JP2797527B2 - Optically active phenols and their production - Google Patents
Optically active phenols and their productionInfo
- Publication number
- JP2797527B2 JP2797527B2 JP1261376A JP26137689A JP2797527B2 JP 2797527 B2 JP2797527 B2 JP 2797527B2 JP 1261376 A JP1261376 A JP 1261376A JP 26137689 A JP26137689 A JP 26137689A JP 2797527 B2 JP2797527 B2 JP 2797527B2
- Authority
- JP
- Japan
- Prior art keywords
- optically active
- phenol
- reaction
- group
- methyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 150000002989 phenols Chemical class 0.000 title claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 100
- -1 (+)-2- (p-benzyloxyphenyl) propyl Chemical group 0.000 claims description 94
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 19
- 125000005843 halogen group Chemical group 0.000 claims description 19
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical class C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000002168 alkylating agent Substances 0.000 claims description 13
- 229940100198 alkylating agent Drugs 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 13
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 11
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 238000005984 hydrogenation reaction Methods 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 49
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- 229910001868 water Inorganic materials 0.000 description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 239000002904 solvent Substances 0.000 description 23
- 230000002829 reductive effect Effects 0.000 description 21
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 239000012044 organic layer Substances 0.000 description 16
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 14
- 239000011541 reaction mixture Substances 0.000 description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 12
- BOTNYLSAWDQNEX-UHFFFAOYSA-N phenoxymethylbenzene Chemical compound C=1C=CC=CC=1COC1=CC=CC=C1 BOTNYLSAWDQNEX-UHFFFAOYSA-N 0.000 description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 10
- OMQAYZNIEILCIY-UHFFFAOYSA-N 3-(4-phenylmethoxyphenyl)butan-1-ol Chemical compound C1=CC(C(CCO)C)=CC=C1OCC1=CC=CC=C1 OMQAYZNIEILCIY-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000006264 debenzylation reaction Methods 0.000 description 9
- 239000000543 intermediate Substances 0.000 description 9
- 238000010898 silica gel chromatography Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 239000003480 eluent Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 7
- 150000004820 halides Chemical class 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000004973 liquid crystal related substance Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- OAMZXMDZZWGPMH-UHFFFAOYSA-N ethyl acetate;toluene Chemical compound CCOC(C)=O.CC1=CC=CC=C1 OAMZXMDZZWGPMH-UHFFFAOYSA-N 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- LYUPJHVGLFETDG-UHFFFAOYSA-N 1-phenylbutan-2-ol Chemical compound CCC(O)CC1=CC=CC=C1 LYUPJHVGLFETDG-UHFFFAOYSA-N 0.000 description 4
- MRXCAJYSXNBGRQ-UHFFFAOYSA-N 4-(3-propoxybutyl)phenol Chemical compound CCCOC(C)CCC1=CC=C(O)C=C1 MRXCAJYSXNBGRQ-UHFFFAOYSA-N 0.000 description 4
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 4
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- 239000000460 chlorine Substances 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 229920005555 halobutyl Polymers 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 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
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 235000001014 amino acid Nutrition 0.000 description 3
- 229940024606 amino acid Drugs 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 150000008282 halocarbons Chemical class 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- 239000012312 sodium hydride Substances 0.000 description 3
- 230000002269 spontaneous effect Effects 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 2
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 2
- BLUKXZMCYVAAKE-UHFFFAOYSA-N 4-(1-propoxypropan-2-yl)phenol Chemical compound CCCOCC(C)C1=CC=C(O)C=C1 BLUKXZMCYVAAKE-UHFFFAOYSA-N 0.000 description 2
- HQVTYOXUVQQMLD-UHFFFAOYSA-N 4-(4-decoxyphenyl)benzoic acid Chemical compound C1=CC(OCCCCCCCCCC)=CC=C1C1=CC=C(C(O)=O)C=C1 HQVTYOXUVQQMLD-UHFFFAOYSA-N 0.000 description 2
- RGUKYNXWOWSRET-UHFFFAOYSA-N 4-pyrrolidin-1-ylpyridine Chemical compound C1CCCN1C1=CC=NC=C1 RGUKYNXWOWSRET-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
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- 229930195733 hydrocarbon Natural products 0.000 description 1
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- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- QJHBJHUKURJDLG-UHFFFAOYSA-N hydroxy-L-lysine Natural products NCCCCC(NO)C(O)=O QJHBJHUKURJDLG-UHFFFAOYSA-N 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 229960000310 isoleucine Drugs 0.000 description 1
- AGPKZVBTJJNPAG-UHFFFAOYSA-N isoleucine Natural products CCC(C)C(N)C(O)=O AGPKZVBTJJNPAG-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229960002510 mandelic acid Drugs 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 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
- 125000005767 propoxymethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])[#8]C([H])([H])* 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000006722 reduction reaction 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
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- NPDBDJFLKKQMCM-UHFFFAOYSA-N tert-butylglycine Chemical compound CC(C)(C)C(N)C(O)=O NPDBDJFLKKQMCM-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004474 valine 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 ＜産業上の利用分野＞ 本発明は有機電子材料の中間体として有用である光学
活性なフェノール類およびその製造法に関する。とりわ
け、液晶材料、特に強誘電性液晶材料等の中間体として
有用である光学活性なフェノール類およびその製造法に
関する。The present invention relates to an optically active phenol useful as an intermediate of an organic electronic material and a method for producing the same. In particular, the present invention relates to an optically active phenol useful as an intermediate for a liquid crystal material, particularly a ferroelectric liquid crystal material, and a method for producing the same.
＜従来の技術＞ 従来から液晶化合物として種々の化学物が開発されて
いるが、高速応答性等の特性が優れた強誘電性液晶材料
は極めて少なく、該液晶化合物およびその中間体の開発
が望まれていた。<Conventional Technology> Various chemicals have been developed as liquid crystal compounds, but there are very few ferroelectric liquid crystal materials having excellent characteristics such as high-speed response, and development of such liquid crystal compounds and intermediates thereof is expected. Was rare.
＜発明が解決しようとする課題＞ 本発明の目的は、上記特性に優れた強誘電性液晶材料
の中間体として有用である光学活性なフェノール類およ
びその製造法を提供し、さらには該化合物の中間体およ
びその製造法をも提供することにある。<Problem to be Solved by the Invention> An object of the present invention is to provide an optically active phenol which is useful as an intermediate of a ferroelectric liquid crystal material excellent in the above-mentioned properties, and a method for producing the same. An object of the present invention is to provide an intermediate and a method for producing the intermediate.
＜課題を解決するための手段＞ すなわち、本発明は、一般式〔Ｉ〕 （式中、Ｒは炭素数１〜20のハロゲン原子を含んでいて
もよいアルキル基またはアルコキシアルキル基を、Ｚは
水素原子またはハロゲン原子を、ｓは０または１を、 をそれぞれ表わす。ここでｎは１〜５の整数を、＊印は
不斉炭素原子であることを表わす。ただし、（＋）−２
−（ｐ−ヒドロキシフェニル）プロピルアルコールメチ
ルエーテルおよび（＋）−２−（ｐ−ヒドロキシフェニ
ル）プロピルアルコールｎ−ブチルエーテルではな
い。）で示される光学活性なフェノール類およびその製
造法に関するものである。<Means for Solving the Problems> That is, the present invention provides a compound represented by the general formula [I]: (Wherein, R represents an alkyl group or an alkoxyalkyl group optionally containing a halogen atom having 1 to 20 carbon atoms, Z represents a hydrogen atom or a halogen atom, s represents 0 or 1, Respectively. Here, n represents an integer of 1 to 5, and * represents an asymmetric carbon atom. However, (+)-2
Not-(p-hydroxyphenyl) propyl alcohol methyl ether and (+)-2- (p-hydroxyphenyl) propyl alcohol n-butyl ether. ) And a method for producing the same.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
上記一般式〔Ｉ〕で示される光学活性なフェノール類
は、一般式〔II〕 （式中、Ａは水素原子、低級アルキル基、低級アルコキ
シル基またはハロゲン原子を表わし、Ｒ、Ｚ、Ｗおよび
ｓは前記と同じ意味を表わす。ただし、（＋）−２−
（ｐ−ベンジルオキシフェニル）プロピルアルコールメ
チルエーテルおよび（＋）−２−（ｐ−ベンジルオキシ
フェニル）プロピルアルコールｎ−ブチルエーテルでは
ない。） で示される光学活性なベンジルエーテル誘導体を、水添
触媒および水素の存在下に脱ベンジル化することにより
製造することができる。The optically active phenols represented by the general formula [I] are represented by the general formula [II] (In the formula, A represents a hydrogen atom, a lower alkyl group, a lower alkoxyl group or a halogen atom, and R, Z, W and s have the same meanings as described above, provided that (+)-2-
Not (p-benzyloxyphenyl) propyl alcohol methyl ether and (+)-2- (p-benzyloxyphenyl) propyl alcohol n-butyl ether. ) Can be produced by debenzylating the optically active benzyl ether derivative represented by the formula (1) in the presence of a hydrogenation catalyst and hydrogen.
上記一般式〔II〕において、ｓが０である光学活性な
ベンジルエーテル誘導体は、一般式〔III〕 （式中、Ａ、ＺおよびＷは前記と同じ意味を表わす。） で示される光学活性なアルコール類と、一般式〔IV〕 Ｒ−Ｘ 〔IV〕 （式中、Ｒは前記と同じ意味を表わし、Ｘはハロゲン原
子またはOSO2R2基を表わす。ここでR2は低級アルキル基
または置換されていてもよいフェニル基を表わす。） で示されるアルキル化剤とを、塩基性物質の存在下に縮
合させることにより製造することができる。In the above general formula [II], the optically active benzyl ether derivative wherein s is 0 is a compound represented by the general formula [III] (Wherein, A, Z and W represent the same meaning as described above), and an optically active alcohol represented by the general formula [IV] RX (IV) (wherein R has the same meaning as described above) represents, X represents a halogen atom or OSO 2 R 2 group. and wherein R 2 represents a lower alkyl group or an optionally substituted phenyl group.) with an alkylating agent represented, the presence of a basic substance It can be produced by condensing under the following conditions.
前記一般式〔II〕においてｓが１である光学活性なベ
ンジルエーテル誘導体は、前記一般式〔III〕で示され
る光学活性なアルコール類と、一般式〔Ｖ〕 Ｒ−COR3 〔Ｖ〕 （式中、Ｒは前記と同じ意味を表わし、R3はハロゲン原
子または水酸基を表わす。） で示されるアシル化剤またはその誘導体とを、触媒また
は縮合剤の存在下に縮合させることにより製造すること
ができる。The optically active benzyl ether derivative in which s is 1 in the general formula [II] can be obtained by mixing the optically active alcohol represented by the general formula [III] with the general formula [V] R-COR 3 [V] (formula In the formula, R represents the same meaning as described above, and R 3 represents a halogen atom or a hydroxyl group.) And an acylating agent or a derivative thereof in the presence of a catalyst or a condensing agent. it can.
光学活性なベンジルエーテル誘導体〔II〕の脱ベンジ
ル化による光学活性なフェノール類〔Ｉ〕の製造におい
て、該反応における水添触媒としてはラネーニッケルや
パラジウム系の金属触媒が好ましく用いられ、その具体
例としてはパラジウム−炭素、酸化パラジウム、パラジ
ウム黒または塩化パラジウム等があげられる。In the production of the optically active phenols [I] by debenzylation of the optically active benzyl ether derivative [II], Raney nickel or a palladium-based metal catalyst is preferably used as a hydrogenation catalyst in the reaction. Is palladium-carbon, palladium oxide, palladium black or palladium chloride.
かかる水添触媒は、光学活性なベンジルエーテル誘導
体〔II〕に対して通常0.001〜0.5重量倍、好ましくは0.
005〜0.3重量倍使用される。Such a hydrogenation catalyst is usually used in an amount of 0.001 to 0.5 times by weight, preferably 0.1 to 0.5 times the weight of the optically active benzyl ether derivative (II).
005-0.3 weight times used.
この反応は通常、溶媒中で行われ、溶媒としては水、
ジオキサン、テトラヒドロフラン、メタノール、エタノ
ール、ｎ−プロピルアルコール、アセトン、ジメチルホ
ルムアミド、トルエン、ジクロルメタン、酢酸エチル等
の炭化水素、アルコール、エーテル、ケトン、エステ
ル、ハロゲン化炭化水素またはアミド等の反応に不活性
な溶媒が例示され、これらは単独または混合して使用さ
れる 反応温度は−10〜100℃、好ましくは10〜60℃であ
る。This reaction is usually performed in a solvent, such as water,
Inactive in the reaction of hydrocarbons such as dioxane, tetrahydrofuran, methanol, ethanol, n-propyl alcohol, acetone, dimethylformamide, toluene, dichloromethane, ethyl acetate, etc., alcohols, ethers, ketones, esters, halogenated hydrocarbons or amides. Solvents are exemplified, and these are used alone or as a mixture. The reaction temperature is -10 to 100 ° C, preferably 10 to 60 ° C.
上記反応は通常、常圧または加圧下に行われ、原料で
ある光学活性なベンジルエーテル誘導体〔II〕を反応系
から検出しなくなったとき、または水素の吸収量が光学
活性なベンジルエーテル誘導体〔II〕に対して１〜1.2
当量倍となったときを反応終点とすることができる。The above reaction is usually carried out under normal pressure or under pressure, and when the optically active benzyl ether derivative [II] as a raw material is no longer detected from the reaction system, or the amount of absorbed hydrogen is an optically active benzyl ether derivative [II] 1 to 1.2
The point at which the equivalent is doubled can be regarded as the reaction end point.
反応終了後、反応混合物から触媒をろ過処理等により
除去したのち、濃縮等の操作により目的とする一般式
〔Ｉ〕で示される光学活性なフェノール類を得ることが
でき、必要に応じて再結晶あるいはカラムクロマトグラ
フィー等により精製することができる。After completion of the reaction, the catalyst is removed from the reaction mixture by filtration or the like, and the desired optically active phenol represented by the general formula [I] can be obtained by an operation such as concentration. Alternatively, it can be purified by column chromatography or the like.
光学活性なアルコール類〔III〕と、アルキル化剤〔I
V〕との縮合によるｓが０であるベンジルエーテル誘導
体〔II〕の製造において、該反応に用いられる塩基性物
質としては水素化ナトリウム、水素化カリウム等のアル
カリ金属水素化物、水酸化ナトリウム、水酸化カリウ
ム、水酸化カルシウム等の水酸化アルカリ金属もしくは
水酸化アルカリ土類金属、炭酸ナトリウム、炭酸カリウ
ム等の炭酸アルカリ金属、ブチルリチウム等の有機リチ
ウムまたはリチウム、ナトリウム、カリウム等のアルカ
リ金属などが例示される。An optically active alcohol [III] and an alkylating agent [I
In the production of the benzyl ether derivative [II] in which s is 0 by condensation with V], basic substances used in the reaction include alkali metal hydrides such as sodium hydride and potassium hydride, sodium hydroxide, water Examples thereof include alkali metal hydroxides or alkaline earth metal hydroxides such as potassium oxide and calcium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic lithium such as butyllithium, and alkali metals such as lithium, sodium and potassium. Is done.
かかる塩基性物質は光学活性なアルコール類〔III〕
に対して１当量倍以上必要であり、上限については特に
制限されないが、好ましくは１〜５当量倍使用される。Such basic substances are optically active alcohols [III]
Is required to be 1 equivalent or more, and the upper limit is not particularly limited, but preferably 1 to 5 equivalents.
この反応で使用されるアルキル化剤とは、以下に例示
されるような炭素数１〜20のハロゲン原子をふくんでい
てもよいアルキル基またはアルコイシアルキル基を有す
るクロリド、ブロミド、ヨージド等のハロゲン化物ある
いは硫酸エステル類（メタンスルホン酸エステル、エタ
ンスルホン酸エステル、ベンゼンスルホン酸エステル、
トルエンスルホン酸エステル等）である。これらのアル
キル化剤は、必要により相当するアルコールから容易に
合成することができる。The alkylating agent used in this reaction refers to a halogen such as a chloride, bromide, iodide or the like having an alkyl group or an alkoxyalkyl group which may contain a halogen atom having 1 to 20 carbon atoms as exemplified below. Or sulfates (methanesulfonate, ethanesulfonate, benzenesulfonate,
Toluene sulfonic acid ester). These alkylating agents can be easily synthesized from the corresponding alcohol if necessary.
メチル、エチル、プロピル、ブチル、ペンチル、ヘキ
シル、ヘプチル、オクチル、ノニル、デシル、ウンデシ
ル、ドデシル、トリデシル、テトラデシル、ペンタデシ
ル、ヘキサデシル、ヘプタデシル、オクタデシル、ノナ
デシル、エイコシル、メトキシメチル、メトキシエチ
ル、メトキシプロピル、メトキシブチル、メトキシペン
チル、メトキシヘキシル、メトキシヘプチル、メトキシ
オクチル、メトキシノニル、メトキシデシル、エトキシ
メチル、エトキシエチル、エトキシプロピル、エトキシ
ブチル、エトキシペンチル、エトキシヘキシル、エトキ
シヘプチル、エトキシオクチル、エトキシノニル、エト
キシデシル、プロポキシメチル、プロポキシエチル、プ
ロポキシプロピル、プロポキシブチル、プロポキシペン
チル、プロポキシヘキシル、プロポキシヘプチル、プロ
ポキシオクチル、プロポキシノニル、プロポキシデシ
ル、ブトキシメチル、ブトキシエチル、ブトキシプロピ
ル、ブトキシブチル、ブトキシペンチル、ブトキシヘキ
シル、ブトキシヘプチル、ブトキシオクチル、ブトキシ
ノニル、ブトキシデシル、ペンチルオキシメチル、ペン
チルオキシエチル、ペンチルオキシプロピル、ペンチル
オキシブチル、ペンチルオキシペンチル、ペンチルオキ
シヘキシル、ペンチルオキシオクチル、ペンチルオキシ
デシル、ヘキシルオキシメチル、ヘキシルオキシエチ
ル、ヘキシルオキシプロピル、ヘキシルオキシブチル、
ヘキシルオキシペンチル、ヘキシルオキシヘキシル、ヘ
キシルオキシオクチル、ヘキシルオキシノニル、ヘキシ
ルオキシデシル、ヘプチルオキシメチル、ヘプチルオキ
シエチル、ヘプチルオキシプロピル、ヘプチルオキシブ
チル、ヘプチルオキシペンチル、オクチルオキシメチ
ル、オクチルオキシエチル、オクチルオキシプロピル、
デシルオキシメチル、デシルオキシエチル、デシルオキ
シプロピル、１−メチルエチル、１−メチルプロピル、
１−メチルブチル、１−メチルペンチル、１−メチルヘ
キシル、１−メチルヘプチル、１−メチルオクチル、２
−メチルエチル、２−メチルブチル、２−トリハロメチ
ルペンチル、２−トリハロメチルヘキシル、２−トリハ
ロメチルプチル、２−ハロエチル、２−ハロプロピル、
３−ハロプロピル、３−ハロ−２−メチルプロプル、2,
3−ジハロプロピル、２−ハロブチル、３−ハロブチ
ル、４−ハロブチル、2,3−ジハロブチル、2,4−ジハロ
ブチル、3,4−ジハロブチル、２−ハロ−３−メチルブ
チル、２−ハロ−3,3−ジメチルブチル、２−ハロペン
チル、３−ハロペンチル、４−ハロペンチル、５−ハロ
ペンチル、2,4−ジハロペンチル、2,5−ジハロペンチ
ル、２−ハロ−３−メチルペンチル、２−ハロ−４−メ
チルペンチル、２−ハロ−３−モノハロメチル−４−メ
チルペンチル、２−ハロヘキシル、３−ハロヘキシル、
４−ハロヘキシル、５−ハロヘキシル、６−ハロヘキシ
ル、２−ハロヘプチル、２−ハロオクチル（但し上記ア
ルキル基中ハロとは、フッ素、塩素、臭素またはヨウ素
を表わす）等。Methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, methoxymethyl, methoxyethyl, methoxypropyl, methoxy Butyl, methoxypentyl, methoxyhexyl, methoxyheptyl, methoxyoctyl, methoxynonyl, methoxydecyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, ethoxypentyl, ethoxyhexyl, ethoxyheptyl, ethoxyoctyl, ethoxynonyl, ethoxydecyl, Propoxymethyl, propoxyethyl, propoxypropyl, propoxybutyl, propoxypentyl, propoxyhex , Propoxyheptyl, propoxyoctyl, propoxynonyl, propoxydecyl, butoxymethyl, butoxyethyl, butoxypropyl, butoxybutyl, butoxypentyl, butoxyhexyl, butoxyheptyl, butoxyoctyl, butoxynonyl, butoxydecyl, pentyloxymethyl, pentyloxy Ethyl, pentyloxypropyl, pentyloxybutyl, pentyloxypentyl, pentyloxyhexyl, pentyloxyoctyl, pentyloxydecyl, hexyloxymethyl, hexyloxyethyl, hexyloxypropyl, hexyloxybutyl,
Hexyloxypentyl, hexyloxyhexyl, hexyloxyoctyl, hexyloxynonyl, hexyloxydecyl, heptyloxymethyl, heptyloxyethyl, heptyloxypropyl, heptyloxybutyl, heptyloxypentyl, octyloxymethyl, octyloxyethyl, octyloxy Propyl,
Decyloxymethyl, decyloxyethyl, decyloxypropyl, 1-methylethyl, 1-methylpropyl,
1-methylbutyl, 1-methylpentyl, 1-methylhexyl, 1-methylheptyl, 1-methyloctyl, 2
-Methylethyl, 2-methylbutyl, 2-trihalomethylpentyl, 2-trihalomethylhexyl, 2-trihalomethylbutyl, 2-haloethyl, 2-halopropyl,
3-halopropyl, 3-halo-2-methylpropyl, 2,
3-dihalopropyl, 2-halobutyl, 3-halobutyl, 4-halobutyl, 2,3-dihalobutyl, 2,4-dihalobutyl, 3,4-dihalobutyl, 2-halo-3-methylbutyl, 2-halo-3,3- Dimethylbutyl, 2-halopentyl, 3-halopentyl, 4-halopentyl, 5-halopentyl, 2,4-dihalopentyl, 2,5-dihalopentyl, 2-halo-3-methylpentyl, 2-halo-4-methylpentyl, 2 -Halo-3-monohalomethyl-4-methylpentyl, 2-halohexyl, 3-halohexyl,
4-halohexyl, 5-halohexyl, 6-halohexyl, 2-haloheptyl, 2-halooctyl (however, halo in the above alkyl group represents fluorine, chlorine, bromine or iodine) and the like.
尚、これらの炭素数１〜20のハロゲン原子を含んでい
てもよいアルキル基またはアルコキシアルキル基は光学
活性基であってもよい。The alkyl group or alkoxyalkyl group which may contain a halogen atom having 1 to 20 carbon atoms may be an optically active group.
これらの光学活性基を有するアルキル化剤（ハロゲン
化物あるいは硫酸エステル類）は必要により相当する光
学活性アルコールから合成される。該光学活性アルコー
ルのうちのあるものは、対応するケトンの不斉金属触媒
または微生物もしくは酵素による不斉還元により容易に
得られる。またあるものは、天然に存在するか、または
分割により得られる次のような光学活性アミノ酸もしく
は光学活性オキシ酸から誘導できる。These alkylating agents having an optically active group (halides or sulfates) are synthesized from the corresponding optically active alcohol as required. Certain of the optically active alcohols are readily obtained by asymmetric metal catalysis of the corresponding ketones or by asymmetric reduction by microorganisms or enzymes. Others can be derived from the following optically active amino acids or optically active oxyacids that are naturally occurring or obtained by resolution.
バリン、ロイシン、イソロイシン、フェニルアラニ
ン、スレオニン、アロスレオニン、ホモセリン、アロイ
ソロイシン、tert−ロイシン、２−アミノ酪酸、ノルバ
リン、ノルロイシン、オルニチン、リジン、ヒドロキシ
リジン、フェニルグリシン、アスパラギン酸、グルタミ
ン酸、マンデル酸、トロパ酸、３−ヒドロキシ酪酸、リ
ンゴ酸、酒石酸、イソプロピルリンゴ酸等。Valine, leucine, isoleucine, phenylalanine, threonine, alosreonine, homoserine, alloisoleucine, tert-leucine, 2-aminobutyric acid, norvaline, norleucine, ornithine, lysine, hydroxylysine, phenylglycine, aspartic acid, glutamic acid, mandelic acid, tropha Acid, 3-hydroxybutyric acid, malic acid, tartaric acid, isopropylmalic acid and the like.
このようなアルキル化剤〔IV〕は、光学活性なアルコ
ール類〔III〕に対して１当量倍以上任意であるが、通
常は１〜５当量倍使用される。Such an alkylating agent [IV] is optional in an amount of 1 equivalent or more to the optically active alcohol [III], but is usually used in an amount of 1 to 5 equivalents.
該反応は通常、溶媒中で行われ、溶媒としてはテトラ
ヒドロフラン、エチルエーテル、アセトン、メチルエチ
ルケトン、トルエン、ベンゼン、クロロホルム、クロロ
ベンゼン、ジクロルメタン、ジクロルエタン、四塩化炭
素、ヘキサン等の脂肪族もしくは芳香族炭化水素、ケト
ン、エーテルまたはハロゲン化炭化水素等の反応に活性
な溶媒が例示される。これらの溶媒は単独あるいは混合
して使用され、その使用量については特に制限されな
い。The reaction is usually performed in a solvent, such as tetrahydrofuran, ethyl ether, acetone, methyl ethyl ketone, toluene, benzene, chloroform, chlorobenzene, dichloromethane, dichloroethane, carbon tetrachloride, aliphatic or aromatic hydrocarbons such as hexane, Solvents active in the reaction such as ketones, ethers or halogenated hydrocarbons are exemplified. These solvents are used alone or as a mixture, and the amount used is not particularly limited.
また、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ルアミドまたはＮ−メチルピ
ロリドン等の非プロトン性極性溶媒を使用することもで
きる。Also, an aprotic polar solvent such as dimethylformamide, dimethylsulfoxide, hexamethylphosphorylamide or N-methylpyrrolidone can be used.
反応温度は、通常、−50〜120℃、好ましくは−30℃
〜100℃である。The reaction temperature is usually -50 to 120C, preferably -30C.
~ 100 ° C.
反応時間は特に制限されず、光学活性なベンジルエー
テル誘導体を反応系から検出しなくなったときを反応終
点とする。The reaction time is not particularly limited, and the time when no optically active benzyl ether derivative is detected from the reaction system is defined as the reaction end point.
反応終了後、通常の分離手段、例えば、抽出、分液ま
たは濃縮等の操作を加えることにより、一般式〔II〕に
おいてｓが０である光学活性なベンジルエーテル誘導体
を収率よく得ることができ、必要に応じてカラムクロマ
トグラフィーまたは再結晶等により精製することができ
るが、次工程へは反応混合物のままで使用することもで
きる。After completion of the reaction, an optically active benzyl ether derivative in which s is 0 in the general formula [II] can be obtained in good yield by adding ordinary separation means, for example, extraction, liquid separation or concentration. It can be purified by column chromatography or recrystallization if necessary, but it can be used as it is in the reaction mixture for the next step.
光学活性なアルコール類〔III〕とアシル化剤〔Ｖ〕
との縮合によるｓが１である光学活性なベンジルエーテ
ル誘導体の製造において、該反応は溶媒の存在もしくは
非存在下に行われる。Optically active alcohol [III] and acylating agent [V]
In the production of an optically active benzyl ether derivative in which s is 1 by condensation with, the reaction is carried out in the presence or absence of a solvent.
溶媒を使用する場合、その溶媒としてはテトラヒドロ
フラン、エチルエーテル、アセトン、メチルエチルケト
ン、トルエン、ベンゼン、クロルベンゼン、ジクロルメ
タン、ジクロルエタン、クロロホルム、四塩化炭素、ジ
メチルホルムアミド、ヘキサン等の脂肪族もしくは芳香
族炭化水素、エーテル、ケトン、非プロトン性極性溶媒
またはハロゲン化炭化水素等の反応に不活性な溶媒が単
独あるいは混合して使用され、その使用量は特に制限さ
れない。When a solvent is used, the solvent may be an aliphatic or aromatic hydrocarbon such as tetrahydrofuran, ethyl ether, acetone, methyl ethyl ketone, toluene, benzene, chlorobenzene, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, dimethylformamide, hexane, etc. Solvents inert to the reaction, such as ethers, ketones, aprotic polar solvents or halogenated hydrocarbons, are used alone or as a mixture, and the amount used is not particularly limited.
この反応で使用されるアシル化剤〔Ｖ〕においてＲは
前記アルキル化剤〔IV〕で用いたＲまたはハロメチル、
１−ハロエチル、１−ハロプロピル、１−ハロブチル、
１−ハロペンチル、１−ハロヘキシル、１−ハロヘプチ
ル、１−ハロオクチル（但し上記アルキル基中ハロと
は、フッ素、塩素、臭素またはヨウ素を表わす）等が例
示される。In the acylating agent [V] used in this reaction, R is R or halomethyl used in the alkylating agent [IV],
1-haloethyl, 1-halopropyl, 1-halobutyl,
Examples thereof include 1-halopentyl, 1-halohexyl, 1-haloheptyl, and 1-halooctyl (however, halo in the above alkyl group represents fluorine, chlorine, bromine, or iodine).
尚、これらのアルキル基もしくはアルコシキアルキル
基は光学活性基であってもよい。In addition, these alkyl groups or alkoxyalkyl groups may be optically active groups.
これらの光学活性基を有する光学活性カルボン酸のう
ちのあるものは、対応するアルコールの酸化、アミノ酸
の還元的脱アミノ化により得られる。またあるものは天
然に存在するか、または分割により得られる前記光学活
性アミノ酸もしくは光学活性オキシ酸から誘導すること
ができる。Some of the optically active carboxylic acids having these optically active groups are obtained by oxidation of the corresponding alcohol and reductive deamination of the amino acid. Others can be derived from said optically active amino acids or optically active oxyacids, which are naturally occurring or obtained by resolution.
また、アシル化剤としては、一般式〔Ｖ〕で示される
脂肪族カルボン酸およびその酸ハライドの他に、上記に
例示したアルキル基またはアルコキシアルキル基を有す
る脂肪族カルボン酸の誘導体、すなわち酸無水物も挙げ
られる。Examples of the acylating agent include, in addition to the aliphatic carboxylic acid represented by the general formula [V] and its acid halide, a derivative of the aliphatic carboxylic acid having an alkyl group or an alkoxyalkyl group exemplified above, that is, an acid anhydride. Things are also mentioned.
該反応において、上記脂肪族カルボン酸無水物もしく
は酸ハライドを用いる場合、その使用量は、光学活性な
アルコール類〔III〕に対して１当量倍以上必要であ
り、上限については特に制限されないが、好ましくは当
量倍以下である。When the aliphatic carboxylic acid anhydride or acid halide is used in the reaction, the amount of the aliphatic carboxylic acid anhydride or the acid halide is required to be 1 equivalent or more with respect to the optically active alcohol [III], and the upper limit is not particularly limited. It is preferably at most equivalent times.
触媒としては、たとえばジメチルアミドピリジン、ト
リエチルアミン、トリ−ｎ−ブチルアミン、ピリジン、
ピコリン、コリジン、イミダゾール、炭酸ナトリウム、
ナトリウムメチラートもしくは炭酸水素カリウム等の有
機あるいは無機塩基性物質があげられる。また、トルエ
ンスルホン酸、メタンスルホン酸、硫酸などの有機ある
いは無機酸を触媒として用いることもできる。Examples of the catalyst include dimethylamidopyridine, triethylamine, tri-n-butylamine, pyridine,
Picoline, collidine, imidazole, sodium carbonate,
Organic or inorganic basic substances such as sodium methylate or potassium bicarbonate can be mentioned. Further, an organic or inorganic acid such as toluenesulfonic acid, methanesulfonic acid, and sulfuric acid can be used as a catalyst.
かかる触媒としてはたとえばアシル化剤〔Ｖ〕として
脂肪族カルボン酸の酸ハライドを使用する場合には、ピ
リジンもしくはトリエチルアミンが特に好ましく使用さ
れる。As the catalyst, for example, when an acid halide of an aliphatic carboxylic acid is used as the acylating agent [V], pyridine or triethylamine is particularly preferably used.
触媒の使用量は脂肪族カルボン酸無水物もしくは酸ハ
ライドの種類と使用する触媒の組合わせ等によっても異
なり、必ずしも特定されないが、たとえば酸ハライドを
使用する場合には、酸ハライドに対して１当量倍以上必
要である。The amount of the catalyst used depends on the combination of the aliphatic carboxylic anhydride or acid halide and the catalyst used, and is not necessarily specified. For example, when an acid halide is used, 1 equivalent of the acid halide is used. More than twice as necessary.
また、該反応において、アシル化剤〔Ｖ〕として脂肪
族カルボン酸を用いる場合は、縮合剤の存在下に行わ
れ、該カルボン酸は光学活性なアルコール類〔III〕に
対して通常、１〜２当量倍用いられる。When an aliphatic carboxylic acid is used as the acylating agent [V] in the reaction, the reaction is carried out in the presence of a condensing agent. Used 2 equivalent times.
縮合剤としてはN,N′−ジシクロヘキシルカルボジイ
ミドのごときカルボジイミド類が好ましく用いられ、ま
た必要により４−ピロリジノピリジン、ピリジンもしく
はトリエチルアミン等の有機塩基が併用される。As the condensing agent, carbodiimides such as N, N'-dicyclohexylcarbodiimide are preferably used, and if necessary, an organic base such as 4-pyrrolidinopyridine, pyridine or triethylamine is used in combination.
縮合剤は、通常、脂肪族カルボン酸に対して１〜1.2
当量倍、塩基を使用する場合には、かかる塩基は縮合剤
に対して通常0.01〜0.2当量倍使用される。The condensing agent is usually 1 to 1.2 relative to the aliphatic carboxylic acid.
When the base is used in an equivalent amount, the base is usually used in an amount of 0.01 to 0.2 equivalent times based on the condensing agent.
反応温度は通常−30℃〜120℃、好ましくは−25℃〜8
0℃である。The reaction temperature is usually -30C to 120C, preferably -25C to 8C.
0 ° C.
反応時間は特に制限されず、原料の光学活性なアルコ
ール類〔III〕が消失したときを反応終点とすることが
できる。The reaction time is not particularly limited, and the time when the optically active alcohol [III] as the raw material disappears can be regarded as the reaction end point.
反応終了後、反応混合物に通常の分離手段、例えば抽
出、分液または濃縮等の操作を加えることにより、一般
式〔II〕においてｓが１である光学活性なベンジルエー
テル誘導体を収率よく得ることができ、必要によりカラ
ムクロマトグラフィー等による精製を行うことができ
る。After the completion of the reaction, the reaction mixture is subjected to ordinary separation means, for example, extraction, liquid separation or concentration, to obtain an optically active benzyl ether derivative of the general formula [II] in which s is 1 in good yield. And, if necessary, purification by column chromatography or the like.
一般式〔III〕で示される光学活性なアルコール類は
下記のルートにより合成することができる。The optically active alcohol represented by the general formula [III] can be synthesized by the following route.
（Ａ、Ｚ、ｎおよび＊印は前記と同じ意味を表わし、R4
およびR5は同一または異なる低級アルキル基を表わ
す。） 以上の工程により得られる一般式〔Ｉ〕で示される光
学活性なフェノール類としては、 ４−（１−メチル−２−アルキルオキシエチル）フェ
ノール、 ４−（１−メチル−３−アルキルオキシプロピル）フ
ェノール、 ４−（１−メチル−４−アルキルオキシブチル）フェ
ノール、 ４−（１−メチル−５−アルキルオキシペンチル）フ
ェノール、 ４−（１−メチル−６−アルキルオキシヘキシル）フ
ェノール、 ４−（１−メチル−２−アルキルカルボニルオキシエ
チル）フェノール、 ４−（１−メチル−３−アルキルカルボニルオキシプ
ロピル）フェノール、 ４−（１−メチル−４−アルキルカルボニルオキシブ
チル）フェノール、 ４−（１−メチル−５−アルキルカルボニルオキシペ
ンチル）フェノール、 ４−（１−メチル−６−アルキルカルボニルオキシヘ
キシル）フェノール、 ４−（１−メチル−２−アルコキシアルキルオキシエ
チル）フェノール、 ４−（１−メチル−３−アルコキシアルキルオキシプ
ロピル）フェノール、 ４−（１−メチル−４−アルコキシアルキルオキシブ
チル）フェノール、 ４−（１−メチル−５−アルコキシアルキルオキシペ
ンチル）フェノール、 ４−（１−メチル−６−アルコキシアルキルオキシヘ
キシル）フェノール、 ４−（１−メチル−２−アルコキシアルキルカルボニ
ルオキシエチル）フェノール ４−（１−メチル−３−アルコキシアルキルカルボニ
ルオキシプロピル）フェノール ４−（１−メチル−４−アルコキシアルキルカルボニ
ルオキシブチル）フェノール ４−（１−メチル−５−アルコキシアルキルカルボニ
ルオキシペンチル）フェノール ４−（１−メチル−６−アルコキシアルキルカルボニ
ルオキシヘキシル）フェノール ４−（２−アルキルオキシプロピル）フェノール、 ４−（３−アルキルオキシブチル）フェノール、 ４−（４−アルキルオキシペンチル）フェノール、 ４−（５−アルキルオキシヘキシル）フェノール、 ４−（６−アルキルオキシヘプチル）フェノール、 ４−（２−アルキルカルボニルオキシプロピル）フェ
ノール、 ４−（３−アルキルカルボニルオキシブチル）フェノ
ール、 ４−（４−アルキルカルボニルオキシペンチル）フェ
ノール、 ４−（５−アルキルカルボニルオキシヘキシル）フェ
ノール、 ４−（６−アルキルカルボニルオキシヘプチル）フェ
ノール、 ４−（２−アルコキシアルキルオキシプロピル）フェ
ノール、 ４−（３−アルコキシアルキルオキシブチル）フェノ
ール、 ４−（４−アルコキシアルキルオキシペンチル）フェ
ノール、 ４−（５−アルコキシアルキルオキシヘキシル）フェ
ノール、 ４−（６−アルコキシアルキルオキシヘプチル）フェ
ノール、 ４−（２−アルコキシアルキルカルボニルオキシプロ
ピル）フェノール、 ４−（３−アルコキシアルキルカルボニルオキシブチ
ル）フェノール、 ４−（４−アルコキシアルキルカルボニルオキシペン
チル）フェノール、 ４−（５−アルコキシアルキルカルボニルオキシヘキ
シル）フェノール、 ４−（６−アルコキシアルキルカルボニルオキシヘプ
チル）フェノール、 （ここで名称中、アルキルとは炭素数１〜20のハロゲン
原子を含んでいてもよいアルキル基を表わし、アルコキ
シアルキルとは炭素数２〜20のハロゲン原子を含んでい
てもよいアルコキシアルキル基を表わす。これらは前記
Ｒとして例示したものがあげられる。また、フェノール
とは、２位あるいは３位がハロゲン原子で置換されてい
てもよいフェノールを表わす。）などが例示される。 (A, Z, n and * mark represent the same meanings as defined above, R 4
And R 5 represent the same or different lower alkyl groups. The optically active phenols represented by the general formula [I] obtained by the above steps include 4- (1-methyl-2-alkyloxyethyl) phenol, 4- (1-methyl-3-alkyloxypropyl) ) Phenol, 4- (1-methyl-4-alkyloxybutyl) phenol, 4- (1-methyl-5-alkyloxypentyl) phenol, 4- (1-methyl-6-alkyloxyhexyl) phenol, 4- (1-methyl-2-alkylcarbonyloxyethyl) phenol, 4- (1-methyl-3-alkylcarbonyloxypropyl) phenol, 4- (1-methyl-4-alkylcarbonyloxybutyl) phenol, 4- (1 -Methyl-5-alkylcarbonyloxypentyl) phenol, 4- (1-methyl-6-a (Alkylcarbonyloxyhexyl) phenol, 4- (1-methyl-2-alkoxyalkyloxyethyl) phenol, 4- (1-methyl-3-alkoxyalkyloxypropyl) phenol, 4- (1-methyl-4-alkoxyalkyl) Oxybutyl) phenol, 4- (1-methyl-5-alkoxyalkyloxypentyl) phenol, 4- (1-methyl-6-alkoxyalkyloxyhexyl) phenol, 4- (1-methyl-2-alkoxyalkylcarbonyloxy) Ethyl) phenol 4- (1-methyl-3-alkoxyalkylcarbonyloxypropyl) phenol 4- (1-methyl-4-alkoxyalkylcarbonyloxybutyl) phenol 4- (1-methyl-5-alkoxyalkylcarbonyloxypropyl) phenol 4- (1-methyl-6-alkoxyalkylcarbonyloxyhexyl) phenol 4- (2-alkyloxypropyl) phenol, 4- (3-alkyloxybutyl) phenol, 4- (4-alkyloxypentyl) Phenol, 4- (5-alkyloxyhexyl) phenol, 4- (6-alkyloxyheptyl) phenol, 4- (2-alkylcarbonyloxypropyl) phenol, 4- (3-alkylcarbonyloxybutyl) phenol, 4- (4-alkylcarbonyloxypentyl) phenol, 4- (5-alkylcarbonyloxyhexyl) phenol, 4- (6-alkylcarbonyloxyheptyl) phenol, 4- (2-alkoxyalkyloxypropyl) phenol, 4 -(3-alkoxyalkyloxybutyl) phenol, 4- (4-alkoxyalkyloxypentyl) phenol, 4- (5-alkoxyalkyloxyhexyl) phenol, 4- (6-alkoxyalkyloxyheptyl) phenol, 4- ( 2-alkoxyalkylcarbonyloxypropyl) phenol, 4- (3-alkoxyalkylcarbonyloxybutyl) phenol, 4- (4-alkoxyalkylcarbonyloxypentyl) phenol, 4- (5-alkoxyalkylcarbonyloxyhexyl) phenol, 4 -(6-alkoxyalkylcarbonyloxyheptyl) phenol, (wherein, alkyl represents an alkyl group which may contain a halogen atom having 1 to 20 carbon atoms, and Also contain halogen atoms of 2 to 20 carbon atoms represent a good alkoxyalkyl group. These include those exemplified as R above. In addition, phenol represents phenol which may be substituted at the 2- or 3-position with a halogen atom. ) Are exemplified.
そして、中間体である光学活性なベンジルエーテル誘
導体〔II〕としては、次の化合物が例示される。The following compounds are exemplified as the optically active benzyl ether derivative [II] as an intermediate.
４−（１−メチル−２−アルコキシエチル）フェニル
ベンジルエーテル、 ４−（１−メチル−３−アルコキシプロピル）フェニ
ル ベンジルエーテル、 ４−（１−メチル−４−アルコキシブチル）フェニル
ベンジルエーテル、 ４−（１−メチル−５−アルコキシペンチル）フェニ
ル ベンジルエーテル、 ４−（１−メチル−６−アルコキシヘキシル）フェニ
ル ベンジルエーテル、 ４−（２−アルコキシプロピル）フェニル ベンジル
エーテル、 ４−（３−アルコキシブチル）フェニル ベンジルエ
ーテル、 ４−（４−アルコキシペンチル）フェニル ベンジル
エーテル、 ４−（５−アルコキシヘキシル）フェニル ベンジル
エーテル、 ４−（６−アルコキシヘプチル）フェニル ベンジル
エーテル等。4- (1-methyl-2-alkoxyethyl) phenyl benzyl ether, 4- (1-methyl-3-alkoxypropyl) phenyl benzyl ether, 4- (1-methyl-4-alkoxybutyl) phenyl benzyl ether, 4- (1-methyl-5-alkoxypentyl) phenyl benzyl ether, 4- (1-methyl-6-alkoxyhexyl) phenyl benzyl ether, 4- (2-alkoxypropyl) phenyl benzyl ether, 4- (3-alkoxybutyl) Phenyl benzyl ether, 4- (4-alkoxypentyl) phenyl benzyl ether, 4- (5-alkoxyhexyl) phenyl benzyl ether, 4- (6-alkoxyheptyl) phenyl benzyl ether and the like.
その他、上記ベンジルエーテル誘導体のベンジル側ベ
ンゼン環の水素がメチル、エチル、プロピル、ブチル、
メトキシ、エトキシ、プロポキシ、ブトキシ、フルオ
ロ、クロロ、ブロモ、またはヨードのいずれかで置換さ
れた化合物。そして、化合物中、アルコキシ基が、アル
コキシアルキルオキシ基、アルキルカルボニルオキシ
基、またはアルコキシアルキルカルボニルオキシ基のい
ずれかに置きかわった化合物。（ここで名称中、アルコ
キシ及びアルコキシアルキルは前記と同じ意味を表わ
し、フェニルとは２位あるいは３位がハロゲン原子で置
換されていてもよいフェニル基を表わす。） ＜発明の効果＞ 本発明化合物である光学活性なフェノール類〔Ｉ〕
は、下記に示す方法により、一般式〔VI〕で示される強
誘電性化合物へと導くことができる。In addition, hydrogen of the benzyl ring on the benzyl side of the benzyl ether derivative is methyl, ethyl, propyl, butyl,
Compounds substituted with any of methoxy, ethoxy, propoxy, butoxy, fluoro, chloro, bromo, or iodo. A compound in which, in the compound, the alkoxy group is replaced by any of an alkoxyalkyloxy group, an alkylcarbonyloxy group, and an alkoxyalkylcarbonyloxy group. (In the names, alkoxy and alkoxyalkyl have the same meanings as described above, and phenyl represents a phenyl group in which the 2- or 3-position may be substituted with a halogen atom.) <Effect of the Invention> Compound of the present invention Optically active phenols [I]
Can be converted to a ferroelectric compound represented by the general formula [VI] by the following method.
（ここでR0はアルキル基、アルコキシル基等をArは1,4
−フェニレン基、4,4′−ビフェニレン基等を、Ｙはハ
ロゲン原子をそれぞれ表わし、Ｚ、Ｗ、ｓおよびＲは前
記と同じ意味を表わす。） 上記一般式〔VI〕で示される液晶化合物は強誘電性化
合物とつて高速応答性、自発分極性、温度範囲の広範性
等の点ですぐれた特性を有している。 (Where R 0 is an alkyl group, an alkoxyl group, etc., and Ar is 1,4
-Phenylene group, 4,4'-biphenylene group and the like, Y represents a halogen atom, and Z, W, s and R have the same meanings as described above. The liquid crystal compound represented by the general formula [VI] has excellent characteristics such as high-speed response, spontaneous polarization, and a wide temperature range as compared with the ferroelectric compound.
また、本発明の製造法により、該フェノール類〔Ｉ〕
を工業的に有利に製造することができる。Further, according to the production method of the present invention, the phenol (I)
Can be industrially advantageously produced.
さらに該フェノール類〔Ｉ〕は農薬、医薬等の中間体
としても利用することができる。Further, the phenols [I] can also be used as intermediates for agricultural chemicals, pharmaceuticals and the like.
＜実施例＞ 以下、実施例により本発明をさらに詳細に説明する
が、本発明は下記の実施例に限定されるものではない。<Example> Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.
（下記実施例中における収率とは特に注釈ない場合、各
単一反応の収率を表わす。） 実施例１ 温度計、撹拌装置を装着した４ツ口フラスコに（＋）
−３−メチル−３−（４−ヒドロキシフェニル）プロピ
オン酸メチル38.8g（0.2モル）と無水炭酸カリウム70g
およびジメチルホルムアミド400mlを仕込み、塩化ベン
ジル30.4g（0.24モル）を添加して、50〜60℃で６時間
反応させた。(The yield in each of the following examples indicates the yield of each single reaction unless otherwise specified.) Example 1 (+) in a four-necked flask equipped with a thermometer and a stirrer
38.8 g (0.2 mol) of methyl -3-methyl-3- (4-hydroxyphenyl) propionate and 70 g of anhydrous potassium carbonate
And 400 ml of dimethylformamide, 30.4 g (0.24 mol) of benzyl chloride was added, and the mixture was reacted at 50 to 60 ° C. for 6 hours.
反応終了後、反応混合物を水１中に注ぎ込み、クロ
ロホルム500mlを加えて抽出処理した。有機層はよく水
洗したのち、減圧下に溶媒を留去して、（＋）−３−メ
チル−３−（４−ベンジルオキシフェニル）プロピオン
酸メチル〔１−ａ〕55.1g（収率97％）を得た。After completion of the reaction, the reaction mixture was poured into water 1 and extracted with 500 ml of chloroform. The organic layer was thoroughly washed with water, and the solvent was distilled off under reduced pressure to give 55.1 g of methyl (+)-3-methyl-3- (4-benzyloxyphenyl) propionate [1-a] (yield 97%). ) Got.
上で得た〔１−ａ〕54g（0.19モル）をテトラヒドロ
フラン300ml中に溶かした後、水素化リチウムアルミニ
ウム7.2g（0.19モル）を懸濁させたテトラヒドロフラン
300ml中に滴下し、30〜40℃で３時間撹拌した。反応混
合物中に注意深くエタノールを加え、水１中に注ぎ出
した後、塩酸でpH2〜３に調整し、その後、トルエン300
mlを加えて抽出処理した。有機層は５％重曹水で洗浄し
たのち、減圧下に溶媒を留去して（＋）−３−メチル−
３−（４−ベンジルオキシフェニル）プロパノール〔II
I−１〕46.7g（収率96％）を得た。After dissolving 54 g (0.19 mol) of [1-a] obtained above in 300 ml of tetrahydrofuran, tetrahydrofuran in which 7.2 g (0.19 mol) of lithium aluminum hydride was suspended.
The mixture was added dropwise to 300 ml and stirred at 30 to 40 ° C for 3 hours. Ethanol was carefully added to the reaction mixture, which was poured into water 1 and then adjusted to pH 2-3 with hydrochloric acid.
ml was added for extraction. The organic layer was washed with 5% aqueous sodium bicarbonate, and the solvent was distilled off under reduced pressure to give (+)-3-methyl-
3- (4-benzyloxyphenyl) propanol [II
I-1] 46.7 g (96% yield) was obtained.
上で得られた（＋）−３−メチル−３−（４−ベンジ
ルオキシフェニル）プロパノール〔III−１〕2.56g（10
ミリモル）をジメチルホルムアミド20ml中にとかした
後、25〜30℃にて60％水素化ナトリウム0.48g（12ミリ
モル）を加えて２時間撹拌した。その後、パラトルエン
スルホン酸プロピルエステル3.0g（14ミリモル）を加え
て30〜40℃で４時間反応させた。反応終了後、反応混合
物を水300ml中に注ぎ出し、トルエン300mlの抽出、分液
した後、有機層はさらに水洗し、無水硫酸マグネシウム
で乾燥させた。減圧下に溶媒を留去したのち、得られた
残渣をシリカゲルカラムクロマトグラフィー（溶出液：
トルエン）で精製することにより、（＋）−１−プロポ
キシ−３−（４−ベンジルオキシ）フェニルブタン〔II
−１〕2.86g（収率96％）｛▲［α］20 D▼＋17.7゜（ｃ
＝1,CHCl3），▲ｎ20 D▼＝1.5222｝を得た。2.56 g of (+)-3-methyl-3- (4-benzyloxyphenyl) propanol [III-1] obtained above (10
Was dissolved in 20 ml of dimethylformamide, and 0.48 g (12 mmol) of 60% sodium hydride was added at 25 to 30 ° C., followed by stirring for 2 hours. Thereafter, 3.0 g (14 mmol) of propyl paratoluenesulfonate was added, and the mixture was reacted at 30 to 40 ° C. for 4 hours. After completion of the reaction, the reaction mixture was poured into 300 ml of water, extracted with 300 ml of toluene and separated, and the organic layer was further washed with water and dried over anhydrous magnesium sulfate. After evaporating the solvent under reduced pressure, the obtained residue is subjected to silica gel column chromatography (eluent:
(+)-1-propoxy-3- (4-benzyloxy) phenylbutane [II
-1] 2.86 g (96% yield) {▲ [α] 20 D ▼ + 17.7} (c
= 1, CHCl 3 ), {n 20 D ▼ = 1.5222}.
ここで得た〔II−１〕1.49g（５ミリモル）をメタノ
ール20ml中にとかした後、５％Pd/C 0.1gを加えて、水
素雰囲気中で脱ベンジル化反応を行った。計算量の水素
（約 110ml）が消費されたところで原料〔II−１〕が完
全に消失していることを確認したうえでPd/Cを濾別し、
メタノール溶液を減圧下に濃縮して、（＋）−４−（１
−メチル−３−プロポキシプロピル）フェノール〔Ｉ−
１〕1.04g（収率100％）｛▲［α］20 D▼＝＋28.2゜
（ｃ＝1,CHCl3）、▲ｎ20 D▼＝1.5011｝を得た。After dissolving 1.49 g (5 mmol) of the obtained [II-1] in 20 ml of methanol, 0.1 g of 5% Pd / C was added, and a debenzylation reaction was carried out in a hydrogen atmosphere. When the calculated amount of hydrogen (about 110 ml) was consumed, it was confirmed that the raw material [II-1] had completely disappeared, and then Pd / C was filtered off.
The methanol solution was concentrated under reduced pressure to give (+)-4- (1
-Methyl-3-propoxypropyl) phenol [I-
1] 1.04 g (100% yield) {％ [α] 20 D ▼ = + 28.2 ゜ (c = 1, CHCl 3 ) and 、 n 20 D D = 1.5011｝.
実施例２〜７ 実施例１で得た（＋）−３−メチル−３−（４−ベン
ジルオキシフェニル）プロパロール〔III−１〕2.56g
（10ミリモル）を用い、表−１に示すアルキル化剤〔I
V〕を使用する以外は実施例１と同様に縮合、脱ベンジ
ル化反応および後処理を行って表−１に志す結果を得
た。Examples 2 to 7 2.56 g of (+)-3-methyl-3- (4-benzyloxyphenyl) propanol [III-1] obtained in Example 1
(10 mmol) and the alkylating agent [I
V], the condensation, debenzylation reaction and post-treatment were carried out in the same manner as in Example 1 to obtain the results shown in Table 1.
実施例８ 温度計、撹拌装置を装着した４ツ口フラスコに（−）
−２−（４−ヒドロキフェニル）プロピオン酸エチル7
7.6g（0.4モル）、ｐ−メチルベンジルアルコール54.9g
（0.45モル）、トリフェニルホスフィン108g（0.41モ
ル）およびテトラヒドロフラン300mlを仕込み、０℃で
ジエチルアゾジカルボキシレート71.4g（0.41モル）を
滴下した。20℃に昇温後、同温度で１日間撹拌したの
ち、反応混合物を濃縮した。得られた残渣をシリカゲル
カラムクロマトグラフィーで精製して（−）−２−｛４
−（ｐ−メチルベンジルオキシフェニル）｝プロピオン
酸エチル〔２−ａ〕85.9g（収率72％）を得た。 Example 8 In a four-necked flask equipped with a thermometer and a stirrer (-)
Ethyl 2- (4-hydroxyphenyl) propionate 7
7.6 g (0.4 mol), p-methylbenzyl alcohol 54.9 g
(0.45 mol), 108 g (0.41 mol) of triphenylphosphine and 300 ml of tetrahydrofuran were charged, and 71.4 g (0.41 mol) of diethyl azodicarboxylate was added dropwise at 0 ° C. After the temperature was raised to 20 ° C., the mixture was stirred at the same temperature for 1 day, and then the reaction mixture was concentrated. The obtained residue was purified by silica gel column chromatography to give (−)-2- ｛4
85.9 g (yield 72%) of ethyl-(p-methylbenzyloxyphenyl)} propionate [2-a] was obtained.
ここで得た〔２−ａ〕56.6g（0.19モル）を、実施例
１に準じて還元、縮合、脱ベンジル化反応および後処理
を行って（＋）−４−（１−メチル−２−プロポキシエ
チル）フェノール〔Ｉ−８〕0.96g（収率99.5％）を得
た。56.6 g (0.19 mol) of [2-a] obtained here was subjected to reduction, condensation, debenzylation and post-treatment according to Example 1 to give (+)-4- (1-methyl-2- 0.96 g (99.5% yield) of propoxyethyl) phenol [I-8] was obtained.
▲［α］20 D＝＋23.0゜（ｃ＝1,CHCl3） 実施例９ 実施例１で得た（＋）−３−メチル−３−（４−ベン
ジルオキシフェニル）プロパノール〔III−１〕2.56g
（10ミリモル）をピリジン20ml中にとかし、30〜40℃に
てブチリルクロリド1.38g（13ミリモル）を加えて２時
間反応させた。反応混合物を水200ml中に注ぎ出し、ト
ルエン200mlで抽出、分液後、1N塩酸水、水、５％重曹
水、水の順に洗浄したのち、無水硫酸マグネシウムで乾
燥させた。減圧下に溶媒を留去したのち、得られた残渣
をシリカゲルカラムクロマトグラフィー（溶出液：トル
エン−酢酸エチル）で精製することにより（＋）−４−
ベンジルオキシ−１−（１−メチル−３−ブチリルオキ
シプロピル）ベンゼン〔II−９〕3.1g（収率95％）を得
た。Α [α] 20 D = + 23.0ｃ (c = 1, CHCl 3 ) Example 9 (+)-3-methyl-3- (4-benzyloxyphenyl) propanol [III-1] obtained in Example 1 2.56g
(10 mmol) was dissolved in 20 ml of pyridine, and 1.38 g (13 mmol) of butyryl chloride was added at 30 to 40 ° C. and reacted for 2 hours. The reaction mixture was poured into 200 ml of water, extracted with 200 ml of toluene, separated, washed with 1N aqueous hydrochloric acid, water, 5% aqueous sodium hydrogen carbonate and water in that order, and dried over anhydrous magnesium sulfate. After evaporating the solvent under reduced pressure, the obtained residue is purified by silica gel column chromatography (eluent: toluene-ethyl acetate) to obtain (+)-4-
3.1 g (yield 95%) of benzyloxy-1- (1-methyl-3-butyryloxypropyl) benzene [II-9] was obtained.
▲［α］20 D▼＝＋11.3゜（ｃ＝1,CHCl3） ここで得た〔II−９〕1.63g（５ミリモル）をメタノ
ール20mlにとかし、５％Pd/C 0.1gを加えて、水素雰囲
気中で脱ベンジル化反応を行った。計算量の水素（約 1
00ml）が消費されたところで、原料〔II−９〕が完全に
消失していることを確認したうえでPd/Cを濾別し、得ら
れたメタノール溶液を減圧下に濃縮して（＋）−４−
（１−メチル−３−ブチリルオキシプロピル）フェノー
ル〔Ｉ−９〕1.18g（収率99.5％）｛▲［α］20 D▼＝＋
18.0゜（ｃ＝1,CHCl3）｝を得た。▲ [α] 20 D ▼ = + 11.3 ゜ (c = 1, CHCl 3 ) 1.63 g (5 mmol) of [II-9] obtained above was dissolved in methanol 20 ml, and 5% Pd / C 0.1 g was added. To carry out a debenzylation reaction in a hydrogen atmosphere. Calculated amount of hydrogen (about 1
(00 ml) was consumed, and after confirming that the raw material [II-9] had completely disappeared, Pd / C was separated by filtration, and the obtained methanol solution was concentrated under reduced pressure (+). -4-
1.18 g of (1-methyl-3-butyryloxypropyl) phenol [I-9] (yield 99.5%) ｛▲ [α] 20 D ▼ = +
18.0 {(c = 1, CHCl 3 )} was obtained.
実施例10〜12 実施例１で得た（＋）−３−メチル−３−（４−ベン
ジルオキシフェニル）プロパノール〔III−１〕2.56g
（10ミリモル）を用い、表−２に示すアシル化剤〔Ｖ〕
を用いる以外は実施例９に準じて縮合、脱ベンジル化反
応および後処理して表−２に示す結果を得た。Examples 10 to 12 2.56 g of (+)-3-methyl-3- (4-benzyloxyphenyl) propanol [III-1] obtained in Example 1
(10 mmol) and the acylating agent [V] shown in Table-2
Was carried out in the same manner as in Example 9 except for using, to obtain the results shown in Table 2.
実施例13 温度計、撹拌装置を装着した４つ口フラスコに４−
（４−ベンジルオキシ）フェニルブタン−２−オン50.8
g（0.2モル）とエタノール200mlおよびクロロホルム200
mlを仕込み、30〜40℃にて水素化ホウ素ナトリウム5.7g
（0.15モル）を約30分間で加えた。同温度で３時間撹拌
したのち、反応混合物を水500mlに注ぎ込み、クロロホ
ルム200mlを加えて抽出した。有機層は水でよく水洗し
たのち、減圧下に溶媒を留去して、４−（４−ベンジル
オキシ）フェニル−２−ブタノール〔３−ａ〕を白色結
晶として51.0g（収率99.5％）得た。 Example 13 A 4-necked flask equipped with a thermometer and a stirrer was
(4-benzyloxy) phenylbutan-2-one 50.8
g (0.2mol), 200ml of ethanol and 200 of chloroform
5.7 g of sodium borohydride at 30-40 ° C.
(0.15 mol) was added in about 30 minutes. After stirring at the same temperature for 3 hours, the reaction mixture was poured into 500 ml of water, and extracted by adding 200 ml of chloroform. The organic layer was thoroughly washed with water, and the solvent was distilled off under reduced pressure to give 4- (4-benzyloxy) phenyl-2-butanol [3-a] as white crystals (51.0 g, yield 99.5%). Obtained.
上で得た〔３−ａ〕48.7g（0.19モル）をトルエン200
mlとピリジン100ml混合溶媒に溶かし、無水酢酸29g（0.
285モル）と４−ジメチルアミノピリジン1gを加えて、4
0〜50℃で６時間撹拌した。48.7 g (0.19 mol) of [3-a] obtained above was treated with toluene 200
dissolved in a mixed solvent of 100 ml of pyridine and 100 ml of pyridine.
285 mol) and 1 g of 4-dimethylaminopyridine,
Stirred at 0-50 ° C for 6 hours.
反応終了後、反応混合物を4N塩酸500ml中に注ぎ出
し、抽出、分液した。得られた有機層はIN塩酸水、水、
５％重曹水、水の順に洗浄し、無水硫酸マグネシウムで
乾燥した後、減圧下に溶媒を留去し、２−アセトキシ−
４−（４−ベンジルオキシ）フェニルブタン〔３−ｂ〕
を白色結晶として56.1g（収率99％）得た。After completion of the reaction, the reaction mixture was poured into 500 ml of 4N hydrochloric acid, extracted and separated. The obtained organic layer is composed of IN hydrochloric acid water, water,
After washing with 5% aqueous sodium bicarbonate and water in that order and drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to give 2-acetoxy-
4- (4-benzyloxy) phenylbutane [3-b]
Was obtained as white crystals (56.1 g, yield 99%).
さらに〔３−ｂ〕50gを3Nリン酸バッファー500mlに懸
濁させ、リパーゼ（「アマノＰ」）2.5gを加えて、36±
２℃で24時間激しく撹拌した。反応終了後、反応液に酢
酸エチル500mlを加えて、濾過したのち、抽出、分液し
得られた有機層を水洗した。有機層を減圧下溶媒留去
し、得られた残渣をシリカゲルカラムクロマトグラフィ
ー（溶出液：トルエン−酢酸エチル）で分離し、（−）
−２−アセトキシ−４−（４−ベンジルオキシ）フェニ
ルブタン25.4g（収率50.8％）▲［α］20 D▼＝−7.8゜
（ｃ＝1,CHCl3）と（−）−４−（４−ベンジルオキ
シ）フェニル−２−ブタノ−ル〔III−３〕20.6g（収率
48％）｛▲［α］20 D▼＝−9.3゜（ｃ＝1,CHCl3）｝を
得た。Further, 50 g of [3-b] was suspended in 500 ml of a 3N phosphate buffer, and 2.5 g of lipase (“Amano P”) was added thereto.
Stirred vigorously at 2 ° C. for 24 hours. After the reaction was completed, 500 ml of ethyl acetate was added to the reaction solution, followed by filtration, extraction, and separation, and the obtained organic layer was washed with water. The solvent was distilled off from the organic layer under reduced pressure, and the obtained residue was separated by silica gel column chromatography (eluent: toluene-ethyl acetate).
25.4 g of 2-acetoxy-4- (4-benzyloxy) phenylbutane (yield 50.8%) {[α] 20 D ▼ = −7.8} (c = 1, CHCl 3 ) and (−)-4- ( 20.6 g of 4-benzyloxy) phenyl-2-butanol [III-3] (yield
48%) {▲ [α] 20 D ▼ = -9.3 ゜ (c = 1, CHCl 3 )｝.
上で得た〔III−３〕2.56g（10ミリモル）をジメチル
ホルムアミド20mlにとかし、25〜30℃にて、60％水素化
ナトリウム0.48g（12ミリモル）を加えて２時間撹拌し
た。その後、パラトルエンスルホン酸プロピルエステル
3.0g（14ミリモル）を加えて30〜40℃で４時間反応させ
た。反応終了後、反応混合物を水300mlに注ぎ出し、ト
ルエン300mlで抽出、分液し、有機層はさらに水洗した
のち、無水硫酸マグネシウムで乾燥させた。2.56 g (10 mmol) of [III-3] obtained above was dissolved in 20 ml of dimethylformamide, and 0.48 g (12 mmol) of 60% sodium hydride was added at 25 to 30 ° C., followed by stirring for 2 hours. Then, para-toluenesulfonic acid propyl ester
3.0 g (14 mmol) was added and reacted at 30-40 ° C for 4 hours. After completion of the reaction, the reaction mixture was poured into 300 ml of water, extracted and separated with 300 ml of toluene, and the organic layer was further washed with water and dried over anhydrous magnesium sulfate.
減圧下に溶媒を留去したのち、得られた残渣をシリカ
ゲルカラムクロマトグラフィー（溶出液：トルエン）で
精製することにより、（−）−２−プロポキシ−４−
（４−ベンジルオキシ）フェニルブタン〔II−13〕2.86
g（収率96％） ｛▲［α］20 D▼＝−8.5゜（ｃ＝1,CHCl3）、 ▲ｎ20 D▼＝1.5231｝を得た。After evaporating the solvent under reduced pressure, the obtained residue is purified by silica gel column chromatography (eluent: toluene) to give (-)-2-propoxy-4-
(4-benzyloxy) phenylbutane [II-13] 2.86
g (96% yield) {） [α] 20 D ▼ = -8.5 ゜ (c = 1, CHCl 3 ) and ｎn 20 D ▼ = 1.5231｝.
ここで得た〔II−13〕1.49g（５ミリモル）をメタノ
ール20mlにとかし、５％Pd/C 0.1gを加えて、水素雰囲
気下、脱ベンジル化反応を行った。計算量の水素（約11
0ml）が消費されたことろで原料が完全に消失している
ことを確認したうえ、Pd/Cを濾別し、メタノール溶液を
減圧下に濃縮して、（−）−４−（３−プロポキシブチ
ル）フェノール1.04g〔Ｉ−13〕（収率100％） ｛▲［α］20 D▼＝−9.9゜（ｃ＝1,CHCl3）、▲ｎ20 D＝
1.4968｝得た。1.49 g (5 mmol) of the obtained [II-13] was dissolved in 20 ml of methanol, and 0.1 g of 5% Pd / C was added thereto, followed by a debenzylation reaction in a hydrogen atmosphere. Calculated amount of hydrogen (about 11
0 ml) was consumed, and it was confirmed that the raw materials had completely disappeared. Then, Pd / C was separated by filtration, and the methanol solution was concentrated under reduced pressure to give (-)-4- (3- Propoxybutyl) phenol 1.04 g [I-13] (100% yield) {[α] 20 D ▼ = -9.9} (c = 1, CHCl 3 ), ▲ n 20 D =
1.4968｝ was obtained.
実施例14〜16 実施例13で得た〔III−３〕2.56g（10ミリモル）を用
い、表−３に示すアルキル化剤〔IV〕を用いる以外は実
施例13に準拠して反応、後処理を行い、表−３に示す結
果を得た。Examples 14 to 16 The reaction was carried out according to Example 13 except that 2.56 g (10 mmol) of [III-3] obtained in Example 13 was used and the alkylating agent [IV] shown in Table 3 was used. The treatment was performed, and the results shown in Table 3 were obtained.
実施例17〜18 実施例13で得た（−）−２−アセトキシ−４−（４−
ベンジルオキシ）フェニルブタン25gをメタノール100ml
とテトラヒドロフラン50mlの溶液に溶かし、20％水酸化
ナトリウム水溶液50mlを加えて、30〜40℃６時間反応さ
せた。反応終了後、4N塩酸でpH9に調整したのち、トル
エン300mlで抽出、分液し、有機層は水洗したのち、無
水硫酸マグネシウムで乾燥した。有機層は減圧下に濃縮
して（＋）−４−（４−ベンジルオキシ）フェニル−２
−ブタノール〔III−３′〕21.2g（収率98.7％）｛▲
［α］20 D▼＝＋9.0゜（ｃ＝1,CHCl3）｝を得た。Examples 17-18 (-)-2-acetoxy-4- (4-) obtained in Example 13
Benzyloxy) phenylbutane 25g methanol 100ml
And 50 ml of a solution of tetrahydrofuran, 50 ml of a 20% aqueous sodium hydroxide solution was added, and the mixture was reacted at 30 to 40 ° C. for 6 hours. After completion of the reaction, the mixture was adjusted to pH 9 with 4N hydrochloric acid, extracted with 300 ml of toluene and separated, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. The organic layer was concentrated under reduced pressure to give (+)-4- (4-benzyloxy) phenyl-2.
-Butanol [III-3 '] 21.2 g (98.7% yield)
[Α] 20 D ▼ = + 9.0 {(c = 1, CHCl 3 )} was obtained.
ここで得た〔III−３′〕2.56g（10ミリモル）を用
い、表−４に示すアルキル化剤〔IV〕を用いる以外は実
施例13と同様のモル数、容量の試薬、溶媒を用いて、表
−４に示す結果を得た。Using 2.56 g (10 mmol) of [III-3 '] obtained here and using the same number of moles and volume of reagents and solvent as in Example 13 except that the alkylating agent [IV] shown in Table 4 was used. Thus, the results shown in Table 4 were obtained.
実施例19 ４−（４−ベンジルオキシ）フェニルブタン−２−オ
ン（0.2モル）に代えて１−（４−ベンジルオキシ）フ
ェニルプロパン−２−オン48.1g（0.2モル）を用いる以
外は実施例14に準じて反応、後処理および精製して
（−）−４−（２−ペンチルオキシプロピル）フェノー
ル〔Ｉ−19〕1.05g（収率94.5％）を得た。▲［α］20 D
＝−15.6゜（ｃ＝1,CHCl3） 実施例20 ４−（４−ベンジルオキシ）フェニルブタン−２−オ
ン（0.2モル）に代えて５−（４−ベンジルオキシ）フ
ェニルペンタン−２−オン53.7g（0.2モル）を用いる以
外は実施例14に準じて反応、後処理および精製をおこな
い、（−）−４−（４−ペンチルオキシペンチル）フェ
ノール〔Ｉ−20〕1.18g（収率94.5％）を得た。 Example 19 Example 19 was repeated except that 48.1 g (0.2 mol) of 1- (4-benzyloxy) phenylpropan-2-one was used instead of 4- (4-benzyloxy) phenylbutan-2-one (0.2 mol). The reaction, work-up and purification were carried out according to 14 to obtain 1.05 g (yield 94.5%) of (-)-4- (2-pentyloxypropyl) phenol [I-19]. ▲ [α] 20 D
= -15.6 ° (c = 1, CHCl 3 ) Example 20 5- (4-benzyloxy) phenylpentan-2-one in place of 4- (4-benzyloxy) phenylbutan-2-one (0.2 mol) The reaction, work-up and purification were carried out according to Example 14 except that 53.7 g (0.2 mol) was used, and 1.18 g of (-)-4- (4-pentyloxypentyl) phenol [I-20] (yield 94.5) %).
▲［α］20 D＝−6.0゜（ｃ＝1,CHCl3） 実施例21〜24 実施例13で得た（−）−４−（４−ベンジルオキシ）
フェニル−２−ブタノール〔III−３〕2.56g（10ミリモ
ル）を用いて表−５に示すアルキル化剤〔IV〕でアルキ
ル化反応および後処理を行う以外は実施例13と同様に脱
ベンジル化および後処理を行って表−５に示す結果を得
た。[Α] 20 D = −6.0− (c = 1, CHCl 3 ) Examples 21 to 24 (−)-4- (4-benzyloxy) obtained in Example 13
Debenzylation was performed in the same manner as in Example 13 except that the alkylation reaction and the post-treatment were carried out with 2.56 g (10 mmol) of phenyl-2-butanol [III-3] using the alkylating agent [IV] shown in Table 5. After performing post-treatment, the results shown in Table 5 were obtained.
実施例25 ４−（４−ベンジルオキシ）フェニルブタン−２−オ
ン（0.2モル）に代えて６−（４−ベンジルオキシ）フ
ェニルヘキサン−２−オン56.5g（0.2モル）を用いる以
外は実施例13に準じて反応および後処理をおこない、
（−）−４−（５−プロピルオキシヘキシル）フェノー
ル〔Ｉ−25〕1.08g（収率91.5％）｛▲［α］20 D▼＝−
3.1゜（ｃ＝1,CHCl3）｝を得た。Example 25 Example 25 was repeated except that 56.5 g (0.2 mol) of 6- (4-benzyloxy) phenylhexan-2-one was used instead of 4- (4-benzyloxy) phenylbutan-2-one (0.2 mol). Perform the reaction and post-treatment according to 13,
1.08 g of (-)-4- (5-propyloxyhexyl) phenol [I-25] (yield 91.5%) ｛▲ [α] 20 D ▼ =-
3.1 {(c = 1, CHCl 3 )} was obtained.
実施例26 ４−（４−ベンジルオキシ）フェニルブタン−２−オ
ン（0.2モル）に代えて４−（３−フルオロ−４−ベン
ジルオキシ）フェニルブタン−２−オン54.5g（0.2モ
ル）を用いる以外は実施例13に準じて反応および後処理
をおこない、（−）−３−フルオロ−４−（３−プロピ
ルオキシブチル）フェノール〔Ｉ−26〕1.1g（収率97
％）｛▲［α］20 D▼＝−17.1゜（ｃ＝1,CHCl3），▲ｎ
20 D▼＝1.5005｝を得た。Example 26 Instead of 4- (4-benzyloxy) phenylbutan-2-one (0.2 mol), 54.5 g (0.2 mol) of 4- (3-fluoro-4-benzyloxy) phenylbutan-2-one is used. The reaction and post-treatment were carried out in the same manner as in Example 13 except for 1.1 g of (-)-3-fluoro-4- (3-propyloxybutyl) phenol [I-26] (yield 97
%) ｛▲ [α] 20 D ▼ = -17.1 ゜ (c = 1, CHCl 3 ), ▲ n
To obtain a 20 D ▼ = 1.5005}.
実施例27 温度計、撹拌装置を装着した４つ口フラスコに４−
｛４−（ｐ−メチルベンジルオキシ）｝フェニルブタン
−２−オン53.7g（0.2モル），エタノール200mlおよび
クロロホルム200mlを仕込み、30〜40℃にて水素化ホウ
素ナトリウム5.7g（0.15モル）を約30分間で加えた。同
温度で３時間撹拌したのち、反応混合物を水500ml中に
注ぎ込み、クロロホルム200mlを加えて抽出処理した。
有機層は水でよく水洗したのち、減圧下に溶媒を留去し
て、４−｛４−（ｐ−メチルベンジルオキシ）｝フェニ
ル−２−ブタノール〔４−ａ〕を白色結晶として53.6g
（収率99.2％）得た。Example 27 In a four-necked flask equipped with a thermometer and a stirrer,
{4- (p-Methylbenzyloxy)} phenylbutan-2-one 53.7 g (0.2 mol), 200 ml of ethanol and 200 ml of chloroform are charged, and 5.7 g (0.15 mol) of sodium borohydride is added at 30 to 40 ° C. Added in 30 minutes. After stirring at the same temperature for 3 hours, the reaction mixture was poured into 500 ml of water, and extracted with 200 ml of chloroform.
The organic layer was thoroughly washed with water, and the solvent was distilled off under reduced pressure to give 4- {4- (p-methylbenzyloxy)} phenyl-2-butanol [4-a] as white crystals (53.6 g).
(99.2% yield).
上で得た〔４−ａ〕51.4g（0.19モル）をトルエン200
mlとピリジン100mlの混合溶媒に溶かし、無水酢酸29g
（0.285モル）と４−ジメチルアミノピリジン1gを加え
て、40〜50℃の反応温度を保ちながら６時間反応させ
た。51.4 g (0.19 mol) of [4-a] obtained above was treated with toluene 200
dissolved in a mixed solvent of 100 ml of pyridine and 100 ml of pyridine, and 29 g of acetic anhydride
(0.285 mol) and 1 g of 4-dimethylaminopyridine were added and reacted for 6 hours while maintaining a reaction temperature of 40 to 50 ° C.
反応終了後、反応混合物を4N塩酸500ml中に注ぎ出
し、抽出、分液した。得られた有機層は1N塩酸水、水、
５％重曹水、水の順に洗浄し、無水硫酸マグネシウムで
乾燥した後、減圧下に溶媒を留去して２−アセトキシ−
４−｛４−（ｐ−メチルベンジルオキシ）｝フェニルブ
タン〔４−ｂ〕を白色結晶として58.8g（収率99％）得
た。After completion of the reaction, the reaction mixture was poured into 500 ml of 4N hydrochloric acid, extracted and separated. The obtained organic layer is 1N hydrochloric acid aqueous solution, water,
After washing with 5% aqueous sodium bicarbonate and water in that order and drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to give 2-acetoxy-
58.8 g (99% yield) of 4- {4- (p-methylbenzyloxy)} phenylbutane [4-b] was obtained as white crystals.
さらに〔４−ｂ〕50gを3Nリン酸バッファー500ml中に
懸濁させ、その後、リパーゼ（「アマノＰ」）2.5gを加
えて、36±２℃で24時間激しく撹拌した。反応終了後、
反応液に酢酸エチル500mlを加えて、濾過したのち、抽
出、分液して得られた有機層を水洗した。有機層を減圧
下に溶媒留去したのち、得られた残渣をシリカゲルカラ
ムクロマチグラフィー（溶出液：トルエン−酢酸エチ
ル）で分離して（−）−２−アセトキシ−４−｛４−
（ｐ−メチルベンジルオキシ）｝フェニルブタン25.5g
（収率51％）｛▲［α］20 D▼＝−7.8゜（ｃ＝1,CHC
l3）｝と（−）−４−（４−ｐ−メチルベンジルオキ
シ）フェニル−２−ブタノール〔III−４〕20.7g（収率
48％）｛▲［α］20 D▼＝−9.0゜（ｃ＝1,CHCl3）｝を
得た。Further, 50 g of [4-b] was suspended in 500 ml of a 3N phosphate buffer, and then 2.5 g of lipase (“Amano P”) was added, followed by vigorous stirring at 36 ± 2 ° C. for 24 hours. After the reaction,
500 ml of ethyl acetate was added to the reaction solution, and the mixture was filtered, extracted and separated, and the obtained organic layer was washed with water. After evaporating the solvent of the organic layer under reduced pressure, the obtained residue was separated by silica gel column chromatography (eluent: toluene-ethyl acetate) to give (-)-2-acetoxy-4- {4-
(P-methylbenzyloxy) @phenylbutane 25.5 g
(Yield 51%) {▲ [α] 20 D ▼ = -7.8} (c = 1, CHC
l 3)} and (-) - 4- (4- p- methyl-benzyloxy) phenyl-2-butanol [III-4] 20.7 g (yield:
48%) {▲ [α] 20 D ▼ = −9.0} (c = 1, CHCl 3 ).
上で得た〔III−４〕2.70g（10ミリモル）をピリジン
20mlにとかして30〜40℃にて、ブチリルクロリド1.38g
（13ミリモル）を加えて２時間反応させた。反応混合物
を水200ml中に注ぎ出し、トルエン200mlで抽出、分液
後、1N塩酸水、水、５％重曹水、水の順に洗浄したの
ち、無水硫酸マグネシウムで乾燥させた。減圧下に溶媒
を留去したのち、得られた残渣をシリカゲルカラムクロ
マトグラフィー（溶出液：トルエン）で精製することに
より、（＋）−２−ブチリルオキシ−４−｛４−（ｐ−
メチルベンジルオキシ）｝フェニルブタン〔II−27〕3.
3g（収率97％） ｛▲［α］20 D▼＝＋3.5゜（ｃ＝1,CHCl3）、ｎ20 D▼＝
1.5272｝を得た。2.70 g (10 mmol) of [III-4] obtained above was treated with pyridine
1.30 g of butyryl chloride at 30-40 ° C in 20 ml
(13 mmol) and reacted for 2 hours. The reaction mixture was poured into 200 ml of water, extracted with 200 ml of toluene, separated, washed with 1N aqueous hydrochloric acid, water, 5% aqueous sodium hydrogen carbonate and water in that order, and dried over anhydrous magnesium sulfate. After evaporating the solvent under reduced pressure, the obtained residue was purified by silica gel column chromatography (eluent: toluene) to give (+)-2-butyryloxy-4- {4- (p-
Methylbenzyloxy)｝ phenylbutane [II-27] 3.
3 g (yield 97%) {▲ [α] 20 D ▼ = + 3.5} (c = 1, CHCl 3 ), n 20 D ▼ =
1.5272｝ was obtained.
ここで得た〔II−27〕1.7g（５ミリモル）をメタノー
ル20mlにとかし、５％Pd/C 0.1gを加えて、水素雰囲気
下に脱ベンジル化反応を行った。計算量の水素（約110m
l）が消費されたところで原料が完全に消失しているこ
とを確認した後、Pd/Cを濾別し、濾液のメタノール溶液
を減圧下に濃縮して、（＋）−４−（３ブチリルオキシ
ブチル）フェノール1.18g〔Ｉ−27〕（収率100％）｛▲
［α］20 D▼＝＋3.4゜（ｃ＝1,CHCl3），▲ｎ20 D▼＝1.
4970｝を得た。1.7 g (5 mmol) of the obtained [II-27] was dissolved in 20 ml of methanol, 0.1 g of 5% Pd / C was added, and a debenzylation reaction was carried out under a hydrogen atmosphere. Calculated amount of hydrogen (about 110m
After confirming that the raw material has completely disappeared when l) has been consumed, Pd / C is filtered off, and the methanol solution of the filtrate is concentrated under reduced pressure to give (+)-4- (3 1.18 g of [ryloxybutyl) phenol [I-27] (100% yield)
[Α] 20 D ▼ = + 3.4 ゜ (c = 1, CHCl 3 ), ▲ n 20 D ▼ = 1.
4970｝.
実施例28 実施例27で得た（−）−２−アセトキシ−４−｛４−
（ｐ−メチルベンジルオキシ）｝フェニルブタン3.12g
（10ミリモル）をテトラヒドロフラン20mlに溶かして５
％Pd/C 0.3gを加えて、水素雰囲気下に脱ベンジル化し
た。計算量の水素（約220ml）が消費されたところで、
原料が完全に消失していることを確認した後、Pd/Cを濾
別し、溶媒を減圧下に留去して、（−）−４−（３−ア
セトキシブチル）フェノール〔Ｉ−28〕2.1g（収率99.5
％）｛▲［α］20 D▼＝−8.3゜（ｃ＝1,CHCl3），▲ｎ
20 D▼＝1.5052｝を得た。Example 28 (−)-2-acetoxy-4- {4-} obtained in Example 27
(P-methylbenzyloxy) @phenylbutane 3.12 g
(10 mmol) in 20 ml of tetrahydrofuran
% Pd / C (0.3 g) was added, followed by debenzylation under a hydrogen atmosphere. When the calculated amount of hydrogen (about 220ml) has been consumed,
After confirming that the raw materials have completely disappeared, Pd / C was separated by filtration, and the solvent was distilled off under reduced pressure to give (-)-4- (3-acetoxybutyl) phenol [I-28]. 2.1 g (Yield 99.5
%) ｛▲ [α] 20 D ▼ = -8.3 ゜ (c = 1, CHCl 3 ), ▲ n
To obtain a 20 D ▼ = 1.5052}.
実施例29〜31 （−）−４−（４−ｐ−メチルベンジルオキシ）フェ
ニル−２−ブタノール〔III−４〕2.70g（10ミリモル）
を使用し、表−６に示すアシル化剤〔Ｖ〕を用いる以外
は実施例27と同様に反応および後処理を行って表−６に
示す結果を得た。Examples 29 to 31 (-)-4- (4-p-methylbenzyloxy) phenyl-2-butanol [III-4] 2.70 g (10 mmol)
And the reaction and post-treatment were carried out in the same manner as in Example 27, except that the acylating agent [V] shown in Table-6 was used to obtain the results shown in Table-6.
実施例8,19,20,25,および26において、中間体として得
られた光学活性なベンジルエーテル誘導体〔II〕の物性
値を表−７に示す。 The physical properties of the optically active benzyl ether derivative [II] obtained as an intermediate in Examples 8, 19, 20, 25 and 26 are shown in Table 7.
実施例32〜36 実施例20および実施例25において得られる光学活性な
アルコール類〔III〕を用いて、表−８に示すアシル化
剤〔Ｖ〕を用いる以外は実施例27と同様に反応および後
処理を行って表−８に示す結果を得た。 Examples 32-36 Using the optically active alcohols [III] obtained in Examples 20 and 25, the reaction and reaction were carried out in the same manner as in Example 27 except for using the acylating agent [V] shown in Table-8. Post-processing was performed to obtain the results shown in Table-8.
実施例37〜40 実施例20および実施例25において得られる光学活性な
アルコール類〔III〕を用いて、表−８に示すアルキル
化剤〔IV〕を用いる以外は実施例13と同様に反応および
後処理を行って表−８に示す結果を得た。Examples 37 to 40 Using the optically active alcohols [III] obtained in Examples 20 and 25, the reaction and reaction were carried out in the same manner as in Example 13 except for using the alkylating agent [IV] shown in Table-8. Post-processing was performed to obtain the results shown in Table-8.
参考例 （液晶化合物製造例１） 撹拌装置、温度計を装着した４ツ口フラスコに実施例
８で得た（＋）−４−（１−メチル−２−プロピルオキ
シエチル）フェノール〔Ｉ−８〕0.49g（2.5ミリモル）
とピリジン20mlを仕込み、20〜25℃で、４−デシルオキ
シ−４′−ビフェニルカルボン酸クロリド1.1g（３ミリ
モル）を加え、同温度で１時間、その後、40℃で４時間
撹拌した。 Reference Example (Liquid Crystal Compound Production Example 1) (+)-4- (1-Methyl-2-propyloxyethyl) phenol [I-8] obtained in Example 8 in a four-necked flask equipped with a stirrer and a thermometer. ] 0.49 g (2.5 mmol)
And 20 ml of pyridine, 1.1 g (3 mmol) of 4-decyloxy-4'-biphenylcarboxylic acid chloride was added at 20 to 25 ° C, and the mixture was stirred at the same temperature for 1 hour and then at 40 ° C for 4 hours.
反応終了後、4N塩酸中に注ぎ出し、トルエン200mlで
抽出した。有機層は、水、５％重曹水、水の順に洗浄し
たのち、無水硫酸マグネシウムで乾燥後、減圧下濃縮し
た。得られた残渣をシリカゲルカラムクロマト精製（溶
出液：トルエン−酢酸エチル）することにより（＋）−
４−デシルオキシ−４′−ビフェニルカルボン酸４−
（１−メチル−２−プロピルオキシエチル）フェニルエ
ステル〔VI−１〕1.27g（収率96％）を得た。After completion of the reaction, the mixture was poured into 4N hydrochloric acid and extracted with 200 ml of toluene. The organic layer was washed with water, 5% aqueous sodium hydrogen carbonate and water in that order, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent: toluene-ethyl acetate) to give (+)-
4-decyloxy-4'-biphenylcarboxylic acid 4-
1.27 g (96% yield) of (1-methyl-2-propyloxyethyl) phenyl ester [VI-1] was obtained.
この化合物は下記の相転移を有する強誘電性液晶化合
物であり、その▲Ｓ* C▼における自発分極値は5nC/cm2
（Ｔ−Tc＝−10℃）であった。This compound is a ferroelectric liquid crystal compound having the following phase transition, and its spontaneous polarization value in (S * C ) is 5 nC / cm 2
(T−Tc = −10 ° C.).
（液晶化合物製造例２） 撹拌装置、温度計を装着した４ツ口フラスコに実施例
13で得た（−）−４−（３−プロポキシブチル）フェノ
ール〔Ｉ−13〕1.04g（５ミリモル）、４−デシルオキ
シ−４′−ビフェニルカルボン酸2.2g（６ミリモル）と
無水ジクロルメタン30mlを仕込み、N,N′−ジシクロヘ
キシルカルボジイミド1.22g（６ミリモル）と４−ピロ
リジノピリジン0.1gを加えて、室温、一昼夜撹拌した。 (Production Example 2 of Liquid Crystal Compound) Example of a four-necked flask equipped with a stirrer and a thermometer
1.04 g (5 mmol) of (-)-4- (3-propoxybutyl) phenol [I-13] obtained in 13, 13 g of 2.2 g (6 mmol) of 4-decyloxy-4'-biphenylcarboxylic acid and 30 ml of anhydrous dichloromethane are added. After charging, 1.22 g (6 mmol) of N, N'-dicyclohexylcarbodiimide and 0.1 g of 4-pyrrolidinopyridine were added, and the mixture was stirred at room temperature for 24 hours.
反応終了後、生じた沈殿を濾別し、トルエン200mlで
希釈した。有機層は、水、５％酢酸水、水、５％重曹
水、水の順に洗浄したのち無水硫酸マグネシウムで乾燥
後、減圧下濃縮した。得られた残渣をシリカゲルカラム
クロマト精製（溶出液：トルエン−酢酸エチル）するこ
とにより（−）−４−デシルオキシ−４′−ビフェニル
カルボン酸４−（３−プロポキシブチル）フェニルエス
テル〔VI−２〕2.95g（収率89％）を得た。After the completion of the reaction, the resulting precipitate was separated by filtration and diluted with 200 ml of toluene. The organic layer was washed with water, 5% aqueous acetic acid, water, 5% aqueous sodium bicarbonate and water in that order, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue is purified by silica gel column chromatography (eluent: toluene-ethyl acetate) to give (-)-4-decyloxy-4'-biphenylcarboxylic acid 4- (3-propoxybutyl) phenyl ester [VI-2]. 2.95 g (89% yield) were obtained.
この化合物は下記相転移を有する強誘電性液晶化合物
であり、その▲Ｓ* C▼相の温度範囲は極めて広い。なお
その▲Ｓ* C▼相における自発分極値は119℃で15.7nC/cm
2であった。This compound is a ferroelectric liquid crystal compound having the following phase transition, and its {S * C } phase temperature range is extremely wide. The spontaneous polarization value in the ▲ S * C ▼ phase was 15.7 nC / cm at 119 ° C.
Was 2 .
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０７Ｃ 69/24 Ｃ０７Ｃ 69/24 69/708 69/708 Ｚ // Ｃ０７Ｍ 7:00 (72)発明者 南井 正好 大阪府大阪市此花区春日出中３丁目１番 98号 住友化学工業株式会社内 (56)参考文献 特開 平１−121246（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) ＣＡ（ＳＴＮ) ＣＡＯＬＤ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code FI C07C 69/24 C07C 69/24 69/708 69/708 Z // C07M 7:00 (72) Inventor Masayoshi Minai Osaka-shi, Osaka 3-1-1 98 Kasuganaka, Konohana-ku Sumitomo Chemical Industries, Ltd. (56) References JP-A-1-121246 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) CA (STN) CAOLD (STN) REGISTRY (STN)
Claims (5)
もよいアルキル基またはアルコキシアルキル基を表わ
し、Ｚは水素原子またはハロゲン原子を表わし、Ａは水
素原子、低級アルキル基、低級アルコキシル基またはハ
ロゲン原子を表わし、ｓは０または１を表わし を表わし、ｎは１〜５の整数を表わし、＊印は不斉炭素
原子であることを表わす。但し（＋）−２−（ｐ−ベン
ジルオキシフェニル）プロピルアルコールメチルエーテ
ルおよび（＋）−２−（ｐベンジルオキシフェニル）プ
ロピルアルコールｎ−ブチルエーテルではない。） で示される光学活性なベンジルエーテル誘導体を、水添
触媒および水素の存在下に脱ベンジル化することを特徴
とする一般式 （式中、Ｒ、Ｚ、ｓおよびＷは前記と同じ意味を表わ
す。但し、（＋）−２−（ｐ−ヒドロキシフェニル）プ
ロピルアルコールメチルエーテルおよび（＋）−２−
（ｐ−ヒドロキシフェニル）プロピルアルコールｎ−ブ
チルエーテルではない。）で示される光学活性なフェノ
ール類の製造法。1. The compound of the general formula (I) (In the formula, R represents an alkyl group or an alkoxyalkyl group which may contain a halogen atom having 1 to 20 carbon atoms, Z represents a hydrogen atom or a halogen atom, and A represents a hydrogen atom, a lower alkyl group, a lower alkoxyl group. Represents a group or a halogen atom, and s represents 0 or 1. Wherein n represents an integer of 1 to 5, and * represents an asymmetric carbon atom. However, it is not (+)-2- (p-benzyloxyphenyl) propyl alcohol methyl ether or (+)-2- (p-benzyloxyphenyl) propyl alcohol n-butyl ether. Wherein the optically active benzyl ether derivative represented by the formula is debenzylated in the presence of a hydrogenation catalyst and hydrogen. (Wherein, R, Z, s and W have the same meaning as described above, provided that (+)-2- (p-hydroxyphenyl) propyl alcohol methyl ether and (+)-2-
It is not (p-hydroxyphenyl) propyl alcohol n-butyl ether. ), A method for producing optically active phenols.
ェノール類。2. The optically active phenol according to claim 1, wherein s is 1.
ル誘導体。3. The optically active benzyl ether derivative according to claim 1.
子または−SO2R2基を表わす。ここでR2は低級アルキル
基または置換されていてもよいフェニル基を表わす。） で示されるアルキル化剤とを、塩基性物質の存在下に縮
合させてｓが０である請求項１記載の光学活性なベンジ
ルエーテル誘導体を得ることを特徴とする請求項１記載
の光学活性なフェノール類の製造法。4. General formula (Wherein A, Z and W have the same meanings as described above), and an optically active alcohol represented by the formula: R—X (wherein R has the same meaning as described above, and X represents a halogen atom) or it represents a -SO 2 R 2 group. here the alkylating agent represented by R 2 is a lower alkyl group or an optionally substituted phenyl group.), by condensing in the presence of a basic substance 2. The process for producing an optically active phenol according to claim 1, wherein s is 0.
と、一般式 Ｒ−COR3 （式中、Ｒは前記と同じ意味を表わし、R3はハロゲン原
子または水酸基を表わす。） で示されるアシル化剤またはその誘導体とを、触媒また
は縮合剤の存在下に縮合させてｓが１である請求項１記
載の光学活性なベンジルエーテル誘導体を得ることを特
徴とする請求項１記載の光学活性なフェノール類の製造
法。5. A with an optically active alcohol according to claim 4, wherein the general formula R-COR 3 (wherein, R represents the same meaning as above, R 3 represents. A halogen atom or a hydroxyl group) represented by 2. The optically active benzyl ether derivative according to claim 1, wherein s is 1 by condensing the acylating agent or a derivative thereof in the presence of a catalyst or a condensing agent. Production method of various phenols.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1261376A JP2797527B2 (en) | 1988-10-11 | 1989-10-05 | Optically active phenols and their production |
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25677388 | 1988-10-11 | ||
| JP63-256773 | 1989-04-27 | ||
| JP1-110416 | 1989-04-27 | ||
| JP1-110417 | 1989-04-27 | ||
| JP11041689 | 1989-04-27 | ||
| JP11041789 | 1989-04-27 | ||
| JP1261376A JP2797527B2 (en) | 1988-10-11 | 1989-10-05 | Optically active phenols and their production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0347143A JPH0347143A (en) | 1991-02-28 |
| JP2797527B2 true JP2797527B2 (en) | 1998-09-17 |
Family
ID=27469821
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1261376A Expired - Fee Related JP2797527B2 (en) | 1988-10-11 | 1989-10-05 | Optically active phenols and their production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2797527B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6624112B2 (en) | 2001-03-06 | 2003-09-23 | N.E. Chemcat Corporation | Hydrogenolysis catalyst |
| CN102821741A (en) * | 2010-04-08 | 2012-12-12 | 花王株式会社 | External skin preparation |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01121246A (en) * | 1987-11-02 | 1989-05-12 | Hamari Yakuhin Kogyo Kk | Novel liquid crystal compound and liquid crystal composition containing said compound |
-
1989
- 1989-10-05 JP JP1261376A patent/JP2797527B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6624112B2 (en) | 2001-03-06 | 2003-09-23 | N.E. Chemcat Corporation | Hydrogenolysis catalyst |
| CN102821741A (en) * | 2010-04-08 | 2012-12-12 | 花王株式会社 | External skin preparation |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0347143A (en) | 1991-02-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |