３−
シラスピロ［５．５］ウンデカンの製造 ３−ｎ−ペンチル−３−フェニル−３−シラスピロ
［５．５］ウンデカン−９−オン３．２９ｇとテトラヒ
ドロフラン２０ｍｌの混合物に、０．７２Ｍの４−クロ
ロフェニルマグネシウムブロミドのテトラヒドロフラン
溶液２０ｍｌを加え、室温で３時間攪拌した。反応混合
物を希塩酸にあけ、エーテルで抽出した。エーテル溶液
を洗浄、乾燥、濃縮して得た残渣にベンゼン８０ｍｌと
ｐ−トルエンスルホン酸一水和物２００ｍｇを加え、還
流しながら生じる水を留去した。水の留出が止まった
ら、ベンゼン溶液を洗浄、乾燥、濃縮し、更にシリカゲ
ルクロマトグラフィーで精製して、９−（４−クロロフ
ェニル）−３−ｎ−ペンチル−３−シラスピロ［５．
５］ウンデカ−８−エン３．８１ｇ（収率９０％）を得
た。[Example 3] 9- (4-chlorophenyl) -3-n-pentyl-3-
Production of silaspiro [5.5] undecane 3-n-pentyl-3-phenyl-3-silapispiro [5.5] undecane-9-one 3.29 g of a mixture of 20 ml of tetrahydrofuran and 0.72M 4-chlorophenylmagnesium. 20 ml of a tetrahydrofuran solution of bromide was added, and the mixture was stirred at room temperature for 3 hours. The reaction mixture was poured into diluted hydrochloric acid and extracted with ether. 80 ml of benzene and 200 mg of p-toluenesulfonic acid monohydrate were added to the residue obtained by washing, drying and concentrating the ether solution, and water generated was distilled off under reflux. When the distillation of water stopped, the benzene solution was washed, dried and concentrated, and further purified by silica gel chromatography to obtain 9- (4-chlorophenyl) -3-n-pentyl-3-silaspiro [5.
5] 3.81 g (yield 90%) of undeca-8-ene was obtained.
【０１６４】このもの３．５０ｇを実施例１と同様にエ
タノール中でパラジウム−炭素を触媒として接触還元
し、９−（４−クロロフェニル）−３−ｎ−ペンチル−
３−シラスピロ［５．５］ウンデカン３．３５ｇ（収率
９５％）を得た。3.50 g of this product was catalytically reduced in ethanol in the same manner as in Example 1 using palladium-carbon as a catalyst to give 9- (4-chlorophenyl) -3-n-pentyl-
3-Silaspiro [5.5] undecane (3.35 g, yield 95%) was obtained.
【０１６５】このもの２．８２ｇを四塩化炭素１０ｍｌ
に溶かし、１．０Ｍの一塩化ヨウ素の四塩化炭素溶液
７．５ｍｌを加え、室温で３時間攪拌した。混合物を濃
縮した残渣をテトラヒドロフラン１０ｍｌに溶かし、水
素化アルミニウムリチウム１．０ｇとテトラヒドロフラ
ン３０ｍｌの混合物へ４０℃で滴下した。この温度で１
１時間攪拌した後、希硫酸にあけ、塩化メチレンで抽出
した。塩化メチレン溶液を洗浄、乾燥、濃縮し、シリカ
ゲルクロマトグラフィーで精製して目的物２．２０ｇ
（収率９５％）を得た。2.82 g of this product was added to 10 ml of carbon tetrachloride.
The resulting solution was dissolved in the above solution, 7.5 ml of a carbon tetrachloride solution of 1.0 M iodine monochloride was added, and the mixture was stirred at room temperature for 3 hours. The residue obtained by concentrating the mixture was dissolved in 10 ml of tetrahydrofuran, and added dropwise to a mixture of 1.0 g of lithium aluminum hydride and 30 ml of tetrahydrofuran at 40 ° C. 1 at this temperature
After stirring for 1 hour, the mixture was poured into diluted sulfuric acid and extracted with methylene chloride. The methylene chloride solution is washed, dried, concentrated, and purified by silica gel chromatography to obtain 2.20 g of the desired product.
(Yield 95%) was obtained.
【０１６６】実施例３と同様な方法で以下の化合物を得
た。The following compounds were obtained in the same manner as in Example 3.
【０１６７】［実施例４］ ９−（３，４−ジフルオロフェニル）−３−ｎ−ペンチ
ル−３−シラスピロ［５．５］ウンデカンExample 4 9- (3,4-difluorophenyl) -3-n-pentyl-3-silaspiro [5.5] undecane
【０１６８】［実施例５］ ９−（４−シアノフェニル）−３−ｎ−ペンチル−３−
シラスピロ［５．５］ウンデカン[Example 5] 9- (4-cyanophenyl) -3-n-pentyl-3-
Silaspiro [5.5] undecane
【０１６９】［実施例６］ ９−（４−トリフルオロメトキシフェニル）−３−ｎ−
プロピル−３−シラスピロ［５．５］ウンデカン[Example 6] 9- (4-trifluoromethoxyphenyl) -3-n-
Propyl-3-silaspiro [5.5] undecane
【０１７０】［実施例７］ ９−（４−ジフルオロメトキシフェニル）−３−ｎ−プ
ロピル−３−シラスピロ［５．５］ウンデカンExample 7 9- (4-Difluoromethoxyphenyl) -3-n-propyl-3-silaspiro [5.5] undecane
【０１７１】［実施例８］ ９−（４−エトキシフェニル）−３−ｎ−プロピル−３
−シラスピロ［５．５］ウンデカンExample 8 9- (4-Ethoxyphenyl) -3-n-propyl-3
-Silaspiro [5.5] undecane
【０１７２】［実施例９］ ９−（３，５−ジフルオロ−４−エトキシフェニル）−
３−ｎ−プロピル−３−シラスピロ［５．５］ウンデカ
ンExample 9 9- (3,5-difluoro-4-ethoxyphenyl)-
3-n-propyl-3-silaspiro [5.5] undecane
【０１７３】［実施例１０］ ９−（３，４−ジフルオロフェニル）−３−（４−ペン
テニル）−３−シラスピロ［５．５］ウンデカンExample 10 9- (3,4-Difluorophenyl) -3- (4-pentenyl) -3-silaspiro [5.5] undecane
【０１７４】［実施例１１］ ９−（３，４−ジフルオロフェニル）−３−（３−メト
キシプロピル）−３−シラスピロ［５．５］ウンデカンExample 11 9- (3,4-Difluorophenyl) -3- (3-methoxypropyl) -3-silaspiro [5.5] undecane
【０１７５】［実施例１２］ ９−（３，４−ジフルオロフェニル）−３−（３−メチ
ルブチル）−３−シラスピロ［５．５］ウンデカン[Example 12] 9- (3,4-difluorophenyl) -3- (3-methylbutyl) -3-silaspiro [5.5] undecane
【０１７６】［実施例１３］ ９−（３，４−ジフルオロフェニル）−３−（４−フル
オロブチル）−３−シラスピロ［５．５］ウンデカンExample 13 9- (3,4-Difluorophenyl) -3- (4-fluorobutyl) -3-silaspiro [5.5] undecane
【０１７７】［実施例１４］ ９−（４−（４−フルオロフェニル）フェニル）−３−
ｎ−ペンチル−３−シラスピロ［５．５］ウンデカンの
製造 実施例３と同様にして、３−ｎ−ペンチル−３−フェニ
ル−３−シラスピロ［５．５］ウンデカン１０．８ｇを
４−（４−フルオロフェニル）フェニルマグネシウムブ
ロミドと反応させ、次いで生じたアルコールを脱水し
て、９−（４−（４−フルオロフェニル）フェニル）−
３−ｎ−ペンチル−３−フェニル−３−シラスピロ
［５．５］ウンデカ−８−エン１０．２ｇ（収率６４
％）を得た。Example 14 9- (4- (4-fluorophenyl) phenyl) -3-
Production of n-pentyl-3-silaspiro [5.5] undecane In the same manner as in Example 3, 1-0.8 g of 3-n-pentyl-3-phenyl-3-silaspiro [5.5] undecane was added to 4- (4). -Fluorophenyl) phenylmagnesium bromide and then the resulting alcohol is dehydrated to give 9- (4- (4-fluorophenyl) phenyl)-
10.2 g of 3-n-pentyl-3-phenyl-3-cilaspiro [5.5] undec-8-ene (yield 64
%) Was obtained.
【０１７８】このもの９．５０ｇを接触還元して、９−
（４−（４−フルオロフェニル）フェニル）−３−ｎ−
ペンチル−３−フェニル−３−シラスピロ［５．５］ウ
ンデカン９．３２ｇ（収率９８％）を得た。9.50 g of this product was catalytically reduced to give 9-
(4- (4-fluorophenyl) phenyl) -3-n-
There was obtained 9.32 g (yield 98%) of pentyl-3-phenyl-3-silaspiro [5.5] undecane.
【０１７９】このもの９．０１ｇを、一塩化ヨウ素、次
いで水素化アルミニウムリチウムと反応させて目的物
６．０２ｇ（収率７９％）を得た。9.01 g of this product was reacted with iodine monochloride and then with lithium aluminum hydride to obtain 6.02 g of the desired product (yield 79%).
【０１８０】実施例１４と同様な方法で以下の化合物を
得た。The following compounds were obtained in the same manner as in Example 14.
【０１８１】［実施例１５］ ９−（４−（４−シアノフェニル）フェニル）−３−ｎ
−プロピル−３−シラスピロ［５．５］ウンデカンExample 15 9- (4- (4-cyanophenyl) phenyl) -3-n
-Propyl-3-silaspiro [5.5] undecane
【０１８２】［実施例１６］ ９−（４−（３−クロロ−４−フルオロフェニル）フェ
ニル）−３−ｎ−プロピル−３−シラスピロ［５．５］
ウンデカンExample 16 9- (4- (3-chloro-4-fluorophenyl) phenyl) -3-n-propyl-3-silaspiro [5.5]
Undecane
【０１８３】［実施例１７］ ９−（４−（３，５−ジフルオロ−４−ジフルオロメト
キシフェニル）フェニル）−３−ｎ−ペンチル−３−シ
ラスピロ［５．５］ウンデカンExample 17 9- (4- (3,5-difluoro-4-difluoromethoxyphenyl) phenyl) -3-n-pentyl-3-cilaspiro [5.5] undecane
【０１８４】［実施例１８］ ９−（４−（４−クロロジフルオロメトキシフェニル）
フェニル）−３−ｎ−ペンチル−３−シラスピロ［５．
５］ウンデカンExample 18 9- (4- (4-chlorodifluoromethoxyphenyl)
Phenyl) -3-n-pentyl-3-silaspiro [5.
5] Undecane
【０１８５】［実施例１９］ ９−（４−（３，４−ジフルオロフェニル）フェニル）
−３−ｎ−ペンチル−３−シラスピロ［５．５］ウンデ
カンの製造 ９−（４−クロロフェニル）−３−ｎ−ペンチル−３−
フェニル−３−シラスピロ［５．５］ウンデカン１．０
０ｇと１，３−ビス（ジフェニルホスフィノ）プロパン
ニッケル（II）クロリド８０ｍｇとエーテル２０ｍｌの
混合物に０．６５Ｍの３，４−ジフルオロフェニルマグ
ネシウムブロミドのエーテル溶液１０ｍｌを加え、室温
で２５時間攪拌した。混合物を塩化アンモニウム水溶液
にあけ、塩化メチレンで抽出した。塩化メチレン溶液を
洗浄、乾燥、濃縮した後、シリカゲルクロマトグラフィ
ーで精製して、９−（４−（３，４−ジフルオロフェニ
ル）フェニル）−３−ｎ−ペンチル−３−フェニル−３
−シラスピロ［５．５］ウンデカン８９０ｍｇ（収率６
２％）を得た。Example 19 9- (4- (3,4-difluorophenyl) phenyl)
Preparation of -3-n-pentyl-3-silaspiro [5.5] undecane 9- (4-chlorophenyl) -3-n-pentyl-3-
Phenyl-3-silaspiro [5.5] undecane 1.0
To a mixture of 0 g, 80 mg of 1,3-bis (diphenylphosphino) propane nickel (II) chloride and 20 ml of ether was added 10 ml of a 0.65 M ether solution of 3,4-difluorophenylmagnesium bromide, and the mixture was stirred at room temperature for 25 hours. . The mixture was poured into an aqueous solution of ammonium chloride and extracted with methylene chloride. The methylene chloride solution was washed, dried and concentrated, and then purified by silica gel chromatography to give 9- (4- (3,4-difluorophenyl) phenyl) -3-n-pentyl-3-phenyl-3.
-890 mg of silaspiro [5.5] undecane (yield 6
2%) was obtained.
【０１８６】このもの７５０ｍｇを、実施例３と同様に
して、一塩化ヨウ素、次いで水素化アルミニウムリチウ
ムと反応させて目的物５１１ｍｇ（収率８０％）を得
た。750 mg of this product was reacted with iodine monochloride and then with lithium aluminum hydride in the same manner as in Example 3 to obtain 511 mg of the desired product (yield 80%).
【０１８７】実施例１９と同様な方法で以下の化合物を
得た。The following compounds were obtained in the same manner as in Example 19.
【０１８８】［実施例２０］ ９−（４−（４−シアノ−３−フルオロフェニル）フェ
ニル）−３−ｎ−ペンチル−３−シラスピロ［５．５］
ウンデカン[Example 20] 9- (4- (4-cyano-3-fluorophenyl) phenyl) -3-n-pentyl-3-silaspiro [5.5]
Undecane
【０１８９】［実施例２１］ ９−（４−（４−トリフルオロメトキシフェニル）フェ
ニル）−３−ｎ−ペンチル−３−シラスピロ［５．５］
ウンデカンExample 21 9- (4- (4-trifluoromethoxyphenyl) phenyl) -3-n-pentyl-3-silaspiro [5.5]
Undecane
【０１９０】［実施例２２］ ９−（４−（４−トリフルオロメチルフェニル）フェニ
ル）−３−ｎ−ペンチル−３−シラスピロ［５．５］ウ
ンデカンExample 22 9- (4- (4-trifluoromethylphenyl) phenyl) -3-n-pentyl-3-silaspiro [5.5] undecane
【０１９１】［実施例２３］ ９−（４−（４−ｎ−プロピルフェニル）フェニル）−
３−ｎ−ペンチル−３−シラスピロ［５．５］ウンデカ
ン[Example 23] 9- (4- (4-n-propylphenyl) phenyl)-
3-n-pentyl-3-silaspiro [5.5] undecane
【０１９２】［実施例２４］ ９−（４−（３−フルオロ−４−（３，４−ジフルオロ
フェニル）フェニル）−３−ｎ−ペンチル−３−シラス
ピロ［５．５］ウンデカンExample 24 9- (4- (3-Fluoro-4- (3,4-difluorophenyl) phenyl) -3-n-pentyl-3-silaspiro [5.5] undecane
【０１９３】［実施例２５］ ９−（３−フルオロ−４−（４−トリフルオロメトキシ
フェニル）フェニル）−３−ｎ−ペンチル−３−シラス
ピロ［５．５］ウンデカンExample 25 9- (3-Fluoro-4- (4-trifluoromethoxyphenyl) phenyl) -3-n-pentyl-3-silaspiro [5.5] undecane
【０１９４】[0194]
【発明の効果】以上説明したように本発明のシラスピロ
化合物は、シラシクロヘキサン化合物よりも更に安定で
あり、液晶組成物の成分として良好である。また、本発
明のシラスピロ化合物は、既存の液晶化合物のようにシ
ス、トランスの立体異性体を形成せず、液晶性を示す唯
一の立体配置しかとらないために、既存の液晶化合物製
造時のコストアップ主要因の一つであったトランス体の
分離精製操作が不要となり、経済的にも優位性を増すも
のである。As described above, the silaspiro compound of the present invention is more stable than the silacyclohexane compound and is a good component of a liquid crystal composition. In addition, the silaspiro compound of the present invention does not form cis and trans stereoisomers unlike existing liquid crystal compounds, and has only one configuration that exhibits liquid crystallinity, so that the cost of existing liquid crystal compound production is low. This eliminates the need for the trans-isolation and purification operation, which was one of the main factors contributing to the increase in cost, thus increasing economic superiority.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｇ０２Ｆ 1/13 ５００ // Ｃ０７Ｂ 61/00 ３００ (72)発明者 荻原 勤 新潟県中頸城郡頸城村大字西福島28番地の １ 信越化学工業株式会社合成技術研究所 内 (72)発明者 金子 達志 新潟県中頸城郡頸城村大字西福島28番地の １ 信越化学工業株式会社合成技術研究所 内 (72)発明者 中島 睦雄 新潟県中頸城郡頸城村大字西福島28番地の １ 信越化学工業株式会社合成技術研究所 内 (72)発明者 栗原 英志 神奈川県川崎市高津区坂戸３丁目２番１号 信越化学工業株式会社コ−ポレ−トリサ −チセンタ−内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Reference number within the agency FI Technical indication location G02F 1/13 500 // C07B 61/00 300 (72) Inventor Tsutomu Ogihara Nagi 1 of 28, Fukushima Nishi-Fukushima, Synthetic Technology Laboratory, Shin-Etsu Chemical Co., Ltd. (72) Inventor Tatsushi Kaneko, 28, Nishi-Fukushima, Nakakubiki-gun, Niigata Prefecture 1 of Synthetic Technology Laboratory, Shin-Etsu Chemical Co., Ltd. ( 72) Inventor Mutsuo Nakajima 28, Nishi-Fukushima, Chugiki-mura, Nakakubiki-gun, Niigata Prefecture 1 Shinetsu Chemical Industry Co., Ltd. Synthetic Technology Laboratory (72) Inventor Eiji Kurihara 3-2-1 Sakado, Takatsu-ku, Kawasaki-shi, Kanagawa Shin-Etsu Chemical Co., Ltd. Inside the corporate tracer center
Claims (8)
化合物。 【化１】 但し、Ｒは炭素数１〜１０の直鎖状アルキル基、モノ又
はジフルオロアルキル基、炭素数３〜８の分枝鎖状アル
キル基、炭素数２〜７のアルコキシアルキル基又は炭素
数２〜８のアルケニル基、ＸはＣＮ、Ｆ、Ｃｌ、Ｂｒ、
ＣＦ3、ＯＣＦ3、ＯＣＨＦ2、ＯＣＨＦＣｌ、ＯＣＦ2Ｃ
ｌ、ＣＦ2Ｃｌ、Ｒ又はＯＲ基、Ｙ及びＺそれぞれ相互
に独立してハロゲン又はＣＨ3、ｉ及びｊはそれぞれ相
互に独立して０から３の整数、ｎは０又は１を表す。1. A silaspiro compound represented by the following general formula (I): Embedded image However, R is a C1-C10 linear alkyl group, a mono- or difluoroalkyl group, a C3-C8 branched alkyl group, a C2-C7 alkoxyalkyl group, or a C2-C8. Alkenyl group, X is CN, F, Cl, Br,
CF 3 , OCF 3 , OCHF 2 , OCHFCl, OCF 2 C
1, CF 2 Cl, R or OR group, Y and Z each independently of each other halogen or CH 3 , i and j each independently of each other represent an integer from 0 to 3, and n represents 0 or 1.
ケトン化合物。 【化２】 但し、Ａｒはフェニル基又はトリル基、ＲはＡｒ、炭素
数１〜１０の直鎖状アルキル基、モノ又はジフルオロア
ルキル基、炭素数３〜８の分枝鎖状アルキル基又は炭素
数２〜７のアルコキシアルキル基を表す。2. A silaspyroketone compound represented by the following general formula (II). Embedded image However, Ar is a phenyl group or a tolyl group, R is Ar, a linear alkyl group having 1 to 10 carbon atoms, a mono- or difluoroalkyl group, a branched chain alkyl group having 3 to 8 carbon atoms or 2 to 7 carbon atoms. Represents an alkoxyalkyl group.
されるシラスピロケトン化合物と、一般式 【化３】 （式中において、ＭはＭｇＰ（Ｐはハロゲンを表
す。）、ＺｎＰ又はＬｉ、ＸはＣＮ、Ｆ、Ｃｌ、Ｂｒ、
ＣＦ3、ＯＣＦ3、ＯＣＨＦ2、ＯＣＨＦＣｌ、ＯＣＦ2Ｃ
ｌ、ＣＦ2Ｃｌ、Ｒ又はＯＲ基、Ｙはハロゲン又はＣ
Ｈ3、ｉは０から２の整数を表す。）で表される有機金
属試薬とを反応させ、一般式 【化４】 で表される化合物を得、次いで加水素分解又は脱水後に
水素添加することにより、一般式 【化５】 で表される化合物を得、次にデシリレーションした後、
還元することにより、一般式 【化６】 で表されるシラスピロ化合物を得ることを特徴とするシ
ラスピロ化合物の製造方法。3. A silaspiroketone compound represented by the general formula (II) according to claim 2 and a general formula: (In the formula, M is MgP (P represents halogen), ZnP or Li, X is CN, F, Cl, Br,
CF 3 , OCF 3 , OCHF 2 , OCHFCl, OCF 2 C
1, CF 2 Cl, R or OR group, Y is halogen or C
H 3 and i represent an integer of 0 to 2. ) With an organometallic reagent represented by the general formula: A compound represented by the following formula is obtained by hydrogenolysis or dehydration followed by hydrogenation. After obtaining the compound represented by
By reduction, the general formula: A method for producing a silaspiro compound, comprising obtaining a silaspiro compound represented by:
されるシラスピロケトン化合物と、一般式 【化７】 （式中において、ＭはＭｇＵ（Ｕはハロゲンを表
す。）、ＺｎＵ又はＬｉ、ＸはＣＮ、Ｆ、Ｃｌ、Ｂｒ、
ＣＦ3、ＯＣＦ3、ＯＣＨＦ2、ＯＣＨＦＣｌ、ＯＣＦ2Ｃ
ｌ、ＣＦ2Ｃｌ、Ｒ又はＯＲ基、Ｙ及びＺはそれぞれ独
立してハロゲン又はＣＨ3、ｉ及びｊはそれぞれ独立し
て０から２の整数を表す。）で表される有機金属試薬と
を反応させ、一般式 【化８】 で表される化合物を得、次いで加水素分解又は脱水後に
水素添加することにより、一般式 【化９】 で表される化合物を得、次にデシリレーションした後、
還元することにより、一般式 【化１０】 で表されるシラスピロ化合物を得ることを特徴とするシ
ラスピロ化合物の製造方法。4. A silaspiroketone compound represented by the general formula (II) according to claim 2 and a general formula: (In the formula, M is MgU (U represents halogen), ZnU or Li, X is CN, F, Cl, Br,
CF 3 , OCF 3 , OCHF 2 , OCHFCl, OCF 2 C
1, CF 2 Cl, R or OR group, Y and Z each independently represent halogen or CH 3 , i and j each independently represent an integer of 0 to 2. ) With an organometallic reagent represented by the general formula: By obtaining a compound represented by the formula (1) and then hydrogenating it after hydrogenolysis or dehydration, a compound represented by the general formula: After obtaining the compound represented by
By reduction, the general formula: A method for producing a silaspiro compound, comprising obtaining a silaspiro compound represented by:
されるシラスピロケトン化合物と、一般式 【化１１】 （式中において、ＭはＭｇＵ（Ｕはハロゲンを表
す。）、ＺｎＵ又はＬｉ、Ｘ’はハロゲン、Ｙはハロゲ
ン又はＣＨ3、ｉは０から２の整数を表す。）で表され
る有機金属試薬とを反応させ、一般式 【化１２】 で表される化合物を得、次いで加水素分解又は脱水後に
水素添加することにより、一般式 【化１３】 で表される化合物を得、次いでこの化合物と、一般式 【化１４】 （式中において、Ｍ’はＭｇＵ（Ｕはハロゲンを表
す。）、ＺｎＵ又はＢ（ＯＶ）2（ＶはＨ又はアルキル
基を表す。）を表す。）で表される有機金属試薬とを遷
移金属触媒の存在下に反応させ、一般式 【化１５】 で表される化合物を得、次にデシリレーションした後、
還元することにより、一般式 【化１６】 で表されるシラスピロ化合物を得ることを特徴とするシ
ラスピロ化合物の製造方法。5. A silaspiroketone compound represented by the general formula (II) according to claim 2 and a general formula: (In the formula, M is MgU (U represents halogen), ZnU or Li, X ′ is halogen, Y is halogen or CH 3 , and i is an integer of 0 to 2.) React with a reagent to give a compound of the general formula: By obtaining a compound represented by the formula (1) and then hydrogenating it after hydrogenolysis or dehydration, a compound of the general formula: A compound represented by the formula: (In the formula, M ′ represents MgU (U represents halogen), ZnU or B (OV) 2 (V represents H or an alkyl group), and a transition with an organometallic reagent. The reaction is carried out in the presence of a metal catalyst to give a compound of the general formula: After obtaining the compound represented by
By reduction, the general formula: A method for producing a silaspiro compound, comprising obtaining a silaspiro compound represented by:
アルキル基又はＲ1とＲ2とで環状をなす−（ＣＨ2）
4−、−（ＣＨ2）5−又は−（ＣＨ2） Ｏ（ＣＨ2）2−の
いずれかを表す。）で表されるエナミン化合物とメチル
ビニルケトンとをマイケル付加反応させ、次いで加水分
解して、一般式 【化１８】 で表されるケトアルデヒド化合物を得、次にこのケトア
ルデヒド化合物を分子内アルドール縮合させることによ
り、一般式 【化１９】 で表される不飽和ケトン化合物を得、次いでこの化合物
を水素添加することにより、一般式（II） 【化２０】 で表されるシラスピロケトン化合物を製造することを特
徴とするシラスピロケトン化合物の製造方法。6. A general formula:(In the formula, R1 And R2Each has 1 to 4 carbon atoms
Alkyl group or R1And R2Form a ring with-(CH2)
Four-,-(CH2)Five-Or- (CH2) O (CH2)2− Of
Represents either. ) Enamine compound and methyl
Michael addition reaction with vinyl ketone, followed by hydrolysis
By solving, the general formulaThe ketoaldehyde compound represented by
Intramolecular aldol condensation of aldehyde compounds
, The general formula:An unsaturated ketone compound represented by
By hydrogenating the compound of the general formula (II)The production of a silaspyroketone compound represented by
A method for producing a silaspyroketone compound.
されるシラスピロ化合物を含有することを特徴とする液
晶組成物。7. A liquid crystal composition comprising the silaspyro compound represented by the general formula (I) according to claim 1.
することを特徴とする液晶表示素子。8. A liquid crystal display device comprising the liquid crystal composition according to claim 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6282741A JPH08119974A (en) | 1994-10-20 | 1994-10-20 | Silaspiro compound, its production and liquid crystal composition containing the same compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6282741A JPH08119974A (en) | 1994-10-20 | 1994-10-20 | Silaspiro compound, its production and liquid crystal composition containing the same compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08119974A true JPH08119974A (en) | 1996-05-14 |
Family
ID=17656452
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6282741A Pending JPH08119974A (en) | 1994-10-20 | 1994-10-20 | Silaspiro compound, its production and liquid crystal composition containing the same compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08119974A (en) |
-
1994
- 1994-10-20 JP JP6282741A patent/JPH08119974A/en active Pending
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