JPH033643B2 - - Google Patents
Info
- Publication number
- JPH033643B2 JPH033643B2 JP57009640A JP964082A JPH033643B2 JP H033643 B2 JPH033643 B2 JP H033643B2 JP 57009640 A JP57009640 A JP 57009640A JP 964082 A JP964082 A JP 964082A JP H033643 B2 JPH033643 B2 JP H033643B2
- Authority
- JP
- Japan
- Prior art keywords
- trans
- formula
- ethane
- mol
- ethyl
- 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
- 150000001875 compounds Chemical class 0.000 claims description 111
- 239000000203 mixture Substances 0.000 claims description 60
- 125000000217 alkyl group Chemical group 0.000 claims description 38
- 239000002253 acid Substances 0.000 claims description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000004973 liquid crystal related substance Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 230000032050 esterification Effects 0.000 claims description 12
- 238000005886 esterification reaction Methods 0.000 claims description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 11
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 150000007942 carboxylates Chemical class 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 52
- 230000008018 melting Effects 0.000 description 52
- 238000002844 melting Methods 0.000 description 52
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 42
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 35
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 125000004093 cyano group Chemical group *C#N 0.000 description 13
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- RGONNDWSVOCREF-UHFFFAOYSA-N 4-(5-pentylpyrimidin-2-yl)benzonitrile Chemical compound N1=CC(CCCCC)=CN=C1C1=CC=C(C#N)C=C1 RGONNDWSVOCREF-UHFFFAOYSA-N 0.000 description 11
- 125000003545 alkoxy group Chemical group 0.000 description 11
- 239000012074 organic phase Substances 0.000 description 11
- 230000008707 rearrangement Effects 0.000 description 11
- VSNGFYYRBATOTN-UHFFFAOYSA-N 4-(5-heptylpyrimidin-2-yl)benzonitrile Chemical compound N1=CC(CCCCCCC)=CN=C1C1=CC=C(C#N)C=C1 VSNGFYYRBATOTN-UHFFFAOYSA-N 0.000 description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 10
- YAZXDRDFNUEKBH-KOMQPUFPSA-N C1C[C@@H](CC)CC[C@@H]1C1=CN=C(C=2C=CC(=CC=2)C#N)N=C1 Chemical compound C1C[C@@H](CC)CC[C@@H]1C1=CN=C(C=2C=CC(=CC=2)C#N)N=C1 YAZXDRDFNUEKBH-KOMQPUFPSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 229910052938 sodium sulfate Inorganic materials 0.000 description 9
- 235000011152 sodium sulphate Nutrition 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- -1 acetal chloride Chemical class 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 230000009467 reduction Effects 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- ZZOKAIFIKJSLJJ-WGSAOQKQSA-N C(CC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)OCCCC Chemical compound C(CC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)OCCCC ZZOKAIFIKJSLJJ-WGSAOQKQSA-N 0.000 description 5
- ZAUPPIHFDVKVJM-IYARVYRRSA-N C1C[C@@H](CCCCC)CC[C@@H]1C(=O)OC1=CC=C(OCCC)C=C1 Chemical compound C1C[C@@H](CCCCC)CC[C@@H]1C(=O)OC1=CC=C(OCCC)C=C1 ZAUPPIHFDVKVJM-IYARVYRRSA-N 0.000 description 5
- LFGDFCLIVISJSO-WGSAOQKQSA-N C1C[C@@H](CCCCC)CC[C@@H]1CCC1=CC=C(OCC)C=C1 Chemical compound C1C[C@@H](CCCCC)CC[C@@H]1CCC1=CC=C(OCC)C=C1 LFGDFCLIVISJSO-WGSAOQKQSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 5
- 239000004990 Smectic liquid crystal Substances 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 5
- 230000005684 electric field Effects 0.000 description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- BALGERHMIXFENA-UHFFFAOYSA-N 4-butylcyclohexane-1-carboxylic acid Chemical compound CCCCC1CCC(C(O)=O)CC1 BALGERHMIXFENA-UHFFFAOYSA-N 0.000 description 4
- HJIVFZUPTYADSP-WKILWMFISA-N C1C[C@@H](CCCCC)CC[C@@H]1C(=O)OC1=CC=C(OC)C=C1 Chemical compound C1C[C@@H](CCCCC)CC[C@@H]1C(=O)OC1=CC=C(OC)C=C1 HJIVFZUPTYADSP-WKILWMFISA-N 0.000 description 4
- XIXOFKHADLKBQN-UAPYVXQJSA-N C1C[C@@H](CCCCC)CC[C@@H]1C1=CN=C(C=2C=CC(=CC=2)C#N)N=C1 Chemical compound C1C[C@@H](CCCCC)CC[C@@H]1C1=CN=C(C=2C=CC(=CC=2)C#N)N=C1 XIXOFKHADLKBQN-UAPYVXQJSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 4
- 230000010933 acylation Effects 0.000 description 4
- 238000005917 acylation reaction Methods 0.000 description 4
- 125000006241 alcohol protecting group Chemical group 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000003098 cholesteric effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 4
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 4
- 229940049953 phenylacetate Drugs 0.000 description 4
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 4
- 229950009215 phenylbutanoic acid Drugs 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- RVLAXPQGTRTHEV-UHFFFAOYSA-N 4-pentylcyclohexane-1-carboxylic acid Chemical compound CCCCCC1CCC(C(O)=O)CC1 RVLAXPQGTRTHEV-UHFFFAOYSA-N 0.000 description 3
- OBKXEAXTFZPCHS-UHFFFAOYSA-N 4-phenylbutyric acid Chemical compound OC(=O)CCCC1=CC=CC=C1 OBKXEAXTFZPCHS-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
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical group [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000007857 hydrazones Chemical class 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 230000017105 transposition Effects 0.000 description 3
- 125000005869 (methoxyethoxy)methanyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])OC([H])([H])* 0.000 description 2
- DHBXNPKRAUYBTH-UHFFFAOYSA-N 1,1-ethanedithiol Chemical compound CC(S)S DHBXNPKRAUYBTH-UHFFFAOYSA-N 0.000 description 2
- 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 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- YCOSWYBBIFLYBE-MEMLXQNLSA-N C(C)OC(C1=CC=C(C=C1)CC[C@@H]1CC[C@H](CC1)CCCCCCC)=O Chemical compound C(C)OC(C1=CC=C(C=C1)CC[C@@H]1CC[C@H](CC1)CCCCCCC)=O YCOSWYBBIFLYBE-MEMLXQNLSA-N 0.000 description 2
- XSNUDALZFTYIQL-AQYVVDRMSA-N C(C)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)C1=CC=C(C=C1)CCC Chemical compound C(C)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)C1=CC=C(C=C1)CCC XSNUDALZFTYIQL-AQYVVDRMSA-N 0.000 description 2
- VBOUAXTWYCBSHT-QAQDUYKDSA-N C(CC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)C(CC)=O Chemical compound C(CC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)C(CC)=O VBOUAXTWYCBSHT-QAQDUYKDSA-N 0.000 description 2
- USVMUDBJZMCIOM-WGSAOQKQSA-N C(CC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)C(CCCC)=O Chemical compound C(CC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)C(CCCC)=O USVMUDBJZMCIOM-WGSAOQKQSA-N 0.000 description 2
- PQDAIILQMXVNQA-AFARHQOCSA-N C(CC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)C1=CC=C(C=C1)CCC Chemical compound C(CC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)C1=CC=C(C=C1)CCC PQDAIILQMXVNQA-AFARHQOCSA-N 0.000 description 2
- BGTCHYVLENTKSG-YHBQERECSA-N C(CC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)C1=CC=C(C=C1)OCCCC Chemical compound C(CC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)C1=CC=C(C=C1)OCCCC BGTCHYVLENTKSG-YHBQERECSA-N 0.000 description 2
- CXZWKWQYEZMOJB-WKILWMFISA-N C(CCC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)O Chemical compound C(CCC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)O CXZWKWQYEZMOJB-WKILWMFISA-N 0.000 description 2
- OZQXBEHPCYKTEE-MEMLXQNLSA-N C(CCCC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)C(CCCC)=O Chemical compound C(CCCC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)C(CCCC)=O OZQXBEHPCYKTEE-MEMLXQNLSA-N 0.000 description 2
- NEKUQYNBNZLDSC-MEMLXQNLSA-N C(CCCCCC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)OCC Chemical compound C(CCCCCC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)OCC NEKUQYNBNZLDSC-MEMLXQNLSA-N 0.000 description 2
- APBBCFNZHALDSW-QAQDUYKDSA-N C1C[C@@H](CCC)CC[C@@H]1CCC1=CC=C(OCC)C=C1 Chemical compound C1C[C@@H](CCC)CC[C@@H]1CCC1=CC=C(OCC)C=C1 APBBCFNZHALDSW-QAQDUYKDSA-N 0.000 description 2
- VJMNQADPCKONIA-XUTJKUGGSA-N C1C[C@@H](CCCCCCC)CC[C@@H]1C1=CN=C(C=2C=CC(=CC=2)C#N)N=C1 Chemical compound C1C[C@@H](CCCCCCC)CC[C@@H]1C1=CN=C(C=2C=CC(=CC=2)C#N)N=C1 VJMNQADPCKONIA-XUTJKUGGSA-N 0.000 description 2
- GZWISYKEAHVUPV-ALOJWSFFSA-N CCCCCc1ccc(cc1)-c1ccc(CC[C@H]2CC[C@H](CCC)CC2)cc1 Chemical compound CCCCCc1ccc(cc1)-c1ccc(CC[C@H]2CC[C@H](CCC)CC2)cc1 GZWISYKEAHVUPV-ALOJWSFFSA-N 0.000 description 2
- ALMDBVQYNHIXSL-QAQDUYKDSA-N COC(C1=CC=C(C=C1)CC[C@@H]1CC[C@H](CC1)CCCC)=O Chemical compound COC(C1=CC=C(C=C1)CC[C@@H]1CC[C@H](CC1)CCCC)=O ALMDBVQYNHIXSL-QAQDUYKDSA-N 0.000 description 2
- AHATZBINIVESDD-MXVIHJGJSA-N COC(C1=CC=C(C=C1)CC[C@@H]1CC[C@H](CC1)CCCCCCC)=O Chemical compound COC(C1=CC=C(C=C1)CC[C@@H]1CC[C@H](CC1)CCCCCCC)=O AHATZBINIVESDD-MXVIHJGJSA-N 0.000 description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 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
- 239000011230 binding agent Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229910052717 sulfur Chemical group 0.000 description 2
- 239000011593 sulfur Chemical group 0.000 description 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- KWGRBVOPPLSCSI-WPRPVWTQSA-N (-)-ephedrine Chemical compound CN[C@@H](C)[C@H](O)C1=CC=CC=C1 KWGRBVOPPLSCSI-WPRPVWTQSA-N 0.000 description 1
- WUWDGVKUXDZLNU-UHFFFAOYSA-M (4-methoxycarbonylphenyl)methyl-triphenylphosphanium;bromide Chemical compound [Br-].C1=CC(C(=O)OC)=CC=C1C[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WUWDGVKUXDZLNU-UHFFFAOYSA-M 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- BIAAQBNMRITRDV-UHFFFAOYSA-N 1-(chloromethoxy)-2-methoxyethane Chemical compound COCCOCCl BIAAQBNMRITRDV-UHFFFAOYSA-N 0.000 description 1
- MUEHGEQAMLEEID-UHFFFAOYSA-N 1-pentyl-2-phenylbenzene Chemical group CCCCCC1=CC=CC=C1C1=CC=CC=C1 MUEHGEQAMLEEID-UHFFFAOYSA-N 0.000 description 1
- MAHPVQDVMLWUAG-UHFFFAOYSA-N 1-phenylhexan-1-one Chemical compound CCCCCC(=O)C1=CC=CC=C1 MAHPVQDVMLWUAG-UHFFFAOYSA-N 0.000 description 1
- WDRUBCBSUBXPSW-UHFFFAOYSA-N 2,4-diphenylpyrimidine Chemical compound C1=CC=CC=C1C1=CC=NC(C=2C=CC=CC=2)=N1 WDRUBCBSUBXPSW-UHFFFAOYSA-N 0.000 description 1
- KVBNAJRQLNFGGK-UHFFFAOYSA-N 2-(4-pentylcyclohexyl)acetic acid Chemical compound CCCCCC1CCC(CC(O)=O)CC1 KVBNAJRQLNFGGK-UHFFFAOYSA-N 0.000 description 1
- RUJHATQMIMUYKD-UHFFFAOYSA-N 2-naphthalen-1-ylethanamine Chemical compound C1=CC=C2C(CCN)=CC=CC2=C1 RUJHATQMIMUYKD-UHFFFAOYSA-N 0.000 description 1
- WLNDDIWESXCXHM-UHFFFAOYSA-N 2-phenyl-1,4-dioxane Chemical compound C1OCCOC1C1=CC=CC=C1 WLNDDIWESXCXHM-UHFFFAOYSA-N 0.000 description 1
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 1
- NSJNMAHQYWYRFF-UHFFFAOYSA-N 4-[2-(4-pentylcyclohexyl)ethyl]benzonitrile Chemical compound C1CC(CCCCC)CCC1CCC1=CC=C(C#N)C=C1 NSJNMAHQYWYRFF-UHFFFAOYSA-N 0.000 description 1
- JFKUBRAOUZEZSL-UHFFFAOYSA-N 4-butylbenzoic acid Chemical compound CCCCC1=CC=C(C(O)=O)C=C1 JFKUBRAOUZEZSL-UHFFFAOYSA-N 0.000 description 1
- BOOGLODHTHQEQO-UHFFFAOYSA-N 4-cyclohexyl-2-phenylpyrimidine Chemical compound C1CCCCC1C1=CC=NC(C=2C=CC=CC=2)=N1 BOOGLODHTHQEQO-UHFFFAOYSA-N 0.000 description 1
- QFFSAGSUDNLFFK-UHFFFAOYSA-N 4-pentylcyclohexane-1-carbaldehyde Chemical compound CCCCCC1CCC(C=O)CC1 QFFSAGSUDNLFFK-UHFFFAOYSA-N 0.000 description 1
- BPMBNLJJRKCCRT-UHFFFAOYSA-N 4-phenylbenzonitrile Chemical group C1=CC(C#N)=CC=C1C1=CC=CC=C1 BPMBNLJJRKCCRT-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- BLMSNGPJWDXDFD-MEMLXQNLSA-N C(C)OC(=O)C1=CC=C(C=C1)C1=CC=C(C=C1)CC[C@@H]1CC[C@H](CC1)CCC Chemical compound C(C)OC(=O)C1=CC=C(C=C1)C1=CC=C(C=C1)CC[C@@H]1CC[C@H](CC1)CCC BLMSNGPJWDXDFD-MEMLXQNLSA-N 0.000 description 1
- GDFSYQAHOIQVTI-YHBQERECSA-N C(C)OC(=O)C1=CC=C(C=C1)C1=CC=C(C=C1)CC[C@@H]1CC[C@H](CC1)CCCCC Chemical compound C(C)OC(=O)C1=CC=C(C=C1)C1=CC=C(C=C1)CC[C@@H]1CC[C@H](CC1)CCCCC GDFSYQAHOIQVTI-YHBQERECSA-N 0.000 description 1
- NEIWYDIFZLWXIP-IYARVYRRSA-N C(C)OC(C1=CC=C(C=C1)CC[C@@H]1CC[C@H](CC1)CCCC)=O Chemical compound C(C)OC(C1=CC=C(C=C1)CC[C@@H]1CC[C@H](CC1)CCCC)=O NEIWYDIFZLWXIP-IYARVYRRSA-N 0.000 description 1
- QGONNXNLGRNZCP-WGSAOQKQSA-N C(C)OC(C1=CC=C(C=C1)CC[C@@H]1CC[C@H](CC1)CCCCC)=O Chemical compound C(C)OC(C1=CC=C(C=C1)CC[C@@H]1CC[C@H](CC1)CCCCC)=O QGONNXNLGRNZCP-WGSAOQKQSA-N 0.000 description 1
- CLKKOLRZGRNHPL-HZCBDIJESA-N C(C)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)C1=CC=C(C=C1)OCCCC Chemical compound C(C)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)C1=CC=C(C=C1)OCCCC CLKKOLRZGRNHPL-HZCBDIJESA-N 0.000 description 1
- LNQZXVITRPDFPZ-WKILWMFISA-N C(C)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)OCC Chemical compound C(C)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)OCC LNQZXVITRPDFPZ-WKILWMFISA-N 0.000 description 1
- RBDXZOPPRMRGLC-IYARVYRRSA-N C(C)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)OCCCC Chemical compound C(C)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)OCCCC RBDXZOPPRMRGLC-IYARVYRRSA-N 0.000 description 1
- BCNXVGGLSXEOAQ-HZCBDIJESA-N C(CC)OC(=O)C1=CC=C(C=C1)C1=CC=C(C=C1)CC[C@@H]1CC[C@H](CC1)CCC Chemical compound C(CC)OC(=O)C1=CC=C(C=C1)C1=CC=C(C=C1)CC[C@@H]1CC[C@H](CC1)CCC BCNXVGGLSXEOAQ-HZCBDIJESA-N 0.000 description 1
- BWNDFVNPOSJBOM-IYARVYRRSA-N C(CC)OC(C1=CC=C(C=C1)CC[C@@H]1CC[C@H](CC1)CCC)=O Chemical compound C(CC)OC(C1=CC=C(C=C1)CC[C@@H]1CC[C@H](CC1)CCC)=O BWNDFVNPOSJBOM-IYARVYRRSA-N 0.000 description 1
- LRTULWLRXPQMAP-HZCBDIJESA-N C(CC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)C1=CC=C(C=C1)C(CCC)=O Chemical compound C(CC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)C1=CC=C(C=C1)C(CCC)=O LRTULWLRXPQMAP-HZCBDIJESA-N 0.000 description 1
- BHDVRRRGQXAIAH-MEMLXQNLSA-N C(CC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)C1=CC=C(C=C1)OCC Chemical compound C(CC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)C1=CC=C(C=C1)OCC BHDVRRRGQXAIAH-MEMLXQNLSA-N 0.000 description 1
- YVBAZHFVEGNIOK-IYARVYRRSA-N C(CC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)OCCC Chemical compound C(CC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)OCCC YVBAZHFVEGNIOK-IYARVYRRSA-N 0.000 description 1
- PZAJMLFNDWUZMY-QAQDUYKDSA-N C(CCC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)OC Chemical compound C(CCC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)OC PZAJMLFNDWUZMY-QAQDUYKDSA-N 0.000 description 1
- ZZNBLOLFOQAYLI-IYARVYRRSA-N C(CCC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)OCC Chemical compound C(CCC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)OCC ZZNBLOLFOQAYLI-IYARVYRRSA-N 0.000 description 1
- HMLFDDJOADSTQA-MXVIHJGJSA-N C(CCC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)OCCCC Chemical compound C(CCC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)OCCCC HMLFDDJOADSTQA-MXVIHJGJSA-N 0.000 description 1
- HNMWMONNGAMWDD-QAQDUYKDSA-N C(CCCC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C(=O)O)C=C1 Chemical compound C(CCCC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C(=O)O)C=C1 HNMWMONNGAMWDD-QAQDUYKDSA-N 0.000 description 1
- UZLCTLRNXAXLNZ-WGSAOQKQSA-N C(CCCC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)C(CC)=O Chemical compound C(CCCC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)C(CC)=O UZLCTLRNXAXLNZ-WGSAOQKQSA-N 0.000 description 1
- WBMVWPJHECDRBJ-SOAUALDESA-N C(CCCC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)C1=CC=C(C=C1)CCC Chemical compound C(CCCC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)C1=CC=C(C=C1)CCC WBMVWPJHECDRBJ-SOAUALDESA-N 0.000 description 1
- UILVEUAKLKEACA-YHBQERECSA-N C(CCCC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)C1=CC=C(C=C1)OCC Chemical compound C(CCCC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)C1=CC=C(C=C1)OCC UILVEUAKLKEACA-YHBQERECSA-N 0.000 description 1
- NNLNVBSFGDAURL-SOAUALDESA-N C(CCCC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)C1=CC=C(C=C1)OCCCC Chemical compound C(CCCC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)C1=CC=C(C=C1)OCCCC NNLNVBSFGDAURL-SOAUALDESA-N 0.000 description 1
- NJDGIFHHIWAVRF-AQYVVDRMSA-N C(CCCC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)CCC Chemical compound C(CCCC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)CCC NJDGIFHHIWAVRF-AQYVVDRMSA-N 0.000 description 1
- RAWYBDUBBUQRBZ-HCGLCNNCSA-N C(CCCC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)CCCCC Chemical compound C(CCCC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)CCCCC RAWYBDUBBUQRBZ-HCGLCNNCSA-N 0.000 description 1
- WGQURFYTYBSGOO-HCGLCNNCSA-N C(CCCC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)CCCCCC Chemical compound C(CCCC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)CCCCCC WGQURFYTYBSGOO-HCGLCNNCSA-N 0.000 description 1
- PZBBCQLBAYBZTE-IYARVYRRSA-N C(CCCC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)OC Chemical compound C(CCCC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)OC PZBBCQLBAYBZTE-IYARVYRRSA-N 0.000 description 1
- FSOVVXABMKBUNR-MEMLXQNLSA-N C(CCCC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)OCCCC Chemical compound C(CCCC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)OCCCC FSOVVXABMKBUNR-MEMLXQNLSA-N 0.000 description 1
- LPKGMNAEGKACDO-DALKXGRXSA-N C1=CC(CCCCC)=CC=C1[C@@H]1CC[C@@H](C(=O)O[C@@H]2CC[C@@H](CCC)CC2)CC1 Chemical compound C1=CC(CCCCC)=CC=C1[C@@H]1CC[C@@H](C(=O)O[C@@H]2CC[C@@H](CCC)CC2)CC1 LPKGMNAEGKACDO-DALKXGRXSA-N 0.000 description 1
- RZBSEGBMCJSSPZ-WGSAOQKQSA-N C1=CC(OCCCCC)=CC=C1OC(=O)[C@@H]1CC[C@@H](CCCC)CC1 Chemical compound C1=CC(OCCCCC)=CC=C1OC(=O)[C@@H]1CC[C@@H](CCCC)CC1 RZBSEGBMCJSSPZ-WGSAOQKQSA-N 0.000 description 1
- JAYBMJPZPJBTQZ-WKILWMFISA-N C1C[C@@H](CCCC)CC[C@@H]1C(=O)OC1=CC=C(OCC)C=C1 Chemical compound C1C[C@@H](CCCC)CC[C@@H]1C(=O)OC1=CC=C(OCC)C=C1 JAYBMJPZPJBTQZ-WKILWMFISA-N 0.000 description 1
- DHSGTSKRYFBIFX-RQNOJGIXSA-N C1C[C@@H](CCCCC)CC[C@@H]1CCC1=CC=C(C=2C=CC(CC)=CC=2)C=C1 Chemical compound C1C[C@@H](CCCCC)CC[C@@H]1CCC1=CC=C(C=2C=CC(CC)=CC=2)C=C1 DHSGTSKRYFBIFX-RQNOJGIXSA-N 0.000 description 1
- JTNGTRJQFQXTLA-HAQNSBGRSA-N CCCCC[C@H]1CC[C@H](CC(Cl)=O)CC1 Chemical compound CCCCC[C@H]1CC[C@H](CC(Cl)=O)CC1 JTNGTRJQFQXTLA-HAQNSBGRSA-N 0.000 description 1
- PBOPHFOJXCGSNK-DDDLIOIYSA-N CCCCC[C@H]1CC[C@H](CCC2=CC=C(C(CC)C(O)=O)C=C2)CC1 Chemical compound CCCCC[C@H]1CC[C@H](CCC2=CC=C(C(CC)C(O)=O)C=C2)CC1 PBOPHFOJXCGSNK-DDDLIOIYSA-N 0.000 description 1
- YJZKKMMYLYIFDY-IYARVYRRSA-N CCCCC[C@H]1CC[C@H](CCC2=CC=C(CC(O)=O)C=C2)CC1 Chemical compound CCCCC[C@H]1CC[C@H](CCC2=CC=C(CC(O)=O)C=C2)CC1 YJZKKMMYLYIFDY-IYARVYRRSA-N 0.000 description 1
- KRYCCZBVEALUFO-MXVIHJGJSA-N CCCCC[C@H]1CC[C@H](CCc2ccc(OCCC)cc2)CC1 Chemical compound CCCCC[C@H]1CC[C@H](CCc2ccc(OCCC)cc2)CC1 KRYCCZBVEALUFO-MXVIHJGJSA-N 0.000 description 1
- UNJFWNOSNPJDHO-QAQDUYKDSA-N CCCC[C@H]1CC[C@H](CCC2=CC=C(CC(O)=O)C=C2)CC1 Chemical compound CCCC[C@H]1CC[C@H](CCC2=CC=C(CC(O)=O)C=C2)CC1 UNJFWNOSNPJDHO-QAQDUYKDSA-N 0.000 description 1
- DLIMSNBHFCCRFY-HZCBDIJESA-N CCC[C@H]1CC[C@H](CCC(C=C2)=CC=C2C2=C(CCCC(O)=O)C=CC=C2)CC1 Chemical compound CCC[C@H]1CC[C@H](CCC(C=C2)=CC=C2C2=C(CCCC(O)=O)C=CC=C2)CC1 DLIMSNBHFCCRFY-HZCBDIJESA-N 0.000 description 1
- XGVLZNWUSXJSKH-MXVIHJGJSA-N CCC[C@H]1CC[C@H](CCC(C=C2)=CC=C2C2=CC=C(CC(O)=O)C=C2)CC1 Chemical compound CCC[C@H]1CC[C@H](CCC(C=C2)=CC=C2C2=CC=C(CC(O)=O)C=C2)CC1 XGVLZNWUSXJSKH-MXVIHJGJSA-N 0.000 description 1
- CBAIMVDQRGXLPS-MXVIHJGJSA-N COC(=O)C1=CC=C(C=C1)C1=CC=C(C=C1)CC[C@@H]1CC[C@H](CC1)CCC Chemical compound COC(=O)C1=CC=C(C=C1)C1=CC=C(C=C1)CC[C@@H]1CC[C@H](CC1)CCC CBAIMVDQRGXLPS-MXVIHJGJSA-N 0.000 description 1
- FRJKEVNBTAKFNS-HZCBDIJESA-N COC(=O)C1=CC=C(C=C1)C1=CC=C(C=C1)CC[C@@H]1CC[C@H](CC1)CCCCC Chemical compound COC(=O)C1=CC=C(C=C1)C1=CC=C(C=C1)CC[C@@H]1CC[C@H](CC1)CCCCC FRJKEVNBTAKFNS-HZCBDIJESA-N 0.000 description 1
- LHNDUERQGWBESL-IYARVYRRSA-N COC(C1=CC=C(C=C1)C=C[C@@H]1CC[C@H](CC1)CCCCC)=O Chemical compound COC(C1=CC=C(C=C1)C=C[C@@H]1CC[C@H](CC1)CCCCC)=O LHNDUERQGWBESL-IYARVYRRSA-N 0.000 description 1
- ASLRVFWGXAGRAF-SHTZXODSSA-N COC(C1=CC=C(C=C1)CC[C@@H]1CC[C@H](CC1)CC)=O Chemical compound COC(C1=CC=C(C=C1)CC[C@@H]1CC[C@H](CC1)CC)=O ASLRVFWGXAGRAF-SHTZXODSSA-N 0.000 description 1
- ZSDJJOYKKYYGMF-WKILWMFISA-N COC(C1=CC=C(C=C1)CC[C@@H]1CC[C@H](CC1)CCC)=O Chemical compound COC(C1=CC=C(C=C1)CC[C@@H]1CC[C@H](CC1)CCC)=O ZSDJJOYKKYYGMF-WKILWMFISA-N 0.000 description 1
- QQLNBRVLXWOJBX-IYARVYRRSA-N COC(C1=CC=C(C=C1)CC[C@@H]1CC[C@H](CC1)CCCCC)=O Chemical compound COC(C1=CC=C(C=C1)CC[C@@H]1CC[C@H](CC1)CCCCC)=O QQLNBRVLXWOJBX-IYARVYRRSA-N 0.000 description 1
- JKZTYEWRGDTWEO-WGSAOQKQSA-N COC(C1=CC=C(C=C1)CC[C@@H]1CC[C@H](CC1)CCCCCC)=O Chemical compound COC(C1=CC=C(C=C1)CC[C@@H]1CC[C@H](CC1)CCCCCC)=O JKZTYEWRGDTWEO-WGSAOQKQSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XJUZRXYOEPSWMB-UHFFFAOYSA-N Chloromethyl methyl ether Chemical compound COCCl XJUZRXYOEPSWMB-UHFFFAOYSA-N 0.000 description 1
- 238000006214 Clemmensen reduction reaction Methods 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical compound C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 description 1
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 238000006856 Wolf-Kishner-Huang Minlon reduction reaction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- SYKNUAWMBRIEKB-UHFFFAOYSA-N [Cl].[Br] Chemical compound [Cl].[Br] SYKNUAWMBRIEKB-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- WJGAPUXHSQQWQF-UHFFFAOYSA-N acetic acid;hydrochloride Chemical compound Cl.CC(O)=O WJGAPUXHSQQWQF-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 1
- GAUZCKBSTZFWCT-UHFFFAOYSA-N azoxybenzene Chemical compound C=1C=CC=CC=1[N+]([O-])=NC1=CC=CC=C1 GAUZCKBSTZFWCT-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- DVECBJCOGJRVPX-UHFFFAOYSA-N butyryl chloride Chemical compound CCCC(Cl)=O DVECBJCOGJRVPX-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 229940061627 chloromethyl methyl ether Drugs 0.000 description 1
- VZWXIQHBIQLMPN-UHFFFAOYSA-N chromane Chemical compound C1=CC=C2CCCOC2=C1 VZWXIQHBIQLMPN-UHFFFAOYSA-N 0.000 description 1
- KMPWYEUPVWOPIM-KODHJQJWSA-N cinchonidine Chemical compound C1=CC=C2C([C@H]([C@H]3[N@]4CC[C@H]([C@H](C4)C=C)C3)O)=CC=NC2=C1 KMPWYEUPVWOPIM-KODHJQJWSA-N 0.000 description 1
- KMPWYEUPVWOPIM-UHFFFAOYSA-N cinchonidine Natural products C1=CC=C2C(C(C3N4CCC(C(C4)C=C)C3)O)=CC=NC2=C1 KMPWYEUPVWOPIM-UHFFFAOYSA-N 0.000 description 1
- 150000001851 cinnamic acid derivatives Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- IGARGHRYKHJQSM-UHFFFAOYSA-N cyclohexylbenzene Chemical compound C1CCCCC1C1=CC=CC=C1 IGARGHRYKHJQSM-UHFFFAOYSA-N 0.000 description 1
- KWGRBVOPPLSCSI-UHFFFAOYSA-N d-ephedrine Natural products CNC(C)C(O)C1=CC=CC=C1 KWGRBVOPPLSCSI-UHFFFAOYSA-N 0.000 description 1
- 125000004855 decalinyl group Chemical group C1(CCCC2CCCCC12)* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005661 deetherification reaction Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229960002179 ephedrine Drugs 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RIFGWPKJUGCATF-UHFFFAOYSA-N ethyl chloroformate Chemical compound CCOC(Cl)=O RIFGWPKJUGCATF-UHFFFAOYSA-N 0.000 description 1
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- OHMBHFSEKCCCBW-UHFFFAOYSA-N hexane-2,5-diol Chemical compound CC(O)CCC(C)O OHMBHFSEKCCCBW-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 description 1
- OPYYWWIJPHKUDZ-UHFFFAOYSA-N phenyl cyclohexanecarboxylate Chemical compound C1CCCCC1C(=O)OC1=CC=CC=C1 OPYYWWIJPHKUDZ-UHFFFAOYSA-N 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- NNBZCPXTIHJBJL-UHFFFAOYSA-N trans-decahydronaphthalene Natural products C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 1
- NNBZCPXTIHJBJL-MGCOHNPYSA-N trans-decalin Chemical compound C1CCC[C@@H]2CCCC[C@H]21 NNBZCPXTIHJBJL-MGCOHNPYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 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
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/38—Acyl halides
- C07C53/44—Acyl halides containing rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/001—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by modification in a side chain
- C07C37/002—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by modification in a side chain by transformation of a functional group, e.g. oxo, carboxyl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/21—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing rings other than six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/782—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic
- C07C49/792—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic containing rings other than six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/132—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen containing rings
- C07C53/134—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen containing rings monocyclic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3028—Cyclohexane rings in which at least two rings are linked by a carbon chain containing carbon to carbon single bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3028—Cyclohexane rings in which at least two rings are linked by a carbon chain containing carbon to carbon single bonds
- C09K2019/3036—Cy-C2H4-Ph
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3028—Cyclohexane rings in which at least two rings are linked by a carbon chain containing carbon to carbon single bonds
- C09K2019/304—Cy-C2H4-Ph-Ph
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
Description
ãçºæã®è©³çŽ°ãªèª¬æã
æ¬çºæã«äžè¬åŒ
åŒäžãR2ã¯åºâR5ãâOR3ãâCOâOR3ãŸãã¯
ââCOâR3ã®äžã€ãè¡šãããR1åã³R3ã¯ççŽ
ååïŒã12åãå«ãçŽéç¶ã®ã¢ã«ãã«åºãè¡šã
ãããããŠïœã¯æ°ïŒãŸãã¯ïŒã®äžã€ãè¡šããã
ã®æ°èŠãªïŒãã©ã³ã¹âïŒâã¢ã«ãã«ã·ã¯ãããã·
ã«ïŒãšã¿ã³é¡ã«é¢ããã[Detailed Description of the Invention] The present invention has a general formula In the formula, R 2 represents one of the groups -R 5 , -OR 3 , -CO-OR 3 or -O-CO-R 3 , and R 1 and R 3 are linear chains containing 1 to 12 carbon atoms. The present invention relates to novel (trans-4-alkylcyclohexyl)ethanes, wherein the formula represents an alkyl group of the form, and n represents one of the numbers 1 or 2.
ãŸããæ¬çºæã¯åŒã®ååç©ã®è£œé æ¹æ³ã該å
åç©ãå«ã液æ¶æ··åç©äžŠã³ã«é»åâå
åŠè£
眮ã«ã
ãããã®çšéã«é¢ããã The invention also relates to a process for the preparation of compounds of the formula, to liquid crystal mixtures containing said compounds and to their use in electro-optical devices.
æ¬æ现æžã«ãããŠçšãããçŽéç¶ã®ã¢ã«ãã«
åºããªãèªã«ã¯åºã¡ãã«ããšãã«ããããã«ãã
ãã«ããã³ãã«ãããã·ã«ããããã«ããªã¯ã
ã«ãããã«ããã·ã«ããŠã³ãã·ã«åã³ããã·ã«ã
å
å«ãããã As used herein, the term "straight chain alkyl group" includes the groups methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl.
æ¬çºæã«ãããååç©ã¯æ¶²æ¶æ··åç©ã®æåãšã
ãŠç¹ã«äŸ¡å€ãããã該ååç©ã®å€§éšåã¯ããèªäœ
液æ¶ããããã€ãã¯ïŒnematicïŒåã³ïŒãŸãã¯ã¹
ã¡ã¯ãã€ãã¯ïŒsmecticïŒãç¹æ§ãæããã The compounds according to the invention are of particular value as components of liquid-crystalline mixtures, most of which have themselves liquid-crystalline (nematic and/or smectic) properties.
æ¬çºæã«ãããååç©ã¯å
šãŠã®æ¢ç¥ã®æ¶²æ¶ãšæ··
åæ§ã§ãããå
šãŠã®æ®éã®é»åâå
åŠè£
眮ã«çšã
ãããšãã§ããäžè¬ã«æ··åç©æåã®éžæã¯ç¹å®ã®
䜿çšç®çã«äŸåãããããããªãããæ¬çºæã«ã
ããååç©ã¯å¥œãŸããã¯èªé»çã®æ£ã®ç°æ¹æ§
ïŒÎµ11ïŒÎµâ¥ãäœãε11ã¯ååã®çžŠè»žã«æ²¿ãèªé»ç
ãè¡šãããεâ¥ã¯ããã«åçŽãªèªé»çãè¡šããïŒ
ãæãããããã€ãã¯åã³ã³ã¬ã¹ããªãã¯
ïŒcholestricïŒæ··åç©ã補é ããéã«çšããããã The compounds according to the invention are miscible with all known liquid crystals and can be used in all common electro-optical devices, the choice of mixture components generally depending on the particular purpose of use. However, the compounds according to the invention preferably have a positive anisotropy of dielectric constant (ε 11 >εâ¥, where ε 11 represents the dielectric constant along the longitudinal axis of the molecule and ε⥠represents the dielectric constant perpendicular to this). )
used in the production of nematic and cholesteric mixtures with
ãããæ··åç©ã¯é»å Žã«ãããŠããèªäœãé»å Žã®
æ¹åãšå¹³è¡ã«ãã®æã倧ããèªé»çã®æ¹åïŒå³ã¡
ãã®çžŠè»žïŒã§é
åããããã®å¹æã¯ãªãã§ãããž
ãšãŒã»ãšããã»ãã€ã«ãã€ã¢ïŒJ.H.HeilmeierïŒ
åã³ãšã«ã»ãšãŒã»ã¶ããïŒL.A.ZanoniïŒ
ïŒApplied Physics Letters13ã91ïŒ1968ïŒãæãã¯
ãã€ãŒã»ãšã«ã»ãã¯ã€ãïŒD.L.WhiteïŒåã³ãž
ãŒã»ãšãã»ãã€ã©ãŒïŒG.N.TaylorïŒãJ.Appl.
Phys.45ã4718ïŒ1974ïŒãã«ããå ±åãããŠããå
没ååïŒembedded moleculesïŒåã³æ¶²æ¶ååé
ã®çžäºäœçšãã²ã¹ãâãã¹ãïŒguestâhostïŒçž
äºäœçšãã«çšãããããèªé»å Žé
åã®æŽã«éèŠãª
é©çšã¯ããšã ã»ã·ã€ããïŒM.SchadtïŒåã³ãã
ãªãŠãŒã»ããªããªããïŒW.HelfrichïŒãApplied
Physics Letters18ã127ïŒ1971ïŒãã«ãã€ãŠçºèŠã
ããå転ã»ã«ïŒrotation cellïŒäžŠã³ã«Molecular
Crystals and Liqiud Crystals17ã355ïŒ1972ïŒã«
èšèŒãããã±ã«ã»ã»ã«ïŒKerr cellïŒã§ããã Such a mixture orients itself in an electric field with its direction of greatest dielectric constant (ie its longitudinal axis) parallel to the direction of the electric field. This effect has been demonstrated by JHHeilmeier, among others.
and LAZanoni
(Applied Letter Physics 13 , 91 (1968)) or DL White and GNTaylor [J.Appl.
Phys. 45 , 4718 (1974)] is used for the interaction between embedded molecules and liquid crystal molecules (guest-host interaction). A further important application of dielectric field orientation is M. Schadt and W. Helfrich [Applied
Physics Letters 18, 127 (1971)] discovered the rotation cell and molecular
Kerr cell described in Crystals and Liqiud Crystals 17 , 355 (1972).
é»åâå
åŠå転ã»ã«ã¯æ¬è³ªçã«éæãªé»æ¥µãæ
ããã³ã³ãã³ãµãŒã§ããããã®èªé»äœã¯Îµ11ïŒÎµ
â¥ããã€ãããã€ã¯çµæ¶ããçããã液æ¶ã®åå
ã®çžŠè»žã¯é»å Žã®ãªãç¶æ
ã§ã¯ã³ã³ãã³ãµãŒã»ãã¬
ãŒãéã«ããããç¶æ
ã§é
åããããã®ãããæ§
é ïŒtwisting strucureïŒã¯ååã®äžããããå£
é
åïŒwall orientionïŒã«ãã€ãŠæ±ºå®ããããã³
ã³ãã³ãµãŒã»ãã¬ãŒãã«é»äœãäžããéãååã¯
ããèªäœãé»å Žã®æ¹åã«ãããŠãã®çžŠè»žã«æŽã
ïŒå³ã¡ãã¬ãŒãã®é¢ã«åçŽïŒãããã«ãã€ãŠåå
ã¯
ãã¯ãèªé»äœã«ãããŠå転ããªãïŒæ¶²æ¶ã¯ãã¬ãŒ
ãã®é¢ã«å¯ŸããŠå軞çã«åçŽã«ãªãïŒããã®å¹æ
ã¯å¯éçã§ããããããŠã³ã³ãã³ãµãŒã®å
åŠçé
éçãé»æ°çã«èª¿ç¯ããããã«çšããããšãã§ã
ãã An electro-optical rotating cell is essentially a capacitor with transparent electrodes whose dielectric has ε 11 >ε
It arises from nematic crystals with â¥. The longitudinal axes of the liquid crystal molecules are arranged in a twisted manner between the capacitor plates in the absence of an electric field, and this twisting structure is determined by the given wall orientation of the molecules. When a potential is applied to the capacitor plates, the molecules align themselves with their longitudinal axes in the direction of the electric field (i.e. perpendicular to the plane of the plates), so that the polarized light no longer rotates in the dielectric (the liquid crystal is uniaxially perpendicular to the plane). This effect is reversible and can be used to electrically adjust the optical transmission of the capacitor.
æŽã«ãèªé»çã®æ£ã®ç°æ¹æ§ããã€ãããã€ã¯æ¶²
æ¶ã®ãããªãã¯ã¹ã«ã³ã¬ã¹ããªãã¯ç©è³ªïŒãŸãã¯
æ··åç©å
šäœã液æ¶æ§ãä¿æããéããäžè¬ã«å¯æº¶
æ§ã®å
åŠç掻æ§ç©è³ªïŒãå ããããšã«ãããã³ã¬
ã¹ããªãã¯æ··åç©ãèªå°ããããã®ãã®ã¯é»å Žã«
é©çšããéã«ãã³ã¬ã¹ããªãã¯âãããã€ãã¯çž
転äœïŒçžâå€åå¹æïŒãåããããšãç¥ãããŠã
ããã³ã¬ã¹ããªãã¯æ·»å ç©ã®æ¿åºŠãé©åœã«éžæã
ãããšã«ããããããæ··åç©ã¯ãŸãå転ã»ã«æ瀺
åšã®é»åâå
åŠç¹æ§ãæ¹åããããã«çšããããš
ãã§ããã Furthermore, a cholesteric mixture is induced by adding a cholesteric substance (or generally a soluble optically active substance, as long as the entire mixture retains liquid crystallinity) to a matrix of nematic liquid crystals with positive anisotropy of dielectric constant, They are known to undergo cholesteric-nematic phase transitions (phase-change effects) when applied to an electric field. By appropriately selecting the concentration of cholesteric additives, such mixtures can also be used to improve the electro-optical properties of rotating cell indicators.
é©ãã¹ãããšã«ä»åãæ¬çºæã«ãããååç©ã¯
äœç²åºŠãæãã液æ¶ååç©ã§ããããšãããã€
ããïœãïŒãè¡šããåŒã®ååç©ã¯ç¹ã«äœç²åºŠå
ã³æ¯èŒçã«äœèç¹ãæããŠãããæŽã«èç¹ã¯åºŠã
倧ããéå·åŽå¯èœã§ãããåŸã€ãŠãæ¬ååç©ã¯ãª
ãã§ã液æ¶æ··åç©ã®ç²åºŠåã³èç¹ãäœäžãããã
ãã«é©ããŠãããäžæ¹ãïœãïŒãè¡šããåŒã®å
åç©ã¯å€§ããªäžéçžç¯å²ã瀺ãããããã®ååç©
ã¯ãªãã§ãäœç²æ§æ··åç©ã®éæç¹ãé«ããããã«
é©ããŠãããããã«ãã€ãŠç²åºŠã¯å¢å€§ããªããæ
ãã¯ãããã®ã¿å¢å€§ããã Surprisingly, it has now been found that the compound in the present invention is a liquid crystal compound with low viscosity. Compounds of the formula in which n represents 1 have particularly low viscosities and relatively low melting points. Furthermore, the melting point is often large and can be supercooled. The compounds are therefore particularly suitable for lowering the viscosity and melting point of liquid-crystal mixtures. On the other hand, compounds of the formula where n represents 2 exhibit a large mesophase range. These compounds are particularly suitable for increasing the clearing point of low-viscosity mixtures, so that the viscosity does not increase or increases only slightly.
æ¬çºæã«ãããååç©ã¯æŽã«è¯å¥œãªååŠçå®å®
æ§ãæããããšãç¡è²ã§ããããšåã³é«åºŠã®UV
âå®å®æ§ãæããããšã«ç¹è²ãããã The compounds of the present invention further have good chemical stability, are colorless and have high UV resistance.
- It is characterized by its stability.
åŒã®ååç©ã®äžã§ãR2ãåºâR3ãâOR3ãŸã
ã¯âCOâOR3ãè¡šããååç©ã奜ãŸãããR2ã
ã¢ã«ãã«åºâR3ãŸãã¯ã¢ã«ã³ãã·åºâOR3ãè¡š
ããåŒã®ååç©ãç¹ã«å¥œãŸãããæŽã«ïœãïŒã
è¡šããåŒã®ååç©ã奜ãŸãããåºR3ã¯å¥œãŸã
ãã¯ççŽ ååïŒã10åãå«ãçŽéç¶ã®ã¢ã«ãã«
åºãç¹ã«ççŽ ååïŒãïŒåãå«ãçŽéç¶ã®ã¢ã«ã
ã«åºã§ãããæŽã«ççŽ ååïŒã10åãæããåº
R1ã奜ãŸãããççŽ ååïŒãïŒåãå«ããã®ã
ç¹ã«å¥œãŸããã Among the compounds of the formula, preference is given to those in which R2 represents the group -R3 , -OR3 or -CO- OR3 . Particularly preferred are compounds of the formula in which R 2 represents an alkyl group -R 3 or an alkoxy group -OR 3 . Furthermore, compounds of the formula in which n represents 1 are preferred. The radical R 3 is preferably a straight-chain alkyl group containing 1 to 10 carbon atoms, especially a straight-chain alkyl group containing 1 to 7 carbon atoms. Furthermore, groups having 2 to 10 carbon atoms
R 1 is preferred, and those containing 3 to 7 carbon atoms are particularly preferred.
奜ãŸããåŒã®ååç©ã®äŸãšããŠæ¬¡ã®ãã®ãæ
ãããšãã§ããïŒ
ïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâãããã«ããšãã«ïŒãšã¿ã³ã
ïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâãã³ãã«ããšãã«ïŒãšã¿ã³ã
ïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâããã·ã«ããšãã«ïŒãšã¿ã³ã
ïŒâïŒãã©ã³ã¹âïŒâããã«ã·ã¯ãããã·ã«ïŒâ
ïŒâïŒïœâãããã«ããšãã«ïŒãšã¿ã³ã
ïŒâïŒãã©ã³ã¹âïŒâããã«ã·ã¯ãããã·ã«ïŒâ
ïŒâïŒïœâãã³ãã«ããšãã«ïŒãšã¿ã³ã
ïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâãããã«ããšãã«ïŒãšã¿ã³ã
ïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâãã³ãã«ããšãã«ïŒãšã¿ã³ã
ïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâããã·ã«ããšãã«ïŒãšã¿ã³ã
ïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâãããã«ããšãã«ïŒãšã¿ã³ã
ïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâããã«ããšãã«ïŒãšã¿ã³ã
ïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâãã³ãã«ããšãã«ïŒãšã¿ã³ã
ïŒâïŒãã©ã³ã¹âïŒâãšãã«ã·ã¯ãããã·ã«ïŒâ
ïŒâïŒïœâãšããã·ããšãã«ïŒãšã¿ã³ã
ïŒâïŒãã©ã³ã¹âïŒâãšãã«ã·ã¯ãããã·ã«ïŒâ
ïŒâïŒïœâããã«ãªãã·ããšãã«ïŒãšã¿ã³ã
ïŒâïŒãã©ã³ã¹âïŒâãšãã«ã·ã¯ãããã·ã«ïŒâ
ïŒâïŒïœâããã·ã«ãªãã·ããšãã«ïŒãšã¿ã³ã
ïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâã¡ããã·ããšãã«ïŒãšã¿ã³ã
ïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâãšããã·ããšãã«ïŒãšã¿ã³ã
ïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâãããã«ãªãã·ããšãã«ïŒãšã¿ã³ã
ïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâããã«ãªãã·ããšãã«ïŒãšã¿ã³ã
ïŒâïŒãã©ã³ã¹âïŒâããã«ã·ã¯ãããã·ã«ïŒâ
ïŒâïŒïœâã¡ããã·ããšãã«ïŒãšã¿ã³ã
ïŒâïŒãã©ã³ã¹âïŒâããã«ã·ã¯ãããã·ã«ïŒâ
ïŒâïŒïœâãšãšããã·ããšãã«ïŒãšã¿ã³ã
ïŒâïŒãã©ã³ã¹âïŒâããã«ã·ã¯ãããã·ã«ïŒâ
ïŒâïŒïœâããã«ãªãã·ããšãã«ïŒãšã¿ã³ã
ïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâã¡ããã·ããšãã«ïŒãšã¿ã³ã
ïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâãšããã·ããšãã«ïŒãšã¿ã³ã
ïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâãããã«ãªãã·ããšãã«ïŒãšã¿ã³ã
ïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâããã«ãªãã·ããšãã«ïŒãšã¿ã³ã
ïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâã¡ããã·ããšãã«ïŒãšã¿ã³ã
ïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâãšããã·ããšãã«ïŒãšã¿ã³ã
ïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâããã«ãªãã·ããšãã«ïŒãšã¿ã³ã
ïœâãïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ããã
ã·ã«ïŒâïŒâãšãã«ãããšãã«ã¢ã»ããŒãã
ïœâãïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ããã
ã·ã«ïŒâïŒâãšãã«ãããšãã«ããã¬ãŒãã
ïœâãïŒâïŒãã©ã³ã¹âïŒâããã«ã·ã¯ãããã·
ã«ïŒâïŒâãšãã«ãããšãã«ã¢ã»ããŒãã
ïœâãïŒâïŒãã©ã³ã¹âïŒâããã«ã·ã¯ãããã·
ã«ïŒâïŒâãšãã«ãããšãã«ããã¬ãŒãã
ïœâãïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ããã
ã·ã«ïŒâïŒâãšãã«ãããšãã«ã¢ã»ããŒãã
ïœâãïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ããã
ã·ã«ïŒâïŒâãšãã«ãããšãã«ããã¬ãŒãã
ïœâãïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ããã
ã·ã«ïŒâïŒâãšãã«ãããšãã«ã¢ã»ããŒãã
ïœâãïŒâïŒãã©ã³ã¹âïŒâãšãã«ã·ã¯ãããã·
ã«ïŒâïŒâãšãã«ãå®æ¯éŠé
žã¡ãã«ãšã¹ãã«ã
ïœâãïŒâïŒãã©ã³ã¹âïŒâãšãã«ã·ã¯ãããã·
ã«ïŒâïŒâãšãã«ãå®æ¯éŠé
žãšãã«ãšã¹ãã«ã
ïœâãïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ããã
ã·ã«ïŒâïŒâãšãã«ãå®æ¯éŠé
žã¡ãã«ãšã¹ãã«ã
ïœâãïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ããã
ã·ã«ïŒâïŒâãšãã«ãå®æ¯éŠé
žãšãã«ãšã¹ãã«ã
ïœâãïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ããã
ã·ã«ïŒâïŒâãšãã«ãå®æ¯éŠé
žãããã«ãšã¹ãã«ã
ïœâãïŒâïŒãã©ã³ã¹âïŒâããã«ã·ã¯ãããã·
ã«ïŒâïŒâãšãã«ãå®æ¯éŠé
žã¡ãã«ãšã¹ãã«ã
ïœâãïŒâïŒãã©ã³ã¹âïŒâããã«ã·ã¯ãããã·
ã«ïŒâïŒâãšãã«ãå®æ¯éŠé
žãšãã«ãšã¹ãã«ã
ïœâãïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ããã
ã·ã«ïŒâïŒâãšãã«ãå®æ¯éŠé
žã¡ãã«ãšã¹ãã«ã
ïœâãïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ããã
ã·ã«ïŒâïŒâãšãã«ãå®æ¯éŠé
žãšãã«ãšã¹ãã«ã
ïœâãïŒâïŒãã©ã³ã¹âïŒâããã·ã«ã·ã¯ããã
ã·ã«ïŒâïŒâãšãã«ãå®æ¯éŠé
žã¡ãã«ãšã¹ãã«ã
ïœâãïŒâïŒãã©ã³ã¹âïŒâããã·ã«ã·ã¯ããã
ã·ã«ïŒâïŒâãšãã«ãå®æ¯éŠé
žãšãã«ãšã¹ãã«ã
ïœâãïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ããã
ã·ã«ïŒâïŒâãšãã«ãå®æ¯éŠé
žã¡ãã«ãšã¹ãã«ã
ïœâãïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ããã
ã·ã«ïŒâïŒâãšãã«ãå®æ¯éŠé
žãšãã«ãšã¹ãã«ã
ïœâãïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ããã
ã·ã«ïŒâïŒâãšãã«ãããããªããšãã³ã
ïœâãïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ããã
ã·ã«ïŒâïŒâãšãã«ããã¬ãããšãã³ã
ïœâãïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ããã
ã·ã«ïŒâïŒâãšãã«ãããããªããšãã³ã
ïœâãïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ããã
ã·ã«ïŒâïŒâãšãã«ããã¬ãããšãã³ã
ïœâãïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ããã
ã·ã«ïŒâïŒâãšãã«ããããµããšãã³ã
ïŒâïŒãã©ã³ã¹âïŒâãšãã«ã·ã¯ãããã·ã«ïŒâ
ïŒâïŒ4â²âãããã«âïŒâãããšããªã«ïŒãšã¿ã³ã
ïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒ4â²âãããã«âïŒâãããšããªã«ïŒãšã¿
ã³ã
ïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒ4â²âãããã«âïŒâãããšããªã«ïŒãšã¿
ã³ã
ïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒ4â²âãã³ãã«âïŒâãããšããªã«ïŒãšã¿
ã³ã
ïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒ4â²âãšãã«âïŒâãããšããªã«ïŒãšã¿ã³ã
ïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒ4â²âãããã«âïŒâãããšããªã«ïŒãšã¿
ã³ã
ïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒ4â²âãã³ãã«âïŒâãããšããªã«ïŒãšã¿
ã³ã
ïŒâïŒãã©ã³ã¹âïŒâãšãã«ã·ã¯ãããã·ã«ïŒâ
ïŒâïŒ4â²âããã«ãªãã·âïŒâãããšããªã«ïŒãš
ã¿ã³ã
ïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒ4â²âãšããã·âïŒâãããšããªã«ïŒãšã¿
ã³ã
ïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒ4â²âããã«ãªãã·âïŒâãããšããªã«ïŒ
ãšã¿ã³ã
ïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒ4â²âãšããã·âïŒâãããšããªã«ïŒãšã¿
ã³ã
ïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒ4â²âããã«ãªãã·âïŒâãããšããªã«ïŒ
ãšã¿ã³ã
4â²ãïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ãããã·
ã«ïŒâïŒâãšãã«ãâïŒâãããšããªã«âã¢ã»ããŒ
ãã
4â²âãïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ããã
ã·ã«ïŒâïŒâãšãã«ãâïŒâãããšããªã«âããã¬
ãŒãã
4â²âãïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ããã
ã·ã«ïŒâïŒâãšãã«ãâïŒâãããšããªã«âã«ã«ã
ã³é
žã¡ãã«ãšã¹ãã«ã
4â²âãïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ããã
ã·ã«ïŒâïŒâãšãã«ãâïŒâãããšããªã«âã«ã«ã
ã³é
žãšãã«ãšã¹ãã«ã
4â²âãïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ããã
ã·ã«ïŒâïŒâãšãã«ãâïŒâãããšããªã«âã«ã«ã
ã³é
žãããã«ãšã¹ãã«ã
4â²âãïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ããã
ã·ã«ïŒâïŒâãšãã«ãâïŒâãããšããªã«âã«ã«ã
ã³é
žã¡ãã«ãšã¹ãã«ã
4â²âãïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ããã
ã·ã«ïŒâïŒâãšãã«ãâïŒâãããšãã«âã«ã«ãã³
é
žãšãã«ãšã¹ãã«åã³ã
ïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒ4â²âãããªã«âïŒâãããšããªã«ïŒãšã¿
ã³ã As examples of compounds of the preferred formula, the following may be mentioned: 2-(trans-4-propylcyclohexyl)
-1-(p-propylphenyl)ethane, 2-(trans-4-propylcyclohexyl)
-1-(p-pentylphenyl)ethane, 2-(trans-4-propylcyclohexyl)
-1-(p-hexylphenyl)ethane, 2-(trans-4-butylcyclohexyl)-
1-(p-propylphenyl)ethane, 2-(trans-4-butylcyclohexyl)-
1-(p-pentylphenyl)ethane, 2-(trans-4-pentylcyclohexyl)
-1-(p-propylphenyl)ethane, 2-(trans-4-pentylcyclohexyl)
-1-(p-pentylphenyl)ethane, 2-(trans-4-pentylcyclohexyl)
-1-(p-hexylphenyl)ethane, 2-(trans-4-heptylcyclohexyl)
-1-(p-propylphenyl)ethane, 2-(trans-4-heptylcyclohexyl)
-1-(p-butylphenyl)ethane, 2-(trans-4-heptylcyclohexyl)
-1-(p-pentylphenyl)ethane, 2-(trans-4-ethylcyclohexyl)-
1-(p-ethoxyphenyl)ethane, 2-(trans-4-ethylcyclohexyl)-
1-(p-butyloxyphenyl)ethane, 2-(trans-4-ethylcyclohexyl)-
1-(p-hexyloxyphenyl)ethane, 2-(trans-4-propylcyclohexyl)
-1-(p-methoxyphenyl)ethane, 2-(trans-4-propylcyclohexyl)
-1-(p-ethoxyphenyl)ethane, 2-(trans-4-propylcyclohexyl)
-1-(p-propyloxyphenyl)ethane, 2-(trans-4-propylcyclohexyl)
-1-(p-butyloxyphenyl)ethane, 2-(trans-4-butylcyclohexyl)-
1-(p-methoxyphenyl)ethane, 2-(trans-4-butylcyclohexyl)-
1-(p-ethoxyphenyl)ethane, 2-(trans-4-butylcyclohexyl)-
1-(p-butyloxyphenyl)ethane, 2-(trans-4-pentylcyclohexyl)
-1-(p-methoxyphenyl)ethane, 2-(trans-4-pentylcyclohexyl)
-1-(p-ethoxyphenyl)ethane, 2-(trans-4-pentylcyclohexyl)
-1-(p-propyloxyphenyl)ethane, 2-(trans-4-pentylcyclohexyl)
-1-(p-butyloxyphenyl)ethane, 2-(trans-4-hebutylcyclohexyl)
-1-(p-methoxyphenyl)ethane, 2-(trans-4-hebutylcyclohexyl)
-1-(p-ethoxyphenyl)ethane, 2-(trans-4-hebutylcyclohexyl)
-1-(p-butyloxyphenyl)ethane, p-[2-(trans-4-propylcyclohexyl)-1-ethyl]phenylacetate, p-[2-(trans-4-propylcyclohexyl)-1 -ethyl]phenylbutyrate, p-[2-(trans-4-butylcyclohexyl)-1-ethyl]phenylacetate, p-[2-(trans-4-butylcyclohexyl)-1-ethyl]phenyl butyrate, p-[2-(trans-4-pentylcyclohexyl)-1-ethyl]phenylacetate, p-[2-(trans-4-pentylcyclohexyl)-1-ethyl]phenylbutyrate, p- [2-(trans-4-heptylcyclohexyl)-1-ethyl]phenylacetate, p-[2-(trans-4-ethylcyclohexyl)-1-ethyl]benzoic acid methyl ester, p-[2-(trans -4-ethylcyclohexyl)-1-ethyl]benzoic acid ethyl ester, p-[2-(trans-4-propylcyclohexyl)-1-ethyl]benzoic acid methyl ester, p-[2-(trans-4-propyl) cyclohexyl)-1-ethyl]benzoic acid ethyl ester, p-[2-(trans-4-propylcyclohexyl)-1-ethyl]benzoic acid propyl ester, p-[2-(trans-4-butylcyclohexyl)-1 -ethyl]benzoic acid methyl ester, p-[2-(trans-4-butylcyclohexyl)-1-ethyl]benzoic acid ethyl ester, p-[2-(trans-4-pentylcyclohexyl)-1-ethyl]benzoic acid acid methyl ester, p-[2-(trans-4-pentylcyclohexyl)-1-ethyl]benzoic acid ethyl ester, p-[2-(trans-4-hexylcyclohexyl)-1-ethyl]benzoic acid methyl ester, p-[2-(trans-4-heptylcyclohexyl)-1-ethyl]benzoic acid ethyl ester, p-[2-(trans-4-heptylcyclohexyl)-1-ethyl]benzoic acid methyl ester, p-[2 -(trans-4-heptylcyclohexyl)-1-ethyl]benzoic acid ethyl ester, p-[2-(trans-4-propylcyclohexyl)-1-ethyl]propiophenone, p-[2-(trans-4 -propylcyclohexyl)-1-ethyl]valerophenone, p-[2-(trans-4-pentylcyclohexyl)-1-ethyl]propiophenone, p-[2-(trans-4-pentylcyclohexyl)-1-ethyl ] Valerophenone, p-[2-(trans-4-pentylcyclohexyl)-1-ethyl]hexaphenone, 2-(trans-4-ethylcyclohexyl)-
1-(4'-propyl-4-biphenylyl)ethane, 2-(trans-4-propylcyclohexyl)
-1-(4'-propyl-4-biphenylyl)ethane, 2-(trans-4-propylcyclohexyl)
-1-(4'-propyl-4-biphenylyl)ethane, 2-(trans-4-propylcyclohexyl)
-1-(4'-pentyl-4-biphenylyl)ethane, 2-(trans-4-pentylcyclohexyl)
-1-(4'-ethyl-4-biphenylyl)ethane, 2-(trans-4-pentylcyclohexyl)
-1-(4'-propyl-4-biphenylyl)ethane, 2-(trans-4-pentylcyclohexyl)
-1-(4'-bentyl-4-biphenylyl)ethane, 2-(trans-4-ethylcyclohexyl)-
1-(4'-butyloxy-4-biphenylyl)ethane, 2-(trans-4-propylcyclohexyl)
-1-(4'-ethoxy-4-biphenylyl)ethane, 2-(trans-4-propylcyclohexyl)
-1-(4'-butyloxy-4-biphenylyl)
Ethane, 2-(trans-4-pentylcyclohexyl)
-1-(4'-ethoxy-4-biphenylyl)ethane, 2-(trans-4-pentylcyclohexyl)
-1-(4'-butyloxy-4-biphenylyl)
Ethane, 4'[2-(trans-4-propylcyclohexyl)-1-ethyl]-4-biphenylyl-acetate, 4'-[2-(trans-4-propylcyclohexyl)-1-ethyl]-4-biphenylyl -butyrate, 4'-[2-(trans-4-propylcyclohexyl)-1-ethyl]-4-biphenylyl-carboxylic acid methyl ester, 4'-[2-(trans-4-propylcyclohexyl)-1-ethyl ]-4-biphenylyl-carboxylic acid ethyl ester, 4'-[2-(trans-4-propylcyclohexyl)-1-ethyl]-4-biphenylyl-carboxylic acid propyl ester, 4'-[2-(trans-4 -pentylcyclohexyl)-1-ethyl]-4-biphenylyl-carboxylic acid methyl ester, 4'-[2-(trans-4-pentylcyclohexyl)-1-ethyl]-4-biphenyl-carboxylic acid ethyl ester, and 2 -(trans-4-propylcyclohexyl)
-1-(4'-butyryl-4-biphenylyl)ethane.
åŒã®ååç©ã¯ãæ¬çºæã«åŸãã°ãäžè¬åŒ
åŒäžãR4ã¯æ°ŽçŽ ãããããã·ãããã²ã³ãŸã
ã¯åºâR3ãããã¯âOR3ãè¡šããããããŠR1ã
R3åã³ïœã¯äžèšã®æå³ãæããã
ã®ååç©ãéå
ãããããŠR4ãæ°ŽçŽ ãè¡šããå Ž
åã«ã¯ãçããäžè¬åŒ
åŒäžãR1ãR4åã³ïœã¯äžèšã®æå³ãæããã
ã®ååç©ãã¢ã·ã«åããããR4ãããããã·ã
è¡šããå Žåã«ã¯ãçããåŒã®ååç©ãåŒ
R3COOHã®ã«ã«ãã³é
žãããã¯ãã®åå¿æ§èªå°
äœã§ãšã¹ãã«åããããæãã¯R4ãããã²ã³ã
è¡šããå Žåã«ã¯ãçããåŒã®ååç©ããã°ãã·
ãŠã ãšã次ãã§äºé
žåççŽ ãšåå¿ãããåŸããã
ã«ã«ããã·ã¬ãŒããå æ°Žå解ãããããŠçããé
ž
ãŸãã¯ãã®åå¿æ§èªå°äœãåŒR3OHã®ã¢ã«ã³ãŒã«
ã§ãšã¹ãã«åããããšã«ãã€ãŠè£œé ããããšãã§
ããã According to the invention, compounds of the general formula In the formula, R 4 represents hydrogen, hydroxy, halogen or a group -R 3 or -OR 3 , and R 1 ,
When reducing the compound in which R 3 and n have the meanings given above, and R 4 represents hydrogen, the resulting general formula wherein R 1 , R 4 and n have the meanings given above, or when R 4 represents hydroxy, the resulting compound of formula
Esterification with a carboxylic acid of R 3 COOH or a reactive derivative thereof or, if R 4 represents a halogen, the resulting compound of formula is reacted with magnesium and then with carbon dioxide and the resulting carboxylate is hydrolyzed. and esterification of the resulting acid or reactive derivative thereof with an alcohol of formula R 3 OH.
åŒã®ååç©ã®éå
ã¯ããèªäœå
¬ç¥ã®æ¹æ³ã«åŸ
ã€ãŠè¡ãããšãã§ããã奜ãŸããã¯åŒã®ååç©
ãå¡©åºïŒäŸãã°æ°Žé
žåã«ãªãŠã ããããªãŠã ãšã
ã¬ãŒããã«ãªãŠã ïœâããã¬ãŒãçïŒã®ååšäžã«
ãããŠäžæŽ»æ§ææ©æº¶åªäŸãã°ãžã¡ãã«ã¹ã«ããã·
ããŸãã¯ã¢ã«ã³ãŒã«ïŒäŸãã°ãšã¿ããŒã«ããžãšã
ã¬ã³ã°ãªã³ãŒã«ãããªãšãã¬ã³ã°ãªã³ãŒã«çïŒäž
ã«ãŠããã©ãžã³ãšåå¿ããã次ãã§çããããã©
ãŸã³ãå解ãããäžè¬ã«çããããã©ãŸã³ã¯ææž©
äžïŒäŸãã°çŽ200âïŒã§ã®ã¿å解ãããããããª
ãã溶åªãšããŠãžã¡ãã«ã¹ã«ããã·ããçšããå Ž
åããã®å解ã¯åºŠã
宀枩ã§ãã§ã«çããã奜ãŸã
ãå
·äœäŸãšããŠã¯ããã®éå
ã¯ãã³ã°ãŒãã³ãã³
ïŒHuangâMinlonïŒæ³ã«è¡ã€ãŠãäŸãã°è©²ã±ãã³
ãããã©ãžã³æ°Žåç©åã³æ°Žé
žåã«ãªãŠã ãšå
±ã«ã
æ°Žãšæ··åãåŸãé«æ²žç¹æº¶åªïŒäŸãã°ãžãšãã¬ã³ã°
ãªã³ãŒã«ãŸãã¯ããªãšãã¬ã³ã°ãªã³ãŒã«ïŒäžã«ãŠ
éæµäžã§å ç±ããç¶ããŠããã©ãŸã³ãå解ãããŸ
ã§æ°ŽãèžçãããããŠéå
ãçµäºãããŸã§éæµäž
ã§æ²žéš°ãç¶ããããšã«ãã€ãŠè¡ãããã Reduction of compounds of the formula can be carried out according to methods known per se. Preferably, a compound of formula is prepared in an inert organic solvent such as dimethyl sulfoxide or an alcohol (such as ethanol, diethylene glycol, triethylene glycol, etc.) in the presence of a base (such as potassium hydroxide, sodium ethylate, potassium t-butyrate, etc.). React with hydrazine and then decompose the resulting hydrazone. Generally occurring hydrazones decompose only at elevated temperatures (eg about 200°C). However, when using dimethyl sulfoxide as solvent, this decomposition often occurs already at room temperature. In a preferred embodiment, this reduction is carried out by the Huang-Minlon method, such as by combining the ketone with hydrazine hydrate and potassium hydroxide.
Heating under reflux in a water-miscible high-boiling solvent (e.g. diethylene glycol or triethylene glycol), followed by distillation of the water until the hydrazone decomposes, and continued boiling under reflux until the reduction is complete. It is carried out by.
åŒã®ååç©ãéå
ããéã«æŽã«å¥œãŸããæ¹æ³
ã¯ã¯ã¬ã¡ã³ãŒã³ïŒClemmensenïŒéå
ã§ãããã
ã®æ¹æ³ã«åŸãã°ãã±ãã³ãã¢ãã«ã¬ã åããäºé
åã³å¡©é
žãšå
±ã«å æž©ãããå¿
èŠã«å¿ããŠææ©æº¶åª
äŸãã°ãšã¿ããŒã«ãé
¢é
žããžãªããµã³ããã«ãšã³
çãå ããããšãã§ããã A more preferred method for reducing compounds of formula is Clemmensen reduction. According to this method, ketones are heated with amalgamated zinc and hydrochloric acid. An organic solvent such as ethanol, acetic acid, dioxane, toluene, etc. can be added as necessary.
æŽã«ãR4ãæ°ŽçŽ ãŸãã¯ã¢ã«ãã«åºãè¡šããåŒ
ã®ååç©ã¯æ¥è§Šæ°ŽçŽ æ·»å ã«ãã€ãŠéå
ããããš
ãã§ããããã®æ°ŽçŽ æ·»å ã¯å¿
èŠã«å¿ããŠäžæŽ»æ§æ
äœç©è³ªïŒäŸãã°ççŽ ïŒã«æ
æãããéåžžã®æ°ŽçŽ æ·»
å 觊åªïŒäŸãã°ãã©ãžãŠã ãçœéãã©ãâããã±
ã«çïŒãçšããŠè¡ãããšãã§ããããã©ãžãŠã å
ã³çœéã奜ãŸãã觊åªã§ããã䜿çšãã溶åªã¯äž
掻æ§ææ©æº¶åªäŸãã°é£œåã¢ã«ã³ãŒã«ããšãŒãã«ã
ãšã¹ãã«ãã«ã«ãã³é
žãçåæ°ŽçŽ çïŒäŸãã°ãšã¿
ããŒã«ããžãªããµã³ãé
¢é
žãšãã«ãæ°·é
¢é
žãŸãã¯
ãããµã³ïŒã§ããããšãã§ããããã®æ¥è§Šæ°ŽçŽ æ·»
å ã«ãããŠæž©åºŠåã³å§åã¯èšççã§ã¯ãªãã宀枩
ä¹è³æ··åç©ã®æ²žç¹éã®æž©åºŠåã³çŽïŒãçŽïŒæ°å§ã®
å§åãæå©ã«çšããããã Furthermore, compounds of the formula in which R 4 represents hydrogen or an alkyl group can be reduced by catalytic hydrogenation. This hydrogenation can optionally be carried out using conventional hydrogenation catalysts (eg palladium, platinum, Raney-nickel, etc.) supported on an inert support material (eg carbon). Palladium and platinum are preferred catalysts. The solvent used is an inert organic solvent such as saturated alcohol, ether,
It can be an ester, a carboxylic acid, a hydrocarbon, etc. (eg ethanol, dioxane, ethyl acetate, glacial acetic acid or hexane). Temperature and pressure are not critical in this catalytic hydrogenation. Temperatures between room temperature and the boiling point of the mixture and pressures of about 1 to about 5 atmospheres are advantageously employed.
ãŸããR4ãæ°ŽçŽ ãŸãã¯ã¢ã«ãã«åºãè¡šããåŒ
ã®ååç©ã®éå
ã¯ã該ååç©ãã¢ã«ã«ã³ããªãŒ
ã«ãŸãã¯ã¢ã«ã«ã³ãžããªãŒã«ïŒäŸãã°ãšã¿ã³ããª
ãŒã«ãïŒïŒïŒâãããã³ãžããªãŒã«ããšã¿ã³ãžã
ãªãŒã«çïŒãšåå¿ããã次ã«åŸãããããªã±ã¿ãŒ
ã«ãã©ãâããã±ã«ã«ããæ¥è§Šæ°ŽçŽ æ·»å ã«ãã€ãŠ
é¢è±ãããŠè¡ãããšãã§ããã奜ãŸããããªãŒã«
ã¯ïŒïŒïŒâãããã³ãžããªãŒã«ãããŠç¹ã«ãšã¿ã³
ãžããªãŒã«ã§ããããã®ãã®ã¯ç°åŒããªã±ã¿ãŒã«
ãçãããããªã±ã¿ãŒã«ã®çæã¯äŸãã°äžããå
ããŠçŽ ãšãŒãã¬ãŒãã«ãã€ãŠè§Šåªããããæå©ã«
ã¯ãããªã±ã¿ãŒã«ã®è£œé åã³æ°ŽçŽ æ·»å ã¯äžæŽ»æ§æ
æ©æº¶åªäŸãã°ãžãšãã«ãšãŒãã«ããžãªããµã³ãå¡©
åã¡ãã¬ã³ãã¯ãããã«ã çäžã«ãŠè¡ãããïŒã
ãããªãããçšããããªãŒã«ã液äœã§ããå Žåã«
ã¯ããã®ãã®ã¯åæã«æº¶åªãšããŠã®åœ¹å²ãæãã
ãšãã§ãããå§ååã³æž©åºŠã¯èšççã§ã¯ãªãïŒå€§
æ°å§åã³å®€æž©ãæå©ã«çšããããã Further, reduction of a compound of the formula in which R 4 represents hydrogen or an alkyl group can be carried out by reacting the compound with an alkanethiol or alkanedithiol (e.g., ethanethiol, 1,3-propanedithiol, ethanedithiol, etc.), and then This can be done by removing the thioketal by catalytic hydrogenation with Raney-nickel. Preferred thiols are 1,3-propanedithiol and especially ethanedithiol, which yields cyclic thioketals. The formation of thioketals is catalyzed, for example, by boron trifluoride etherate. Advantageously, the preparation and hydrogenation of the thioketal is carried out in an inert organic solvent such as diethyl ether, dioxane, methylene chloride, chloroform, etc.; however, if the thiol used is a liquid, it is simultaneously used as a solvent. can play the role of Pressure and temperature are not critical; atmospheric pressure and room temperature are advantageously used.
R4ãåºâR3ãŸãã¯âOR3ãè¡šããåŒã®åå
ç©ã¯äžèšã®éå
ã«ãã€ãŠçŽæ¥åŒã®å¯Ÿå¿ããåå
ç©ã«è»¢åãããïŒå³ã¡åŒã®ååç©ããã®å Žåã®
ç®ççæç©ã§ããïŒãäžæ¹ãR4ãæ°ŽçŽ ããããã
ã·ãŸãã¯ããã²ã³ãè¡šããåŒã®ååç©ãåŒã®
ååç©ã«éå
åŸã«æŽã«åå¿ãããªããã°ãªããª
ãã Compounds of the formula in which R 4 represents the group -R 3 or -OR 3 are directly converted to the corresponding compounds of the formula by the reduction described above (ie the compound of the formula is the desired product in this case). On the other hand, compounds of the formula in which R 4 represents hydrogen, hydroxy or halogen must be further reacted after reduction to the compound of the formula.
R4ãæ°ŽçŽ ãè¡šããåŒã®ååç©ã®ã¢ã·ã«åã¯
ããªãŒãã«âã¯ã©ããã»ã¢ã·ã«åã«å¯Ÿããããèª
äœå
¬ç¥ã®æ¹æ³ã«åŸã€ãŠãã«ã€ã¹ïŒLewisïŒé
žäŸã
ã°äžå¡©åã¢ã«ãããŠã ãåå¡©åã¹ãºãäžããåã
ãŠçŽ çã奜ãŸããã¯äžå¡©åã¢ã«ãããŠã ã®ååšäž
ã«ãããŠãã«ã«ãã³é
žã¯ãã©ã€ãããããã€ããŸ
ãã¯ç¡æ°Žç©ã奜ãŸããã¯å¯Ÿå¿ããã«ã«ãã³é
žã¯ã
ã©ã€ããšã®åå¿ã«ãã€ãŠè¡ãããšãã§ããããã®
åå¿ã¯äžæŽ»æ§ææ©æº¶åªãäŸãã°äºç¡«åççŽ ãŸãã¯
å¡©çŽ åãããçåæ°ŽçŽ ã奜ãŸããã¯å¡©åã¡ãã¬ã³
ãŸãã¯ã¯ãããã«ã äžã«ãŠè¡ãããããã®åå¿ã¯
æå©ã«ã¯çŽïŒâä¹è³åå¿æ··åç©ã®éæµæž©åºŠéã§è¡
ããããå§åã¯èšççã§ã¯ãªãããã®åå¿ã¯å€§æ°
å§åã³å®€æž©ã§æå©ã«è¡ãããã Acylation of compounds of the formula in which R 4 represents hydrogen is carried out according to methods known per se for Friedel-Crafts acylation using Lewis acids such as aluminum trichloride, tin tetrachloride, boron trifluoride, etc. This can be carried out by reaction with a carboxylic acid chloride, bromide or anhydride, preferably the corresponding carboxylic acid chloride, preferably in the presence of aluminum trichloride. The reaction is carried out in an inert organic solvent, such as carbon disulfide or a chlorinated hydrocarbon, preferably methylene chloride or chloroform. The reaction is advantageously carried out between about 0°C and the reflux temperature of the reaction mixture. Pressure is not critical; the reaction is advantageously carried out at atmospheric pressure and room temperature.
R4ãããããã·ãè¡šããåŒã®ååç©ã®åŒ
R3COOHã®ã¢ã«ã«ã³ã«ã«ãã³é
žãŸãã¯ãã®åå¿
æ§èªå°äœïŒäŸãã°ç¡æ°Žç©ãŸãã¯é
žããã²ã³åç©ïŒ
ã«ãããšã¹ãã«åã¯ããèªäœå
¬ç¥ã®æ¹æ³ã«ãããŠ
è¡ãããšãã§ãããã«ã«ãã³é
žã«ããã¢ã«ã³ãŒã«
ã®ãšã¹ãã«åã¯äžæŽ»æ§ææ©æº¶åªã®ååšäžã«ãããŠ
ãŸãã¯è©²æº¶åªãçšããã«ã觊åªéã®åŒ·é
žïŒäŸãã°
ç¡«é
žãŸãã¯ããã²ã³åæ°ŽçŽ é
žïŒã®ååšäžã«ãããŠ
æå©ã«è¡ããããããããªãããŸãããã®ãšã¹ã
ã«åã¯ïŒ®ïŒNâ²âãžã·ã¯ãããã·ã«ã«ã«ããžã€ã
ãåã³ïŒâïŒãžã¡ãã«ã¢ããïŒâããªãžã³ã®ååšäž
ã«ãããŠè¡ãããšãã§ãããããããªããã奜ãŸ
ããæ¹æ³ã¯é
žå¡©åç©ã«ããã¢ã«ã³ãŒã«ã®ãšã¹ãã«
åã§ããããã®ãšã¹ãã«åã¯äžæŽ»æ§ææ©æº¶åªäŸã
ã°ãžãšãã«ãšãŒãã«ãŸãã¯ããã©ããããã©ã³ã®
åŠããšãŒãã«ããžã¡ãã«ãã«ã ã¢ããããã³ãŒ
ã³ããã«ãšã³ãã·ã¯ããããµã³ãåå¡©åççŽ çäž
ã§æå©ã«è¡ãããããšã¹ãã«åäžã«éé¢ããå¡©å
æ°ŽçŽ ãçµåãããããã«ãé
žçµåå€ïŒäŸãã°ç¬¬äž
çŽã¢ãã³ãããªãžã³çïŒãçšããããšãæå©ã§ã
ããé
žçµåå€ã倧éå°éã§çšããããšã奜ãŸã
ããåŸã€ãŠé
žçµåå€ãåæã«æº¶åªãšããŠã®åœ¹å²ã
æãããšãã§ããã枩床åã³å§åã¯èšççã§ã¯ãª
ããäžè¬ã«ãã®ãšã¹ãã«åã¯å€§æ°å§åã³å®€æž©ä¹è³
æ··åç©ã®æ²žç¹éã®æž©åºŠã§è¡ãããããŸããR4ã
ããããã·ãè¡šããåŒã®ååç©ã¯ãåŒã®å¯Ÿå¿
ããååç©ã®ä»£ãã«ãããèªäœå
¬ç¥ã®ãšãŒãã«é
è£æ³ã«åŸã€ãŠR4ãã¢ã«ã³ãã·ãè¡šããåŒã®å
åç©ããåŸãããšãã§ããã Formula of a compound in which R 4 represents hydroxy
R 3 COOH alkanecarboxylic acid or its reactive derivative (e.g. anhydride or acid halide)
The esterification can be carried out in a manner known per se. The esterification of alcohols with carboxylic acids is advantageously carried out in the presence of catalytic amounts of strong acids (for example sulfuric acid or hydrohalic acids), with or without inert organic solvents. However, the esterification can also be carried out in the presence of N,N'-dicyclohexylcarbodiimide and 4-(dimethylamino)-pyridine. However, a preferred method is esterification of alcohols with acid chlorides. This esterification is advantageously carried out in an inert organic solvent such as an ether such as diethyl ether or tetrahydrofuran, dimethylformamide, benzene, toluene, cyclohexane, carbon tetrachloride and the like. It is advantageous to use acid binders (eg tertiary amines, pyridine, etc.) to bind the hydrogen chloride liberated during esterification. It is preferred to use a large excess of the acid binder, so that it can simultaneously serve as a solvent. Temperature and pressure are not critical, and generally the esterification is carried out at atmospheric pressure and a temperature between room temperature and the boiling point of the mixture. Compounds of the formula in which R 4 represents hydroxy can also be obtained from compounds of the formula in which R 4 represents alkoxy, instead of the corresponding compounds of the formula, according to ether cleavage methods known per se.
R4ãããã²ã³ãè¡šããåŒã®ååç©ã¯ããèª
äœå
¬ç¥ã®æ¹æ³ã«ãããŠãã°ãã·ãŠã ã«ãã察å¿ã
ãã°ãªãã¢ãŒã«ååç©ã«è»¢åããããšãã§ããã
çšãã溶åªã¯æå©ã«ã¯ãšãŒãã«ã奜ãŸããã¯ãžãš
ãã«ãšãŒãã«ãŸãã¯ããã©ããããã©ã³ã§ããã
ãã®åå¿ãè¡ãå§ååã³æž©åºŠã¯èšççã§ã¯ãªãã
äžè¬ã«ãã®åå¿ã¯å€§æ°å§åã³çŽïŒâä¹è³åå¿æ··å
ç©ã®éå
枩床éã奜ãŸããã¯ã»ãŒå®€æž©ã§è¡ãã
ããæ¬æ现æžã«ãããŠçšãããããã²ã³ããªãèª
ã¯å¡©çŽ èçŽ ãŸãã¯ãšãŠçŽ ãç¹ã«èçŽ ãè¡šããã Compounds of the formula in which R 4 represents halogen can be converted into the corresponding Grignard compounds with magnesium in methods known per se.
The solvent used is advantageously an ether, preferably diethyl ether or tetrahydrofuran.
The pressure and temperature at which this reaction is conducted are not critical.
Generally, the reaction is conducted at atmospheric pressure and between about 0° C. and the reducing temperature of the reaction mixture, preferably at about room temperature. The term "halogen" as used herein refers to chlorine bromine or iodine, especially bromine.
åŸãããã°ãªãã¢ãŒã«ååç©ãäºé
žåççŽ ã«ã
ã€ãŠå¯Ÿå¿ããã«ã«ããã·ã¬ãŒãã«è»¢åããããšã
ã§ãã次ãã§ãã®ãã®ãã«ã«ãã³é
žã«å æ°Žå解ã
ãããšãã§ãããäºé
žåççŽ ãšã®åå¿ã¯ãäžèšã®
åŠãããŠåŸãããã°ãªãã¢ãŒã«ååç©ã®æº¶æ¶²äžã«
çŽïŒâã§äºé
žåççŽ ã¬ã¹ãå°å
¥ãããããŸãã¯è©²
溶液ããã©ã€ã¢ã€ã¹äžã«æ³šãããšã«ãã€ãŠæå©ã«
è¡ããããã«ã«ããã·ã¬ãŒãã®å æ°Žå解ã¯åŒ·é
žã
奜ãŸããã¯åžéç¡æ©é
žäŸãã°å¡©é
žãç¡é
žçãçšã
ãŠè¡ãããšãã§ããã The Grignard compounds obtained can be converted with carbon dioxide to the corresponding carboxylates, which can then be hydrolyzed to the carboxylic acids. The reaction with carbon dioxide is advantageously carried out by introducing carbon dioxide gas at about 0° C. into the solution of the Grignard compound obtained as described above, or by pouring the solution onto dry ice. Hydrolysis of carboxylates is performed using strong acids,
Preferably, this can be carried out using a diluted inorganic acid such as hydrochloric acid or nitric acid.
çããé
žãŸãã¯å¯Ÿå¿ããé
žããã²ã³åç©ããã
ã¯ç¡æ°Žç©ã®åŒR3OHã®ã¢ã«ã«ããŒã«ã«ãããšã¹ã
ã«åã¯äžèšã®ãšã¹ãã«åãšåæ§ã®æ¹æ³ã§è¡ãããš
ãã§ãããé
žããã²ã³åç©åã³ç¡æ°Žç©ã¯ããèªäœ
å
¬ç¥ã®æ¹æ³ã«ãããŠè£œé ããããšãã§ããïŒäŸã
ã°é
žå¡©åç©ã¯è©²é
žãäžå¡©åãªã³ãäºå¡©åãªã³ãå¡©
åããªãã«çãšã®åå¿ã«ãã€ãŠåŸãããç¡æ°Žç©ã¯
該é
žãé
¢é
žç¡æ°Žç©ãã¢ã»ã¿ã«ã¯ãã©ã€ãããšãã«
ã¯ãããã«ã¡ãŒãçãšåå¿ãããŠåŸãããããŸã
ã¡ãã«ãšã¹ãã«ã¯å¯Ÿå¿ããã«ã«ãã³é
žãäžæŽ»æ§æ
æ©æº¶åªã奜ãŸããã¯ãžãšãã«ãšãŒãã«äžã«ãŠãžã¢
ãŸã¡ã¿ã³ãšåå¿ãããŠåŸãããšãã§ããã Esterification of the resulting acid or the corresponding acid halide or anhydride of formula R 3 OH with an alkanol can be carried out in a similar manner to the esterification described above. Acid halides and anhydrides can be prepared in a manner known per se; for example, acid chlorides are obtained by reacting the acids with phosphorus trichloride, phosphorus pentachloride, thionyl chloride, etc.; It is obtained by reacting the acid with acetic anhydride, acetal chloride, ethyl chloroformate, etc. Methyl esters can also be obtained by reacting the corresponding carboxylic acids with diazomethane in an inert organic solvent, preferably diethyl ether.
åºçºç©è³ªãšããŠçšããåŒã®ååç©ã¯äžè¬åŒ
åŒäžãR4åã³ïœã¯äžèšã®æå³ãæããã
ã®ååç©ãäžè¬åŒ
åŒäžãR1ã¯äžèšã®æå³ãæããã
ã®ååç©ããèªå°ãããé
žå¡©åç©ã§ã¢ã·ã«åããŠ
補é ããããšãã§ããããã®åå¿ã¯ããªãŒãã«â
ã¯ã©ããã»ã¢ã·ã«åã«å¯Ÿããããèªäœå
¬ç¥ã®æ¹æ³
ïŒåã³ç¹ã«äžèšã®ããªãŒãã«âã¯ã©ããã»ã¢ã·ã«
åæ³ãšåæ§ïŒã«åŸã€ãŠè¡ãããšãã§ãããé
žå¡©å
ç©ã¯äŸãã°å¯Ÿå¿ããåŒã®é
žãå¡©åããªãã«ãšå
±
ã«å ç±ããŠè£œé ããããšãã§ããã The compound of the formula used as a starting material has the general formula In the formula, R 4 and n have the above meanings, and a compound of the general formula In the formula, R 1 has the above meaning, and can be produced by acylation with an acid chloride derived from the compound. This reaction is Friedel-
It can be carried out according to methods known per se for Crafts acylation (and in particular analogous to the Friedel-Crafts acylation method described above). Acid chlorides can be prepared, for example, by heating acids of the corresponding formula with thionyl chloride.
åŒåã³ã®ååç©ã¯å
¬ç¥ã§ãããããŸãã¯å
¬
ç¥ã®ååç©ã®åæäœã§ããã Compounds of formula and are known or are homologs of known compounds.
åŒã®ååç©ã¯ä»ã®æ¶²æ¶æãã¯é液æ¶ç©è³ªäŸã
ã°ã·ããïŒSchibbïŒå¡©åºãã¢ãŸãã³ãŒã³ãã¢ãŸ
ãã·ãã³ãŒã³ãå®æ¯éŠé
žããšãã«ãã·ã¯ããããµ
ã³ã«ã«ãã³é
žããšãã«ãšã¹ãã«ããããšãã«ãã¿
ãŒããšãã«ãããšãã«ã·ã¯ããããµã³ãã±ã€ç®é
ž
èªå°äœãããšãã«ããªããžã³ããžããšãã«ããªã
ãžã³ãããšãã«ãžãªããµã³ãã·ã¯ãããã·ã«ããš
ãã«ããªããžã³ãã·ã¯ãããã·ã«ãšã¿ã³çãšã®æ··
åç©ã®åœ¢æ
ã§çšããããšãã§ããããããååç©
ã¯åœè©²åéã«ç²Ÿéããè
ã«ãšã€ãŠã¯ããç¥ããã
å
¬ç¥ã®ååç©ã§ããïŒäŸãã°æ¬¡ã®ç¹èš±åç
§ïŒãã€
ãåœç¹èš±åºé¡å
¬éæ现æžç¬¬2306738å·ãå第
2306739å·ãå第2429093å·ãå第2356085å·ãå
第2636684å·ãå第2459374å·ãå第2547737å·ã
å第2641724å·ãå第2708276å·ãå第2811001å·ã
å第2922236å·ãæ±ãã€ãåœç¹èš±ç¬¬139852å·ãå
第139867å·ããšãŒãããç¹èš±åºé¡å
¬é第0014885
å·ãæŽã«ããããç©è³ªã®å€ãã®ãã®ã¯åžè²©ãããŠ
ããã Compounds of the formula may also contain other liquid crystal or non-liquid crystal substances such as Schibb base, azobenzene, azoxybenzene, phenyl benzoate, cyclohexanecarboxylic acid phenyl ester, biphenyl, terphenyl, phenylcyclohexane, cinnamic acid derivatives, phenyl It can be used in the form of a mixture with pyrimidine, diphenylpyrimidine, phenyldioxane, cyclohexylphenylpyrimidine, cyclohexylethane, and the like. Such compounds are well known compounds to those skilled in the art; see, for example, the following patents: DE-A-2306-738;
No. 2306739, No. 2429093, No. 2356085, No. 2636684, No. 2459374, No. 2547737,
Same No. 2641724, Same No. 2708276, Same No. 2811001,
East German Patent No. 2922236, East German Patent No. 139852, East German Patent No. 139867, European Patent Application Publication No. 0014885
issue. Additionally, many such materials are commercially available.
æ¬çºæã«ãããæ··åç©ã¯å ããŠãäžè¬åŒ
åŒäžãç°ïŒ¢ã¯é£œåãããŠãããããŸãã¯è³éŠæ
ã§ãããååšãåŸã飜åããç°ïŒ¢ã¯ç¬¬äºã®ç°ã«ã
ã©ã³ã¹âçµåããŠããïŒR13ã¯ççŽ ååïŒã11å
ãå«ãçŽéç¶ã®ã¢ã«ãã«ãŸãã¯ã¢ã«ã³ãã·åºãè¡š
ããïŒR14ã¯ã·ã¢ããççŽ ååïŒã11åãå«ãçŽ
éç¶ã®ã¢ã«ãã«ãäžè¬åŒ
ã®ãšã¹ãã«åºããŸãã¯ç°ïŒ¢ã飜åãããŠããå Žå
ã«ã¯ãè¿œå çã«ççŽ ååïŒã11åãå«ãçŽéç¶ã®
ã¢ã«ã³ãã·åºãè¡šããïŒããã«åŒXIIã®ãšã¹ãã«
åºã«ãããŠãç°ïŒ¡ã¯è³éŠæã§ãããã¯é
žçŽ ãŸã
ã¯ç¡«é»ãè¡šããããããŠR15ã¯ã·ã¢ããŸãã¯ççŽ
ååïŒã10åãå«ãçŽéç¶ã®ã¢ã«ãã«ãããã¯ã¢
ã«ã³ãã·åºãè¡šããããæãã¯ç°ïŒ¡ã¯ãã©ã³ã¹â
ïŒïŒïŒâäºçœ®æãããã·ã¯ããããµã³ç°ãè¡šã
ããã¯é
žçŽ ãè¡šããããããŠR15ã¯ã·ã¢ããŸã
ã¯ççŽ ååïŒã10åãå«ãçŽéç¶ã®ã¢ã«ãã«åºã
è¡šããïŒååšããã¢ã«ãã«åã³ïŒãŸãã¯ã¢ã«ã³ã
ã·åºã«ãããççŽ ååã®ç·æ°ã¯å€ããšã12åã§ã
ãã
ã®æ°ŽçŽ æ·»å ãããããã¿ã¬ã³åã³ïŒãŸãã¯äžè¬åŒ
åŒäžãR16ã¯ççŽ ååïŒã11åãå«ãçŽéç¶ã®
ã¢ã«ãã«åºãè¡šããïŒR17ã¯ã·ã¢ããççŽ ååïŒ
ã11åãå«ãçŽéç¶ã®ã¢ã«ãã«åºãŸãã¯äžèšåŒ
XIIã®ãšã¹ãã«åºãè¡šãããããã«ïŒžãåã³R15
ã¯äžèšã®æå³ãæãïŒãããŠååšããã¢ã«ãã«å
ã³ã¢ã«ã³ãã·åºã«ãããççŽ ååã®ç·æ°ã¯å€ããš
ã12åã§ããã
ã®ãã³ãŸãªããµã³åã³ïŒãŸãã¯äžè¬åŒ
åŒäžãèšå·ïŒ¹ã¯çªçŽ ãè¡šããããããŠèšå·ïŒºã¯
ïŒCHâãè¡šããããæãã¯èšå·ïŒºã¯çªçŽ ãè¡šã
ãããããŠèšå·ïŒ¹ã¯ïŒCHâãè¡šãããR18ã¯ã¢
ã«ãã«ãè¡šããããããŠR19ã¯ã·ã¢ããã¢ã«ã
ã«ãïœâã¢ã«ãã«ããšãã«ãŸãã¯ãã©ã³ã¹âïŒâ
ã¢ã«ãã«ã·ã¯ãããã·ã«ãè¡šãããã¢ã«ãã«ãªã
èªã¯ççŽ ååïŒã12åãå«ãçŽéç¶ã®ã¢ã«ãã«ã
è¡šãããæãã¯ãŸãæ®åºR18ãŸãã¯R19ã®äžã€ã¯
åæéç¶ã®ã¢ã«ãã«åºC2H5âCHïŒCH3ïŒâïŒCH2ïŒ
ïœâãè¡šãããããã«ïœã¯ïŒãïŒã®æŽæ°ã§ããã
ãããŠååšããã¢ã«ãã«åºã«ãããççŽ ååã®å
ã¯å€ããšã14åã§ããã
ã®ãã©ã³ã¹âïŒïŒâã¢ã«ãã«ã·ã¯ãããã·ã«ïŒã
ãªããžã³åã³ïŒãŸãã¯äžè¬åŒ
åŒäžãç°ïŒ¡ã¯è³éŠæã§ãããããŸãã¯ãã©ã³ã¹
âïŒïŒïŒâäºçœ®æãããã·ã¯ããããµã³ç°ãè¡šã
ãïŒR24ã¯ã¡ãã«ãŸãã¯åºâCH2Râ²ãâORâ²ãâCO
âRâ²ãâCNãâCOOHãâCRâORâ²ãâCRâ
SRâ²ãŸãã¯ââCOâRâ²ã®äžã€ãè¡šããïŒR23ã¯
æ°ŽçŽ ãã¡ãã«ãŸãã¯åºâCH2RãâORãâCH2OR
ã®äžã€ãè¡šããããæãã¯R24ãã¡ãã«ãŸãã¯åº
âCH2Râ²ãâORâ²ãããã¯âCOâRâ²ã®äžã€ãè¡šã
ãå ŽåãR23ã¯âCNãâCOOHãâCOâORãâ
COâSRãŸãã¯ââCOâãè¡šããïŒããã«
åã³Râ²ã¯çŽéç¶ãŸãã¯åæéç¶ã®ã¢ã«ãã«åº
ãè¡šããïŒR23ãŸãã¯R24ã«ãããççŽ ååã®æ°
ã¯12åãŸã§ã§ããããããŠR23åã³R24ã«ããã
ççŽ ååã®æ°ã¯äžç·ã«ããŠå€ããšã14åã§ããã
ã®èµ€éçã«ïŒequatoriallyïŒçœ®æããããã©ã³ã¹
âãã«ãªã³ãå«ãããšãã§ããã The mixture according to the invention may additionally have the general formula where ring B is saturated or aromatic and any saturated ring B is trans-bonded to the second ring; R 13 is a straight chain containing 1 to 11 carbon atoms; represents an alkyl or alkoxy group; R 14 is cyano, straight-chain alkyl containing 1 to 11 carbon atoms, general formula or, if ring B is saturated, additionally represents a straight-chain alkoxy group containing 1 to 11 carbon atoms; in the ester group of formula XII, ring A is an aromatic , X represents oxygen or sulfur, and R 15 represents cyano or a straight-chain alkyl or alkoxy group containing 1 to 10 carbon atoms, or ring A is trans-
represents a 1,4-disubstituted cyclohexane ring, X represents oxygen and R 15 represents cyano or a linear alkyl group containing 1 to 10 carbon atoms; the alkyl and/or alkoxy groups present the total number of carbon atoms in is at most 12, and/or a hydrogenated naphthalene of the general formula In the formula, R 16 represents a linear alkyl group containing 1 to 11 carbon atoms; R 17 is cyano, 1 carbon atom
A linear alkyl group containing ~11 or the above formula
represents the ester group of XII, where X, A and R 15
has the abovementioned meaning; and the total number of carbon atoms in the alkyl and alkoxy groups present is at most 12, benzoxane and/or of the general formula In the formula, the symbol Y represents nitrogen and the symbol Z represents =CH-, or the symbol Z represents nitrogen and the symbol Y represents =CH-, R 18 represents alkyl, and R 19 cyano, alkyl, p-alkylphenyl or trans-4-
Alkylcyclohexyl stands for straight-chain alkyl containing 1 to 12 carbon atoms, or alternatively one of the residues R 18 or R 19 is a branched alkyl group C 2 H 5 â CH( CH3 )â( CH2 )
m-, where m is an integer from 1 to 3,
and the sum of carbon atoms in the alkyl groups present is at most 14, trans-(4-alkylcyclohexyl)pyrimidine and/or of the general formula In the formula, ring A is aromatic or represents a trans-1,4-disubstituted cyclohexane ring; R24 is methyl or a group -CH2R ', -OR', -CO
âRâ², âCN, âCOOH, âCRâORâ², âCRâ
SR' or -O-CO-R'; R23 is hydrogen, methyl or a group -CH2R , -OR, -CH2OR
or if R 24 represents methyl or one of the groups -CH 2 R', -OR' or -CO-R', R 23 represents -CN, -COOH, -CO-OR, â
represents CO-SR or -O-CO-R; where R and R' represent a straight-chain or branched alkyl group; the number of carbon atoms in R 23 or R 24 is up to 12; , and the number of carbon atoms in R 23 and R 24 together is at most 14.
åŒXIããåã³ã®ååç©
ã¯æ°èŠã®ãã®ã§ãããR14ãã·ã¢ããçŽéç¶ã®ã¢
ã«ãã«ãŸãã¯çŽéç¶ã®ã¢ã«ã³ãã·ãè¡šããåŒXI
ã®ååç©åã³R17ãã·ã¢ããŸãã¯çŽéç¶ã®ã¢ã«ã
ã«ãè¡šããåŒã®ååç©ã¯ãªãã§ãã液æ¶æ··
åç©ã«ãããããŒãã³ã°ïŒdopingïŒå€ãšããŠé©
ããŠãããäžè¬ã«ãã®ãã®èªäœã¯æ¶²æ¶æ§ã§ã¯ãª
ããåŸã€ãŠããããããŒãã³ã°å€ãå«ãæ··åç©ã®
å Žåã«ã¯ãæ··åç©å
šäœã液æ¶ç¹æ§ãæããæ§ã«å
åãªéã®æ¶²æ¶ç¹æ§ããã€å°ãªããšãïŒçš®ã®ååç©
ãå ããŠå«ãããã«æ³šæããªããã°ãªããªããäž
æ¹ãæ®ãã®åŒXIåã³ã®ååç©äžŠã³ã«åŒ
åã³ã®ååç©ã¯çžåœã®çšåºŠã§ããèª
äœæ¶²æ¶ã§ããã The compounds of formula XI, and are new. Formula XI in which R 14 represents cyano, linear alkyl or linear alkoxy
and compounds of the formula in which R 17 represents cyano or straight-chain alkyl are particularly suitable as doping agents in liquid-crystal mixtures, which are generally not themselves liquid-crystalline. Therefore, in the case of mixtures containing such doping agents, care must be taken to include in addition a sufficient amount of at least one compound having liquid-crystalline properties so that the entire mixture has liquid-crystalline properties. On the other hand, the remaining compounds of formula XI and as well as compounds of formula and are themselves liquid-crystalline to a considerable extent.
åŒXIã®ååç©ã¯ã
(a) R14ãåŒXIIã®ãšã¹ãã«åºãè¡šããåŒXIã®
ååç©ã補é ããããã«ãäžè¬åŒ
åŒäžãR13åã³ïŒ¢ã¯äžèšã®æå³ãæããã
ã®ååç©ãŸãã¯ãã®åå¿æ§èªå°äœãäŸãã°å¯Ÿå¿
ããé
žå¡©å¡©åç©ãäžè¬åŒ
åŒäžããåã³R15ã¯äžèšã®æå³ãæã
ãã
ã®ååç©ã§ãšã¹ãã«åãã
(b) R14ãã·ã¢ã¢ããè¡šããåŒXIã®ååç©ã補
é ããããã«ãäžè¬åŒ
åŒäžãR13åã³ïŒ¢ã¯äžèšã®æå³ãæããã
ã®ååç©ãè±æ°Žãã
(c) R14ãçŽéç¶ã®ã¢ã«ãã«åºãè¡šããåŒXIã®
ååç©ã補é ããããã«ãäžè¬åŒ
åŒäžãn1ã¯ïŒã10ã®æŽæ°ãè¡šããããããŠ
R13åã³ïŒ¢ã¯äžèšã®æå³ãæããã
ã®ååç©ãå¡©åºã®ååšäžã«ãããŠããã©ãžã³ãš
åå¿ããã
(d) ç°ïŒ¢ã飜åãããŠããããããŠR14ãçŽéç¶
ã®ã¢ã«ã³ãã·åºãè¡šããåŒXIã®ååç©ã補é
ããããã«ãäžè¬åŒ
åŒäžãR13ã¯äžèšã®æå³ãæãã
ã®ååç©ããšãŒãã«åããã
ããšã«ãã€ãŠè£œé ããããšãã§ããã Compounds of formula XI may be prepared from the general formula or a reactive derivative thereof, such as the corresponding acid chloride, in which R 13 and B have the meanings given above, (b) in order to produce a compound of formula XI in which R 14 represents cyano, the general formula ( c ) in order to prepare a compound of formula In the formula, n1 represents an integer from 0 to 10, and
(d) a compound of formula XI in which ring B is saturated and R 14 represents a linear alkoxy group; To produce a compound, the general formula In the formula, R 13 can be produced by etherifying a compound having the above meaning.
åŒã®ååç©ã¯å
¬ç¥ã§ãããããŸãã¯å
¬ç¥
ã®ååç©ã®åæäœã§ãããåŒXIãã®å
åç©ã®è£œæ³ã次ã®åå¿ïŒ¡ãã«ãã€ãŠç€ºãïŒåå¿
åŒäžãR13ãåã³n1ã¯äžèšã®æå³ãæããn2ã¯
ïŒã10ã®æŽæ°ãè¡šãããèšå·ïŒããïŒã¯ãã®çœ®æ
åºãαâãŸãã¯Î²âé
眮ïŒåŒã®é¢ã®äžãŸãã¯äžïŒ
ãæããããšã瀺ããç¹ç·ïŒâŠâŠïŒã¯ããã«ãã€
ãŠè¡šããããçµåã®äžã€ãäºéçµåã§ããããšã
瀺ãã Compounds of formula are known or are homologs of known compounds. The method for producing compounds of formulas XI~ is shown by the following reactions A~C; in the reaction formula, R 13 , B and n 1 have the above meanings, n 2 represents an integer from 1 to 10, and the symbol (ãã) means that the substituent is in the α- or β-configuration (below or above the plane of the formula)
The dotted line (...) indicates that one of the bonds represented by this is a double bond.
åŒã®ååç©ã¯ã
(a) R17ãåŒXIIã®ãšã¹ãã«åºãè¡šããåŒ
ã®ååç©ã補é ããããã«ãäžè¬åŒ
åŒäžãR16ã¯äžèšã®æå³ãæããã
ã®ååç©ãåèšã®åŒã®ååç©ã§ãšã¹ãã«
åãã
(b) R17ãã·ã¢ããè¡šããåŒã®ååç©ã補
é ããããã«ãäžè¬åŒ
åŒäžãR16ã¯äžèšã®æå³ãæããã
ã®ååç©ãè±æ°Žãã
(c) R17ãççŽ ååïŒã11åãå«ãçŽéç¶ã®ã¢ã«
ãã«åºãè¡šããåŒã®ååç©ã補é ããã
ãã«ãäžè¬åŒ
åŒäžãn3ã¯ïŒãïŒã®æŽæ°ãè¡šããããããŠ
R16ã¯äžèšã®æå³ãæããã
ã®ååç©ãæ¥è§Šæ°ŽçŽ æ·»å ãã
(d) R17ãã¡ãã«åºãè¡šããåŒã®ååç©ã
補é ããããã«ãäžè¬åŒ
åŒäžãR16ã¯äžèšã®æå³ãæããã
ã®ååç©ãå¡©åºã®ã®ååšäžã«ãããŠããã©ãžã³
ãšåå¿ãããã
ããšã«ãã€ãŠè£œé ããããšãã§ããã (a) In order to prepare a compound of formula in which R 17 represents an ester group of formula XII, the compound of general formula in which R 16 has the abovementioned meaning, is esterified with a compound of the above formula, (b) to produce a compound of the formula in which R 17 represents cyano, (c) In order to produce a compound of the formula in which R 16 has the above meaning, (c) R 17 represents a linear alkyl group containing 2 to 11 carbon atoms, general formula In the formula, n 3 represents an integer from 0 to 9, and
R 16 has the above meaning, by catalytic hydrogenation of a compound of formula (d) in which R 17 represents a methyl group, a compound of the general formula In the formula, R 16 has the above-mentioned meaning, and it can be produced by reacting the compound of with hydrazine in the presence of a base.
åºçºç©è³ªãšããŠçšããåŒãã®å
åç©ã¯æ¬¡ã®åå¿åŒïŒ€ã«åŸã€ãŠè£œé ããããšãã§ã
ãïŒåå¿åŒäžãR16åã³n3ã¯äžèšã®æå³ãæããã The compounds of formula ~ used as starting materials can be prepared according to the following reaction scheme D; in the reaction scheme, R 16 and n 3 have the above meanings.
åŒã®ååç©ã¯
(a) R19ã¯ã¢ã«ãã«ãïœâã¢ã«ãã«ããšãã«ãŸã
ã¯ãã©ã³ã¹âïŒâã¢ã«ãã«ã·ã¯ãããã·ã«ãè¡š
ããåŒã®ååç©ã補é ããããã«ãäžè¬
åŒ
ã®ååç©ãå¡©åºã奜ãŸããã¯ã¢ã«ã³ã¬ãŒãã®å
åšäžã«ãããŠäžè¬åŒ
åŒäžãR20åã³R22ã®äžæ¹ã¯ãã©ã³ã¹âïŒâ
ã¢ã«ãã«ã·ã¯ãããã·ã«ãè¡šãããä»æ¹ã¯ã¢ã«
ãã«ãïœâã¢ã«ãã«ããšãã«ãŸãã¯ãã©ã³ã¹â
ïŒâã¢ã«ãã«ã·ã¯ãããã·ã«ãè¡šããããããŠ
R21ã¯äœçŽã¢ã«ãã«ãè¡šããã
ã®ååç©ã®é
žä»å å¡©ã奜ãŸããã¯å¡©é
žå¡©ãšåå¿
ããã
(b) R19ãã·ã¢ããè¡šããåŒã®ååç©ã補
é ããããã«ãäžè¬åŒ
åŒäžãR16ãåã³ïŒºã¯äžèšã®æå³ãæã
ãã
ã®ååç©ãè±æ°Žãã
(c) èšå·ïŒ¹ãïŒCHâãè¡šããããçªçŽ ãè¡šã
ãããããŠR19ãã·ã¢ããè¡šããåŒã®å
åç©ã補é ããããã«ãäžè¬åŒ
åŒäžãR18ã¯äžèšã®æå³ãæããã
ã®ååç©ãè±æ°Žããã
ããšã«ãã€ãŠè£œé ããããšãã§ããã Compounds of the formula (a) R 19 represents alkyl, p-alkylphenyl or trans-4-alkylcyclohexyl can be prepared by the general formula In the presence of a base, preferably an alcoholate, a compound of the general formula In the formula, one of R 20 and R 22 is trans-4-
represents alkylcyclohexyl, the other being alkyl, p-alkylphenyl or trans-
represents 4-alkylcyclohexyl, and
R 21 represents lower alkyl, react with an acid addition salt, preferably a hydrochloride , of a compound of the general formula (c) a compound of the formula in which the symbol Y represents = CH- , Z represents nitrogen and R 19 represents cyano; To produce the general formula In the formula, R 18 has the above meaning, and can be produced by dehydrating the compound.
ãäœçŽã¢ã«ãã«ããªãèªã«ã¯ççŽ ååïŒãïŒå
ãå«ãã¢ã«ãã«åºãå
å«ãããã The term "lower alkyl" includes alkyl groups containing 1 to 5 carbon atoms.
åŒåã³ã®ååç©ã¯å
¬ç¥ã§ãã
ããŸãã¯å
¬ç¥ã®ååç©ã®åæäœã§ãããZ.
Naturforsch.33bã433ïŒ1978ïŒåã³34bã1535
ïŒ1979ïŒãã The compounds of formula and are known or are homologs of known compounds [Z.
Naturforsch. 33b , 433 (1978) and 34b , 1535
(1979)].
åŒåã³ã®åºçºç©è³ªã®è£œé ã¯æ¬¡
ã®åå¿åŒïŒ¥åã³ïŒŠã«ãã€ãŠèª¬æãããïŒåå¿åŒ
äžãR13ã¯äžèšã®æå³ãæããã The preparation of the starting materials of formulas and is illustrated by the following schemes E and F; in which R 13 has the meaning given above.
åå¿åŒïŒ¥åã³ïŒŠã«çšããåºçºç©è³ªãŸãã¯ããã
ã®ååç©ã®åæäœã¯äŸãã°Z.Naturforsch.34bã
1535ïŒ1979ïŒåã³Mol.Cryst.Liq.Cryst.37ã189
ïŒ1976ïŒãŸãã¯42ã215ïŒ1977ïŒã«èšèŒãããŠããã The starting materials used in schemes E and F or homologs of these compounds are described, for example, in Z.Naturforsch. 34b ,
1535 (1979) and Mol.Cryst.Liq.Cryst. 37 , 189
(1976) or 42 , 215 (1977).
åŒã®ååç©ã¯æ¬¡ã®åå¿åŒïŒ§ãïŒã«åºã¥
ããŠè£œé ããããšãã§ãããåå¿åŒäžããå
ã³Râ²ã¯äžèšã®æå³ãæããRâ³ã¯å®¹æã«é¢è±ãã
ã¢ã«ã³ãŒã«ä¿è·åºãè¡šããïŒR25ã¯æ°ŽçŽ ãã¡ãã«
ãŸãã¯åºâCH2RãâORãâORâ³âCH2ORãŸãã¯
âCH2ORâ³ã®äžã€ãè¡šããïŒR26ã¯æ°ŽçŽ ãŸãã¯ã¢
ã«ãã«ãè¡šããïŒR27ã¯R25ã«å¯Ÿå¿ããç䟡ã®äž
ã€ãŸãã¯åºâCOâORãããã¯ââCOâã
è¡šããïŒR23ã¯R25ã«å¯Ÿå¿ããåœäŸ¡ã®äžã€ãŸãã¯
âCOâORãââCOâãããã¯âCOOHã®äž
ã€ãè¡šããïŒïŒžã¯é
žçŽ ãŸãã¯ç¡«é»ãè¡šããïŒX1
ã¯èçŽ ãŸãã¯ãšãŠçŽ ãè¡šããïŒTsã¯ïœâãã·ã«
åºãè¡šããïŒèšå·ããã¯ãã®çµåãå³é¢ã®äžãŸã
ã¯äžã«ããããšãã§ãããå³ã¡åŒã®åå
ç©ã«ãããã·ã¢ãåºã¯è»žãŸãã¯èµ€éäžã®é
眮ãæ
ããããšãã§ããããæãã¯åŒïŒ¬ã®ååç©ã«
ãããã·ã¯ããããµã³ç°ã¯ãã©ã³ã¹âãŸãã¯ã·ã¹
âäºçœ®æãããŠããŠãããããšã瀺ãïŒæ®ãã®å Ž
åã«ãããŠãçšããïŒé£œåïŒãã«ãªã³æ§é åŒã¯çœ®
æåºã®èµ€éçé
眮ãæãããã©ã³ã¹âãã«ãªã³ã
æå³ãããšãšç解ããããã Compounds of the formula can be produced based on the following reaction formulas G to M. In the reaction formula, A, R and R' have the above meanings, R'' represents an alcohol protecting group that is easily removed; R25 is hydrogen, methyl or a group -CH2R , -OR, -OR'' -CH 2 OR or -CH 2 OR''; R 26 represents hydrogen or alkyl; R 27 represents one equivalent corresponding to R 25 or a group -CO-OR or -O-CO-R R 23 represents one of the equivalents corresponding to R 25 or one of -CO-OR, -O-CO-R or -COOH; X represents oxygen or sulfur; X 1
represents bromine or iodine; Ts represents a p-tosyl group; the symbol ~ can have its bond above or below the drawing, i.e. the cyano group in a compound of formula has an axial or equatorial configuration or that the cyclohexane ring in compounds of formula L may be trans- or cis-disubstituted; in the remaining cases, the (saturated) decalin structure used reflects the equatorial configuration of the substituents. is understood to mean trans-decalin having .
åŒã®ååç©ã®ãžã¢ã¹ãã¬ãªããŒæ··åç©
ã¯ã¯ãããã°ã©ãã€ãŒã«ãã€ãŠåé¢ããããšãã§
ãããããããªãããåŒïŒ¬ã®é
žãžã®è»¢åãå
å¥çµæ¶ã«ããåé¢åã³åŒïœã®ãããªã«ãž
ã®è»¢åãããé©åœã§ãããäžæ¹ãåŒã®ã
ããªã«ãåŒïŒ¬ã®ååç©ã«è»¢åããå Žåããã®å
é¢ã¯ã°ãªãã¢ãŒã«åå¿ããç¶ããŠå¹³è¡¡å æ°Žæ«è§£ã®
åŸã«ã®ã¿ãåŒïŒ¬ã®ååç©ã®çµæ¶åã«ãã€ãŠæå©
ã«è¡ãããã Diastereomeric mixtures of compounds of formula can be separated by chromatography. However, conversion to acids of formula L, separation by fractional crystallization and conversion to nitriles of formula a are more suitable. If, on the other hand, a nitrile of the formula is converted into a compound of the formula L, the separation is advantageously carried out by a Grignard reaction followed by crystallization of the compound of the formula L only after equilibrium hydrolysis.
ãŸãåŒïŒ¬ã®é
žã¯äŸãã°åŒïŒ¬ã®ã¢ã«ãã
ãããéãã³ã¬ã³é
žã«ãªãŠã ã«ããé
žåã«ãã€ãŠ
åŸãããšãã§ããã Acids of formula L can also be obtained, for example, from aldehydes of formula L by oxidation with potassium permanganate.
å¿
èŠã«å¿ããŠåŒïŒ¬ã®é
žã®ã©ã»ãäœãå
åŠç
察æäœã«åå²ããããšãã§ãããããããŠãæå©
ã«ã¯åŒïŒ¬ã®é
žãå
åŠç掻æ§å¡©åºãäŸãã°å
åŠ
ç掻æ§ããšãã«ãšãã«ã¢ãã³ããšããšããªã³ãã·
ã³ã³ããžã³ããããã«ãšãã«ã¢ãã³ãã¡ãã«ãã³
ãžã«ã¢ãã³çãšåå¿ãããåŸããããžã¢ã¹ãã¬ãª
ããŒå¡©ã®æ··åç©ãçµæ¶åã«ãã€ãŠåé¢ããåŸãã
ãå
åŠç掻æ§å¡©ãå æ°Žå解ããããããŠåŒ
ã®å
šãŠã®ååç©ã¯ãåŒïŒ¬ã®å
åŠç掻æ§ãã
åºçºããŠãå
åŠç掻æ§åã§åŸãããšãã§ããã If desired, the racemic form of the acid of formula L can be resolved into its optical antipodes. Thus, advantageously, the acid of formula L is reacted with an optically active base, such as optically active phenylethylamine, ephedrin, cinchonidine, naphthylethylamine, methylbenzylamine, etc., and the resulting mixture of diastereomeric salts is subjected to crystallization. The resulting optically active salt is then hydrolyzed. All compounds of the formula can thus be obtained in optically active form starting from the optical activity of formula L.
åºRâ³ã«å¯ŸããŠçšããã容æã«é¢è±ããåŸãã¢
ã«ã³ãŒã«ä¿è·åºããªãèªã«ã¯ã¢ã«ã³ãã·åºã«åœ±é¿
ãåãŒãã¬æ¡ä»¶äžã§é¢è±ããåŸãã¢ã«ã³ãŒã«ä¿è·
åºãå
å«ãããããããåºRâ³ã®å¥œãŸããäŸã¯ã
ã³ãžã«åºåã³ããã©ããããã©ãã«åºãAdv.
Org.Chem.ïŒïŒ1963ïŒ216ããåŒâCH2OCH3ãJ.
Amer.Chem.Soc.99ã1275ïŒ1977ïŒãåã³â
CH2OCH2CH2OCH3ïŒTetrahedron Letters1976ã
809ïŒã®åºãïœâããã«âãžã¡ãã«âã·ãªã«åº
ãJ.Amer.Chem.Soc.94ã6190ïŒ1972ïŒãçã§ããã
ãã³ãžã«åºã¯äŸãã°æ¥è§Šæ°ŽçŽ æ·»å ã«ãã€ãŠé¢è±ã
ããããšãã§ããïŒãã©ãžãŠã ïŒççŽ ã奜ãŸãã
觊åªã§ãããåºâCH2OCH3ãããã©ããããã©
ãã«åºåã³ïœâããã«âãžã¡ãã«âã·ãªã«åºã¯åŒ·
é
žäŸãã°ç¡«é
žãå¡©åæ°ŽçŽ é
žãïœâãã«ãšã³ã¹ã«ã
ã³é
žçãšã®åå¿ã«ãã€ãŠé€å»ããããšãã§ããã
åºâCH2OCH2CH2OCH3ã®é€å»ã¯äŸãã°å¡©åã¡
ãã¬ã³äžã«ãŠå®€æž©ã§èåäºéïŒïŒãŸãã¯å¡©åã
ã¿ã³ïŒïŒãšã®åå¿ã«ãã€ãŠè¡ãããšãã§ããã
ãŸãïœâããã«âãžã¡ãã«âã·ãªã«åºã¯ãã«ãªã©
ã€ãã奜ãŸããã¯ã¢ã«ã«ãªéå±ãã«ãªã©ã€ããŸã
ã¯ããã©ã¢ã«ãã«ã¢ã³ã¢ããŠã ãã«ãªã©ã€ããäŸ
ãã°ããåã«ãªãŠã ãããã©ããã«ããåã¢ã³ã¢
ããŠã çãšã®åå¿ã«ãã€ãŠé¢è±ãããããšãã§ã
ãããããä¿è·åºã®å°å
¥ã¯ãäŸãã°ä¿è·ããã¢ã«
ã³ãŒã«ãå¿
èŠã«å¿ããŠå¡©åºã®ååšäžã«ãããŠå¡©å
ãã³ãžã«ããžããããã©ã³ãã¯ããã¡ãã«ã¡ãã«
ãšãŒãã«ãβâã¡ããã·ãšããã·âã¡ãã«ã¯ãã©
ã€ããïœâããã«âãžã¡ãã«âã·ãªã«ã¯ãã©ã€ã
çãšåå¿ãããããšã«ãã€ãŠè¡ãããšãã§ããã
ã¢ã«ã³ãŒã«ä¿è·åºã®å°å
¥åã³é¢è±ã«é¢ãã詳现ã¯
äžèšã®æç®ã«èšèŒãããŠããã The term "readily removable alcohol-protecting group" used for the group R'' includes alcohol-protecting groups that can be removable under conditions that do not affect the alkoxy group. Preferred examples of such groups R'' are benzyl and tetrahydropyranyl [Adv.
Org.Chem. 3 (1963) 216], formula -CH 2 OCH 3 [J.
Amer.Chem.Soc. 99 , 1275 (1977)] and -
CH 2 OCH 2 CH 2 OCH 3 (Tetrahedron Letters 1976 ,
809), t-butyl-dimethyl-silyl group [J.Amer.Chem.Soc. 94 , 6190 (1972)], and the like.
The benzyl group can be removed, for example, by catalytic hydrogenation; palladium/carbon is the preferred catalyst. The groups -CH 2 OCH 3 , tetrahydropyranyl and t-butyl-dimethyl-silyl groups can be removed by reaction with strong acids such as sulfuric acid, hydrochloric acid, p-toluenesulfonic acid and the like.
Removal of the group -CH 2 OCH 2 CH 2 OCH 3 can be carried out, for example, by reaction with zinc bromide () or titanium chloride () in methylene chloride at room temperature.
The t-butyl-dimethyl-silyl group can also be removed by reaction with a fluoride, preferably an alkali metal fluoride or a tetraalkylammonium fluoride, such as potassium fluoride, tetrabutylammonium fluoride, and the like. Introduction of such a protecting group can be carried out, for example, by converting the alcohol to be protected with benzyl chloride, dihydropyran, chloromethyl methyl ether, β-methoxyethoxy-methyl chloride, t-butyl-dimethyl-silyl chloride, etc. in the presence of a base if necessary. This can be done by reacting.
Details regarding the introduction and removal of alcohol protecting groups are described in the above-mentioned literature.
æ¬çºæã«ããã液æ¶æ··åç©ã¯ãïŒçš®ãŸãã¯ãã
以äžã®åŒã®ååç©ã«å ããŠã奜ãŸããã¯ïŒçš®ãŸ
ãã¯ãã以äžã®æ¬¡ã®ååç©ãå«æããïŒ
äžè¬åŒ
åŒäžãR29ã¯ççŽ ååïŒãïŒåãå«ãçŽéç¶ã®
ã¢ã«ãã«ãŸãã¯ã¢ã«ã³ãã·åºãè¡šããã
ã®ïŒâã·ã¢ããããšãã«ãäžè¬åŒ
åŒäžãR30ã¯ççŽ ååïŒãïŒåãå«ãçŽéç¶ã®
ã¢ã«ãã«åºãè¡šããã
ã®ãã©ã³ã¹âïœâïŒïŒâã¢ã«ãã«ã·ã¯ãããã·ã«ïŒ
ãã³ãŸãããªã«ãäžè¬åŒ
åŒäžãR30ã¯äžèšã®æå³ãæããã
ã®ïœâïŒïŒâã¢ã«ãã«âïŒâããªããžãã«ïŒãã³
ãŸãããªã«ãäžè¬åŒ
åŒäžãR30ã¯äžèšã®æå³ãæããã
ã®ïœâïŒãã©ã³ã¹âïŒâã¢ã«ãã«âïœâãžãªããµ
ã³âïŒâã€ã«ïŒãã³ãŸãããªã«ãäžè¬åŒ
åŒäžãR31ã¯ççŽ ååïŒãïŒåãå«ãçŽéç¶ã®
ã¢ã«ãã«åºãè¡šããã
ã®ïœâã¢ã«ãã«å®æ¯éŠé
žpâ²âã·ã¢ãããšãã«ãšã¹
ãã«ãäžè¬åŒ
åŒäžãR30ã¯äžèšã®æå³ãæãããããŠR32ã¯
ã·ã¢ããŸãã¯ççŽ ååïŒãïŒåãå«ãçŽéç¶ã®ã¢
ã«ã³ãã·åºãè¡šããã
ã®ãã©ã³ã¹âïŒâã¢ã«ãã«ã·ã¯ããããµã³ã«ã«ã
ã³é
žããšãã«ãšã¹ãã«ãäžè¬åŒ
åŒäžãR31ã¯äžèšã®æå³ãæããã
ã®ãã©ã³ã¹âïœâãïŒâïŒïŒâã¢ã«ãã«ã·ã¯ããã
ã·ã«ïŒâïŒâããªããžãã«ããã³ãŸãããªã«åã³
äžè¬åŒ
åŒäžãR30ã¯äžèšã®æå³ãæããã
ã®ïŒâïŒãã©ã³ã¹âïŒâã¢ã«ãã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâã·ã¢ãããšãã«ïŒâãšã¿ã³ã In addition to one or more compounds of the formula, the liquid crystal mixture according to the invention preferably contains one or more of the following compounds: 4-cyanobiphenyl of the general formula, where R 29 represents a linear alkyl or alkoxy group containing 2 to 7 carbon atoms; In the formula, R 30 represents a linear alkyl group containing 3 to 7 carbon atoms, trans-p-(4-alkylcyclohexyl)
Benzonitrile, general formula In the formula, R 30 has the above meaning, p-(5-alkyl-2-pyrimidinyl)benzonitrile, general formula In the formula, R 30 has the above meaning, p-(trans-5-alkyl-m-dioxan-2-yl)benzonitrile, general formula In the formula, R 31 represents a linear alkyl group containing 2 to 7 carbon atoms, p-alkylbenzoic acid p'-cyanophenyl ester of the general formula trans-4-alkylcyclohexanecarboxylic acid phenyl esters, general formula In the formula, R 31 has the above meaning, trans-p-[5-(4-alkylcyclohexyl)-2-pyrimidinyl]benzonitrile and the general formula In the formula, R 30 has the above meaning, 2-(trans-4-alkylcyclohexyl)
-1-(p-cyanophenyl)-ethane.
æ··åç©ã®åæåã®ééæ¯ã¯å¥œãŸããã¯å
±è
ïŒeutecticïŒçµæç©ã«å¯Ÿå¿ãããã®ã§ããããã
ããªãããæ¬çºæã«ããã液æ¶æ··åç©äžã®åŒã®
ååç©ã®éã¯äžè¬åŒã«çŽïŒãçŽ90ã¢ã«ïŒ
ã奜ãŸã
ãã¯çŽ10ãçŽ85ã¢ã«ïŒ
ã§ãããããããªãããã
ã®æ··åç©ã¯ããŸãæ··åç©å
šäœã液æ¶ç¹æ§ãæãã
ããã«ãååãªéã§å°ãªããšãïŒçš®ã®æ¶²æ¶ååç©
ãå«ãã§ããªããã°ãªããªãã The weight ratio of each component of the mixture preferably corresponds to a eutectic composition. However, the amount of the compound of formula in the liquid crystal mixture in the present invention is from about 1 to about 90 mole percent, preferably from about 10 to about 85 mole percent, based on the general formula. However, this mixture must also contain at least one liquid-crystalline compound in a sufficient amount so that the entire mixture has liquid-crystalline properties.
æŽã«ãæ¬çºæã«ãããæ··åç©ã¯å
åŠç掻æ§åå
ç©ãäŸãã°å
åŠç掻æ§ãããšãã«é¡ã䞊ã³ã«ïŒãŸ
ãã¯äºè²æ§ïŒdichroicïŒçè²ç©è³ªãäŸãã°ã¢ãŸã
ã¢ãŸãã³åã³ã¢ã³ãã©ããã³çè²ç©è³ªãå«ãããš
ãã§ããããããååç©ã®éã¯ææã®ããã
ïŒpitchïŒè²èª¿ãåžå
ïŒextinctionïŒã溶解床çã«
ãã€ãŠæ±ºå®ãããã Furthermore, the mixtures according to the invention contain optically active compounds, such as optically active biphenyls, and/or dichroic colored substances, such as azo,
Azoquine and anthraquinone colorants may be included. The amount of such compound is determined by the desired pitch, extinction, solubility, etc.
æ¬çºæã«ããã液æ¶æ··åç©ã®è£œé ã¯ããèªäœå
¬
ç¥ã®æ¹æ³ã«ãããŠãäŸãã°åæåã®æ··åç©ããã
ãã«éæç¹ãããé«ã枩床ã«å ç±ãã次ã«å·åŽã
ãããšã«ãã€ãŠè¡ãããšãã§ããã The liquid-crystal mixture according to the invention can be produced in a manner known per se, for example by heating the mixture of the individual components to a temperature slightly above the clearing point and then cooling.
ãŸãåŒã®ååç©ã®ïŒçš®ãŸãã¯ãã以äžãå«ã
é»åâå
åŠè£
眮ã®è£œé ã¯ããèªäœå
¬ç¥ã®æ¹æ³ã«ã
ããŠãäŸãã°é©åœãªã»ã«ã空ã«ãããããŠãã®ç©º
ã«ããã»ã«ã«å¯Ÿå¿ããååç©ãŸãã¯æ··åç©ãå°å
¥
ããããšã«ãã€ãŠè¡ãããšãã§ããã Electro-optical devices containing one or more compounds of the formula can also be produced in a manner known per se, for example by emptying a suitable cell and introducing into this emptied cell the corresponding compound or mixture. This can be done by
ãŸããæ¬çºæã¯æ¬æ现æžã«èšèŒããå
šãŠã®æ°èŠ
ãªååç©ãæ··åç©ã補æ³ãçšéåã³è£
眮ã«é¢ã
ãã The present invention also relates to all novel compounds, mixtures, processes, uses and devices described herein.
奜ãŸããæ··åç©ã®äŸã¯æ¬¡ã®æ··åç©å®æœäŸïŒã12
ã§ããã該å®æœäŸã«ãããŠÎ·ã¯ç²åºŠïŒãã«ã¯ç²
床ïŒãè¡šãããâ³Îµã¯èªé»ç°æ¹æ§ãè¡šãããåŒ
XIåã³ã®ååç©ãïŒã€ã®èµ€éçïŒïŒïŒâ
äºçœ®æãããç°æ§äœãšããŠåã
ã®å Žåã«çšããã Examples of preferred mixtures are the following mixture examples 1 to 12.
In the examples, η represents viscosity (bulk viscosity), and Îε represents dielectric anisotropy. formula
XI and the compound of two equatorial 2,6-
The disubstituted isomer was used in each case.
æ··åç©å®æœäŸ ïŒ
ïœâïŒïŒâãã³ãã«âïŒâããªããžãã«ïŒãã³
ãŸãããªã«ïŒã¢ã«ïŒ
ã
ïœâïŒïŒâãããã«âïŒâããªããžãã«ïŒãã³
ãŸããã«ïŒïŒ
ã
ãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ããããµã³ã«ã«ã
ã³é
žïœâã¡ããã·ããšãã«ãšã¹ãã«16ã¢ã«ïŒ
ã
ãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ããããµã³ã«ã«ã
ã³é
žïœâãããã«ãªãã·ããšãã«ãšã¹ãã«25ã¢ã«
ïŒ
ã
ïœâãïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ããã
ã·ã«ïŒâïŒâããªããžãã«ããã³ãŸãããªã«ïŒã¢
ã«ïŒ
ã
ïœâãïŒ4aαHïŒ8aβHïŒâãã«ãããâ6βâãã
ãã«â2αâãããã«ããã³ãŸãããªã«ïŒã¢ã«ïŒ
ã
βâãïŒ4aαHïŒ8aβHïŒâãã«ãããâ6βâãã³
ãã«â2αâãããã«ããã³ãŸãããªã«ïŒã¢ã«ïŒ
ã
ïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâãšããã·ããšãã«ïŒãšã¿ã³25ã¢ã«
ïŒ
ïŒ
èç¹ïŒïŒâãéæç¹69âãηïŒ22âïŒïŒ28.2cpã
ãããã€ãã¯ãMixture Example 1 5 mol% p-(5-pentyl-2-pyrimidinyl)benzonitrile, 9% p-(5-heptyl-2-pyrimidinyl)benzonitrile, trans-4-pentylcyclohexanecarboxylic acid p-methoxyphenyl ester 16 mol%, trans-4-pentylcyclohexanecarboxylic acid p-propyloxyphenyl ester 25 mol%, p-[5-(trans-4-pentylcyclohexyl)-2-pyrimidinyl]benzonitrile 6 mol%, p-[ (4aαH, 8aβH)-decahydro-6β-propyl-2α-naphthyl]benzonitrile 8 mol%, β-[(4aαH, 8aβH)-decahydro-6β-pentyl-2α-naphthyl]benzonitrile 6 mol%, 2-( trans-4-pentylcyclohexyl)
-1-(p-ethoxyphenyl)ethane 25 mol%; melting point <0°C, clearing point 69°C, η (22°C) = 28.2cp,
Nematetsk.
æ··åç©å®æœäŸ ïŒ
ïœâïŒïŒâãã³ãã«âïŒâããªããžãã«ïŒãã³
ãŸãããªã«ïŒã¢ã«ïŒ
ã
ïœâïŒïŒâãããã«âïŒâããªããžãã«ïŒãã³
ãŸãããªã«12ã¢ã«ïŒ
ã
ãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ããããµã³ã«ã«ã
ã³é
žïœâã¡ããã·ããšãã«ãšã¹ãã«20ã¢ã«ïŒ
ã
ãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ããããµã³ã«ã«ã
ã³é
žïœâãããã«ãªãã·ããšãã«ãšã¹ãã«26ã¢ã«
ïŒ
ã
ïœâãïŒ4aαHïŒ8aβHïŒâãã«ãããâ6βâãšã
ã«â2αâãããã«ããã³ãŸãããªã«ïŒã¢ã«ïŒ
ïœâãïŒ4aαHïŒ8aβHïŒâãã«ãããâ6βâãã
ãã«â2αâãããã«ããã³ãŸãããªã«ïŒã¢ã«ïŒ
ã
ïœâãïŒ4aαHïŒ8aβHïŒâãã«ãããâ6βâãã³
ãã«â2αâãããã«ããã³ãŸãããªã«ïŒã¢ã«ïŒ
ã
ïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâãšããã·ããšãã«ïŒãšã¿ã³ïŒ
èç¹ïŒïŒâãéæç¹63.5âãηïŒ22âïŒïŒ
32.5cpããããã€ãã¯ãMixture Example 2 p-(5-pentyl-2-pyrimidinyl)benzonitrile 6 mol%, p-(5-heptyl-2-pyrimidinyl)benzonitrile 12 mol%, trans-4-pentylcyclohexanecarboxylic acid p-methoxyph p-[(4aαH, 8aβH)-decahydro-6β-ethyl-2α-naphthyl]benzonitrile 8 mol% p -[(4aαH, 8aβH)-decahydro-6β-propyl-2α-naphthyl]benzonitrile 8 mol%, p-[(4aαH, 8aβH)-decahydro-6β-pentyl-2α-naphthyl]benzonitrile 8 mol%, 2 -(trans-4-heptylcyclohexyl)
-1-(p-ethoxyphenyl)ethane; melting point <0°C, clearing point 63.5°C, η (22°C) =
32.5 cp, tematetsuk.
æ··åç©å®æœäŸ ïŒ
ïœâïŒïŒâãã³ãã«âïŒâããªããžãã«ïŒãã³
ãŸãããªã«ïŒã¢ã«ïŒ
ã
ïœâïŒïŒâãããã«âïŒâããªããžãã«ïŒãã³
ãŸãããªã«13ã¢ã«ïŒ
ãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ããããµã³ã«ã«ã
ã³é
žïœâã¡ããã·ããšãã«ãšã¹ãã«21ã¢ã«ïŒ
ã
ãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ããããµã³ã«ã«ã
ã³é
žïœâãããã«ãªãã·ããšãã«ãšã¹ãã«27ã¢ã«
ïŒ
ã
ïœâãïŒâïŒãã©ã³ã¹âïŒâãšãã«ã·ã¯ãããã·
ã«ïŒâïŒâããªããžãã«ããã³ãŸãããªã«11ã¢ã«
ïŒ
ã
ïœâãïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ããã
ã·ã«ïŒâïŒâããªããžãã«ããã³ãŸãããªã«ïŒã¢
ã«ïŒ
ã
ïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâãšããã·ããšãã«ïŒãšã¿ã³13ã¢ã«
ïŒ
ïŒ
èç¹ïŒïŒâãéæç¹80âããããã€ãã¯ãMixture Example 3 p-(5-pentyl-2-pyrimidinyl)benzonitrile 7 mol%, p-(5-hebutyl-2-pyrimidinyl)benzonitrile 13 mol% p-methoxyphenyl trans-4-pentylcyclohexanecarboxylate ester 21 mol%, trans-4-pentylcyclohexanecarboxylic acid p-propyloxyphenyl ester 27 mol%, p-[5-(trans-4-ethylcyclohexyl)-2-pyrimidinyl]benzonitrile 11 mol%, p- [5-(trans-4-pentylcyclohexyl)-2-pyrimidinyl]benzonitrile 8 mol%, 2-(trans-4-heptylcyclohexyl)
-1-(p-ethoxyphenyl)ethane 13 mol%; melting point <0°C, clearing point 80°C, nematic.
æ··åç©å®æœäŸ ïŒ
ïœâïŒïŒâãã³ãã«âïŒâããªããžãã«ïŒãã³
ãŸãããªã«ïŒã¢ã«ïŒ
ã
ïœâïŒïŒâãããã«âïŒâããªããžãã«ïŒãã³
ãŸãããªã«ïŒã¢ã«ïŒ
ã
ãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ããããµã³ã«ã«ã
ã³é
žïœâã¡ããã·ããšãã«ãšã¹ãã«14ã¢ã«ïŒ
ã
ãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ããããµã³ã«ã«ã
ã³é
žïœâãããã«ãªãã·ããšãã«ãšã¹ãã«21ã¢ã«
ïŒ
ã
ïœâãïŒâïŒãã©ã³ã¹âïŒâãšãã«ã·ã¯ãããã·
ã«ïŒâïŒâããªããžãã«ããã³ãŸãããªã«ïŒã¢ã«
ïŒ
ã
ïœâãïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ããã
ã·ã«ïŒâïŒâããªããžãã«ããã³ãŸãããªã«ïŒã¢
ã«ïŒ
ã
ïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâãšããã·ããšãã«ïŒãšã¿ã³37ã¢ã«
ïŒ
ïŒ
èç¹ïŒïŒâãéæç¹70âãηïŒ22âïŒïŒ26.3cpã
ãããã€ãã¯ãMixture Example 4 p-(5-pentyl-2-pyrimidinyl)benzonitrile 5 mol%, p-(5-heptyl-2-pyrimidinyl)benzonitrile 8 mol%, trans-4-pentylcyclohexanecarboxylic acid p-methoxyph p-[5-(trans-4-ethylcyclohexyl)-2-pyrimidinyl]benzonitrile 9 mol%, p-[5-(trans-4-ethylcyclohexyl)-2-pyrimidinyl]benzonitrile 9 mol%, -[5-(trans-4-pentylcyclohexyl)-2-pyrimidinyl]benzonitrile 6 mol%, 2-(trans-4-pentylcyclohexyl)
-1-(p-ethoxyphenyl)ethane 37 mol%; melting point <0°C, clearing point 70°C, η (22°C) = 26.3 cp,
Nematetsk.
æ··åç©å®æœäŸ ïŒ
ãã©ã³ã¹âïŒâããã«ã·ã¯ããããµã³ã«ã«ãã³
é
žïœâãšããã·ããšãã«ãšã¹ãã«17ã¢ã«ïŒ
ã
ãã©ã³ã¹âïŒâããã«ã·ã¯ããããµã³ã«ã«ãã³
é
žïœâãã³ãã«ãªãã·ããšãã«ãšã¹ãã«19ã¢ã«
ïŒ
ã
ãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ããããµã³ã«ã«ã
ã³é
žïœâã¡ããã·ããšãã«ãšã¹ãã«16ã¢ã«ïŒ
ã
ãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ããããµã³ã«ã«ã
ã³é
žïœâãããã«ãªãã·ããšãã«ãšã¹ãã«22ã¢ã«
ïŒ
ã
ïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâãšããã·ããšãã«ïŒãšã¿ã³26ã¢ã«
ïŒ
ïŒ
èç¹ïŒïŒâãéæç¹62.2âãηïŒ22âïŒïŒ
21.0cpãâ³ÎµïŒâ1.09ããããã€ãã¯ãMixture Example 5 Trans-4-butylcyclohexanecarboxylic acid p-ethoxyphenyl ester 17 mol%, trans-4-butylcyclohexanecarboxylic acid p-pentyloxyphenyl ester 19 mol%, trans-4-pentylcyclohexanecarboxylic acid p -Methoxyphenyl ester 16 mol%, trans-4-pentylcyclohexanecarboxylic acid p-propyloxyphenyl ester 22 mol%, 2-(trans-4-pentylcyclohexyl)
-1-(p-ethoxyphenyl)ethane 26 mol%; melting point <0°C, clearing point 62.2°C, η (22°C) =
21.0cp, â³Îµ=â1.09, nematic.
æ··åç©å®æœäŸ ïŒ
ïœâïŒïŒâãã³ãã«âïŒâããªããžãã«ïŒãã³
ãŸãããªã«ïŒïŒ
ã
ïœâïŒïŒâãããã«âïŒâããªããžãã«ïŒãã³
ãŸãããªã«12ã¢ã«ïŒ
ã
ãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ãããã·ã«ã«ã«ã
ã³é
žïœâã¡ããã·ããšãã«ãšã¹ãã«19ã¢ã«ïŒ
ã
ïœâãïŒâïŒãã©ã³ã¹âïŒâãšãã«ã·ã¯ãããã·
ã«ïŒâïŒâããªããžãã«ããã³ãŸãããªã«12ã¢ã«
ïŒ
ã
ïœâãïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ããã
ã·ã«ïŒâïŒâããªããžãã«ããã³ãŸãããªã«ïŒã¢
ã«ïŒ
ã
ïœâãïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ããã
ã·ã«ïŒãšãã«ããã³ãŸãããªã«12ã¢ã«ïŒ
ã
ïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâããã«ãªãã·ããšãã«ïŒãšã¿ã³32ã¢
ã«ïŒ
ïŒ
èç¹ïŒïŒâãéæç¹69âãηïŒ22âïŒïŒ28.5cpã
ãããã€ãã¯ãMixture Example 6 p-(5-pentyl-2-pyrimidinyl)benzonitrile 6%, p-(5-heptyl-2-pyrimidinyl)benzonitrile 12 mol%, trans-4-pentylcyclohexylcarboxylic acid p-methoxyphenyl Ester 19 mol%, p-[5-(trans-4-ethylcyclohexyl)-2-pyrimidinyl]benzonitrile 12 mol%, p-[5-(trans-4-pentylcyclohexyl)-2-pyrimidinyl]benzonitrile 7 Mol%, p-[2-(trans-4-hebutylcyclohexyl)ethyl]benzonitrile 12 mol%, 2-(trans-4-propylcyclohexyl)
-1-(p-butyloxyphenyl)ethane 32 mol%; melting point <0°C, clearing point 69°C, η (22°C) = 28.5 cp,
Nematetsk.
æ··åç©å®æœäŸ ïŒ
ïœâïŒïŒâãã³ãã«âïŒâããªããžãã«ïŒãã³
ãŸãããªã«ïŒã¢ã«ïŒ
ã
ïœâïŒïŒâãããã«âïŒâããªããžãã«ïŒãã³
ãŸãããªã«ïŒã¢ã«ïŒ
ã
ãã©ã³ã¹âïŒâããã«ã·ã¯ããããµã³ã«ã«ãã³
é
žïœâãšããã·ããšãã«ãšã¹ãã«16ã¢ã«ïŒ
ã
ãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ããããµã³ã«ã«ã
ã³é
žïœâã¡ããã·ããšãã«ãšã¹ãã«15ã¢ã«ïŒ
ã
ïœâãïŒâïŒãã©ã³ã¹âïŒâãšãã«ã·ã¯ãããã·
ã«ïŒâïŒâããªããžãã«ããã³ãŸãããªã«11ã¢ã«
ïŒ
ã
ïœâãïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ããã
ã·ã«ïŒâïŒâããªããžãã«ããã³ãŸãããªã«ïŒã¢
ã«ïŒ
ã
ïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâãšããã·ããšãã«ïŒãšã¿ã³37ã¢ã«
ïŒ
ïŒ
èç¹ïŒïŒâãéæç¹71âãηïŒ22âïŒïŒ28.2pã
ãããã€ãã¯ãMixture Example 7 p-(5-pentyl-2-pyrimidinyl)benzonitrile 5 mol%, p-(5-heptyl-2-pyrimidinyl)benzonitrile 9 mol%, trans-4-butylcyclohexanecarboxylic acid p-ethoxyph p-[5-(trans-4-ethylcyclohexyl)-2-pyrimidinyl]benzonitrile 11 mol%, p- [5-(trans-4-pentylcyclohexyl)-2-pyrimidinyl]benzonitrile 7 mol%, 2-(trans-4-propylcyclohexyl)
-1-(p-ethoxyphenyl)ethane 37 mol%; melting point <0°C, clearing point 71°C, η (22°C) = 28.2p,
Nematetsk.
æ··åç©å®æœäŸ ïŒ
ïœâããã«å®æ¯éŠé
žpâ²âã·ã¢ãããšãã«ãšã¹ã
ã«ïŒã¢ã«ïŒ
ã
ïœâïŒïŒâãã³ãã«âïŒâããªããžãã«ïŒãã³
ãŸãããªã«ïŒã¢ã«ïŒ
ã
ïœâïŒïŒâãããã«âïŒâããªããžãã«ïŒãã³
ãŸãããªã«ïŒã¢ã«ïŒ
ã
ïœâãïŒâïŒãã©ã³ã¹âïŒâãšãã«ã·ã¯ãããã·
ã«ïŒâïŒâããªããžãã«ããã³ãŸãããªã«10ã¢ã«
ïŒ
ã
ïœâãïŒâãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ããã
ã·ã«ïŒãšãã«ããã³ãŸãããªã«34ã¢ã«ïŒ
ã
ïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâãšããã·ããšãã«ïŒãšã¿ã³37ã¢ã«
ïŒ
ïŒ
èç¹ïŒ10âãéæç¹54âãηïŒ22âïŒïŒ27.0cpã
ãããã€ãã¯ãMixture Example 8 p-Butylbenzoic acid p'-cyanophenyl ester 5 mol%, p-(5-pentyl-2-pyrimidinyl)benzonitrile 5 mol%, p-(5-heptyl-2-pyrimidinyl)benzonitrile 9 mol%, p-[5-(trans-4-ethylcyclohexyl)-2-pyrimidinyl]benzonitrile 10 mol%, p-[2-trans-4-pentylcyclohexyl)ethyl]benzonitrile 34 mol%, 2- (trans-4-propylcyclohexyl)
-1-(p-ethoxyphenyl)ethane 37 mol%; melting point <10°C, clearing point 54°C, η (22°C) = 27.0cp,
Nematetsk.
æ··åç©å®æœäŸ ïŒ
ïœâïŒïŒâãã³ãã«âïŒâããªããžãã«ïŒãã³
ãŸãããªã«ïŒã¢ã«ïŒ
ã
ïœâïŒïŒâãããã«âïŒâããªããžãã«ïŒãã³
ãŸãããªã«ïŒã¢ã«ïŒ
ã
ãã©ã³ã¹âïŒâããã«ã·ã¯ããããµã³ã«ã«ãã³
é
žïœâãšããã·ããšãã«ãšã¹ãã«12ã¢ã«ïŒ
ã
ãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ãããã·ãµã³ã«ã«
ãã³é
žïœâã¡ããã·ããšãã«ãšã¹ãã«11ã¢ã«ïŒ
ã
ïœâãïŒâïŒãã©ã³ã¹âïŒâãšãã«ã·ã¯ãããã·
ã«ïŒâïŒâããªããžãã«ããã³ãŸãããªã«ïŒã¢ã«
ïŒ
ã
ïŒâãã³ãã«âãã©ã³ã¹âãã«ãªã³âïŒâã«ã«
ãã³é
žïœâãšãã«ããšãã«ãšã¹ãã«ïŒã¢ã«ïŒ
ã
ïŒâããã«âãã©ã³ã¹âãã«ãªã³âïŒâã«ã«ã
ã³é
žãã©ã³ã¹âïŒâãã³ãã«âïŒâã·ã¯ãããã·
ã«ãšã¹ãã«ïŒã¢ã«ïŒ
ã
ïœâãïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ããã
ã·ã«ïŒãšãã«ããã³ãŸãããªã«27ã¢ã«ïŒ
ã
ïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâããã«ãªãã·ããšãã«ïŒãšã¿ã³18ã¢
ã«ïŒ
ïŒ
èç¹ïŒâ10âãéæç¹63âãηïŒ22âïŒïŒ
27.0cpããããã€ãã¯ãMixture Example 9 4 mol% p-(5-pentyl-2-pyrimidinyl)benzonitrile, 7 mol% p-(5-heptyl-2-pyrimidinyl)benzonitrile, trans-4-butylcyclohexanecarboxylic acid p-ethoxyph p-[5-(trans-4-ethylcyclohexyl)-2-pyrimidinyl]benzonitrile 9 mol%, 6-pentyl-trans-decalin-2-carboxylic acid p-ethyl phenyl ester 5 mol%, 6-butyl-trans-decalin-2-carboxylic acid trans-4-pentyl-1-cyclohexyl ester 7 mol%, p- [2-(trans-4-pentylcyclohexyl)ethyl]benzonitrile 27 mol%, 2-(trans-4-propylcyclohexyl)
-1-(p-butyloxyphenyl)ethane 18 mol%; melting point <-10°C, clearing point 63°C, η (22°C) =
27.0cp, nematic.
æ··åç©å®æœäŸ 10
ïœâïŒïŒâãã³ãã«âïŒâããªããžãã«ïŒãã³
ãŸãããªã«ïŒã¢ã«ïŒ
ã
ïœâïŒïŒâãããã«âïŒâããªããžãã«ïŒãã³
ãŸãããªã«ïŒã¢ã«ïŒ
ã
ãã©ã³ã¹âïŒâããã«ã·ã¯ããããµã³ã«ã«ãã³
é
žïœâãšããã·ããšãã«ãšã¹ãã«10ã¢ã«ïŒ
ã
ãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ãããã·ã«ã«ã«ã
ã³é
žïœâã¡ããã·ããšãã«ãšã¹ãã«ïŒã¢ã«ïŒ
ã
ãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ããããµã³ã«ã«ã
ã³é
žïœâãããã«ãªãã·ããšãã«ãšã¹ãã«15ã¢ã«
ïŒ
ã
ïœâãïŒâïŒãã©ã³ã¹âïŒâãšãã«ã·ã¯ãããã·
ã«ïŒâïŒâããªããžãã«ããã³ãŸãããªã«ïŒã¢ã«
ïŒ
ã
ïœâãïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ããã
ã·ã«ïŒâïŒâããªããžãã«ããã³ãŸãããªã«ïŒã¢
ã«ïŒ
ã
ïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâãšããã·ããšãã«ïŒãšã¿ã³24ã¢ã«ïŒ
ã
ïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâããã«ãªãã·ããšãã«ïŒãšã¿ã³15ã¢
ã«ïŒ
ïŒ
èç¹ïŒâ10âãéæç¹69âãηïŒ22âïŒïŒ
25.8cpããããã€ãã¯ãMixture Example 10 3 mol% p-(5-pentyl-2-pyrimidinyl)benzonitrile, 8 mol% p-(5-heptyl-2-pyrimidinyl)benzonitrile, trans-4-butylcyclohexanecarboxylic acid p-ethoxyph 10 mol% trans-4-pentylcyclohexylcarboxylic acid p-methoxyphenyl ester, 15 mol% trans-4-pentylcyclohexanecarboxylic acid p-propyloxyphenyl ester, p-[5-(trans -4-ethylcyclohexyl)-2-pyrimidinyl]benzonitrile 7 mol%, p-[5-(trans-4-heptylcyclohexyl)-2-pyrimidinyl]benzonitrile 9 mol%, 2-(trans-4-propylcyclohexyl) )
-1-(p-ethoxyphenyl)ethane 24 mol%, 2-(trans-4-propylcyclohexyl)
-1-(p-butyloxyphenyl)ethane 15 mol%; melting point <-10°C, clearing point 69°C, η (22°C) =
25.8 cp, nematic.
æ··åç©å®æœäŸ 11
ïœâïŒïŒâãã³ãã«âïŒâããªããžãã«ïŒãã³
ãŸãããªã«ïŒã¢ã«ïŒ
ã
ïœâïŒïŒâãããã«âïŒâããªããžãã«ïŒãã³
ãŸãããªã«ïŒã¢ã«ïŒ
ã
ãã©ã³ã¹âïŒâããã«ã·ã¯ããããµã³ã«ã«ãã³
é
žïœâãšããã·ããšãã«ãšã¹ãã«13ã¢ã«ïŒ
ã
ãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ãããã·ã«ã«ã«ã
ã³é
žïœâã¡ããã·ããšãã«ãšã¹ãã«12ã¢ã«ïŒ
ã
ïœâãïŒâïŒãã©ã³ã¹âïŒâãšãã«ã·ã¯ãããã·
ã«ïŒâïŒâããªããžãã«ããã³ãŸãããªã«ïŒã¢ã«
ïŒ
ã
ïœâãïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ããã
ã·ã«ïŒâïŒâããªããžãã«ããã³ãŸãããªã«10ã¢
ã«ïŒ
ã
ïœâãïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ããã
ã·ã«ïŒãšãã«ããã³ãŸãããªã«29ã¢ã«ïŒ
ã
ïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâããã«ãªãã·ããšãã«ïŒãšã¿ã³18ã¢
ã«ïŒ
ïŒ
èç¹ïŒâ10âãéæç¹74âãηïŒ22âïŒïŒ
28.3cpããããã€ãã¯ãMixture Example 11 4 mol% p-(5-pentyl-2-pyrimidinyl)benzonitrile, 6 mol% p-(5-heptyl-2-pyrimidinyl)benzonitrile, trans-4-butylcyclohexanecarboxylic acid p-ethoxyph p-[5-(trans-4-ethylcyclohexyl)-2-pyrimidinyl]benzonitrile 8 mol%, p- [5-(trans-4-heptylcyclohexyl)-2-pyrimidinyl]benzonitrile 10 mol%, p-[2-(trans-4-pentolcyclohexyl)ethyl]benzonitrile 29 mol%, 2-(trans-4 -propylcyclohexyl)
-1-(p-butyloxyphenyl)ethane 18 mol%; melting point <-10°C, clearing point 74°C, η (22°C) =
28.3 cp, nematic.
æ··åç©å®æœäŸ 12
ïœâïŒïŒâãã³ãã«âïŒâããªããžãã«ïŒãã³
ãŸãããªã«ïŒã¢ã«ïŒ
ã
ïœâïŒïŒâãããã«âïŒâããªããžãã«ïŒãã³
ãŸãããªã«14ã¢ã«ïŒ
ã
ãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ããããµã³ã«ã«ã
ã³é
žïœâã¡ããã·ããšãã«ãšã¹ãã«23ã¢ã«ïŒ
ã
ãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ããããµã³ã«ã«ã
ã³é
žïœâãããã«ãªãã·ããšãã«ãšã¹ãã«29ã¢ã«
ïŒ
ã
ãã©ã³ã¹âïŒâïŒïœâãã³ãã«ããšãã«ïŒã·ã¯
ããããµã³ã«ã«ãã³é
žãã©ã³ã¹âïŒâãããã«ã·
ã¯ãããã·ã«ãšã¹ãã«11ã¢ã«ïŒ
ã
ïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâãšããã·ããšãã«ïŒãšã¿ã³15ã¢ã«
ïŒ
ïŒ
èç¹ïŒïŒâãéæç¹60.3âãηïŒ22âïŒïŒ
30.0cpããããã€ãã¯ãMixture Example 12 p-(5-pentyl-2-pyrimidinyl)benzonitrile 8 mol%, p-(5-heptyl-2-pyrimidinyl)benzonitrile 14 mol%, trans-4-pentylcyclohexanecarboxylic acid p-methoxyph 23 mol% of trans-4-pentylcyclohexanecarboxylic acid p-propyloxyphenyl ester, 29 mol% of trans-4-(p-pentylphenyl)cyclohexanecarboxylic acid trans-4-propylcyclohexyl ester, 2-(trans-4-pentylcyclohexyl)
-1-(p-ethoxyphenyl)ethane 15 mol%; melting point <0°C, clearing point 60.3°C, η (22°C) =
30.0cp, nematic.
æ¬çºæã«ãããåŒã®ååç©ã®è£œé ã次ã®å®æœ
äŸãåºã«ããŠèª¬æãããçžè»¢äœã«å¯ŸããŠçšããç¥
å·ã¯æ¬¡ã®æå³ãæããïŒïŒ£ã¯çµæ¶æ§ãè¡šããã
SAã¯ã¹ã¡ã¯ãã€ãã¯ïŒ¡ãè¡šãããSBã¯ã¹ã¡ã¯ã
ã€ãã¯ïŒ¢ãè¡šãããã¯ãããã€ãã¯ãè¡šããã
ããŠïŒ©ã¯çæ¹æ§çžãè¡šããïŒåŸã€ãŠãäŸãã°SBâ
ã¯çžè»¢äœã¹ã¡ã¯ãã€ãã¯ïŒ¢âãããã€ãã¯ãè¡š
ããïŒã The preparation of compounds of the formula according to the invention will be explained based on the following examples. The abbreviations used for phase transitions have the following meanings; C stands for crystallinity;
S A stands for smectic A, S B stands for smectic B, N stands for nematic and I stands for the isotropic phase (thus, for example, S B -
N represents the phase change smectic B-nematic).
å®æœäŸ ïŒ
ïŒâãšããã·âαâïŒãã©ã³ã¹âïŒâãã³ãã«
ã·ã¯ãããã·ã«ïŒã¢ã»ãããšãã³9.7ïœããžãšã
ã¬ã³ã°ãªã³ãŒã«125mlããšã¿ããŒã«50mlãããã©
ãžã³æ°Žåç©6.2ïœåã³æ°Žé
žåã«ãªãŠã 8.2ïœã®æ··å
ç©ã济枩110âã§ïŒæéå ç±æ²žéš°ãããããã®åŸã
济枩ã220âã«äžæããããšã¿ããŒã«åã³éå°é
ã®ããã©ãžã³æ°Žåç©ãçåºãããã次ã«æ··åç©ã
å
éšæž©åºŠ180âã«æŽã«4.5æéå ç±ããäžå€æŸçœ®
ããæ··åç©ãæ°·æ°Žã«æ³šããçæç©ããšãŒãã«å
150mlã«ïŒåæ¡ãå
¥ãããå液ããææ©çžãæ°Žã§
æŽæµããŠäžæ§ã«ããç¡«é
žãããªãŠã äžã§ä¹Ÿç¥ãã
èžçºãããç管äžã«ãŠ180âïŒçŽ1Torrã§èžçã
ããçããïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ã
ããã·ã«ïŒâïŒâïŒïœâãšããã·ããšãã«ïŒãšã¿ã³
7.4ïœïŒçŽåºŠçŽ98.5ïŒ
ïŒãçŽâ20âã§ã€ãœããã
ããŒã«ããïŒåããããŠãžã€ãœãããããŒã«ãã
ïŒååçµæ¶ãããïŒèç¹ïŒïŒ£âïŒ18âãŸãã¯27
âïŒïŒã€ã®å€æ
ïŒã転äœç¹SBâN8âïŒã¢ãããã
ãã¯ïŒãéæç¹ïŒïŒ®âïŒïŒ47âãExample 1 A mixture of 9.7 g of 4-ethoxy-α-(trans-4-pentylcyclohexyl)acetophenone, 125 ml of diethylene glycol, 50 ml of ethanol, 6.2 g of hydrazine hydrate, and 8.2 g of potassium hydroxide was heated at a bath temperature of 110°C for 4 hours. Boiled. after that,
The bath temperature was raised to 220°C to distill off ethanol and excess hydrazine hydrate. The mixture was then heated to an internal temperature of 180°C for a further 4.5 hours, left overnight, the mixture was poured into ice water and the product was evaporated into ether.
The sample was added three times to 150 ml. The combined organic phases were washed neutral with water, dried over sodium sulfate,
It was evaporated and distilled in a bulb tube at 180°C/approximately 1 Torr. The resulting 2-(trans-4-pentylcyclohexyl)-1-(p-ethoxyphenyl)ethane
7.4 g (approximately 98.5% purity) was recrystallized at approximately -20°C once from isopropanol and once from diisopropanol; melting point (C-N) 18°C or 27
°C (two transformations), transposition point S B -N8 °C (monotropic), clearing point (N-1) 47 °C.
åºçºç©è³ªãšããŠçšããïŒâãšããã·âαâïŒã
ã©ã³ã¹âïŒâãã³ãã«ã·ã¯ãããã·ã«ïŒã¢ã»ãã
ãšãã³ã¯æ¬¡ã®åŠãããŠè£œé ããããšãã§ããïŒ
ãžã¯ããã¡ã¿ã³120mläžã®ãã©ã³ã¹âïŒâãã³
ãã«ã·ã¯ãããã·ã«é
¢é
žã¯ãã©ã€ãïŒãã©ã³ã¹â
ïŒâãã³ãã«ã·ã¯ãããã·ã«é
¢é
ž8.0ïœããã³ãŒ
ã³75mläžã®å¡©åããªãã«4.1mlãšå
±ã«ïŒæé沞隰
ããã次ã«çæç©ãèžçºãããŠè£œé ãããã®ïŒ
8.7ïœåã³ããšãã¬ãŒã4.6ïœãäžæŽ»æ§ã¬ã¹é°å²æ°
äžã«ãŠå¡©åã¢ã«ãããŠã 5.5ïœã§äžéšã¥ã€åŠçã
ãããã®æ··åç©ã宀枩ã§ïŒæéæ¹æãã次ã«æ¿å¡©
é
ž50mlãå«ãæ°·æ°Žäžã«æ³šãã ãææ©çžãåé¢ãã
æ°Žçžããžã¯ããã¡ã¿ã³300mlã§éæœåºãããå液
ããææ©çžãé 次氎ã3Næ°Žé
žåãããªãŠã ãæ°Ž
åã³é£œåå¡©åãããªãŠã 溶液ã§æŽæµããç¡«é
žãã
ãªãŠã äžã§ä¹Ÿç¥ããéãããããŠèžçºãããã
ç²è£œã®æ²¹ç¶ã®ïŒâãšããã·âαâïŒãã©ã³ã¹âïŒ
âãã³ãã«ã·ã¯ãããã·ã«ïŒã¢ã»ãããšãã³9.7
ïœãåŸãããã 4-Ethoxy-α-(trans-4-pentylcyclohexyl)acetophenone used as starting material could be prepared as follows: trans-4-pentylcyclohexyl acetic chloride (trans-
(Prepared by boiling 8.0 g of 4-pentylcyclohexyl acetic acid with 4.1 ml of thionyl chloride in 75 ml of benzene for 2 hours and then evaporating the product)
8.7 g and 4.6 g of phenolate were treated in portions with 5.5 g of aluminum chloride under an inert gas atmosphere. The mixture was stirred at room temperature for 5 hours and then poured into ice water containing 50 ml of concentrated hydrochloric acid. Separate the organic phase;
The aqueous phase was back-extracted with 300 ml of dichloromethane. The combined organic phases were washed successively with water, 3N sodium hydroxide, water and saturated sodium chloride solution, dried over sodium sulfate, filtered and evaporated.
Crude oily 4-ethoxy-α-(trans-4
-pentylcyclohexyl)acetophenone 9.7
g was obtained.
äžèšåæ§ã®æ¹æ³ã§æ¬¡ã®ååç©ã補é ããããšã
ã§ããïŒ
ïŒâïŒãã©ã³ã¹âïŒâãšãã«ã·ã¯ãããã·ã«ïŒâ
ïŒâïŒïœâãšããã·ããšãã«ïŒãšã¿ã³ïŒèç¹ïŒïŒ£
âïŒ20.5âãéæç¹ïŒSBâïŒïŒâãã¢ããã
ããã¯ïŒmonotropicïŒãïŒ
ïŒâïŒãã©ã³ã¹âïŒâãšãã«ã·ã¯ãããã·ã«ïŒâ
ïŒâïŒïœâããã«ãªãã·ããšãã«ïŒãšã¿ã³ïŒèç¹
ïŒïŒ£âïŒïŒâã転äœç¹SBâN0âïŒã¢ããããã
ã¯ïŒãéæç¹ïŒïŒ®âïŒ6.5âïŒ
ïŒâïŒãã©ã³ã¹âïŒâãšãã«ã·ã¯ãããã·ã«ïŒâ
ïŒâïŒïœâããã·ã«ãªãã·ããšãã«ïŒãšã¿ã³ïŒè
ç¹ïŒïŒ£âïŒ10âã転äœç¹SBâN1âïŒã¢ããã
ããã¯ïŒãéæç¹ïŒïŒ®âïŒ13âïŒ
ïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâãšããã·ããšãã«ïŒãšã¿ã³ïŒèç¹
ïŒïŒ£âïŒ21âãéæç¹ïŒïŒ®âïŒ34âïŒ
ïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâãããã«ãªãã·ããšãã«ïŒãšã¿ã³ïŒ
èç¹ïŒïŒ£âïŒ20.5âã転äœç¹SBâN13.5âïŒã¢
ãããããã¯ïŒãéæç¹ïŒïŒ®âïŒ19.5âïŒã¢ã
ããããã¯ïŒïŒ
ïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâããã«ãªãã·ããšãã«ïŒãšã¿ã³ïŒè
ç¹ïŒïŒ£âïŒ20.5âã転äœç¹SBâN20âïŒã¢ãã
ãããã¯ïŒãéæç¹ïŒïŒ®âïŒ33âïŒ
ïŒâïŒãã©ã³ã¹âïŒâããã«ã·ã¯ãããã·ã«ïŒâ
ïŒâïŒïœâã¡ããã·ããšãã«ïŒãšã¿ã³ïŒèç¹ïŒïŒ£
âïŒ28âãéæç¹ïŒïŒ®âïŒ16.5âïŒã¢ããã
ããã¯ïŒïŒ
ïŒâïŒãã©ã³ã¹âïŒâããã«ã·ã¯ãããã·ã«ïŒâ
ïŒâïŒïœâãšããã·ããšãã«ïŒãšã¿ã³ïŒèç¹ïŒïŒ£
âSBïŒ10âã転äœç¹SBâN11âãéæç¹ïŒïŒ®â
ïŒ32âïŒ
ïŒâïŒãã©ã³ã¹âïŒâããã«ã·ã¯ãããã·ã«ïŒâ
ïŒâïŒïœâããã«ãªãã·ããšãã«ïŒãšã¿ã³ïŒèç¹
ïŒïŒ£âSBïŒ11âãéæç¹ïŒSBâïŒ37âïŒ
ïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâã¡ããã·ããšãã«ïŒãšã¿ã³ïŒèç¹
ïŒïŒ£âïŒ31âãéæç¹ïŒïŒ®âïŒïŒ33âïŒ
ïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâãããã«ãªãã·ããšãã«ïŒãšã¿ã³ïŒ
èç¹ïŒïŒ£âSBïŒ4.5âã転äœç¹SBâN32.5âãéæ
ç¹ïŒïŒ®âïŒ33.5âïŒ
ïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâããã«ãªãã·ããšãã«ïŒãšã¿ã³ïŒè
ç¹ïŒïŒ£âSBïŒ25.5âã転äœç¹SBâN44âãéæç¹
ïŒïŒ®âïŒ45âïŒ
ïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâã¡ããã·ããšãã«ïŒãšã¿ã³ïŒèç¹
ïŒïŒ£âïŒ28.5âã転äœç¹SBâN17âïŒã¢ããã
ããã¯ïŒãéæç¹ïŒïŒ®âïŒ40âïŒ
ïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâãšããã·ããšãã«ïŒãšã¿ã³ïŒèç¹
ïŒïŒ£âïŒ36âã転äœç¹SBâN30âïŒã¢ãããã
ãã¯ïŒãéæç¹ïŒïŒ®âïŒ51âïŒ
ïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâãã³ãã«ããšãã«ïŒãšã¿ã³ïŒèç¹
ïŒïŒ£âSBïŒïŒâãéæç¹ïŒSBâïŒïŒâïŒ
ïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ãããã·ã«ïŒ
âïŒïœâãããã«ããšãã«ïŒãšã¿ã³ïŒèç¹ïŒïŒ£â
SBïŒ4.5âãéæç¹ïŒSBâïŒ18âïŒ
ïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâãã³ãã«ããšãã«ïŒãšã¿ã³ïŒèç¹
ïŒïŒ£âSBïŒ9.5âãéæç¹ïŒSBâïŒ30âïŒ
ïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâããã·ã«ããšãã«ïŒãšã¿ã³ïŒèç¹
ïŒïŒ£âSBïŒ11âãéæç¹ïŒSBâïŒ34âïŒ
ïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒïœâããã«ããšãã«ïŒãšã¿ã³ïŒèç¹ïŒïŒ£
âSBïŒ3.5âãéæç¹ïŒSBâïŒ30.5âïŒSBäžçž
ããã®çµæ¶ã¯â24âã«å·åŽããŠãã§ããªãã€ãã The following compound could be prepared in the same manner as above: 2-(trans-4-ethylcyclohexyl)-
1-(p-ethoxyphenyl)ethane; melting point (C
-I) 20.5°C, clearing point (S B -I) 3°C [monotropic]; 2-(trans-4-ethylcyclohexyl)-
1-(p-butyloxyphenyl)ethane; melting point (C-N) 4°C, rearrangement point S B -N0°C (monotropic), clearing point (N-I) 6.5°C; 2-(trans-4-ethyl) cyclohexyl)-
1-(p-hexyloxyphenyl)ethane; melting point (C-N) 10°C, rearrangement point S B -N1°C (monotropic), clearing point (N-I) 13°C; 2-(trans-4-propyl) cyclohexyl)
-1-(p-ethoxyphenyl)ethane; melting point (C-N) 21°C, clearing point (N-I) 34°C; 2-(trans-4-propylcyclohexyl)
-1-(p-propyloxyphenyl)ethane;
Melting point (C-I) 20.5°C, rearrangement point S B -N 13.5°C (monotropic), clearing point (N-I) 19.5°C (monotropic); 2-(trans-4-propylcyclohexyl)
-1-(p-butyloxyphenyl)ethane; melting point (C-N) 20.5°C, rearrangement point S B -N 20°C (monotropic), clearing point (N-I) 33°C; 2-(trans-4- butylcyclohexyl)-
1-(p-methoxyphenyl)ethane; melting point (C
-I) 28°C, clearing point (N-I) 16.5°C (monotropic); 2-(trans-4-butylcyclohexyl)-
1-(p-ethoxyphenyl)ethane; melting point (C
âS B ) 10â, dislocation point S B âN11â, clearing point (Nâ
I) 32°C; 2-(trans-4-butylcyclohexyl)-
1-(p-butyloxyphenyl)ethane; melting point (C-S B ) 11°C, clearing point (S B -I) 37°C; 2-(trans-4-pentylcyclohexyl)
-1-(p-methoxyphenyl)ethane; melting point (C-N) 31°C, clearing point (N-1) 33°C; 2-(trans-4-pentylcyclohexyl)
-1-(p-propyloxyphenyl)ethane;
Melting point (C-S B ) 4.5°C, rearrangement point S B -N 32.5°C, clearing point (N-I) 33.5°C; 2-(trans-4-pentylcyclohexyl)
-1-(p-butyloxyphenyl)ethane; melting point (C-S B ) 25.5°C, rearrangement point S B -N44°C, clearing point (N-I) 45°C; 2-(trans-4-heptylcyclohexyl) )
-1-(p-methoxyphenyl)ethane; melting point (C-N) 28.5°C, rearrangement point S B -N 17°C (monotropic), clearing point (N-I) 40°C; 2-(trans-4-pentyl) cyclohexyl)
-1-(p-ethoxyphenyl)ethane; melting point (C-N) 36°C, rearrangement point S B -N 30°C (monotropic), clearing point (N-I) 51°C; 2-(trans-4-propyl) cyclohexyl)
-1-(p-bentylphenyl)ethane; melting point (C-S B ) 3°C, clearing point (S B -I) 6°C; 2-(trans-4-pentylcyclohexyl)
-(p-propylphenyl)ethane; melting point (C-
S B ) 4.5â, clearing point (S B -I) 18â; 2-(trans-4-pentylcyclohexyl)
-1-(p-pentylphenyl)ethane; melting point (C-S B ) 9.5°C, clearing point (S B -I) 30°C; 2-(trans-4-pentylcyclohexyl)
-1-(p-hexylphenyl)ethane; melting point (C-S B ) 11°C, clearing point (S B -I) 34°C; 2-(trans-4-pentylcyclohexyl)
-1-(p-butylphenyl)ethane; melting point (C
-S B ) 3.5°C, clearing point (S B -I) 30.5°C; crystals from the S B single phase could not be formed even when cooled to -24°C.
å®æœäŸ ïŒ
ïŒâïŒ4â²âãã³ãã«ããšãã«ïŒâαâïŒãã©ã³ã¹
âïŒâãããã«ã·ã¯ãããã·ã«ïŒã¢ã»ãããšãã³
4.3ïœããžãšãã¬ã³ã°ãªã³ãŒã«75mlããšã¿ããŒã«
25mlãããã©ãžã³æ°Žåç©2.2ïœåã³æ°Žé
žåã«ãªãŠ
ã 7.0ïœã®æ··åç©ã济枩110âã§ïŒæéå ç±æ²žéš°ã
ããããã®åŸã济枩ã220âã«äžæããããšã¿ã
ãŒã«åã³éå°éã®ããã©ãžã³æ°Žåç©ãçåºãã
ãã次ã«ãã®æ··åç©ãå
éšæž©åºŠ180âã«æŽã«ïŒæ
éå ç±ããæŸå·ããæ°Žã§åžéãããžãšãã«ãšãŒã
ã«ã§æœåºãããææ©çžãæ°Žã§æŽæµããŠäžæ§ã«ãã
ç¡«é
žãããªãŠã äžã§ä¹Ÿç¥ãããããŠèžçºãããã
åŸãããé»è²æ³¡ç¶ç©ïŒ3.9ïœïŒãã€ãœãããããŒ
ã«ããïŒåããããŠãšã¿ããŒã«ããïŒåãåçµ
æ¶ãããããïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯
ãããã·ã«ïŒâïŒâïŒ4â²âãã³ãã«âïŒâãããšã
ãªã«ïŒãšã¿ã³2.7ïœãåŸããããã®ãã®ã¯ãã¶ã
宀枩ã§ã¹ã¡ã¯ãã€ã¯ã§ããïŒçžè»¢äœç¹43.5âåã³
130âã転äœç¹SAâN132.5âãéæç¹ïŒïŒ®âïŒ
141.5âãExample 2 4-(4'-pentylphenyl)-α-(trans-4-propylcyclohexyl)acetophenone
4.3g, diethylene glycol 75ml, ethanol
A mixture of 25 ml, 2.2 g of hydrazine hydrate, and 7.0 g of potassium hydroxide was boiled at a bath temperature of 110° C. for 4 hours. Thereafter, the bath temperature was raised to 220°C, and ethanol and excess hydrazine hydrate were distilled out. The mixture was then heated to an internal temperature of 180° C. for a further 5 hours, allowed to cool, diluted with water and extracted with diethyl ether. Wash the organic phase with water to make it neutral;
Dry over sodium sulphate and evaporate.
The resulting yellow foam (3.9 g) was "recrystallized" once from isopropanol and once from ethanol. 2.7 g of 2-(trans-4-propylcyclohexyl)-1-(4'-pentyl-4-biphenylyl)ethane are obtained, which is probably smectic at room temperature; the phase transition point is 43.5°C and
130â, dislocation point S A -N132.5â, clearing point (N-I)
141.5â.
åºçºç©è³ªãšããŠçšããïŒâïŒ4â²âãã³ãã«ããš
ãã«ïŒâαâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ããã
ã·ã«ïŒã¢ã»ãããšãã³ã¯æ¬¡ã®åŠãããŠè£œé ããã
ãšãã§ããïŒ
ãžã¯ããã¡ã¿ã³125mläžã®ãã©ã³ã¹âïŒâãã
ãã«ã·ã¯ãããã·ã«é
¢é
žã¯ãã©ã€ã3.5ïœåã³ïŒ
âãã³ãã«ãããšãã«4.0ïœã®æ··åç©ã15å以å
ã«å¡©åã¢ã«ãããŠã 2.6ïœã§äžéšã¥ã€åŠçããã
ãã®æ··åç©ã宀枩ã§ïŒæéæ¹æãã次ã«2Nå¡©é
ž
250mlã泚ãã ãææ©çžãåé¢ããæ°Žçžããžã¯ã
ãã¡ã¿ã³å150mlã§ïŒåéæœåºãããå液ããæ
æ©çžãé 次氎ã1Næ°Žé
žåãããªãŠã 溶液åã³æ°Ž
ã§æŽæµããç¡«é
žãããªãŠã äžã§ä¹Ÿç¥ãããããŠèž
çºããããç²è£œã®çæç©ã沞隰ã¢ã»ãã³ã«æº¶è§£
ããå°éã®æŽ»æ§çãçšããŠç±æéãããå·åŽã
ãéã«ãïŒâïŒ4â²âãã³ãã«ããšãã«ïŒâαâïŒã
ã©ã³ã¹âïŒâãããã«ã·ã¯ãããã·ã«ïŒã¢ã»ãã
ãšãã³ãæ¶åºãããåé4.3ïœïŒèç¹ïŒïŒ£âSAïŒ
100âãéæç¹ïŒSAâïŒ143âã The 4-(4'-pentylphenyl)-α-(trans-4-propylcyclohexyl)acetophenone used as starting material could be prepared as follows: trans-4-propylcyclohexyl in 125 ml of dichloromethane. Acetate chloride 3.5g and 4
- A mixture of 4.0 g of pentylbiphenyl was treated in portions within 15 minutes with 2.6 g of aluminum chloride.
The mixture was stirred at room temperature for 5 hours, then 2N hydrochloric acid
Poured 250ml. The organic phase was separated and the aqueous phase was back-extracted twice with 150 ml each of dichloromethane. The combined organic phases were washed successively with water, 1N sodium hydroxide solution and water, dried over sodium sulfate and evaporated. The crude product was dissolved in boiling acetone and heated over a small amount of activated carbon. Upon cooling, 4-(4'-pentylphenyl)-α-(trans-4-propylcyclohexyl)acetophenone crystallized. Yield 4.3g; Melting point (C-S A )
100â, clearing point (S A âI) 143â.
äžèšåæ§ã®æ¹æ³ã§æ¬¡ã®ååç©ã補é ããããšã
ã§ããïŒ
ïŒâïŒãã©ã³ã¹âïŒâãšãã«ã·ã¯ãããã·ã«ïŒâ
ïŒâïŒ4â²âãããã«âïŒâãããšããªã«ïŒãšã¿
ã³ïŒèç¹çŽ55âã転äœç¹ïŒ³âSB51.5âã転äœç¹SB
âN98.5âãéæç¹ïŒïŒ®âïŒ121.5âïŒ
ïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ãããã·ã«ïŒ
âïŒâïŒ4â²âããã«ãªãã·âïŒâãããšããªã«ïŒ
ãšã¿ã³ïŒèç¹ïŒïŒ£âïŒ84.5âã転äœç¹ïŒ³âSA
139.5âã転äœç¹SAâN152.5âãéæç¹ïŒïŒ®âïŒ
172.5âã The following compound could be prepared in the same manner as above: 2-(trans-4-ethylcyclohexyl)-
1-(4'-propyl-4-biphenylyl)ethane; melting point approximately 55â, rearrangement point S-S B 51.5â, rearrangement point S B
-N98.5â, clearing point (N-I) 121.5â; 2-(trans-4-propylcyclohexyl)
-1-(4'-butyloxy-4-biphenylyl)
Ethane; melting point (C-S) 84.5â, dislocation point S-S A
139.5â, dislocation point S A -N152.5â, clearing point (N-I)
172.5â.
å®æœäŸ ïŒ
(a) å®æœäŸïŒãšåæ§ã®æ¹æ³ã§ãïœâãïŒâïŒãã©ã³
ã¹âïŒâããã«ã·ã¯ãããã·ã«ïŒãšãã«ãããš
ããŒã«ã補é ããïŒããšããŒã«ã®ããªãŒãã«â
ã¯ã©ããã¢ã·ã«åã«å¯Ÿãã溶åªïŒããããã³ãŒ
ã³ãŸãã¯ãããã¡ã¿ã³ïŒïŒèç¹101.5ã102.5âãExample 3 (a) p-[2-(trans-4-butylcyclohexyl)ethyl]phenol was produced in the same manner as in Example 1.
Solvent for Crafts acylation; nitrobenzene or nitromethane); melting point 101.5-102.5°C.
(b) ãã³ãŒã³ïŒmläžã®é
ªé
žã¯ãã©ã€ã0.68ïœã®æº¶
液ãæ¹æããªããã也ç¥ããªãžã³ïŒmläžã®ïœâ
ãïŒâïŒãã©ã³ã¹âïŒâããã«ã·ã¯ãããã·ã«ïŒ
ãšãã«ãããšããŒã«1.6ïœã®æº¶æ¶²ã«æ»Žäžããã
ãã®æ··åç©ãäžå€æŸçœ®ããæ°·ïŒæ°Žã«æ³šãããžãš
ãã«ãšãŒãã«ã§æœåºãããææ©çžã3Nå¡©é
žã§
æ°åæŽæµããæ°Žã§æŽæµããŠäžæ§ã«ããç¡«é
žãã
ãªãŠã äžã§ä¹Ÿç¥ãããããŠèžçºãããããã®ã¹
ã¡ã¯ãã€ã¯ç²è£œã®çæç©ïŒ2.05ïœïŒãã·ãªã«ã²
ã«äžã§ãžããµã³ïŒãžãšãã«ãšãŒãã«ïŒ19ïŒïŒïŒ
ãçšããŠã¯ãããã°ã©ãã«ãã€ãŠç²Ÿè£œãããè
å±€ã¯ãããã°ã©ãã«ãã€ãŠçŽç²ãªç©è³ªã§ããã
ã©ã¯ã·ãšã³ïŒ1.9ïœïŒãâ20âã§ã€ãœãããã
ãŒã«ããïŒåããããŠãšã¿ããŒã«ããïŒååçµ
æ¶ãããåæçã«çŽïœâãïŒâïŒãã©ã³ã¹âïŒâ
ããã«ã·ã¯ãããã·ã«ïŒâïŒâãšãã«ãããšã
ã«ããã¬ãŒã0.8ïœãåŸãïŒèç¹â13âãŸãã¯
ïŒïŒâïŒïŒã€ã®å€æ
ïŒãéæç¹ïŒSBâïŒ45âã(b) While stirring a solution of 0.68 g of butyric chloride in 3 ml of benzene, a solution of p-
[2-(trans-4-butylcyclohexyl)
It was added dropwise to a solution of 1.6 g of ethylphenol.
The mixture was left overnight, poured into ice/water and extracted with diethyl ether. The organic phase was washed several times with 3N hydrochloric acid, neutralized with water, dried over sodium sulphate and evaporated. This smectate crude product (2.05 g) was purified on silica gel with hexane/diethyl ether (19:1).
It was purified by chromatography using The fraction (1.9 g), pure material by thin layer chromatography, was recrystallized at -20 DEG C. once from isopropanol and once from ethanol. Analytically pure p-[2-(trans-4-
0.8 g of butylcyclohexyl)-1-ethyl phenylbutyrate were obtained; melting point -13°C or +4°C (two modifications), clearing point (S B -I) 45°C.
ïœâãïŒâïŒãã©ã³ã¹âïŒâããã«ã·ã¯ãããã·
ã«ïŒãšãã«ãããšããŒã«ã¯æ¬¡ã®æ¹æ³ã§åŸãããšã
ã§ããïŒ
ãžã¯ããã¡ã¿ã³50mläžã®ïŒâïŒãã©ã³ã¹âïŒâ
ããã«ã·ã¯ãããã·ã«ïŒâïŒâïŒïœâã¡ããã·ããš
ãã«ïŒãšã¿ã³ïŒå®æœäŸïŒã«ãããåŠãããŠè£œé ã
ããã®ïŒ4.7ïœã®æº¶æ¶²ããžã¯ãããšã¿ã³100mlåã³
ãšãã«ã¡ã«ã«ãã¿ã³10mläžã®å¡©åã¢ã«ãããŠã
6.9ïœã®æº¶æ¶²ã«æ»Žäžãããã®æ··åç©ã宀枩ã§ïŒæ
éæ¹æãã次ã«æ°·ïŒæ°Žã«æ³šããææ©çžãåé¢ãã
æ°Žçžããžã¯ããã¡ã¿ã³å100mlã§ïŒåæœåºããã
å液ããææ©çžã飜åå¡©åãããªãŠã 溶液ã§æŽæµ
ããŠäžæ§ã«ããç¡«é
žãããªãŠã äžã§ä¹Ÿç¥ãããã
ãŠèžçºããããçããç²è£œã®ïœâãïŒâïŒãã©ã³ã¹
âïŒâããã«ã·ã¯ãããã·ã«ïŒãšãã«ïŒãšãã«ã
ããšããŒã«ïŒ4.4ïœïŒããããµã³ããåçµæ¶ãã
ããåé3.8ïœïŒèç¹101.5ã102.5âã p-[2-(trans-4-butylcyclohexyl)ethyl]phenol could be obtained in the following way: 2-(trans-4-
A solution of 4.7 g of butylcyclohexyl)-1-(p-methoxyphenyl)ethane (prepared as in Example 1) was prepared using aluminum chloride in 100 ml of dichloroethane and 10 ml of ethyl mercaptan.
6.9 g of solution was added dropwise, the mixture was stirred at room temperature for 4 hours, then poured onto ice/water, the organic phase was separated,
The aqueous phase was extracted twice with 100 ml each of dichloromethane.
The combined organic phases were washed neutral with saturated sodium chloride solution, dried over sodium sulphate and evaporated. The resulting crude p-[2-(trans-4-butylcyclohexyl)ethyl)ethyl]
Phenol (4.4g) was recrystallized from hexane. Yield 3.8g; melting point 101.5-102.5°C.
äžèšåæ§ã®æ¹æ³ã§æ¬¡ã®ååç©ã補é ããããšã
ã§ããïŒ
ïœâãïŒâïŒãã©ã³ã¹âïŒâããã«ã·ã¯ãããã·
ã«ïŒâïŒâãšãã«ãããšãã«ã¢ã»ããŒãïŒèç¹
ïŒïŒ£âïŒ32.5âãéæç¹ïŒïŒ®âïŒ23âïŒã¢ã
ããããã¯ïŒïŒ
ïœâãïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ããã
ã·ã«ïŒâïŒâãšãã«ãããšãã«ã¢ã»ããŒãïŒèç¹
ïŒïŒ£âïŒ41.5âãéæç¹ïŒïŒ®âïŒ40.5âïŒã¢
ãããããã¯ïŒïŒ
ïœâãïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ããã
ã·ã«ïŒâïŒâãšãã«ãããšãã«ããã¬ãŒãïŒèç¹
ïŒïŒ£âSBïŒ31âãéæç¹ïŒSBâïŒ52âã The following compound could be prepared in the same manner as above: p-[2-(trans-4-butylcyclohexyl)-1-ethyl]phenylacetate; melting point (C-I) 32.5°C, clearing point ( N-I) 23°C (monotropic); p-[2-(trans-4-pentylcyclohexyl)-1-ethyl]phenylacetate; melting point (C-I) 41.5°C, clearing point (N-I) 40.5°C (Monotropic); p-[2-(trans-4-pentylcyclohexyl)-1-ethyl]phenylbutyrate; melting point (C-S B ) 31°C, clearing point (S B -I) 52°C.
å®æœäŸ ïŒ
ãžã¯ããã¡ã¿ã³100mläžã®ïŒâïŒãã©ã³ã¹âïŒâ
ãããã«ã·ã¯ãããã·ã«ïŒâïŒâããšãã«ãšã¿ã³
ïŒãã³ãŒã³ã®ããªãŒãã«âã¯ã©ããã¢ã·ã«ååã³
åŸãããã±ãã³ã®éå
ã«ãã€ãŠå®æœäŸïŒãšåæ§ã«
ããŠè£œé ãããã®ïŒ4.6ïœåã³ããããªã³é
žã¯ã
ã©ã€ã1.94ïœã®æ··åç©ãäžæŽ»æ§ã¬ã¹é°å²æ°äžã«ãŠ
å¡©åã¢ã«ãããŠã 3.2ïœã§äžéšã¥ã€åŠçãããã
ã®æ··åç©ã宀枩ã§ïŒæéæ¹æããæ¿å¡©é
ž25mlãšæ··
åããæ°·ïŒæ°Žã«æ³šãã ãææ©çžãåé¢ããæ°Žçžã
ãžã¯ããã¡ã¿ã³å100mlã§éæœåºãããå液ãã
ææ©çžã1Næ°Žé
žåãããªãŠã ã§æŽæµããæ°Žã§æŽ
æµããŠäžæ§ã«ããç¡«é
žãããªãŠã äžã§ä¹Ÿç¥ããã
ããŠèžçºããããçããïœâãïŒâïŒãã©ã³ã¹âïŒ
âãããã«ã·ã¯ãããã·ã«ïŒâïŒâãšãã«ããã
ããªããšãã³ïŒ5.5ïœïŒããšã¿ããŒã«ããïŒåå
çµæ¶ããïŒèç¹ïŒïŒ£âïŒ40âãéæç¹ïŒïŒ®â
ïŒ56âãExample 4 2-(trans-4-
A mixture of 4.6 g of propylcyclohexyl)-1-phenylethane (prepared analogously to Example 1 by Friedel-Crafts acylation of benzene and reduction of the resulting ketone) and 1.94 g of propionic acid chloride was inactivated. Portions were treated with 3.2 g of aluminum chloride under a gas atmosphere. The mixture was stirred at room temperature for 5 hours and poured onto ice/water mixed with 25 ml of concentrated hydrochloric acid. The organic phase was separated and the aqueous phase was back-extracted with 100 ml each of dichloromethane. The combined organic phases were washed with 1N sodium hydroxide, neutralized with water, dried over sodium sulfate and evaporated. The resulting p-[2-(trans-4
-propylcyclohexyl)-1-ethyl]propiophenone (5.5 g) was recrystallized twice from ethanol; melting point (C-N) 40°C, clearing point (N-
I) 56â.
äžèšåæ§ã®æ¹æ³ã§æ¬¡ã®ååç©ã補é ããããšã
ã§ããïŒ
ïœâãïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ããã
ã·ã«ïŒâïŒâãšãã«ããã¬ãããšãã³ïŒèç¹ïŒïŒ£
âïŒ47.5âã転äœç¹SBâN30âïŒã¢ããããã€
ãã¯ïŒãéæç¹ïŒïŒ®âïŒ46âïŒã¢ããããã
ã¯ïŒïŒ
ïœâãïŒâïŒãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ããã
ã·ã«ïŒâïŒâãšãã«ããã¬ãããšãã³ïŒèç¹ïŒïŒ£
âïŒ48.5âã転äœç¹SBâSA33âïŒã¢ããããã
ã¯ïŒã転äœç¹SAâN39âïŒã¢ãããããã¯ïŒãéæ
ç¹ïŒïŒ®âïŒ57âã The following compound could be prepared in the same manner as above: p-[2-(trans-4-propylcyclohexyl)-1-ethyl]valerophenone; melting point (C
-I) 47.5â, rearrangement point S B -N30â (monotropic), clearing point (N-I) 46â (monotropic); p-[2-(trans-4-pentylcyclohexyl)-1-ethyl] Valerophenone; melting point (C
-N) 48.5°C, transposition point S B -S A 33°C (monotropic), transposition point S A -N 39°C (monotropic), clearing point (N-I) 57°C.
å®æœäŸ ïŒ
(a) ãã©ã³ã¹âïŒâãã³ãã«ã·ã¯ããããµã³ã«ã«
ããã·ã¢ã«ããã182.3ïœãå¡©åã¡ãã¬ã³ïŒ
åã³ïŒïœâã¡ããã·ã«ã«ããã«ããšãã«ïŒã¡ã
ã«ãŒããªããšãã«ãã¹ãããŠã ãããã€ã
589.6ïœã®æ··åç©ãïŒãïŒâã«å·åŽãããã®å·
溶液ãïŒãïŒâã§çŽïŒæé以å
ã«ãã¡ã¿ããŒã«
276mläžã®ãããªãŠã 27.6ïœã®æº¶æ¶²ïŒãããªãŠ
ã ã¡ãã¬ãŒã1.2ã¢ã«ïŒã§åŠçãããåŸããã
è€âèµ€è²æº¶æ¶²ãïŒãïŒâã§æŽã«15åéæ¹æãã
次ã«æž©åºŠãæŸçœ®ããŠå®€æž©ã«äžæãããããã®æº¶
液ã宀枩ã§ïŒæéæ¹æããæ¹æ溶åšäžã«æ³šãã
ïŒïŒ
éçé
žãããªãŠã 溶液ïŒã§æŽæµãããäž
éšã®ç¡è²ã®çžãå¡©åã¡ãã¬ã³250mlã§éæœåºã
ããå液ããå¡©åã¡ãã¬ã³çžãç¡«é
žãããªãŠã
äžã§ä¹Ÿç¥ããéãã滎äžããŒããä»ããŠé£ç¶
çã«åèšïŒã®ã¡ã¿ããŒã«ãå ããªãããäžéš
èžçºããããåå¿å®¹éïŒåã³èžç枩床63âã«
ãªã€ãéãåå¿æ··åç©ãâ20âã«å·åŽãããã®
枩床ã§æ¹æããªãã30å以å
ã«æ°Ž400mlã§åŠç
ãããæ¶åºããïœâãïŒâïŒãã©ã³ã¹âïŒâãã³
ãã«ã·ã¯ãããã·ã«ïŒãšããã«ãå®æ¯éŠé
žã¡ã
ã«ãšã¹ãã«ãåžåŒéããâ20âã§90ïŒ
ã¡ã¿ã
ãŒã«ïŒã§æŽæµããçµæ¶æ§ã®å¡ããååå§æŸã
ãŠæº¶æ¶²ãé€å»ãããExample 5 (a) 182.3 g of trans-4-pentylcyclohexanecarboxaldehyde, 2 methylene chloride
and (p-methoxycarbonylphenyl)methyltriphenylphosphonium bromide
589.6 g of the mixture was cooled to 0-5°C, and the cold solution was dissolved in methanol within about 1 hour at 0-5°C.
Treated with a solution of 27.6 g of sodium (1.2 mol of sodium methylate) in 276 ml. The resulting brown-red solution was stirred for an additional 15 minutes at 0-5°C,
The temperature was then allowed to rise to room temperature. The solution was stirred at room temperature for 1 hour, poured into a stirred vessel,
Washed with 1 part of 5% sodium bicarbonate solution. The upper colorless phase was back-extracted with 250 ml of methylene chloride. The combined methylene chloride phases were dried over sodium sulfate, filtered and partially evaporated with continuous addition of a total of 5 portions of methanol via the dropping funnel. Upon reaching a reaction volume of 4 and a distillation temperature of 63 DEG C., the reaction mixture was cooled to -20 DEG C. and treated with 400 ml of water within 30 minutes while stirring at this temperature. The crystallized p-[2-(trans-4-pentylcyclohexyl)ethenyl]benzoic acid methyl ester was filtered under suction, washed with 90% methanol 1 at -20°C, and thoroughly squeezed from the crystalline mass to remove the solution. Removed.
(b) åŸãããçµæ¶æ§ã®å¡ãå¡©åã¡ãã¬ã³1.5ã«
溶解ããæ°Ž750mlã§æŽæµãããæ°Žçžãå¡©åã¡ã
ã¬ã³250mlã§éæœåºããå液ããå¡©åã¡ãã¬ã³
çžãç¡«é
žãããªãŠã äžã§ä¹Ÿç¥ããéãã容é
1.5ã«æ¿çž®ãããããªãšãã«ã¢ãã³ïŒmlåã³
ãã©ãžãŠã ïŒççŽ ïŒïŒïŒ
ïŒïŒïœãå ãããã®æ··
åç©ããæ°ŽçŽ æ·»å ãã©ã¹ã³ã«æ°ŽçŽ ãïŒåéæ°ã
ãåŸã宀枩ã§æ¯çªããªããæ°ŽçŽ æ·»å ãããïŒæ
éåŸãæ°ŽçŽ ã®åžåã¯åæ¢ãã觊åªãå¥ããå¡©
åã¡ãã¬ã³250mlã§æŽæµããã液ã掻æ§ç30
ïœã§åŠçããæ¹æãããããŠéãããéæ®
枣ãå¡©åã¡ãã¬ã³250mlã§éæŽæµãã液ãå
転èžçºæ©ã§èžçºããããç¡è²ã®æ²¹ç¶æ®æž£ãã¡ã¿
ããŒã«ïŒã§åŠçããèžæ°æµŽäžã§æ¹æããªãã
éæµäžã§å ç±ããããã«ãã€ãŠæ²¹ã¯ã»ãšãã©å®
å
šã«æº¶è§£ããããã®æ··åç©ãæ¹æããªããå·åŽ
ããçæç©ãâ25âã§æ¶åºããããçµæ¶æ§ã®ç
æç©ãå¥ããâ25âã«ãŠã¡ã¿ããŒã«250mlã§æŽ
æµããçµæ¶æ§ã®å¡ããå§æŸããŠæº¶åªãé€å»ã
ããæžå§äžã«ãŠçªçŽ æ°æµäžã§å®€æž©ã§ä¹Ÿç¥ãã
åŸãçµæ¶æ§ã®ïœâãïŒâïŒãã©ã³ã¹âïŒâãã³ã
ã«ã·ã¯ãããã·ã«ïŒâïŒâãšãã«ãå®æ¯éŠé
žã¡
ãã«ãšã¹ãã«252ïœãåŸããããã®ãã®ãæŽã«
ã·ãªã«ã²ã«äžã§ãã«ãšã³ã«ããã¬ã¹ã¯ãããã°
ã©ãã€åã³ãã³ã¿ã³ããåçµæ¶ã«ãã€ãŠç²Ÿè£œã
ãããšãã§ããïŒèç¹ïŒïŒ£âïŒ36.7âãéæ
ç¹ïŒïŒ®âïŒ48.7âã(b) The resulting crystalline mass was dissolved in 1.5 methylene chloride and washed with 750 ml of water. The aqueous phase was back-extracted with 250 ml of methylene chloride, and the combined methylene chloride phases were dried over sodium sulfate, filtered, and the volume
It was concentrated to 1.5. 5 ml of triethylamine and 5 g of palladium/carbon (5%) were added and the mixture was hydrogenated with shaking at room temperature after bubbling hydrogen twice into the hydrogenation flask. After 2 hours, hydrogen absorption had ceased and the catalyst was separated and washed with 250 ml of methylene chloride. Activated carbon liquid 30
g, stirred and filtered. The excess residue was backwashed with 250 ml of methylene chloride and the liquid was evaporated on a rotary evaporator. The colorless oily residue was treated with methanol 1 and heated under reflux with stirring on a steam bath, whereby the oil almost completely dissolved. The mixture was cooled with stirring and the product crystallized at -25°C. The crystalline product was separated, washed with 250 ml of methanol at -25°C, and the solvent was removed by squeezing the crystalline mass. After drying at room temperature in a nitrogen stream under reduced pressure, 252 g of crystalline p-[2-(trans-4-pentylcyclohexyl)-1-ethyl]benzoic acid methyl ester was obtained, which was further purified on silica gel. It could be purified by gas chromatography with toluene and recrystallization from pentane; melting point (C-N) 36.7°C, clearing point (N-I) 48.7°C.
äžèšåæ§ã®æ¹æ³ã§æ¬¡ã®ååç©ã補é ããããšã
ã§ããïŒ
ïœâãïŒâïŒãã©ã³ã¹âïŒâãšãã«ã·ã¯ãããã·
ã«ïŒâïŒâãšãã«ãå®æ¯éŠé
žã¡ãã«ãšã¹ãã«ã«ïŒ
èç¹ïŒïŒ£âïŒ34.2âïŒ
ïœâãïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ããã
ã·ã«ïŒâïŒâãšãã«ãå®æ¯éŠé
žã¡ãã«ãšã¹ãã«ïŒ
èç¹ïŒïŒ£âïŒ38.3âãéæç¹ïŒïŒ®âïŒ37.7
âïŒ
ïœâãïŒâïŒãã©ã³ã¹âïŒâããã«ã·ã¯ãããã·
ã«ïŒâïŒâãšãã«ãå®æ¯éŠé
žã¡ãã«ãšã¹ãã«ïŒè
ç¹ïŒïŒ£âïŒ39.6âãéæç¹ïŒïŒ®âïŒ32âïŒ
ïœâãïŒâïŒãã©ã³ã¹âïŒâãããã«ã·ã¯ããã
ã·ã«ïŒâïŒâãšãã«ãå®æ¯éŠé
žã¡ãã«ãšã¹ãã«ïŒ
èç¹ïŒïŒ£âïŒ33.5âãéæç¹ïŒïŒ®âïŒ53âã The following compounds could be prepared in the same manner as above: p-[2-(trans-4-ethylcyclohexyl)-1-ethyl]benzoic acid methyl ester;
Melting point (C-I) 34.2°C; p-[2-(trans-4-propylcyclohexyl)-1-ethyl]benzoic acid methyl ester;
Melting point (C-I) 38.3â, clearing point (N-I) 37.7
°C; p-[2-(trans-4-butylcyclohexyl)-1-ethyl]benzoic acid methyl ester; melting point (C-I) 39.6 °C, clearing point (N-I) 32 °C; p-[2-( trans-4-heptylcyclohexyl)-1-ethyl]benzoic acid methyl ester;
Melting point (C-N) 33.5°C, clearing point (N-I) 53°C.
Claims (1)
OR3ãŸãã¯ââCOâR3ã®äžã€ãè¡šãããR1å
ã³R3ã¯ççŽ ååïŒã12åãå«ãçŽéç¶ã®ã¢ã«ã
ã«åºãè¡šããããããŠïœã¯æ°ïŒãŸãã¯ïŒã®äžã€ã
è¡šããã ã®ååç©ã ïŒ R2ãåºâR3ãâOR3ãŸãã¯âCOâOR3ã®äž
ã€ãè¡šããç¹èš±è«æ±ã®ç¯å²ç¬¬ïŒé èšèŒã®ååç©ã ïŒ R2ãåºâR3ãŸãã¯âOR3ã®äžã€ãè¡šããç¹
èš±è«æ±ã®ç¯å²ç¬¬ïŒé èšèŒã®ååç©ã ïŒ ïœãæ°ïŒãè¡šããç¹èš±è«æ±ã®ç¯å²ç¬¬ïŒãïŒé
ã®ããããã«èšèŒã®ååç©ã ïŒ R3ãççŽ ååïŒã10åã奜ãŸããã¯ïŒãïŒ
åãå«ãçŽéç¶ã®ã¢ã«ãã«åºãè¡šããç¹èš±è«æ±ã®
ç¯å²ç¬¬ïŒãïŒé ã®ããããã«èšèŒã®ååç©ã ïŒ R1ãççŽ ååïŒã10åã奜ãŸããã¯ïŒãïŒ
åãå«ãçŽéç¶ã®ã¢ã«ãã«åºãè¡šããç¹èš±è«æ±ã®
ç¯å²ç¬¬ïŒãïŒé ã®ããããã«èšèŒã®ååç©ã ïŒ å°ãªããšãäžæåãäžè¬åŒ åŒäžãR2ã¯åºâR3ãâOR3ãâCOâR3ãâCOâ
OR3ãŸãã¯ââCOâR3ã®äžã€ãè¡šãããR1å
ã³R3ã¯ççŽ ååïŒã12åãå«ãçŽéç¶ã®ã¢ã«ã
ã«åºãè¡šããããããŠïœã¯æ°ïŒãŸãã¯ïŒã®äžã€ã
è¡šããã ã®ååç©ã§ããå°ãªããšãäºæåãå«ãããšãç¹
城ãšãã液æ¶æ··åç©ã ïŒ äžè¬åŒ åŒäžãR4ã¯æ°ŽçŽ ãããããã·ãããã²ã³ãŸã
ã¯åºâR3ãããã¯âOR3ã®äžã€ãè¡šãããR1å
ã³R3ã¯ççŽ ååïŒã12åãå«ãçŽéç¶ã®ã¢ã«ã
ã«åºãè¡šããããããŠïœã¯æ°ïŒãŸãã¯ïŒã®äžã€ã
è¡šããã ã®ååç©ãéå ãããããŠR4ãæ°ŽçŽ ãè¡šããå Ž
åã«ã¯ãçããäžè¬åŒ åŒäžãR1ãR4åã³ïœã¯äžèšã®æå³ãæããã
ã®ååç©ãã¢ã·ã«åããããR4ãããããã·ã
è¡šããå Žåã«ã¯ãçããåŒã®ååç©ãåŒ
R3COOHã®ã«ã«ãã³é žãããã¯ãã®åå¿æ§èªå°
äœã§ãšã¹ãã«åããããæãã¯R4ãããã²ã³ã
è¡šããå Žåã«ã¯ãçããåŒã®ååç©ããã°ãã·
ãŠã ãšã次ãã§äºé žåççŽ ãšåå¿ãããåŸããã
ã«ã«ããã·ã¬ãŒããå æ°Žå解ãããããŠçããé ž
ãŸãã¯ãã®åå¿æ§èªå°äœãåŒR3OHã®ã¢ã«ã³ãŒã«
ã§ãšã¹ãã«åããããšãç¹åŸŽãšããäžè¬åŒ åŒäžãR2ã¯åºâR3ãâOR3ãâCOâR3ãâCOâ
OR3ãŸãã¯ââCOâR3ã®äžã€ãè¡šããããã
ãŠR1ãR3åã³ïœã¯äžèšã®æå³ãæããã ã®ååç©ã®è£œé æ¹æ³ã[Claims] 1. General formula In the formula, R 2 is a group -R 3 , -OR 3 , -CO-R 3 , -CO-
represents one of OR 3 or -O-CO-R 3 , R 1 and R 3 represent a linear alkyl group containing 1 to 12 carbon atoms, and n represents one of the numbers 1 or 2. A compound represented by . 2. A compound according to claim 1, wherein R2 represents one of the groups -R3 , -OR3 or -CO- OR3 . 3. A compound according to claim 2 , wherein R2 represents one of the groups -R3 or -OR3 . 4. The compound according to any one of claims 1 to 3, wherein n represents the number 1. 5 R 3 is 1 to 10 carbon atoms, preferably 1 to 7
5. The compound according to any one of claims 1 to 4, which represents a linear alkyl group containing . 6 R 1 is 2 to 10 carbon atoms, preferably 3 to 7
The compound according to any one of claims 1 to 5, which represents a linear alkyl group containing . 7 At least one component has a general formula In the formula, R 2 is a group -R 3 , -OR 3 , -CO-R 3 , -CO-
represents one of OR 3 or -O-CO-R 3 , R 1 and R 3 represent a linear alkyl group containing 1 to 12 carbon atoms, and n represents one of the numbers 1 or 2. A liquid crystal mixture comprising at least two components which are compounds of the following. 8 General formula In the formula, R 4 represents hydrogen, hydroxy, halogen or one of the groups -R 3 or -OR 3 , R 1 and R 3 represent a linear alkyl group containing 1 to 12 carbon atoms, and n represents one of the numbers 1 or 2, and when R 4 represents hydrogen, the resulting general formula In the formula, R 1 , R 4 and n have the above meanings,
or, if R 4 represents hydroxy, the resulting compound of formula
esterification with a carboxylic acid of R 3 COOH or a reactive derivative thereof, or, if R 4 represents a halogen, the resulting compound of formula is reacted with magnesium and then with carbon dioxide and the resulting carboxylate is hydrolyzed. and the resulting acid or its reactive derivative is esterified with an alcohol of the formula R 3 OH. In the formula, R 2 is a group -R 3 , -OR 3 , -CO-R 3 , -CO-
represents one of OR 3 or -O-CO-R 3 and R 1 , R 3 and n have the meanings given above.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH61981A CH646675A5 (en) | 1981-01-30 | 1981-01-30 | Disubstituted ethanes |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS57144229A JPS57144229A (en) | 1982-09-06 |
JPH033643B2 true JPH033643B2 (en) | 1991-01-21 |
Family
ID=4191221
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP57009640A Granted JPS57144229A (en) | 1981-01-30 | 1982-01-26 | (trans-4-alkylcyclohexyl) ethanes |
Country Status (2)
Country | Link |
---|---|
JP (1) | JPS57144229A (en) |
CH (1) | CH646675A5 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3268468D1 (en) * | 1981-02-13 | 1986-02-27 | Secr Defence Brit | Liquid crystal compounds exhibiting a small dielectric anisotropy and liquid crystal materials and devices incorporating such compounds |
JPS5841827A (en) * | 1981-08-06 | 1983-03-11 | ã€ã®ãªã¹åœ | Liquid crystal substance, compound therefor and electrooptical liquid crystal device |
CH648539A5 (en) * | 1981-10-14 | 1985-03-29 | Hoffmann La Roche | Phenylethanes and use thereof in liquid-crystalline mixtures |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS54148184A (en) * | 1978-05-12 | 1979-11-20 | Hitachi Ltd | Phase transition liquid crystal composition |
DE2922236A1 (en) * | 1978-05-31 | 1979-12-06 | Secr Defence Brit | LIQUID CRYSTAL COMPOUNDS AND THEIR USES |
JPS54159384A (en) * | 1978-06-08 | 1979-12-17 | Seiko Epson Corp | Liquid crystal composition |
-
1981
- 1981-01-30 CH CH61981A patent/CH646675A5/en not_active IP Right Cessation
-
1982
- 1982-01-26 JP JP57009640A patent/JPS57144229A/en active Granted
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS54148184A (en) * | 1978-05-12 | 1979-11-20 | Hitachi Ltd | Phase transition liquid crystal composition |
DE2922236A1 (en) * | 1978-05-31 | 1979-12-06 | Secr Defence Brit | LIQUID CRYSTAL COMPOUNDS AND THEIR USES |
JPS54159384A (en) * | 1978-06-08 | 1979-12-17 | Seiko Epson Corp | Liquid crystal composition |
Also Published As
Publication number | Publication date |
---|---|
JPS57144229A (en) | 1982-09-06 |
CH646675A5 (en) | 1984-12-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4439015A (en) | Disubstituted ethanes | |
US4620938A (en) | Hydroterphenyls | |
US4724097A (en) | Bicyclohexylethanes | |
US4330426A (en) | Cyclohexylbiphenyls, their preparation and use in dielectrics and electrooptical display elements | |
US4545922A (en) | Liquid crystalline fluorine-containing cyclohexylbiphenyls and dielectrics and electro-optical display elements based thereon | |
US4550981A (en) | Liquid crystalline esters and mixtures | |
US4526704A (en) | Multiring liquid crystal esters | |
JPS6257168B2 (en) | ||
JP2599136B2 (en) | Liquid crystalline ester | |
JPH0217528B2 (en) | ||
JP2000169403A (en) | Cross-linked cyclohexane derivative and liquid crystalline medium | |
JPS6246527B2 (en) | ||
JPH03505742A (en) | Mesophase forming compound | |
JP4722490B2 (en) | Cyclopenta [b] naphthalene derivative | |
EP0090671B1 (en) | Carbocylic esters having liquid-crystal properties at high temperatures | |
JPH05286873A (en) | Diene derivative | |
JPS63502505A (en) | chiral compound | |
JPH1112202A (en) | Fluorocyclohexane derivative and liquid crystal medium | |
JP2746711B2 (en) | Fluorinated 4 â³ -cyano substituted terphenyl | |
JPH033643B2 (en) | ||
KR100281380B1 (en) | Chlorobenzene derivative and liquid crystal composition containing the same | |
JPS5818348A (en) | Novel trans-4-(2-(trans-4-alkylcyclohexyl)ethyl)cyclohexane ethyl)cyclohexane carbonitrile | |
JP2927957B2 (en) | Phenylcyclohexanes and liquid crystal media | |
JP3981844B2 (en) | New alkenyltolane derivatives | |
JPH06211711A (en) | Derivative of cyclohexane |