JP2903598B2 - Optically active aromatic carboxylic acid derivative and method for producing the same - Google Patents
Optically active aromatic carboxylic acid derivative and method for producing the sameInfo
- Publication number
- JP2903598B2 JP2903598B2 JP3339490A JP3339490A JP2903598B2 JP 2903598 B2 JP2903598 B2 JP 2903598B2 JP 3339490 A JP3339490 A JP 3339490A JP 3339490 A JP3339490 A JP 3339490A JP 2903598 B2 JP2903598 B2 JP 2903598B2
- Authority
- JP
- Japan
- Prior art keywords
- optically active
- carboxylic acid
- group
- acid
- reaction
- 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 - Lifetime
Links
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical class OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 title claims description 70
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 125000005843 halogen group Chemical group 0.000 claims description 13
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 12
- 125000006239 protecting group Chemical group 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 9
- 150000001735 carboxylic acids Chemical class 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 238000010511 deprotection reaction Methods 0.000 claims description 4
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 3
- 150000001491 aromatic compounds Chemical class 0.000 claims description 3
- 239000013543 active substance Substances 0.000 claims description 2
- 230000010933 acylation Effects 0.000 claims description 2
- 238000005917 acylation reaction Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 3
- -1 methoxyethoxymethyl group Chemical group 0.000 description 97
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 78
- 238000006243 chemical reaction Methods 0.000 description 61
- 239000002904 solvent Substances 0.000 description 40
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 27
- 239000000203 mixture Substances 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 239000005711 Benzoic acid Substances 0.000 description 24
- 235000010233 benzoic acid Nutrition 0.000 description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 19
- 230000002829 reductive effect Effects 0.000 description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000012044 organic layer Substances 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 239000003480 eluent Substances 0.000 description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 238000010898 silica gel chromatography Methods 0.000 description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 239000012267 brine Substances 0.000 description 8
- DVECBJCOGJRVPX-UHFFFAOYSA-N butyryl chloride Chemical compound CCCC(Cl)=O DVECBJCOGJRVPX-UHFFFAOYSA-N 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 8
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 239000004973 liquid crystal related substance Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 6
- 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 239000003223 protective agent Substances 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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 150000008062 acetophenones Chemical class 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 150000004820 halides Chemical class 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 description 5
- RZWGTXHSYZGXKF-UHFFFAOYSA-N 2-(2-methylphenyl)acetic acid Chemical compound CC1=CC=CC=C1CC(O)=O RZWGTXHSYZGXKF-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-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
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 229920005555 halobutyl Polymers 0.000 description 4
- 235000010265 sodium sulphite Nutrition 0.000 description 4
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 3
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 239000012351 deprotecting agent Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 150000008282 halocarbons Chemical class 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229940098779 methanesulfonic acid Drugs 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 3
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 description 3
- 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 2
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 2
- NSCJIRYCAPFUSS-UHFFFAOYSA-N 4-(2-hydroxypropyl)benzoic acid Chemical compound CC(O)CC1=CC=C(C(O)=O)C=C1 NSCJIRYCAPFUSS-UHFFFAOYSA-N 0.000 description 2
- SQVHRJXGOIGDTD-UHFFFAOYSA-N 4-(3-hydroxypropyl)benzoic acid Chemical compound OCCCC1=CC=C(C(O)=O)C=C1 SQVHRJXGOIGDTD-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- NNJMFJSKMRYHSR-UHFFFAOYSA-N 4-phenylbenzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=CC=C1 NNJMFJSKMRYHSR-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- QWCKQJZIFLGMSD-UHFFFAOYSA-N alpha-aminobutyric acid Chemical compound CCC(N)C(O)=O QWCKQJZIFLGMSD-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 235000001014 amino acid Nutrition 0.000 description 2
- 229940024606 amino acid Drugs 0.000 description 2
- 150000001413 amino acids Chemical class 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
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 238000006264 debenzylation reaction Methods 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 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
- OAMZXMDZZWGPMH-UHFFFAOYSA-N ethyl acetate;toluene Chemical compound CCOC(C)=O.CC1=CC=CC=C1 OAMZXMDZZWGPMH-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- ARBOVOVUTSQWSS-UHFFFAOYSA-N hexadecanoyl chloride Chemical compound CCCCCCCCCCCCCCCC(Cl)=O ARBOVOVUTSQWSS-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- XGISHOFUAFNYQF-UHFFFAOYSA-N pentanoyl chloride Chemical compound CCCCC(Cl)=O XGISHOFUAFNYQF-UHFFFAOYSA-N 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 2
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229940032330 sulfuric acid Drugs 0.000 description 2
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 description 1
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- UKAUYVFTDYCKQA-UHFFFAOYSA-N -2-Amino-4-hydroxybutanoic acid Natural products OC(=O)C(N)CCO UKAUYVFTDYCKQA-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- NQHKRTXDDLZBCP-UHFFFAOYSA-N 1-[4-[4-(3-hydroxypropyl)phenyl]phenyl]ethanone Chemical group C1=CC(C(=O)C)=CC=C1C1=CC=C(CCCO)C=C1 NQHKRTXDDLZBCP-UHFFFAOYSA-N 0.000 description 1
- OBQPKGCVMCIETH-UHFFFAOYSA-N 1-chloro-1-(1-chloroethoxy)ethane Chemical compound CC(Cl)OC(C)Cl OBQPKGCVMCIETH-UHFFFAOYSA-N 0.000 description 1
- VBSTXRUAXCTZBQ-UHFFFAOYSA-N 1-hexyl-4-phenylpiperazine Chemical compound C1CN(CCCCCC)CCN1C1=CC=CC=C1 VBSTXRUAXCTZBQ-UHFFFAOYSA-N 0.000 description 1
- AXMJMQYZYMLMSO-UHFFFAOYSA-N 1-pyrrolidin-1-yl-2h-pyridine Chemical compound C1CCCN1N1C=CC=CC1 AXMJMQYZYMLMSO-UHFFFAOYSA-N 0.000 description 1
- OFZVOZGWCBEPBB-UHFFFAOYSA-N 2,3,4,5-tetrabutylfuran Chemical compound CCCCC=1OC(CCCC)=C(CCCC)C=1CCCC OFZVOZGWCBEPBB-UHFFFAOYSA-N 0.000 description 1
- JKTCBAGSMQIFNL-UHFFFAOYSA-N 2,3-dihydrofuran Chemical compound C1CC=CO1 JKTCBAGSMQIFNL-UHFFFAOYSA-N 0.000 description 1
- 125000003660 2,3-dimethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000003764 2,4-dimethylpentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- ZPMWWAIBJJFPPQ-UHFFFAOYSA-N 2-ethoxyacetyl chloride Chemical compound CCOCC(Cl)=O ZPMWWAIBJJFPPQ-UHFFFAOYSA-N 0.000 description 1
- BITYXLXUCSKTJS-UHFFFAOYSA-N 2-isopropylmalic acid Chemical compound CC(C)C(O)(C(O)=O)CC(O)=O BITYXLXUCSKTJS-UHFFFAOYSA-N 0.000 description 1
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
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- 238000000746 purification Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 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
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000007858 starting material 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
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 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
- HMJQKIDUCWWIBW-PVQJCKRUSA-N trifluoroalanine Chemical compound OC(=O)[C@@H](N)C(F)(F)F HMJQKIDUCWWIBW-PVQJCKRUSA-N 0.000 description 1
- 239000013638 trimer Chemical group 0.000 description 1
- JBWKIWSBJXDJDT-UHFFFAOYSA-N triphenylmethyl chloride Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 JBWKIWSBJXDJDT-UHFFFAOYSA-N 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
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 ＜産業上の利用分野＞ 本発明は、有機電子材料特に、液晶材料の中間体とし
て有用な新規な光学活性な芳香族カルボン酸誘導体およ
びその製造法に関する。Description: TECHNICAL FIELD The present invention relates to a novel optically active aromatic carboxylic acid derivative useful as an intermediate of an organic electronic material, particularly a liquid crystal material, and a method for producing the same.
＜従来の技術および発明が解決しようとする課題＞ 従来液晶化合物として種々の化合物が開発されている
が、優れた特性を有する化合物は極めて少なく従って該
液晶化合物の中間体の開発に関しても未だ十分とは言え
ない。<Problems to be Solved by Conventional Techniques and Inventions> Conventionally, various compounds have been developed as liquid crystal compounds. However, there are very few compounds having excellent properties, and therefore it is still sufficient for the development of intermediates of the liquid crystal compounds. I can't say.
本発明者らは、一般式（Ｘ） （式中、R1はアルキル基、アルコキシ基等、Ａはフェ
ニレン、ビフェニレン等、X1は２価の結合基を示す。
Ｒ′はアルキル基またはアルコキシアルキル基を示す。
ｋは１または２を示し、Ｚは を示す。ここでｐは１〜５の整数を示し、＊印は不斉炭
素原子を示す。） で示される液晶性化合物が優れた特性を有することを見
い出した。The present inventors have found that the general formula (X) (Wherein, R 1 represents an alkyl group, an alkoxy group, etc., A represents phenylene, biphenylene, etc., and X 1 represents a divalent linking group.
R 'represents an alkyl group or an alkoxyalkyl group.
k represents 1 or 2, and Z represents Is shown. Here, p represents an integer of 1 to 5, and * represents an asymmetric carbon atom. ) Was found to have excellent properties.
本発明は、上記一般式（Ｘ）で示される特性に優れた
液晶化合物の中間体として有用な新規な光学活性な芳香
族カルボン酸誘導体およびその製造法を提供するもので
ある。The present invention provides a novel optically active aromatic carboxylic acid derivative useful as an intermediate of a liquid crystal compound having excellent properties represented by the general formula (X) and a method for producing the same.
＜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′はハロゲン原子で置換されていてもよい
炭素数１〜20のアルキル基またはハロゲン原子で置換さ
れていてもよい炭素数２〜20のアルコキシアルキル基を
示し、ｋは１または２を示す。Ｚは または−（CH2）p−を示す。ここでｐは１〜５の整数
を示し、＊印は不斉炭素原子を示す。但し、Ｚが−（CH
2）p−のとき、Ｒ′は光学活性体である。） で示される光学活性な芳香族カルボン酸誘導体およびそ
の製造法に関する。光学活性な光学活性な芳香族カルボ
ン酸誘導体（Ｉ）は例えば以下のルートにより製造する
ことができる。<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 having 1 to 20 carbon atoms which may be substituted with a halogen atom or an alkoxyalkyl group having 2 to 20 carbon atoms which may be substituted with a halogen atom, and k represents 1 or 2 and Z is Or-(CH 2 ) p- . Here, p represents an integer of 1 to 5, and * represents an asymmetric carbon atom. However, if Z is-(CH
2 ) When p- , R 'is an optically active substance. ) And a method for producing the same. The optically active optically active aromatic carboxylic acid derivative (I) can be produced, for example, by the following route.
一般式（II） （式中、ｋおよびＺは前記と同じ意味を有する。） で示される光学活性なアルコール類の水酸基に保護基を
導入し、 一般式（III） （式中、Ａは水酸基の保護基を示し、ｋおよびＺは前
記と同じ意味を有する。） で示される光学活性なアセトフェノン類を得、次にこの
アセチル基を酸化して、一般式（IV） （式中、Ａ、ｋおよびＺは前記と同じ意味を有す
る。） で示される光学活性なカルボン酸類を得た後、この保護
基を脱保護して、一般式（Ｖ） （式中、ｋおよびＺは前記と同じ意味を有する。） で示される光学活性なヒドロキシカルボン酸類を得、こ
れを一般式（VI） （式中、Ｒ′は前記と同じ意味を有し、Ｘはハロゲン
原子または、 基を示す。General formula (II) Wherein k and Z have the same meanings as described above. A protecting group is introduced into a hydroxyl group of an optically active alcohol represented by the following formula: (Wherein A represents a hydroxyl-protecting group, and k and Z have the same meanings as described above), and the acetyl group is then oxidized to obtain a compound represented by the general formula (IV) ) (Wherein, A, k and Z have the same meanings as described above). After obtaining an optically active carboxylic acid represented by the formula: (Where k and Z have the same meanings as described above), which is represented by the general formula (VI) (Wherein, R ′ has the same meaning as described above, and X is a halogen atom or Represents a group.
で示されるアシル化剤を用いてアシル化することにより
一般式（Ｉ）で示される光学活性な芳香族カルボン酸誘
導体を得る方法。A method for obtaining an optically active aromatic carboxylic acid derivative represented by the general formula (I) by acylation using an acylating agent represented by the following formula (I).
以下、これらの製造法について説明する。 Hereinafter, these production methods will be described.
尚、原料である光学活性なアルコール類（II）は、以
下のようにして合成することができる。Incidentally, the optically active alcohols (II) as the raw materials can be synthesized as follows.
（式中、Ｒ″は低級アルキル基を示し、Ｒ′、ｋ、ｐ
および＊印は前記と同じ意味を有する。） 一般式（II）で示される光学活性なアルコール類か
ら、一般式（III）で示される光学活性なアセトフェノ
ン類を得る反応は、水酸基の保護化剤と、助触媒を用い
保護基を導入することによりおこなわれる。 (Wherein, R ″ represents a lower alkyl group, and R ′, k, p
And * have the same meaning as described above. The reaction for obtaining an optically active acetophenone represented by the general formula (III) from an optically active alcohol represented by the general formula (II) involves introducing a protecting group using a protecting agent for a hydroxyl group and a promoter. It is done by doing.
水酸基の保護基としては、メチル基、ベンジル基、ト
リメル基のごときアルキルまたはアリール基；メトキシ
メチル基、メトキシエトキシメチル基、エトキシエチル
基、テトラヒドロフリル基、テトラヒドロピラニル基の
ごときアルコキシアルキル基;t−ブチルジメチルシリル
基のごときシリル基があげられる。Examples of the hydroxyl-protecting group include an alkyl or aryl group such as a methyl group, a benzyl group and a trimer group; an alkoxyalkyl group such as a methoxymethyl group, a methoxyethoxymethyl group, an ethoxyethyl group, a tetrahydrofuryl group and a tetrahydropyranyl group; And silyl groups such as -butyldimethylsilyl group.
助触媒としては、保護化剤に寄っても異なるが、一般
的には、保護基がアルキル、アリール基または１部のア
ルコキシアルキル基の場合、塩基性物質が用いられる。
たとえば、水酸化ナトリウム、水酸化カリウム、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、ナトリウムメチラート、ナトリウムエチラ
ート、水素化ナトリウム、水素化カリウム、ｎ−ブチル
リチウム、sec−ブチルリチウム酸化銀等の無機もしく
は有機塩基性物質があげられる。The cocatalyst varies depending on the protecting agent, but in general, when the protecting group is an alkyl, an aryl group or a part of an alkoxyalkyl group, a basic substance is used.
For example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium methylate, sodium ethylate, sodium hydride, potassium hydride, n-butyllithium, sec-butyllithium oxide Inorganic or organic basic substances such as silver.
反応に用いられる保護化剤としては、具体的には、ヨ
ウ化メチル、臭化メチル、ベンジルクロリド、ベンジル
ブロミド、トリチルクロリド、メチルクロロメチルエー
テル、メトキシエトキシクロロメチルエーテル等があげ
られる。反応試剤の使用量は、使用するアルキルまたは
アリール化剤の種類によって異なり、必ずしも特定され
ないが、一般には、使用する原料（II）に対して、助触
媒１〜４当量倍、保護化剤１〜５当量倍である。Specific examples of the protecting agent used in the reaction include methyl iodide, methyl bromide, benzyl chloride, benzyl bromide, trityl chloride, methyl chloromethyl ether, methoxyethoxy chloromethyl ether and the like. The amount of the reaction reagent used depends on the type of the alkyl or arylating agent used, and is not necessarily specified. It is 5 equivalent times.
この反応は、通常、溶媒の存在下におこなわれ、かか
る溶媒としては、たとえば、エチルエーテル、テトラヒ
ドロフラン、ジオキサン、アセトン、メチルエチルケト
ン、メチルイソブチルケトン、トルエン、ベンゼン、ク
ロルベンゼン、ジクロルメタン、1,2−ジクロルエタ
ン、クロロホルム、四塩化炭素、酢酸エチル、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、アセトニトリル、ヘキサン、ヘ
プタン等のエーテル、ハロゲン化炭化水素、飽和もしく
は不飽和炭化水素、エステル、非プロトン性極性溶媒等
の反応に不活性な溶媒の単独または混合物があげられ、
その使用量については、特に制限なく使用することがで
きる。This reaction is usually carried out in the presence of a solvent. Examples of such a solvent include ethyl ether, tetrahydrofuran, dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, chlorobenzene, dichloromethane, 1,2-dichloroethane. , Chloroform, carbon tetrachloride, ethyl acetate, dimethylformamide, dimethylsulfoxide, hexamethylphosphoric triamide, acetonitrile, hexane, heptane and other ethers, halogenated hydrocarbons, saturated or unsaturated hydrocarbons, esters, aprotic polarities A single or mixture of solvents inert to the reaction such as a solvent,
The amount can be used without any particular limitation.
反応温度は、−20から150℃の範囲である。 Reaction temperatures range from -20 to 150 ° C.
反応時間についても、特に制限されない。 The reaction time is not particularly limited.
保護基が、アルコキシアルキル基の場合、助触媒とし
て、酸性物質たとえば、ｐ−トルエンスルホン酸、ベン
ゼンスルホン酸、メタンスルホン酸、硫酸、硫酸水素カ
リウム、塩酸、リン酸、酢酸、塩化アンモニウム等の無
機もしくは有機酸性物質があげられる。When the protecting group is an alkoxyalkyl group, an acidic substance such as p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, sulfuric acid, potassium hydrogen sulfate, hydrochloric acid, phosphoric acid, acetic acid, or ammonium chloride may be used as a co-catalyst. Or an organic acidic substance is mentioned.
このときの保護化剤としては、具体的には、ジメトキ
シメタン、エチルビニルエーテル、ジヒドロフラン、ジ
ヒドロピラン等があげられる。Specific examples of the protecting agent at this time include dimethoxymethane, ethyl vinyl ether, dihydrofuran, dihydropyran and the like.
反応試剤の使用量は、使用するアルコキシアルキル化
剤によっても異なり、必ずしも特定されないが、一般に
は、使用する原料（II）に対して、助触媒0.005〜１当
量、保護化剤１〜５当量倍である。The amount of the reaction agent used varies depending on the alkoxyalkylating agent used and is not necessarily specified. However, in general, 0.005 to 1 equivalent of the cocatalyst and 1 to 5 equivalents of the co-catalyst are used based on the raw material (II) used. It is.
この反応は、通常、溶媒の存在下におこなわれ、かか
る溶媒としては、たとえば前述の溶媒があげられ、その
使用量についても特に制限されない。This reaction is usually performed in the presence of a solvent, and examples of such a solvent include the above-mentioned solvents, and the amount of the solvent is not particularly limited.
反応温度は−20から150℃の範囲である。 Reaction temperatures range from -20 to 150 ° C.
また反応時間についても特に制限されない。 The reaction time is not particularly limited.
保護基が、シリル基の場合、助触媒としては、塩基性
物質があげられ、具体例としては、前述の塩基性物質の
他に、イミダゾール、ピリジン、４−ジメチルアミノピ
リジン等があげられる。When the protecting group is a silyl group, examples of the co-catalyst include basic substances, and specific examples thereof include imidazole, pyridine, 4-dimethylaminopyridine and the like in addition to the above-mentioned basic substances.
このときの保護化剤としては、具体的には、トリメチ
ルシリルクロリド、トリメチルシリルブロミド、ｔ−ブ
チルジメチルシリルクロリド等があげられる。Specific examples of the protecting agent at this time include trimethylsilyl chloride, trimethylsilyl bromide, t-butyldimethylsilyl chloride and the like.
これらの使用量は、使用するシリル化剤によっても異
なり必ずしも特定できないが、一般には、使用する原料
（II）に対して、助触媒１〜４当量倍、保護化剤１〜５
当量倍である。The amount of these used differs depending on the silylating agent used and cannot always be specified. However, in general, the amount of the cocatalyst is 1 to 4 equivalent times, and the amount of the protecting agent 1 to 5 is based on the used raw material (II).
Equivalent times.
この反応もまた、通常、溶媒の存在下におこなわれ、
かかる溶媒としては、たとえば、前述の溶媒があげら
れ、その使用量についても特に制限されない。This reaction is also usually carried out in the presence of a solvent,
Examples of such a solvent include the above-mentioned solvents, and the amount of the solvent is not particularly limited.
反応温度は−20〜150℃の範囲である。 Reaction temperatures range from -20 to 150 ° C.
また反応時間についても特に制限されない。 The reaction time is not particularly limited.
このようにして得られた反応混合物は、通常の分離手
段たとえば、抽出、分液、濃縮等の操作により、光学活
性なアセトフェノン類（III）を得ることができ、これ
は必要に応じて、カラムクロマトグラフィー、再結晶等
により精製することもできる。From the reaction mixture thus obtained, optically active acetophenones (III) can be obtained by ordinary separation means, for example, extraction, separation, concentration and the like. It can also be purified by chromatography, recrystallization and the like.
次に上記で得られた一般式（III）で示される光学活
性なアセトフェノン類から、一般式（IV）で示される光
学活性なカルボン酸類を得る反応は、光学活性なアセト
フェノン類（III）のアセチル基を酸化することにより
おこなわれる。Next, the reaction for obtaining the optically active carboxylic acid represented by the general formula (IV) from the optically active acetophenone represented by the general formula (III) obtained above is carried out by acetylation of the optically active acetophenone (III). This is done by oxidizing the group.
この反応で用いられる酸化剤としては、通常アセチル
基を酸化してカルボン酸とするものであれば特に制限な
く用いることができ、かかる酸化剤としては、たとえ
ば、重クロム酸カリウム、重クロム酸ナトリウム、過マ
ンガン酸カリウム、過マンガン酸ナトリウム、次亜塩素
酸カリウム、次亜塩素酸ナトリウム、次亜臭素酸カリウ
ム、次亜臭素酸ナトリウム等が例示される。The oxidizing agent used in this reaction can be used without particular limitation as long as it can oxidize an acetyl group to a carboxylic acid. Examples of such an oxidizing agent include potassium dichromate and sodium dichromate. , Potassium permanganate, sodium permanganate, potassium hypochlorite, sodium hypochlorite, potassium hypobromite, sodium hypobromite and the like.
かかる酸化剤の使用量は光学活性なアセトフェノン類
（III）に対して、１当量以上必要であり、上限につい
ては特に制限されないが、好ましくは10当量倍である。The amount of the oxidizing agent to be used is at least 1 equivalent to the optically active acetophenones (III), and the upper limit is not particularly limited, but is preferably 10 equivalents.
この反応で使用される溶媒としては、通常酸化反応に
不活性な溶媒が使用され、かかる溶媒としては、たとえ
ば、水、ジオキサン、テトラヒドロフラン、Ｎ−メチル
ピロリドン等が例示される。As a solvent used in this reaction, a solvent which is generally inert to the oxidation reaction is used, and examples of such a solvent include water, dioxane, tetrahydrofuran, N-methylpyrrolidone and the like.
反応温度は、通常−20〜180℃、好ましくは、−10〜1
00℃の範囲である。The reaction temperature is usually -20 to 180 ° C, preferably -10 to 1
It is in the range of 00 ° C.
反応終了後、通常の分離手段、過、酸析、抽出、分
液、濃縮等の操作により光学活性なカルボン酸類（IV）
を収率よく得ることができ、これは必要に応じてカラム
クロマトグラフィー、再結晶等により精製することもで
きる。After completion of the reaction, optically active carboxylic acids (IV) can be obtained by ordinary separation means, operations such as filtration, acid precipitation, extraction, liquid separation and concentration
Can be obtained in good yield, which can be purified by column chromatography, recrystallization or the like, if necessary.
光学活性なカルボン酸類（IV）から、光学活性なヒド
ロキシカルボン酸類（Ｖ）を得る反応は、得られた光学
活性なカルボン酸類（IV）の保護基をのぞくことにより
おこなわれる。The reaction for obtaining the optically active hydroxycarboxylic acid (V) from the optically active carboxylic acid (IV) is carried out by removing the protecting group of the obtained optically active carboxylic acid (IV).
具体的には、一般式（IV）で示される光学活性なカル
ボン酸類の保護基Ａの種類により方法が異なり、例えば
以下の方法によりおこなわれる。Specifically, the method differs depending on the type of the protective group A of the optically active carboxylic acid represented by the general formula (IV), and is performed, for example, by the following method.
１）Ａがアルキルまたはアリール基の場合、 脱保護剤としては、三臭化リン、三フッ化ホウ素、塩
化アルミニウムなどのルイス酸が用いられ、その使用量
は、光学活性なカルボン酸類（IV）に対して１〜５当量
倍である。1) When A is an alkyl or aryl group, a Lewis acid such as phosphorus tribromide, boron trifluoride or aluminum chloride is used as a deprotecting agent, and the amount of the deprotecting agent is an optically active carboxylic acid (IV) 1 to 5 equivalent times.
使用する溶媒は、ベンゼン、トルエン、ヘキサン、ヘ
プタン、ジクロルメタン、1,2−ジクロルエタン、クロ
ロホルム等の炭化水素ハロゲン化炭化水素等反応に不活
性な溶媒の単独または混合物が使用される。As a solvent to be used, a single or a mixture of solvents inert to a reaction such as a hydrocarbon halogenated hydrocarbon such as benzene, toluene, hexane, heptane, dichloromethane, 1,2-dichloroethane, and chloroform is used.
また特にＡがベンジル基の場合、水添触媒の存在下、
水素により接触水添して脱ベンジル化することもでき
る。In particular, when A is a benzyl group, in the presence of a hydrogenation catalyst,
Debenzylation can also be carried out by catalytic hydrogenation with hydrogen.
この脱ベンジル化反応において、水添触媒としては、
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、塩化パラジウム等が挙げられる。かかる触媒
の使用量は、光学活性なカルボン酸類（IV）に対して通
常0.001〜0.5重量倍である。反応は通常溶媒中でおこな
われ、溶媒としては、前記のほかに、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、
酢酸エチル等のアルコール、エーテル、ケトン、エステ
ル、非プロトン性極性溶媒等の反応に不活性な溶媒の単
独または混合物が使用される。In this debenzylation reaction, as a hydrogenation catalyst,
Palladium-based metal catalysts are preferably used, and specific examples thereof include palladium / carbon, palladium oxide, palladium black, and palladium chloride. The use amount of such a catalyst is usually 0.001 to 0.5 times by weight based on the optically active carboxylic acid (IV). The reaction is usually performed in a solvent, and as the solvent, in addition to the above, water, dioxane,
Tetrahydrofuran, methanol, ethanol, n-propyl alcohol, acetone, dimethylformamide,
A single or mixture of solvents inert to the reaction, such as alcohols such as ethyl acetate, ethers, ketones, esters, and aprotic polar solvents is used.
２）Ａが前記１）以外の場合、 脱保護剤としては、主として酸触媒が用いられ、その
使用量は光学活性なカルボン酸類（IV）に対して、0.00
1〜１当量倍である。2) When A is other than the above 1), an acid catalyst is mainly used as a deprotecting agent, and its use amount is 0.00
It is 1 to 1 equivalent times.
かかる酸触媒としては、ｐ−トルエンスルホン酸、ベ
ンゼンスルホン酸、メタンスルホン酸、硫酸、硫酸水素
カリウム、塩酸、リン酸、酢酸、トリフルオロ酢酸等の
無機もしくは有機酸性物質が用いられる。As such an acid catalyst, inorganic or organic acidic substances such as p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, sulfuric acid, potassium hydrogen sulfate, hydrochloric acid, phosphoric acid, acetic acid, and trifluoroacetic acid are used.
この反応に際しては、反応系内に水、メタノール、エ
タノール等のプロトン性溶媒が存在することが必要であ
り、それらに下記溶媒の存在もしくは非存在下に反応を
おこなう。すなわち、溶媒としては、ジオキサン、テト
ラヒドロフラン、アセトン、アセトニトリル、ジメチル
ホルムアミド、酢酸エチル、ベンゼン、トルエン、ヘキ
サン、ヘプタン、ジクロルメタン、1,2−ジクロルエタ
ン、クロロホルム等のエーテル、ケトン、エステル、非
プロトン性極性溶媒、炭化水素、ハロゲン化炭化水素等
の反応に不活性な溶媒の単独または混合物があげられ
る。At the time of this reaction, it is necessary that a protic solvent such as water, methanol, or ethanol is present in the reaction system, and the reaction is carried out in the presence or absence of the following solvent. That is, as the solvent, dioxane, tetrahydrofuran, acetone, acetonitrile, dimethylformamide, ethyl acetate, benzene, toluene, hexane, heptane, dichloromethane, 1,2-dichloroethane, ether such as chloroform, ketone, ester, aprotic polar solvent , Hydrocarbons, halogenated hydrocarbons, and other solvents inert to the reaction alone or as a mixture.
また特にＡがシリル基の場合、フッ素イオンの存在
下、脱シリル化することもできる。In particular, when A is a silyl group, it can be desilylated in the presence of a fluorine ion.
この脱シリル化反応において、フッ素イオン源として
は、例えば、テトラブチルアンモニウムフルオライド、
フッ化水素、リチウムテトラフルオロボレートがあげら
れ、その使用量は光学活性なカルボン酸類（IV）に対し
て１〜５当量倍である。反応は通常、溶媒中でおこなわ
れ、溶媒としては、前記の溶媒があげられる。In this desilylation reaction, as a fluorine ion source, for example, tetrabutylammonium fluoride,
Examples thereof include hydrogen fluoride and lithium tetrafluoroborate, and the amount of use is 1 to 5 equivalents to the optically active carboxylic acids (IV). The reaction is usually performed in a solvent, and examples of the solvent include the above-mentioned solvents.
反応時間については、いずれの場合も特に制限され
ず、また反応温度については、−20〜150℃の範囲であ
る。The reaction time is not particularly limited in any case, and the reaction temperature is in the range of −20 to 150 ° C.
反応終了後、通常の分離手段、抽出、分液、濃縮等の
操作により光学活性なヒドロキシカルボン酸類（Ｖ）を
得ることができ、これは必要に応じて、カラムクロマト
グラフィー等により精製することもできる。After completion of the reaction, the optically active hydroxycarboxylic acids (V) can be obtained by ordinary separation means, extraction, liquid separation, concentration, etc., which can be purified by column chromatography or the like, if necessary. it can.
なお、脱保護化の反応工程は、一般式（IV）で示され
る光学活性なカルボン酸類の保護基Ａの種類によって
は、光学活性なカルボン酸類（IV）を得る後処理工程に
おいて、脱保護が同時に進行する場合がある。その場合
は、前述の脱保護工程なしに後処理工程をおこない、次
反応へ進めることもできる。In the deprotection reaction step, depending on the type of the protecting group A of the optically active carboxylic acid represented by the general formula (IV), the deprotection may be carried out in the post-treatment step of obtaining the optically active carboxylic acid (IV). May progress at the same time. In that case, a post-treatment step can be performed without the above-described deprotection step, and the reaction can proceed to the next reaction.
光学活性なヒドロキシカルボン酸類（Ｖ）から光学活
性な芳香族カルボン酸誘導体（Ｉ）を得る反応は、光学
活性なヒドロキシカルボン酸類（Ｖ）を一般式（VI）で
示されるアシル化剤と反応させることによりおこなわれ
る。In the reaction for obtaining the optically active aromatic carboxylic acid derivative (I) from the optically active hydroxycarboxylic acid (V), the optically active hydroxycarboxylic acid (V) is reacted with an acylating agent represented by the general formula (VI). It is done by doing.
一般式（VI）において、Ｒ′としては以下に例示され
るアルキル基またはアルコキシアルキル基があげられ
る。In the general formula (VI), examples of R ′ include an alkyl group and an alkoxyalkyl group exemplified below.
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、
ヘキシルヘキシペンチル、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、2,8−ジメチルブ
チル、2,3,3−トリメチルブチル、２−メチルペンチ
ル、３−メチルペンチル、2,3−ジメチルペンチル、2,4
−ジメチルペンチル、2,3,3,4−テトラメチルペンチ
ル、２−メチルヘキシル、８−メチルヘキシル、４−メ
チルヘキシル、2,5−ジメチルヘキシル、２−メチルヘ
プチル、２−メチルオクチル、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
ルヘプチル、２−ハロエチル、２−ハロプロピル、３−
ハロプロピル、８−ハロ−２−メチルプロピル、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、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、臭素又はヨウ素を表わす） 尚、これらのアルキル基もしくはアルコキシアルキル
基は光学活性基であってもよい。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,
Hexylhexylpentyl, hexyloxyhexyl, hexyloxyoctyl, hexyloxynonyl, hexyloxydecyl, heptyloxymethyl, heptyloxyethyl, heptyloxypropyl, heptyloxybutyl, heptyloxypentyl, octyloxymethyl, octyloxyethyl, octyl Oxypropyl,
Decyloxymethyl, decyloxyethyl, decyloxypropyl, 1-methylethyl, 1-methylpropyl,
1-methylbutyl, 1-methylpentyl, 1-methylhexyl, 1-methylheptyl, 1-methyloctyl, 2
-Methylethyl, 2-methylbutyl, 2,8-dimethylbutyl, 2,3,3-trimethylbutyl, 2-methylpentyl, 3-methylpentyl, 2,3-dimethylpentyl, 2,4
-Dimethylpentyl, 2,3,3,4-tetramethylpentyl, 2-methylhexyl, 8-methylhexyl, 4-methylhexyl, 2,5-dimethylhexyl, 2-methylheptyl, 2-methyloctyl, 2-methylhexyl Trihalomethylpentyl, 2-trihalomethylhexyl, 2-trihalomethylheptyl, 2-haloethyl, 2-halopropyl, 3-
Halopropyl, 8-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, halomethyl, 1
-Haloethyl, 1-halopropyl, 1-halobutyl, 1
-Halopentyl, 1-halohexyl, 1-haloheptyl, 1-halooctyl (however, halo in the above alkyl group means fluorine, chlorine, bromine or iodine) Note that these alkyl groups or alkoxyalkyl groups are optically active groups. You may.
これらの光学活性基を有する光学活性なアシル化剤
（VI）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、又は分割により得られる
次のような光学活性アミノ酸及び光学活性オキシ酸から
誘導することができる。Some of these optically active acylating agents (VI) having an optically active group are obtained by oxidation of the corresponding alcohol and reductive deamination of the amino acid. Others can be derived from optically active amino acids and optically active oxyacids that are naturally occurring or obtained by resolution, such as:
アラニン、バリン、ロイシン、イソロイシン、フェニ
ルアラニン、セリン、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、トリフル
オロアラニン、アスパラギン酸、グルタミン酸、乳酸、
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。Alanine, valine, leucine, isoleucine, phenylalanine, serine, threonine, alosreonine, homoserine, alloisoleucine, tert-leucine, 2-aminobutyric acid, norvaline, norleucine, ornithine, lysine, hydroxylysine, phenylglycine, trifluoroalanine, asparagine Acid, glutamic acid, lactic acid,
Mandelic acid, tropic acid, 3-hydroxybutyric acid, malic acid, tartaric acid, isopropylmalic acid and the like.
一般式（VI）で示されるアシル化剤としては、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即ち、Ｒ′COOHの酸無水物、さらに
は酸クロリド及び酸ブロミドのごとき酸ハライドが例示
される。Examples of the acylating agent represented by the general formula (VI) include the above-mentioned aliphatic carboxylic acids having an alkyl group or an alkoxyalkyl group, that is, acid anhydrides of R'COOH, and acids such as acid chloride and acid bromide. A halide is exemplified.
光学活性なヒドロキシカルボン酸類（Ｖ）とアシル化
剤（VI）との反応は、通常溶媒の存在もしくは非存在下
に、一般には触媒の存在下に行われる。The reaction between the optically active hydroxycarboxylic acids (V) and the acylating agent (VI) is usually carried out in the presence or absence of a solvent, generally in the presence of a catalyst.
この反応において溶媒を使用する場合、その溶媒とし
てはたとえば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、ハロゲン化炭化水素等の反応に不活性な溶媒の単独
または混合物があげられる。その使用量については特に
制限なく使用することができる。When a solvent is used in this reaction, examples of the solvent include aliphatic or aromatic solvents such as tetrahydrofuran, ethyl ether, acetone, methyl ethyl ketone, toluene, benzene, chlorobenzene, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, dimethylformamide, and hexane. Solvents which are inert to the reaction of group hydrocarbons, ethers, ketones, halogenated hydrocarbons and the like, alone or in a mixture. The amount can be used without any particular limitation.
該反応に於て、アシル化剤（VI）の使用量は、光学活
性なヒドロキシカルボン酸類（Ｖ）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1.1〜４当量倍である。In the reaction, the amount of the acylating agent (VI) to be used is 1 equivalent or more times the amount of the optically active hydroxycarboxylic acid (V), and the upper limit is not particularly limited, but is preferably 1.1 to 4 times. Equivalent times.
触媒としては、たとえばジメチルアミノピリジン、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、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、硫酸などの有機酸あるいは
無機酸を触媒として用いることもできる。Examples of the catalyst include dimethylaminopyridine, triethylamine, tri-n-butylamine, pyridine,
Picoline, collidine, imidazole, sodium carbonate,
Organic or inorganic basic substances such as sodium methylate and potassium bicarbonate can be mentioned. Further, an organic acid or an inorganic acid such as toluenesulfonic acid, methanesulfonic acid, or sulfuric acid can be used as a catalyst.
かかる触媒を使用するにあたり、たとえばアリル化剤
として酸ハライドを使用する場合にはピリジン、トリエ
チルアミンが特に好ましく使用される。In using such a catalyst, for example, when an acid halide is used as the allylating agent, pyridine and triethylamine are particularly preferably used.
触媒の使用量は、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当量倍以上である。The amount of the catalyst used depends on the type of the acid anhydride or acid halide and the combination of the catalyst to be used, etc., and is not necessarily specified. For example, when the acid halide is used, it is 1 equivalent or more times the acid halide. It is.
反応温度は通常−80〜100℃であるが、好ましくは−2
5〜80℃である。The reaction temperature is usually -80 to 100 ° C, preferably -2.
5 to 80 ° C.
反応時間は特に制限されず、原料の光学活性なヒドロ
キシカルボン酸類（Ｖ）が消失したときを反応の終点と
することができる。The reaction time is not particularly limited, and the time when the optically active hydroxycarboxylic acids (V) as the raw materials disappear can be regarded as the end point of the reaction.
反応終了後、通常の分離手段、たとえば抽出、分液、
濃縮等の操作により反応混合物から一般式（Ｉ）で示さ
れる光学活性な芳香族カルボン酸誘導体を収率よく得る
ことができ、これは必要によりカラムクロマトグラフィ
ーなどで精製することもできる。After completion of the reaction, usual separation means such as extraction, liquid separation,
An optically active aromatic carboxylic acid derivative represented by the general formula (I) can be obtained from the reaction mixture by a procedure such as concentration in a good yield, and can be purified by column chromatography or the like, if necessary.
以上の製造法により得られる一般式（Ｉ）で示される
光学活性な芳香族カルボン酸誘導体としては、下記のも
のがあげられる。Examples of the optically active aromatic carboxylic acid derivative represented by the general formula (I) obtained by the above production method include the following.
４−（１−メチル−２−アルキルカルボニルオキシエチ
ル）安息香酸、 ４−（１−メチル−３−アルキルカルボニルオキシプロ
ピル）安息香酸、 ４−（１−メチル−４−アルキルカルボニルオキシブチ
ル）安息香酸、 ４−（１−メチル−５−アルキルカルボニルオキシペン
チル）安息香酸、 ４−（１−メチル−６−アルキルカルボニルオキシヘキ
シル）安息香酸、 ４−（２−アルキルカルボニルオキシプロピル）安息香
酸、 ４−（３−アルキルカルボニルオキシブチル）安息香
酸、 ４−（４−アルキルカルボニルオキシペンチル）安息香
酸、 ４−（５−アルキルカルボニルオキシヘキシル）安息香
酸、 ４−（６−アルキルカルボニルオキシヘプチル）安息香
酸、 および上記化合物において安息香酸が、４′−ビフェ
ニルカルボン酸である化合物。4- (1-methyl-2-alkylcarbonyloxyethyl) benzoic acid, 4- (1-methyl-3-alkylcarbonyloxypropyl) benzoic acid, 4- (1-methyl-4-alkylcarbonyloxybutyl) benzoic acid 4- (1-methyl-5-alkylcarbonyloxypentyl) benzoic acid, 4- (1-methyl-6-alkylcarbonyloxyhexyl) benzoic acid, 4- (2-alkylcarbonyloxypropyl) benzoic acid, 4- (3-alkylcarbonyloxybutyl) benzoic acid, 4- (4-alkylcarbonyloxypentyl) benzoic acid, 4- (5-alkylcarbonyloxyhexyl) benzoic acid, 4- (6-alkylcarbonyloxyheptyl) benzoic acid, And benzoic acid in the above compound is 4'-biphenylcarboxylic acid Compound.
ここで、アルキルとはハロゲン原子を含んでいてもよ
い炭素数１〜20のアルキル基または、ハロゲン原子を含
んでいてもよい炭素数２〜20のアルコキシアルキル基を
示す。Here, alkyl refers to an alkyl group having 1 to 20 carbon atoms that may contain a halogen atom or an alkoxyalkyl group having 2 to 20 carbon atoms that may contain a halogen atom.
その他、 ４−（アルキルカルボニルオキシメチル）安息香酸、 ４−（２−アルキルカルボニルオキシエチル）安息香
酸、 ４−（３−アルキルカルボニルオキシプロピル）安息香
酸、 ４−（４−アルキルカルボニルオキシブチル）安息香
酸、 ４−（５−アルキルカルボニルオキシペンチル）安息香
酸、 および、上記化合物において安息香酸が、４′−ビフ
ェニルカルボン酸である化合物。Others, 4- (alkylcarbonyloxymethyl) benzoic acid, 4- (2-alkylcarbonyloxyethyl) benzoic acid, 4- (3-alkylcarbonyloxypropyl) benzoic acid, 4- (4-alkylcarbonyloxybutyl) benzoic acid An acid, 4- (5-alkylcarbonyloxypentyl) benzoic acid, and a compound in which benzoic acid is 4'-biphenylcarboxylic acid in the above compounds.
ここで、アルキルとはハロゲン原子を含んでいてもよ
い光学活性な炭素数８〜20のアルキル基またはハロゲン
原子を含んでいてもよい光学活性な炭素数４〜20のアル
コキシアルキル基を示す。Here, alkyl refers to an optically active alkyl group having 8 to 20 carbon atoms that may contain a halogen atom or an optically active alkoxyalkyl group having 4 to 20 carbon atoms that may contain a halogen atom.
さらに、下記の光学活性な芳香族化合物も例示され
る。Further, the following optically active aromatic compounds are also exemplified.
４−（１−メチル−２−ヒドロキシエチル）安息香酸、 ４−（１−メチル−３−ヒドロキシプロピル）安息香
酸、 ４−（１−メチル−４−ヒドロキシブチル）安息香酸、 ４−（１−メチル−５−ヒドロキシペンチル）安息香
酸、 ４−（１−メチル−６−ヒドロキシヘキシル）安息香
酸、 ４−（２−ヒドロキシプロピル）安息香酸、 ４−（３−ヒドロキシブチル）安息香酸、 ４−（４−ヒドロキシペンチル）安息香酸、 ４−（５−ヒドロキシヘキシル）安息香酸、 ４−（６−ヒドロキシヘプチル）安息香酸および、上記
化合物において安息香酸が、４′−ビフェニルカルボン
酸である化合物。4- (1-methyl-2-hydroxyethyl) benzoic acid, 4- (1-methyl-3-hydroxypropyl) benzoic acid, 4- (1-methyl-4-hydroxybutyl) benzoic acid, 4- (1- Methyl-5-hydroxypentyl) benzoic acid, 4- (1-methyl-6-hydroxyhexyl) benzoic acid, 4- (2-hydroxypropyl) benzoic acid, 4- (3-hydroxybutyl) benzoic acid, 4- ( 4-hydroxypentyl) benzoic acid, 4- (5-hydroxyhexyl) benzoic acid, 4- (6-hydroxyheptyl) benzoic acid, and compounds in which benzoic acid is 4'-biphenylcarboxylic acid.
＜発明の効果＞ 本発明の一般式（Ｉ）で示される光学活性な芳香族カ
ルボン酸誘導体は、液晶用材料の中間体として有用であ
り、また農医薬の中間体としても利用することができ
る。さらに、本発明の製造法は、該誘導体を工業的に有
利に提供するものである。<Effect of the Invention> The optically active aromatic carboxylic acid derivative represented by the general formula (I) of the present invention is useful as an intermediate of a liquid crystal material, and can also be used as an intermediate of agrochemicals. . Further, the production method of the present invention provides the derivative industrially advantageously.
＜実施例＞ 以下、実施例により本発明を説明する。<Example> Hereinafter, the present invention will be described with reference to examples.
実施例１ （−）−４−（２−ヒドロキシプロピル）アセトフェ
ノン17.8g（0.1モル）を無水ジメチルホルムアミド100m
lに溶かし、25〜30℃にて、イミダゾール7.15g（0.105
モル）とｔ−ブチルジメチルシリルクロリド15.8g（0.1
05モル）を加えて、６時間反応させた。Example 1 17.8 g (0.1 mol) of (-)-4- (2-hydroxypropyl) acetophenone was added to 100 m of anhydrous dimethylformamide.
and imidazole at 25-30 ° C at 7.15 g (0.105 g).
Mol) and 15.8 g of t-butyldimethylsilyl chloride (0.1
05 mol) and reacted for 6 hours.
反応終了後、水400mlに注ぎ出し、トルエン400mlを加
えてから、塩酸でpH1〜２とし、抽出、分液し、得られ
た有機層は水、５％重曹水、水の順に洗浄し、減圧下に
濃縮して、（−）−４−（２−ｔ−ブチルジメチルシリ
ルオキシプロピル）アセトフェノン（III-1）28.9g（収
率99％）を得た。After completion of the reaction, the mixture was poured into 400 ml of water, 400 ml of toluene was added, and the mixture was adjusted to pH 1 to 2 with hydrochloric acid, extracted and separated. The solution was concentrated under reduced pressure to obtain 28.9 g of (-)-4- (2-t-butyldimethylsilyloxypropyl) acetophenone (III-1) (yield: 99%).
上で得た（III-1）14.6g（50ミリモル）を、ジオキサ
ン200mlに溶かし、20％水酸化ナトリウム600mlと臭素30
mlから調製した次亜臭素酸ナトリウム溶液を加えて、30
〜35℃で一昼夜攪拌した。反応終了後は、水500mlと亜
硫酸ナトリウム50gを加えて30分間攪拌したのち塩酸でp
H1〜２とし、トルエン400mlで抽出、水洗した。有機層
を減圧下濃縮して、得られた残渣をシリカゲルカラムク
ロマトグラフィー（溶離液；トルエン：酢酸＝20:1）で
精製して、（−）−４−（２−ｔ−ブチルジメチルシリ
ルオキシプロピル）安息香酸（IV-1）12.5g（収率85
％）を得た。14.6 g (50 mmol) of (III-1) obtained above was dissolved in 200 ml of dioxane, and 600 ml of 20% sodium hydroxide and 30 ml of bromine were dissolved.
Add sodium hypobromite solution prepared from
Stirred overnight at ~ 35 ° C. After the reaction is completed, add 500 ml of water and 50 g of sodium sulfite, stir for 30 minutes, and add
H1 to H2, extracted with 400 ml of toluene and washed with water. The organic layer was concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (eluent; toluene: acetic acid = 20: 1) to give (-)-4- (2-t-butyldimethylsilyloxy). Propyl) benzoic acid (IV-1) 12.5 g (yield 85
%).
▲〔α〕20 D▼＝−25.0°（Ｃ＝1,CHCl3） ▲n20 D▼＝1.4913 上記で得られた（IV-1）10.0g（84ミリモル）をテト
ラヒドロフラン100mlに溶かし、テトラブチルアンモニ
ウムフルオリドの1M-THF溶液50mlを加えて、室温で12時
間攪拌した。反応終了後、水300ml中に注ぎ出し、塩酸
でpH1〜２にしてから、トルエン300mlで抽出し、得られ
た有機層は食塩水で洗浄した。溶媒を減圧下留去して、
（−）−４−（２−ヒドロキシプロピル）安息香酸（Ｖ
−１）5.7g（収率94％）を得た。▲ [α] 20 D ▼ = -25.0 ° (C = 1, CHCl 3 ) ▲ n 20 D ▼ = 1.4913 10.0 g (84 mmol) of (IV-1) obtained above was dissolved in 100 ml of tetrahydrofuran and tetrabutylfuran was dissolved. 50 ml of a 1M-THF solution of ammonium fluoride was added, and the mixture was stirred at room temperature for 12 hours. After completion of the reaction, the mixture was poured into 300 ml of water, adjusted to pH 1 to 2 with hydrochloric acid, extracted with 300 ml of toluene, and the obtained organic layer was washed with brine. The solvent is distilled off under reduced pressure,
(-)-4- (2-hydroxypropyl) benzoic acid (V
-1) 5.7 g (94% yield) was obtained.
▲〔α〕20 D▼＝−32.1°（Ｃ＝1,CHCl3） 上記で得られた（Ｖ−１）0.54g（３ミリモル）をピ
リジン10mlに溶かし、ｎ−ブチリルクロリド0.32g（３
ミリモル）を加えて、30〜35℃で１時間反応させた。▲ [α] 20 D ▼ = -32.1 ° (C = 1, CHCl 3 ) 0.54 g (3 mmol) of (V-1) obtained above was dissolved in 10 ml of pyridine, and 0.32 g of n-butyryl chloride (3
Mmol) and reacted at 30-35 ° C. for 1 hour.
反応終了後、水100mlに注ぎ出し、塩酸でpH1〜２とし
たのち、トルエン100mlで抽出し、有機層は食塩水で洗
浄したのち、減圧下溶媒を留去した。得られた残渣をシ
リカゲルカラムクロマトグラフィー（溶離液；トルエ
ン：酢酸）にて精製し、（＋）−４−（２−プロピルカ
ルボニルオキシプロピル）安息香酸0.57g（収率76％）
を得た。After the completion of the reaction, the mixture was poured into 100 ml of water, adjusted to pH 1 to 2 with hydrochloric acid, extracted with 100 ml of toluene, and the organic layer was washed with brine and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent; toluene: acetic acid), and 0.57 g of (+)-4- (2-propylcarbonyloxypropyl) benzoic acid was obtained (76% yield).
I got
▲〔α〕20 D▼＝＋15.9°（Ｃ＝1,CHCl3） 実施例２ 実施例１で得た（Ｖ−１）0.54g（８ミリモル）をピ
リジン10mlに溶かし、無水ヘキサン酸0.64g（３ミリモ
ル）を加えて、30〜35℃で４時間反応させた。反応終了
後、水100ml中に注ぎ出し、塩酸でpH1〜２としたのち、
トルエン100mlで抽出し、有機層は、食塩水で洗浄した
のち、減圧下溶媒を留去した。得られた残渣をシリカゲ
ルカラムクロマトグラフィー（溶離液；トルエン：酢
酸）にて精製し、（＋）−４−（２−ペンチルカルボニ
ルオキシプロピル）安息香酸0.54g（収率65％）を得
た。▲ [α] 20 D ▼ = + 15.9 ° (C = 1, CHCl 3 ) Example 2 0.54 g (8 mmol) of (V-1) obtained in Example 1 was dissolved in 10 ml of pyridine, and 0.64 of hexanoic anhydride was added. g (3 mmol) was added and reacted at 30-35 ° C for 4 hours. After the completion of the reaction, the mixture is poured into 100 ml of water and adjusted to pH 1 to 2 with hydrochloric acid.
After extraction with 100 ml of toluene, the organic layer was washed with brine and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent: toluene: acetic acid) to obtain 0.54 g (yield: 65%) of (+)-4- (2-pentylcarbonyloxypropyl) benzoic acid.
▲〔α〕20 D▼＝＋13.1°（Ｃ＝1,CHCl3） 実施例３ 実施例１で得た（Ｖ−１）0.54gを用い、ブチリルク
ロリドに代えて、ノナノイルクロリド0.53g（３ミリモ
ル）を用いる以外は、実施例１と同様に反応、後処理し
て、（＋）−４−（２−オクチルカルボニルオキシプロ
ピル）安息香酸0.68g（収率71％）を得た。▲ [α] 20 D ▼ = + 13.1 ° (C = 1, CHCl 3 ) Example 3 Using 0.54 g of (V-1) obtained in Example 1 and replacing non-butyryl chloride with 0.53 g of nonanoyl chloride. Except for using g (3 mmol), the reaction and post-treatment were conducted in the same manner as in Example 1 to obtain 0.68 g (yield 71%) of (+)-4- (2-octylcarbonyloxypropyl) benzoic acid. .
▲〔α〕20 D▼＝＋10.9°（Ｃ＝1,CHCl3） 実施例４ 実施例１で得た（Ｖ−１）0.54gを用い、ブチリルク
ロリドに代えて、ヘキサデカノイルクロリド0.82g（３
ミリモル）を用いる以外は実施例１と同様に反応、後処
理して、（＋）−４−（２−ペンタデシルカルボニルオ
キシプロピル）安息香酸0.98g（収率78％）を得た。▲ [α] 20 D ▼ = + 10.9 ° (C = 1, CHCl 3 ) Example 4 0.54 g of (V-1) obtained in Example 1 was used, and hexadecanoyl chloride was used in place of butyryl chloride. 0.82g (3
(+)-4- (2-Pentadecylcarbonyloxypropyl) benzoic acid (0.98 g, yield 78%).
▲〔α〕20 D▼＝＋7.7°（Ｃ＝1,CHCl3） 実施例５ （＋）−４−（１−メチル−２−ヒドロキシエチル）
アセトフェノン17.8g（0.1モル）を無水ジクロルメタン
100mlに溶かし、2,3−ジヒドロピラン9.3g（0.11モル）
とｐ−トルエンスルホン酸0.1gを加えて、20〜30℃に保
温して一昼夜攪拌した。▲ [α] 20 D ▼ = + 7.7 ° (C = 1, CHCl 3 ) Example 5 (+)-4- (1-methyl-2-hydroxyethyl)
17.8 g (0.1 mol) of acetophenone in anhydrous dichloromethane
Dissolve in 100 ml and 9.3 g (0.11 mol) of 2,3-dihydropyran
And 0.1 g of p-toluenesulfonic acid, and the mixture was kept warm at 20 to 30 ° C. and stirred for 24 hours.
反応終了後、５％重曹水300ml中にあけて抽出、分液
した。有機層は無水硫酸ナトリウムで乾燥後、減圧下溶
媒を留去して、残渣として薄かっ色の（＋）−４−（１
−メチル−２−テトラヒドロピラニルオキシエチル）ア
セトフェノン（III-5）26.3g（収率100％）を得た。After completion of the reaction, the mixture was poured into 300 ml of 5% aqueous sodium bicarbonate, extracted and separated. After the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and a pale brown (+)-4- (1
-Methyl-2-tetrahydropyranyloxyethyl) acetophenone (III-5) (26.3 g, 100% yield) was obtained.
▲〔α〕20 D▼＝＋6.0°（Ｃ＝1,CHCl3） 上で得た（III-5）13.1g（50ミリモル）をジオキサン
200mlに溶かし、20％水酸化ナトリウム600mlと臭素30ml
から調製した次亜臭素酸ナトリウム溶液を加えて、30〜
35℃で一昼夜攪拌した。反応終了後は、水500mlと亜硫
酸ナトリウム50mlを加えて30分間攪拌したのち、塩酸で
pH1〜２とし、トルエン400mlで抽出、水洗した。有機層
を減圧下濃縮して、得られた残渣をシリカゲルカラムク
ロマトグラフィー（溶離液；トルエン：酢酸＝20:1）で
精製して、（＋）−４−（１−メチル−２−ヒドロキシ
エチル）安息香酸（Ｖ−５）8.3g（収率92％）を得た。▲ [α] 20 D ▼ = + 6.0 ° (C = 1, CHCl 3 ) 13.1 g (50 mmol) of (III-5) obtained above
Dissolve in 200 ml, 600 ml of 20% sodium hydroxide and 30 ml of bromine
Add the sodium hypobromite solution prepared from
The mixture was stirred overnight at 35 ° C. After the reaction is completed, add 500 ml of water and 50 ml of sodium sulfite, stir for 30 minutes, and add hydrochloric acid.
The mixture was adjusted to pH 1-2, extracted with 400 ml of toluene, and washed with water. The organic layer was concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (eluent; toluene: acetic acid = 20: 1) to give (+)-4- (1-methyl-2-hydroxyethyl) ) 8.3 g (yield 92%) of benzoic acid (V-5) was obtained.
▲〔α〕20 D▼＝＋19.5°（Ｃ＝1,CHCl3） 上記で得られた（Ｖ−５）0.54g（３ミリモル）をピ
リジン10mlに溶かし、ｎ−ブチリルクロリド0.32g（３
ミリモル）を加えて、30〜35℃で１時間反応させた。▲ [α] 20 D ▼ = 19.5 ° (C = 1, CHCl 3 ) 0.54 g (3 mmol) of (V-5) obtained above was dissolved in 10 ml of pyridine, and 0.32 g of n-butyryl chloride (0.32 g) was obtained. 3
Mmol) and reacted at 30-35 ° C. for 1 hour.
反応終了後、水100mlに注ぎ出し、塩酸でpH1〜２とし
たのち、トルエン100mlで抽出し、有機層は食塩水で洗
浄したのち、減圧下溶媒を留去した。得られた残渣をシ
リカゲルカラムクロマトグラフィー（溶離液；トルエン
−酢酸）にて精製し、（＋）−４−（１−メチル−２−
ブチリル−オキシエチル）安息香酸0.58g（収率77％）
を得た。After the completion of the reaction, the mixture was poured into 100 ml of water, adjusted to pH 1 to 2 with hydrochloric acid, extracted with 100 ml of toluene, and the organic layer was washed with brine and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent; toluene-acetic acid) to give (+)-4- (1-methyl-2-
Butyryl-oxyethyl) benzoic acid 0.58 g (77% yield)
I got
▲〔α〕20 D▼＝＋7.1°（Ｃ＝1,CHCl3） 実施例６ 実施例５で得た（Ｖ−５）0.54g（３ミリモル）をピ
リジン10mlに溶かし、エトキシアセチルクロリド0.33g
（３ミリモル）を加えて、30〜35℃で１時間反応させ
た。反応終了後、水100ml中に注ぎ出し、塩酸でpH1〜２
としたのち、トルエン100mlで抽出し、有機層は、食塩
水で洗浄したのち、減圧下溶媒を留去した。得られた残
渣をシリカゲルカラムクロマトグラフィー（溶離液；ト
ルエン−酢酸）にて精製し、（＋）−（１−メチル−２
−エトキシアセトキシエチル）安息香酸0.57g（収率71
％）を得た。▲ [α] 20 D ▼ = + 7.1 ° (C = 1, CHCl 3 ) Example 6 0.54 g (3 mmol) of (V-5) obtained in Example 5 was dissolved in 10 ml of pyridine, and ethoxyacetyl chloride 0.33 was dissolved. g
(3 mmol) and reacted at 30-35 ° C. for 1 hour. After the reaction is completed, pour the mixture into 100 ml of water, and add hydrochloric acid to pH 1-2.
After extraction with 100 ml of toluene, the organic layer was washed with brine and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent; toluene-acetic acid) to give (+)-(1-methyl-2).
-Ethoxyethoxyacetoxyethyl) benzoic acid 0.57 g (yield 71
%).
▲〔α〕20 D▼＝＋5.9°（Ｃ＝1,CHCl3） 実施例７ 実施例５で得た（Ｖ−５）0.54gを用い、ブチリルク
ロリドに代えて、２−フルオロヘプタノイルクロリド0.
5g（３ミリモル）を用いる以外は、実施例５と同様に反
応および後処理をして、（＋）−４−｛１−メチル−２
−（２−フルオロヘプタノイルオキシ）エチル）安息香
酸0.7g（収率75％）を得た。▲ [α] 20 D ▼ = + 5.9 ° (C = 1, CHCl 3 ) Example 7 Using 0.54 g of (V-5) obtained in Example 5, 2-fluorohepta was used instead of butyryl chloride. Noyl chloride 0.
Except for using 5 g (3 mmol), the reaction and post-treatment were conducted in the same manner as in Example 5 to obtain (+)-4- {1-methyl-2
0.7 g (yield 75%) of-(2-fluoroheptanoyloxy) ethyl) benzoic acid was obtained.
▲〔α〕20 D▼＝＋4.1°（Ｃ＝1,CHCl3） 実施例８ 実施例５で得た（Ｖ−５）0.54gを用い、ブチリルク
ロリドに代えて、ヘキサデカノイルクロリド0.82g（３
ミリモル）を用いる以外は実施例５と同様に反応および
後処理をして、（＋）−４−（１−メチル−２−ペンタ
デシルカルボニルオキシエチル）安息香酸0.97g（収率7
7％）を得た。▲ [α] 20 D ▼ = + 4.1 ° (C = 1, CHCl 3 ) Example 8 Using 0.54 g of (V-5) obtained in Example 5, hexadecanoyl chloride was used instead of butyryl chloride. 0.82g (3
(+)-4- (1-Methyl-2-pentadecylcarbonyloxyethyl) benzoic acid 0.97 g (yield 7)
7%).
▲〔α〕20 D▼＝＋3.1°（Ｃ＝1,CHCl3） 実施例９〜12 実施例１において（＋）−４−（２−ヒドロキシプロ
ピル）アセトフェノンに代えて、表−１に示す原料を用
いる以外は実施例１と同様に反応および後処理をして、
表−１に示す化合物（Ｉ−９）、（I-10）、（I-11）お
よび（I-12）を得た。▲ [α] 20 D ▼ = + 3.1 ° (C = 1, CHCl 3 ) Examples 9 to 12 Instead of (+)-4- (2-hydroxypropyl) acetophenone in Example 1, Table 1 The reaction and post-treatment were performed in the same manner as in Example 1 except that the starting materials shown were used.
Compounds (I-9), (I-10), (I-11) and (I-12) shown in Table 1 were obtained.
実施例13 （＋）−４−（１−メチル−３−ヒドロキシプロピ
ル）アセトフェノン19.2g（0.1モル）を無水ジメチルホ
ルムアミド20mlと臭化ベンジル40mlに溶かし、酸化銀40
gを加えて、２日間30〜35℃で攪拌した。 Example 13 19.2 g (0.1 mol) of (+)-4- (1-methyl-3-hydroxypropyl) acetophenone was dissolved in 20 ml of anhydrous dimethylformamide and 40 ml of benzyl bromide.
g was added and stirred for 2 days at 30-35 ° C.
反応終了後、反応混合物を水に注ぎ出しトルエンで抽
出した。After completion of the reaction, the reaction mixture was poured into water and extracted with toluene.
得られた有機層は減圧下濃縮し、残渣をシリカゲルカ
ラムクロマト精製（溶離液；トルエン−酢酸エチル）し
て、（＋）−４−（１−メチル−３−ベンジルオキシプ
ロピル）アセトフェノン（III-13）15.5g（収率55％）
を得た。The obtained organic layer was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (eluent; toluene-ethyl acetate) to give (+)-4- (1-methyl-3-benzyloxypropyl) acetophenone (III- 13) 15.5 g (55% yield)
I got
上で得た（III-13）14.1g（50ミリモル）を、ジオキ
サン200mlに溶かし、20％水酸化ナトリウム600mlと臭素
30mlから調製した次亜臭素酸ナトリウム溶液を加えて、
30〜35℃で一昼夜攪拌した。反応終了後は、水500mlと
亜硫酸ナトリウム50gを加えて30分間攪拌したのち、塩
酸でpH1〜２とし、トルエン400mlで抽出、水洗した。有
機層を減圧下濃縮して、得られた残渣をシリカゲルカラ
ムクロマトグラフィー（溶離液；トルエン：酢酸＝20:
1）で精製して、（＋）−４−（１−メチル−３−ベン
ジルオキシプロピル）安息香酸（IV-13）12.8g（収率90
％）を得た。14.1 g (50 mmol) of (III-13) obtained above was dissolved in 200 ml of dioxane, and 600 ml of 20% sodium hydroxide and bromine were dissolved.
Add sodium hypobromite solution prepared from 30 ml,
The mixture was stirred overnight at 30 to 35 ° C. After completion of the reaction, 500 ml of water and 50 g of sodium sulfite were added, and the mixture was stirred for 30 minutes, adjusted to pH 1-2 with hydrochloric acid, extracted with 400 ml of toluene, and washed with water. The organic layer is concentrated under reduced pressure, and the obtained residue is subjected to silica gel column chromatography (eluent; toluene: acetic acid = 20:
After purification in 1), 12.8 g of (+)-4- (1-methyl-3-benzyloxypropyl) benzoic acid (IV-13) (yield 90)
%).
▲〔α〕20 D▼＝＋27.2°（Ｃ＝1,CHCl3） 上で得られた（IV-13）10.0g（35ミリモル）をテトラ
ヒドロフラン100mlに溶かし、10％Pd-C0.5を加えて、水
素雰囲気下、常圧で水素添加反応を行なった。水素吸収
が停止したところ（約800cm2）で、反応混合物をとり出
し、Pd-Cを別後、溶媒を減圧下留去して、（＋）−４
−（１−メチル−３−ヒドロキシプロピル）安息香酸
（V-13）6.8g（収率100％）を得た。▲ [α] 20 D ▼ = + 27.2 ° (C = 1, CHCl 3 ) 10.0 g (35 mmol) of (IV-13) obtained above was dissolved in 100 ml of tetrahydrofuran to give 10% Pd-C0.5. In addition, a hydrogenation reaction was performed under a hydrogen atmosphere at normal pressure. When the hydrogen absorption stopped (about 800 cm 2 ), the reaction mixture was taken out, and after separating Pd-C, the solvent was distilled off under reduced pressure to obtain (+)-4.
6.8 g (yield 100%) of-(1-methyl-3-hydroxypropyl) benzoic acid (V-13) was obtained.
▲〔α〕20 D▼＝＋25.8°（Ｃ＝1,CHCl3） 上で得られた（IV-13）0.58g（３ミリモル）をピリジ
ン10mlに溶かし、ｎ−ブチリルクロリド0.32g（３ミリ
モル）を加えて、30〜35℃で１時間反応させた。▲ [α] 20 D ▼ = + 25.8 ° (C = 1, CHCl 3 ) 0.58 g (3 mmol) of (IV-13) obtained above was dissolved in 10 ml of pyridine, and 0.32 g of n-butyryl chloride (0.32 g) was obtained. 3 mmol) and reacted at 30-35 ° C. for 1 hour.
反応終了後、水100mlに注ぎ出し、塩酸でpH1〜２とし
たのち、トルエン100mlで抽出し、有機層は食塩水で洗
浄したのち、減圧下溶媒を留去した。得られた残渣をシ
リカゲルカラムクロマトグラフィー（溶離液；トルエン
−酢酸）にて精製して（＋）−４−（１−メチル−３−
ブチリルオキシプロピル）安息香酸0.57g（収率72％）
を得た。After the completion of the reaction, the mixture was poured into 100 ml of water, adjusted to pH 1 to 2 with hydrochloric acid, extracted with 100 ml of toluene, and the organic layer was washed with brine and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent; toluene-acetic acid) to give (+)-4- (1-methyl-3-
Butyryloxypropyl) benzoic acid 0.57 g (72% yield)
I got
▲〔α〕20 D▼＝＋12.4°（Ｃ＝1,CHCl3） 実施例14 ４−（３−ヒドロキシプロピル）アセトフェニル17.8
g（0.1モル）を無水ジメチルホルムアミド100mlに溶か
し、25〜30℃にて、イミダゾール7.15g（0.105モル）と
ｔ−ブチルジメチルシリルクロリド15.8g（0.105モル）
を加えて、６時間反応させた。▲ [α] 20 D ▼ = + 12.4 ° (C = 1, CHCl 3 ) Example 14 4- (3-hydroxypropyl) acetophenyl 17.8
g (0.1 mol) was dissolved in 100 ml of anhydrous dimethylformamide, and at 25-30 ° C, 7.15 g (0.105 mol) of imidazole and 15.8 g (0.105 mol) of t-butyldimethylsilyl chloride were dissolved.
Was added and reacted for 6 hours.
反応終了後、水400mlに注ぎ出し、トルエン400mlを加
えてから、塩酸でpH1〜２とし、抽出し、分液した。得
られた有機層は水、５％重曹水、水の順に洗浄し、減圧
下濃縮して、４−（３−ｔ−ブチルジメチルシリルオキ
シプロピル）アセトフェノン（III-14）28.8g（収率99
％）を得た。After the completion of the reaction, the mixture was poured into 400 ml of water, 400 ml of toluene was added, and the mixture was adjusted to pH 1 to 2 with hydrochloric acid, extracted, and separated. The obtained organic layer was washed with water, 5% aqueous sodium hydrogen carbonate and water in that order, and concentrated under reduced pressure to give 28.8 g of 4- (3-t-butyldimethylsilyloxypropyl) acetophenone (III-14) (yield: 99).
%).
上で得られた（III-14）14.6g（50ミリモル）を、ジ
オキサン200mlに溶かし、20％水酸化ナトリウム600mlと
臭素30mlから調製した次亜臭素酸ナトリウム溶液を加え
て、30〜35℃で一昼夜攪拌した。反応終了後、水500ml
と亜硫酸ナトリウム50gを加えて30分間攪拌したのち塩
酸でpH1〜２とし、トルエン400mlで抽出し、水洗した。
有機層を減圧下濃縮して、得られた残渣をシリカゲルカ
ラムクロマトグラフィー（溶離液；トルエン：酢酸＝2
0:1）で精製して、４−（３−ｔ−ブチルジメチルシリ
ルオキシプロピル）安息香酸（IV-14）12.3g（収率83
％）を得た。14.6 g (50 mmol) of (III-14) obtained above was dissolved in 200 ml of dioxane, and a sodium hypobromite solution prepared from 600 ml of 20% sodium hydroxide and 30 ml of bromine was added. Stirred all day long. After the reaction, 500 ml of water
And 50 g of sodium sulfite, and the mixture was stirred for 30 minutes, adjusted to pH 1-2 with hydrochloric acid, extracted with 400 ml of toluene, and washed with water.
The organic layer is concentrated under reduced pressure, and the obtained residue is subjected to silica gel column chromatography (eluent; toluene: acetic acid = 2).
0: 1) to give 12.3 g of 4- (3-t-butyldimethylsilyloxypropyl) benzoic acid (IV-14) (yield: 83).
%).
上で得られた（IV-14）10.0g（34ミリモル）をテトラ
ヒドロフラン100mlに溶かし、テトラブチルアンモニウ
ムフルオリドの1M-THF溶液50mlを加えて、室温で12時間
攪拌した。反応終了後、水300ml中に注ぎ出し、塩酸でp
H1〜２にしたてから、トルエン300mlで抽出し、得られ
た有機層は食塩水で洗浄した。溶媒を減圧下留去して、
４−（３−ヒドロキシプロピル）安息香酸（V-14）5.6g
（収率92％）を得た。10.0 g (34 mmol) of (IV-14) obtained above was dissolved in 100 ml of tetrahydrofuran, 50 ml of a 1 M solution of tetrabutylammonium fluoride in THF was added, and the mixture was stirred at room temperature for 12 hours. After the completion of the reaction, pour into 300 ml of water and p
After adjusting to H1 to H2, the mixture was extracted with 300 ml of toluene, and the obtained organic layer was washed with brine. The solvent is distilled off under reduced pressure,
5.6 g of 4- (3-hydroxypropyl) benzoic acid (V-14)
(92% yield).
上で得られた（V-14）0.54g（３ミリモル）をピリジ
ン10mlに溶かし、（＋）−メチルブチリルクロリド0.36
g（３ミリモル）を加えて、30〜35℃で１時間反応させ
た。0.54 g (3 mmol) of (V-14) obtained above was dissolved in 10 ml of pyridine, and 0.36 g of (+)-methylbutyryl chloride was dissolved.
g (3 mmol) was added and reacted at 30-35 ° C. for 1 hour.
反応終了後、水100mlに注ぎ出し、塩酸でpH1〜２とし
たのち、トルエン100mlで抽出し、有機層は食塩水で洗
浄したのち、減圧下で溶媒を留去した。得られた残渣を
シリカゲルカラムクロマトグラフィー（溶離液；トルエ
ン−酢酸）にて精製して（＋）−４−｛３−（ｓ）−メ
チルブチリルオキシプロピル｝安息香酸0.55g（収率70
％）を得た。After the completion of the reaction, the mixture was poured into 100 ml of water, adjusted to pH 1 to 2 with hydrochloric acid, extracted with 100 ml of toluene, and the organic layer was washed with brine and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent; toluene-acetic acid) to give (+)-4- {3- (s) -methylbutyryloxypropyl} benzoic acid 0.55 g (yield 70).
%).
▲〔α〕20 D▼＝＋1.5°（Ｃ＝1,CHCl3） 実施例15 実施例14において、４−（３−ヒドロキシプロピル）
アセトフェノンに代えて、４−（４−ヒドロキシブチ
ル）アセトフェノン19.2gを、（＋）−メチルブチリル
クロリドに代えて、（＋）−２−フルオロヘプタノイル
クロリド0.5gを用いる以外は、実施例14と同様に反応お
よび後処理をして、（＋）−４−｛４−（２−フルオロ
ヘプタノイル）オキシブチル｝安息香酸を得た。▲ [α] 20 D ▼ = + 1.5 ° (C = 1, CHCl 3 ) Example 15 In Example 14, 4- (3-hydroxypropyl)
Example 14 except that 19.2 g of 4- (4-hydroxybutyl) acetophenone was used instead of acetophenone and 0.5 g of (+)-2-fluoroheptanoyl chloride was used instead of (+)-methylbutyryl chloride. The reaction and post-treatment were carried out in the same manner as in to obtain (+)-4- {4- (2-fluoroheptanoyl) oxybutyl} benzoic acid.
▲〔α〕20 D▼＝＋1.2°（Ｃ＝1,CHCl3） 実施例16〜20 実施例１において、（＋）−４−（２−ヒドロキシプ
ロピル）アセトフェノンに代えて、表−２に示す原料を
用いる以外は、実施例１と同様に反応および後処理をし
て、表−１に示す化合物を得た。▲ [α] 20 D ▼ = + 1.2 ° (C = 1, CHCl 3 ) Examples 16 to 20 In Example 1, instead of (+)-4- (2-hydroxypropyl) acetophenone, Table 2 was used. The reaction and post-treatment were carried out in the same manner as in Example 1 except for using the raw materials shown in Table 1 to obtain the compounds shown in Table 1.
実施例21〜24 実施例５において、（＋）−４−（２−ヒドロキシプ
ロピル）アセトフェノンに代えて、（−）−４−（４−
ヒドロキシペンチル）−４′−アセチルビフェニル（0.
1モル）を原料とし、かつアシル化剤として用いたｎ−
ブチリルクロリドに代えて表−３に記載のアシル化剤を
用いる以外は実施例５と同様に反応および後処理をし
て、表−３に示す化合物を得た。 Examples 21 to 24 In Example 5, instead of (+)-4- (2-hydroxypropyl) acetophenone, (-)-4- (4-
(Hydroxypentyl) -4'-acetylbiphenyl (0.
1 mol) as a raw material and n-
The reaction and post-treatment were carried out in the same manner as in Example 5 except that the acylating agent shown in Table 3 was used instead of butyryl chloride, to obtain a compound shown in Table 3.
実施例25および26 実施例14において、４−（３−ヒドロキシプロピル）
アセトフェノンに代えて、４−（３−ヒドロキシプロピ
ル）−４′−アセチルビフェニルを原料とし、使用する
アシル化剤を表−４に示す化合物とする以外は実施例14
と同様に反応および後処理をして、表−４に示す化合物
を得た。 Examples 25 and 26 In Example 14, 4- (3-hydroxypropyl)
Example 14 was repeated except that acetophenone was replaced by 4- (3-hydroxypropyl) -4'-acetylbiphenyl as a raw material and the acylating agent used was a compound shown in Table 4.
The reaction and post-treatment were carried out in the same manner as in to obtain the compounds shown in Table-4.
参考例 実施例10で得られた（＋）−４−（５−ブチリルオキ
シヘキシル）安息香酸0.29g（１ミリモル）と４−デシ
ルオキシ−４′−ヒドロキシビフェニル0.33g（１ミリ
モル）をジクロルメタン20mlに加え、そこへ、N,N′−
ジシクロヘキシルカルボジイミド0.25g（1.2ミリモル）
とＮ−ピロリジノピリジン0.05gを加えて、20〜25℃で
一昼夜攪拌した。 Reference Example 0.29 g (1 mmol) of (+)-4- (5-butyryloxyhexyl) benzoic acid obtained in Example 10 and 0.33 g (1 mmol) of 4-decyloxy-4'-hydroxybiphenyl were added to 20 ml of dichloromethane. In addition to N, N'-
0.25 g (1.2 mmol) of dicyclohexylcarbodiimide
And 0.05 g of N-pyrrolidinopyridine were added, and the mixture was stirred at 20 to 25 ° C for 24 hours.
反応終了後、トルエン200mlで希釈したのち、水、５
％酢酸、水、５％重曹水、および水で順次洗浄したの
ち、無水硫酸マグネシウムで乾燥し、減圧下濃縮した。After the reaction is completed, the reaction mixture is diluted with 200 ml of toluene,
The extract was washed successively with 5% acetic acid, water, 5% aqueous sodium bicarbonate and water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure.
得られた残渣をシリカゲルカラムクロマトグラフィー
にて精製（溶出液；トルエン−酢酸エチル）して、0.47
gの（＋）−４−デシルオキシ−４′−ビフェニリル４
−（５−ブチリルオキシヘキシル）ベンゾエートを得
た。The obtained residue was purified by silica gel column chromatography (eluent; toluene-ethyl acetate) to give 0.47
g of (+)-4-decyloxy-4'-biphenylyl 4
-(5-butyryloxyhexyl) benzoate was obtained.
透明電極が設けられたガラス基板上にポリイミド系高
分子膜を設け、ラビング処理をしたのち、２枚の基板の
ラビング方向が平行になるようにガラスファイバー（径
５μｍ）をスペーサーとして、液晶セルとして組立て、
これに上記化合物を封入して液晶素子を得た。A polyimide polymer film is provided on a glass substrate on which a transparent electrode is provided, and rubbing treatment is performed. Then, a glass fiber (diameter: 5 μm) is used as a spacer so that the rubbing directions of the two substrates are parallel to each other. Assembly,
The above compound was sealed therein to obtain a liquid crystal device.
この液晶素子を偏光子と組み合わせ、電界を±20Vに
印加しながら、温度変化させていくと、透過光強度の変
化が観察され、上記化合物が強誘電性液晶であることが
わかった。When this liquid crystal element was combined with a polarizer and the temperature was changed while applying an electric field of ± 20 V, a change in transmitted light intensity was observed, indicating that the compound was a ferroelectric liquid crystal.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０７Ｃ 69/63 Ｃ０７Ｃ 69/63 // Ｃ０７Ｍ 7:00 (72)発明者 南井 正好 大阪府高槻市塚原２丁目10番１号 住友 化学工業株式会社内 (56)参考文献 特開 平２−202860（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C07C 69/157,69/24 C07C 69/63,65/01 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. 6 Identification symbol FI C07C 69/63 C07C 69/63 // C07M 7:00 (72) Inventor Masayoshi Minami 2-10-1, Tsukahara, Takatsuki-shi, Osaka (56) References JP-A-2-202860 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) C07C 69/157, 69/24 C07C 69/63 , 65/01 CA (STN) REGISTRY (STN)
Claims (12)
素数１〜20のアルキル基またはハロゲン原子で置換され
ていてもよい炭素数２〜20のアルコキシアルキル基を示
し、ｋは１または２を示す。Ｚは または−（CH2）p−を示す。ここでｐは１〜５の整数を
示し、＊印は不斉炭素原子を示す。但し、Ｚが−（C
H2）p−のとき、Ｒ′は光学活性体である。） で示される光学活性な芳香族カルボン酸誘導体。(1) General formula (Wherein R ′ represents an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom or an alkoxyalkyl group having 2 to 20 carbon atoms which may be substituted with a halogen atom, and k represents 1 or 2 and Z is Or-(CH 2 ) p- . Here, p represents an integer of 1 to 5, and * represents an asymmetric carbon atom. However, if Z is-(C
In the case of H 2 ) p —, R ′ is an optically active substance. ) An optically active aromatic carboxylic acid derivative represented by the formula:
素原子を示す。） で示される光学活性なヒドロキシカルボン酸類を 一般式 （式中、Ｒ′はハロゲン原子で置換されていてもよい炭
素数１〜20のアルキル基またはハロゲン原子で置換され
ていてもよい炭素数２〜20のアルコキシアルキル基を示
し、Ｘはハロゲン原子または 基を示す。） で示されるアシル化剤を用いてアシル化することを特徴
とする請求項１記載の光学活性な芳香族カルボン酸誘導
体（Ｉ）の製造法。2. The general formula (Where k represents 1 or 2, and Z represents Is shown. Here, p represents an integer of 1 to 5, and * represents an asymmetric carbon atom. An optically active hydroxycarboxylic acid represented by the general formula (Wherein, R ′ represents an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom or an alkoxyalkyl group having 2 to 20 carbon atoms which may be substituted with a halogen atom, and X represents a halogen atom Or Represents a group. The method for producing an optically active aromatic carboxylic acid derivative (I) according to claim 1, wherein the acylation is carried out using an acylating agent represented by the formula:
素原子を示す。Ａは水酸基の保護基を示す。） で示される光学活性なカルボン酸類から水酸基の保護基
を脱保護し、光学活性なヒドロキシカルボン酸類（Ｖ）
を得ることを特徴とする請求項２記載の光学活性な芳香
族カルボン酸誘導体（Ｉ）の製造法。3. The general formula (Where k represents 1 or 2, and Z represents Is shown. Here, p represents an integer of 1 to 5, and * represents an asymmetric carbon atom. A represents a protecting group for a hydroxyl group. The deprotection of a hydroxyl-protecting group from the optically active carboxylic acid represented by the formula (1) gives an optically active hydroxycarboxylic acid (V)
3. The process for producing an optically active aromatic carboxylic acid derivative (I) according to claim 2, wherein
素原子を示す。Ａは水酸基の保護基を示す。） で示される光学活性なアセトフェノン類のアセチル基を
酸化して、光学活性なカルボン酸類（IV）を得ることを
特徴とする請求項３記載の光学活性な芳香族カルボン酸
誘導体（Ｉ）の製造法。4. General formula (Where k represents 1 or 2, and Z represents Is shown. Here, p represents an integer of 1 to 5, and * represents an asymmetric carbon atom. A represents a protecting group for a hydroxyl group. 4. The production of the optically active aromatic carboxylic acid derivative (I) according to claim 3, wherein the acetyl group of the optically active acetophenone represented by the formula is oxidized to obtain an optically active carboxylic acid (IV). Law.
素原子を示す。） で示される光学活性なアルコール類の水酸基に保護基を
導入し、光学活性なアセトフェノン類（III）を得るこ
とを特徴とする請求項４記載の光学活性な芳香族カルボ
ン酸誘導体（Ｉ）の製造法。5. The general formula (Where k represents 1 or 2, and Z represents Is shown. Here, p represents an integer of 1 to 5, and * represents an asymmetric carbon atom. 5. The optically active aromatic carboxylic acid derivative (I) according to claim 4, wherein a protecting group is introduced into a hydroxyl group of the optically active alcohol represented by the formula (1) to obtain an optically active acetophenone (III). Manufacturing method.
素原子を示す。Ｒは水素原子または水酸基の保護基を示
す。ただし、ｋおよびｐが１でかつＲが水素原子である
場合を除く。） で示される光学活性な芳香族化合物。6. The general formula (Where k represents 1 or 2, and Z ′ represents Is shown. Here, p represents an integer of 1 to 5, and * represents an asymmetric carbon atom. R represents a hydrogen atom or a hydroxyl-protecting group. However, the case where k and p are 1 and R is a hydrogen atom is excluded. ) An optically active aromatic compound represented by the formula:
性な芳香族化合物。7. The optically active aromatic compound according to claim 6, wherein R is a hydrogen atom.
体。8. The method according to claim 1, wherein Z is The optically active aromatic carboxylic acid derivative according to claim 1, which is:
ン酸誘導体。9. When Z is The optically active aromatic carboxylic acid derivative according to claim 1, wherein p is 1.
ン酸誘導体。10. Z is The optically active aromatic carboxylic acid derivative according to claim 1, wherein p is 2.
香族カルボン酸誘導体。11. When Z is The optically active aromatic carboxylic acid derivative according to claim 1, wherein p is an integer of 3 to 5.
基である請求項１記載の光学活性な芳香族カルボン酸誘
導体。12. The optically active aromatic carboxylic acid derivative according to claim 1, wherein Z is-(CH 2 ) p- and R 'is an optically active group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3339490A JP2903598B2 (en) | 1990-02-13 | 1990-02-13 | Optically active aromatic carboxylic acid derivative and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3339490A JP2903598B2 (en) | 1990-02-13 | 1990-02-13 | Optically active aromatic carboxylic acid derivative and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03236347A JPH03236347A (en) | 1991-10-22 |
| JP2903598B2 true JP2903598B2 (en) | 1999-06-07 |
Family
ID=12385376
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3339490A Expired - Lifetime JP2903598B2 (en) | 1990-02-13 | 1990-02-13 | Optically active aromatic carboxylic acid derivative and method for producing the same |
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| Country | Link |
|---|---|
| JP (1) | JP2903598B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL1015313C2 (en) | 2000-05-26 | 2001-11-27 | Dsm Nv | Process for the preparation of enantiomerically enriched esters and alcohols. |
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1990
- 1990-02-13 JP JP3339490A patent/JP2903598B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03236347A (en) | 1991-10-22 |
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