JPH0242801B2 - - Google Patents
Info
- Publication number
- JPH0242801B2 JPH0242801B2 JP55182407A JP18240780A JPH0242801B2 JP H0242801 B2 JPH0242801 B2 JP H0242801B2 JP 55182407 A JP55182407 A JP 55182407A JP 18240780 A JP18240780 A JP 18240780A JP H0242801 B2 JPH0242801 B2 JP H0242801B2
- Authority
- JP
- Japan
- Prior art keywords
- dimethyl
- triazol
- penten
- acid
- compound
- 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
- -1 triazolyl alcohol derivative Chemical class 0.000 claims description 73
- 230000003287 optical effect Effects 0.000 claims description 8
- 239000005648 plant growth regulator Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Chemical group 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 58
- 239000000243 solution Substances 0.000 description 40
- 150000001875 compounds Chemical class 0.000 description 37
- 239000000203 mixture Substances 0.000 description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 28
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 25
- 230000002829 reductive effect Effects 0.000 description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 17
- 239000002904 solvent Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 241000196324 Embryophyta Species 0.000 description 13
- 150000002148 esters Chemical class 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000004009 herbicide Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 229910010082 LiAlH Inorganic materials 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 238000009472 formulation Methods 0.000 description 9
- 239000010446 mirabilite Substances 0.000 description 9
- 239000012044 organic layer Substances 0.000 description 9
- 229920006395 saturated elastomer Polymers 0.000 description 9
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 235000017557 sodium bicarbonate Nutrition 0.000 description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 8
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 150000003852 triazoles Chemical group 0.000 description 8
- YNWVFADWVLCOPU-MDWZMJQESA-N (1E)-1-(4-chlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl)pent-1-en-3-ol Chemical compound C1=NC=NN1/C(C(O)C(C)(C)C)=C/C1=CC=C(Cl)C=C1 YNWVFADWVLCOPU-MDWZMJQESA-N 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 230000012010 growth Effects 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 7
- 239000012046 mixed solvent Substances 0.000 description 7
- 238000010898 silica gel chromatography Methods 0.000 description 7
- 239000002689 soil Substances 0.000 description 7
- NOOLISFMXDJSKH-KXUCPTDWSA-N (-)-Menthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@H]1O NOOLISFMXDJSKH-KXUCPTDWSA-N 0.000 description 6
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 230000000844 anti-bacterial effect Effects 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000012280 lithium aluminium hydride Substances 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- FBOUIAKEJMZPQG-AWNIVKPZSA-N (1E)-1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)pent-1-en-3-ol Chemical compound C1=NC=NN1/C(C(O)C(C)(C)C)=C/C1=CC=C(Cl)C=C1Cl FBOUIAKEJMZPQG-AWNIVKPZSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Substances OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 5
- 239000000417 fungicide Substances 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- 230000008635 plant growth Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- LFLAXRVXFCJYOI-AWNIVKPZSA-N (e)-1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)pent-1-en-3-one Chemical compound C1=NC=NN1/C(C(=O)C(C)(C)C)=C/C1=CC=C(Cl)C=C1Cl LFLAXRVXFCJYOI-AWNIVKPZSA-N 0.000 description 4
- 241000723353 Chrysanthemum Species 0.000 description 4
- 235000007516 Chrysanthemum Nutrition 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 241000209140 Triticum Species 0.000 description 4
- 235000021307 Triticum Nutrition 0.000 description 4
- 150000001336 alkenes Chemical group 0.000 description 4
- 150000001414 amino alcohols Chemical class 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 239000012279 sodium borohydride Substances 0.000 description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- DTGKSKDOIYIVQL-QXFUBDJGSA-N (-)-borneol Chemical compound C1C[C@]2(C)[C@H](O)C[C@H]1C2(C)C DTGKSKDOIYIVQL-QXFUBDJGSA-N 0.000 description 3
- 229930006703 (-)-borneol Natural products 0.000 description 3
- LACMLEGEQFCFAZ-MDWZMJQESA-N (e)-1-(4-chlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)pent-1-en-3-one Chemical compound C1=NC=NN1/C(C(=O)C(C)(C)C)=C/C1=CC=C(Cl)C=C1 LACMLEGEQFCFAZ-MDWZMJQESA-N 0.000 description 3
- 125000004201 2,4-dichlorophenyl group Chemical group [H]C1=C([H])C(*)=C(Cl)C([H])=C1Cl 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229920001817 Agar Polymers 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 3
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 description 3
- 244000141359 Malus pumila Species 0.000 description 3
- 240000007594 Oryza sativa Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- ZKWVEWDWYSIYKA-FSJBWODESA-N [5-[(E)-1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)pent-1-en-3-yl]-5-methyl-2-propan-2-ylcyclohexyl] ethaneperoxoate Chemical compound C(C)(=O)OOC1CC(CCC1C(C)C)(C)C(\C(=C/C1=C(C=C(C=C1)Cl)Cl)\N1N=CN=C1)C(C)(C)C ZKWVEWDWYSIYKA-FSJBWODESA-N 0.000 description 3
- 239000008272 agar Substances 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000003337 fertilizer Substances 0.000 description 3
- 230000000855 fungicidal effect Effects 0.000 description 3
- 230000009036 growth inhibition Effects 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- GTVRLHPVICIJFQ-UHFFFAOYSA-N hexane;tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl.CCCCCC GTVRLHPVICIJFQ-UHFFFAOYSA-N 0.000 description 3
- 229960004873 levomenthol Drugs 0.000 description 3
- MAGPZHKLEZXLNU-UHFFFAOYSA-N mandelamide Chemical compound NC(=O)C(O)C1=CC=CC=C1 MAGPZHKLEZXLNU-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VIUQEVFZJAFLTR-UHFFFAOYSA-N (5-methyl-2-propan-2-ylcyclohexyl) ethaneperoxoate Chemical compound CC(C)C1CCC(C)CC1OOC(C)=O VIUQEVFZJAFLTR-UHFFFAOYSA-N 0.000 description 2
- IWYDHOAUDWTVEP-SSDOTTSWSA-N (R)-mandelic acid Chemical compound OC(=O)[C@H](O)C1=CC=CC=C1 IWYDHOAUDWTVEP-SSDOTTSWSA-N 0.000 description 2
- VNMCKLVHDJADEB-OUAUKWLOSA-N 2-[(1r,2s,5r)-5-methyl-2-propan-2-ylcyclohexyl]oxyacetyl chloride Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@H]1OCC(Cl)=O VNMCKLVHDJADEB-OUAUKWLOSA-N 0.000 description 2
- FOGYNLXERPKEGN-UHFFFAOYSA-N 3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfopropyl)phenoxy]propane-1-sulfonic acid Chemical compound COC1=CC=CC(CC(CS(O)(=O)=O)OC=2C(=CC(CCCS(O)(=O)=O)=CC=2)OC)=C1O FOGYNLXERPKEGN-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- IFWRTGJDSLZNQE-OEAKJJBVSA-N C(C)(=O)OOC1CC(CCC1C(C)C)(C)C(\C(=C/C1=CC=C(C=C1)Cl)\N1N=CN=C1)C(C)(C)C Chemical compound C(C)(=O)OOC1CC(CCC1C(C)C)(C)C(\C(=C/C1=CC=C(C=C1)Cl)\N1N=CN=C1)C(C)(C)C IFWRTGJDSLZNQE-OEAKJJBVSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 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 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- LOUPRKONTZGTKE-WZBLMQSHSA-N Quinine Chemical compound C([C@H]([C@H](C1)C=C)C2)C[N@@]1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-WZBLMQSHSA-N 0.000 description 2
- 241000208422 Rhododendron Species 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- SAXHIDRUJXPDOD-UHFFFAOYSA-N ethyl hydroxy(phenyl)acetate Chemical compound CCOC(=O)C(O)C1=CC=CC=C1 SAXHIDRUJXPDOD-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000001640 fractional crystallisation Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- IWYDHOAUDWTVEP-UHFFFAOYSA-N mandelic acid Chemical compound OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 2
- BTFQKIATRPGRBS-UHFFFAOYSA-N o-tolualdehyde Chemical compound CC1=CC=CC=C1C=O BTFQKIATRPGRBS-UHFFFAOYSA-N 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- ULSIYEODSMZIPX-UHFFFAOYSA-N phenylethanolamine Chemical compound NCC(O)C1=CC=CC=C1 ULSIYEODSMZIPX-UHFFFAOYSA-N 0.000 description 2
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- UCSJYZPVAKXKNQ-HZYVHMACSA-N streptomycin Chemical compound CN[C@H]1[C@H](O)[C@@H](O)[C@H](CO)O[C@H]1O[C@@H]1[C@](C=O)(O)[C@H](C)O[C@H]1O[C@@H]1[C@@H](NC(N)=N)[C@H](O)[C@@H](NC(N)=N)[C@H](O)[C@H]1O UCSJYZPVAKXKNQ-HZYVHMACSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 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
- 239000004563 wettable powder Substances 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- FMCGSUUBYTWNDP-ONGXEEELSA-N (1R,2S)-2-(dimethylamino)-1-phenyl-1-propanol Chemical compound CN(C)[C@@H](C)[C@H](O)C1=CC=CC=C1 FMCGSUUBYTWNDP-ONGXEEELSA-N 0.000 description 1
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- 239000004094 surface-active agent Substances 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
- 229940035893 uracil Drugs 0.000 description 1
- 244000045561 useful plants Species 0.000 description 1
- LWHIYPYQKDPFBK-UHFFFAOYSA-L zinc;n,n-dimethylcarbamothioate Chemical compound [Zn+2].CN(C)C([O-])=S.CN(C)C([O-])=S LWHIYPYQKDPFBK-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
本発明は、一般式（）
〔式中、Ｘは水素原子または塩素原子を表し、
＊印は不斉炭素原子を意味する。〕
で示され、かつ光学活性が（＋）であるトリアゾ
リルアルコール誘導体を有効成分として含有する
植物生長調節剤に関するものである。
ラセミのトリアゾリルアルコール誘導体ならび
にそれらが優れた殺菌作用、植物生長調節作用お
よび除草作用を示すことは、既に特開昭55−
124771号公報および特開昭56−25105号公報に記
載されている。
ところで、一般式（）で示されるトリアゾリ
ルアルコール誘導体には不斉炭素原子（＊Ｃ）に
よつてもたらされる光学異性体が存在する。上記
ラセミ体を、植物の生長調節作用を目的として施
用した場合、その半分の量である（−）体は、本
来の目的である生長調節作用に寄与することは殆
んどなく、しかも前述の殺菌剤としての適切な時
期、適切な生育段階、適切な施用方法について充
分に考慮しないで用いた場合には、殺菌剤として
の目的をも達成することができず、いたずらに前
述の薬剤抵抗性発現の可能性を増加させることと
なり非常に不利益なことになることがあり、いま
だ充分とは言えない。
本考案の光学活性が（＋）であるトリアゾリル
アルコール誘導体とは、クロロホルム中ナトリウ
ムＤ線で（＋）の施光度を示す一般式（）で表
される化合物であり、以後（＋）−トリアゾリル
アルコール誘導体と称し、他方、クロロホルム
中、ナトリウムＤ線で（−）の施光度を示す一般
式（）で表される化合物は以後（−）−トリア
ゾリルアルコール誘導体と称する。
また、本発明には、本トリアゾリルアルコール
誘導体の塩も含まれ、塩としては、植物生理学上
許容される酸、たとえば臭化水素酸、塩酸、ヨウ
化水素酸等のハロゲン化水素酸、酢酸、トリクロ
ロ酢酸、マレイン酸、コハク酸等のカルボン酸、
ｐ−トルエンスルホン酸、メタンスルホン酸等の
スルホン酸、硝酸、硫酸そしてリン酸などとの塩
であり、必要に応じてこれらと（−）−トリアゾ
ール誘導体との塩が従来の方法によつて得られ
る。
本発明者らは、本発明の方法によつて得られる
（＋）−トリアゾリルアルコール誘導体（）の有
用性を詳しく検討した結果、植物生長調節効果の
強さは対応するラセミ体および（−）−トリアゾ
リルアルコール体との比較において、（＋）−トリ
アゾリルアルコール誘導体＞ラセミ体のトリアゾ
リルアルコール誘導体＞（−）−トリアゾリルアル
コール誘導体という関係にあり、一方殺菌効果が
（−）−トリアゾリルアルコール誘導体＞ラセミ体
のトリアゾリルアルコール誘導体＞（＋）−トリア
ゾリルアルコール誘導体という関係にあることを
見出した。即ち、ラセミ体の光学分割を行なうこ
とにより、生物活性を殺菌作用と植物生長調節作
用に分割できることおよび（＋）−トリアゾリル
アルコール誘導体に極めて優れた植物生長調節活
性が存在するという全く新しい知見を見出した。
本発明は、農園芸分野におけるより健全な植物の
栽培に大きく貢献するものである。
すなわち、たとえばより活性の高い薬剤を使用
することは、より少量の薬剤を適切に使用するこ
とにつながり、製造、輸送、施用各プロセスにお
ける経済性の向上と共に、環境汚染の可能性を最
少限に約束するものであり安全性の向上に寄与す
る。
また、一方の光学異性体を分割により取得する
場合、通常、他方の光学異性体は、回収→ラセミ
化→分割という操作を繰り返すことが必要とな
る。ところが、本発明の化合物は、植物生長調節
作用を有し、他方の操作を繰り返す必要がなく、
本発明は製造上および経済上も極めて優れてい
る。
本発明の（＋）−トリアゾリルアルコール誘導
体は、前述のごとく、植物生長調節剤として使用
でき、有用植物体に施用してその生長を制御す
る。たとえば稲、ムギ類、芝生、生垣用樹木、果
樹等の徒長防止、あるいは鉢植菊、ユリ、パンジ
ー、ポインセチヤ、ツツジ、シヤクナゲ等の園芸
作物の矮化などに用いることができる。
稲作あるいは麦作は、肥料の多施用や強風など
によつて生ずる稲や麦の倒伏がしばしば重要な問
題となるが、上記誘導体を適期に処理することに
より、稲や麦の草丈を適度に抑制し、徒長をおさ
え、倒伏の防止に有効である。鉢植菊の栽培にお
いては、上記誘導体の施用により花には影響を与
えず、茎の長さを短くすることにより商品価値を
高めることができる。
一方、上記誘導体は人畜、魚類に対して高い安
全性を有し、かつ農業上有用な作物に対して実際
の使用上ほとんど害を及ぼすことなく使用できる
ことも明らかとなつた。
本発明の（＋）−トリアゾリルアルコール誘導
体を製造する方法としては、通常の光学活性体の
取得に用いられる方法、すなわち不斉還元による
方法やラセミ化合物と光学活性な反応性化合物か
ら得られるジアステレオマーの分割による方法な
どがあげられる。以下順に説明する。
(1) 不斉還元による製造法
一般式（）で示される化合物のラセミ体は、
一般式（）で示されるケトン化合物を水素化ア
ルミニウムリチウム（LiAlH4）や水素化ホウ素
ナトリウム（NaBH4）のごとき金属水素錯化合
物で還元することにより得られる（特開昭和55−
124771号公報）。
〔式中、Ｘは水素原子または塩素原子を表す。〕
不斉還元の方法としては、キラルな金属水素錯化
合物であるケトン化合物（）を還元するとエナ
ンチオ面区別反応が起こることを利用するのが通
常であり、以下その方法のいくつかを述べる。
(a) キラルな金属水素錯化合物としては、水素化
アルミニウムリチウムを光学活性アルコールで
部分分解したキラルな修飾水素化アルミニウム
リチウム系還元剤を用いるのが一般的である
〔文献；Tetrahedron，Vol.29，913（1973）；
Bull.Soc.Chim.Fr.，1968，3795；J.Org.
Chem.，38（10），1973，Tetrahedron，
Letters，Vol.36，3165（1976）等〕。
本発明において、不斉源として用いられる光
学活性アルコールの例としては、（−）−メント
ール、（−）−ボルネオール、（−）−Ｎ−メチル
エフエドリン、（−）−２−Ｎ，Ｎ−ジメチルア
ミノ−１−フエニルエタノールがあげられる
が、むろんこの他の光学活性アルコール、たと
えばキニーネ、シス−ミルテノール、２−Ｎ−
ベンジル−Ｎ−メチルアミノ−１−フエニルエ
タノール、４−ジメチルアミノ−３−メチル−
１，２−ジフエニル−２−ブタノール等のアル
カロイド、炭水化物あるいはアミノアルコール
類の一方の光学活性体を使用することができ
る。
光学活性アルコールを不斉源とするキラルな
修飾水素化アルミニウムリチウム還元剤を調製
するには、適当な溶媒中にサスペンドした
LiAlH41当量比に光学活性アルコール１〜３当
量比を加えればよい。溶媒はジエチルエーテ
ル、THF、ジオキサン等のエーテル類を用い
るのが最も一般的であるが、ベンゼン、トルエ
ン等の芳香族炭化水素類あるいはｎ−ヘキサ
ン、ｎ−ペンタン等の脂肪族炭化水素類も使用
できる。
(b) キラルな金属水素錯化合物として光学活性ア
ルコール１当量比と一般式（）
〔式中、R2は低級アルキル基またはフエニル
基を表す。〕
で示されるＮ−置換アニリン２当量比と水素化ア
ルミニウムリチウム１当量比とを反応させて得ら
れるキラルな修飾水素化アルミニウムリチウム系
還元剤を用いる方法が有利な場合もある〔文献；
Tetrahedron Letters，Vol.21，2753（1980）〕。
本発明において不斉源として用いられる光学活
性アルコールとしては、たとえば（−）−Ｎ−メ
チルエフエドリンあるいは（−）−２−Ｎ，Ｎ−
ジメチルアミノ−１−フエニルエタノールのごと
き光学活性アミノアルコールの一方の光学活性体
であげられる。
Ｎ−置換アニリンとしては、Ｎ−メチルアニリ
ン、Ｎ−エチルアニリン等の低級アルキル置換ア
ニリンあるいはジフエニルアミン等が好結果をも
たらす。
このキラルな修飾水素化アルミニウムリチウム
還元剤を調製するには、LiAlH41当量比を適切な
溶媒にサスペンドし、光学活性アルコール１当量
比を加えたのち、Ｎ−置換アニリンの２当量比を
加えればよく、溶媒は(a)項で述べたものが同様に
使用できる。
このようにして(a)または(b)で調製されたキラル
な修飾水素化アルミニウムリチウムに適当な溶媒
に溶解したケトン化合物（）を加えることによ
り不斉還元を行なう。溶媒としては(a)項で述べた
ものが使用できる。この時の反応温度は−80℃か
ら溶媒の沸点までの範囲が可能であるが、０℃以
下で行なうことが好ましい。反応終了後、希酸性
水溶液を加え錯化合物を分解したのち抽出、シリ
カゲルカラムクロマトグラフイーあるいは再結晶
操作により目的物を得る。
(2) ジアステレオマーの分割による方法
ラセミアルコール化合物と反応性光学活性化合
物から得られるジアステレオマーエステルにより
光学異性体を分割する方法は知られている（文
献；Org.Reaction Vol.2，380）。
トリアゾリルアルコール体（）のラセミ体と
光学活性カルボン酸の反応性誘導体とを塩基の存
在下に反応させることにより、ジアステレオマー
エステルの混合物（）を得る。これをクロマト
操作あるいは分別結晶により、（＋）−トリアゾリ
ルアルコールのエステルと（−）−トリアゾリル
アルコールのエステルを分割し、ついで（＋）−
トリアゾリルアルコールのエステルを分解するこ
とにより、（＋）−トリアゾリルアルコール誘導体
（）を得る。
〔式中、Ｘおよび＊は前述のとおりである。〕
The present invention is based on the general formula () [In the formula, X represents a hydrogen atom or a chlorine atom,
* indicates an asymmetric carbon atom. ] The present invention relates to a plant growth regulator containing a triazolyl alcohol derivative as an active ingredient, which is represented by the following formula and has an optical activity of (+). Racemic triazolyl alcohol derivatives and their excellent bactericidal, plant growth regulating, and herbicidal effects have already been reported in Japanese Patent Application Laid-Open No. 55-1981.
It is described in Japanese Patent Application Laid-open No. 124771 and Japanese Patent Application Laid-open No. 56-25105. By the way, the triazolyl alcohol derivative represented by the general formula () has optical isomers resulting from the asymmetric carbon atom (*C). When the above racemic form is applied for the purpose of regulating the growth of plants, the (-) form, which is half the amount, hardly contributes to the original purpose of controlling the growth, and moreover, the above-mentioned If it is used as a fungicide without giving due consideration to the appropriate timing, appropriate growth stage, and appropriate application method, it will not be able to achieve its purpose as a fungicide, and the above-mentioned drug resistance may occur. This can be extremely disadvantageous as it increases the possibility of occurrence, and is still not considered sufficient. The triazolyl alcohol derivative of the present invention whose optical activity is (+) is a compound represented by the general formula () that exhibits a degree of light absorption of (+) at the sodium D line in chloroform, and hereinafter referred to as (+)- On the other hand, a compound represented by the general formula () exhibiting a (-) degree of light absorption with the sodium D line in chloroform will be hereinafter referred to as a (-)-triazolyl alcohol derivative. The present invention also includes salts of the triazolyl alcohol derivatives, and examples of the salts include acids that are physiologically acceptable to plants, such as hydrohalic acids such as hydrobromic acid, hydrochloric acid, and hydroiodic acid; Carboxylic acids such as acetic acid, trichloroacetic acid, maleic acid, succinic acid,
These are salts with sulfonic acids such as p-toluenesulfonic acid and methanesulfonic acid, nitric acid, sulfuric acid, phosphoric acid, etc., and if necessary, salts of these with (-)-triazole derivatives can be obtained by conventional methods. It will be done. The present inventors have investigated in detail the usefulness of the (+)-triazolyl alcohol derivative () obtained by the method of the present invention. )-triazolyl alcohol derivatives, the relationship is that (+)-triazolyl alcohol derivatives > racemic triazolyl alcohol derivatives > (-)-triazolyl alcohol derivatives; on the other hand, the bactericidal effect is It has been found that the following relationship exists: -)-triazolyl alcohol derivative>racemic triazolyl alcohol derivative>(+)-triazolyl alcohol derivative. In other words, this is a completely new finding that biological activity can be divided into bactericidal activity and plant growth regulation activity by optical resolution of racemic substances, and that (+)-triazolyl alcohol derivatives have extremely excellent plant growth regulation activity. I found out.
The present invention greatly contributes to the cultivation of healthier plants in the field of agriculture and horticulture. This means, for example, that the use of more active agents leads to the appropriate use of smaller amounts of agents, which improves economic efficiency in manufacturing, transport and application processes, while minimizing the potential for environmental pollution. This is a promise and contributes to improving safety. Moreover, when one optical isomer is obtained by resolution, the other optical isomer usually requires repeating the operations of recovery → racemization → resolution. However, the compound of the present invention has a plant growth regulating effect, and there is no need to repeat the other operation.
The present invention is also extremely superior in terms of manufacturing and economy. As mentioned above, the (+)-triazolyl alcohol derivative of the present invention can be used as a plant growth regulator, and is applied to useful plants to control their growth. For example, it can be used to prevent the growth of rice, wheat, lawns, hedge trees, fruit trees, etc., or to dwarf garden crops such as potted chrysanthemums, lilies, pansies, poinsettias, azaleas, and rhododendrons. In rice and wheat cultivation, lodging of rice and wheat caused by heavy application of fertilizers and strong winds is often a serious problem, but by applying the above derivatives at the appropriate time, the plant height of rice and wheat can be moderately suppressed. It is effective in controlling the length and preventing lodging. In the cultivation of potted chrysanthemums, application of the above derivatives does not affect the flowers, and the commercial value can be increased by shortening the length of the stems. On the other hand, it has also become clear that the above-mentioned derivatives have high safety for humans, livestock, and fish, and can be used practically without causing any harm to agriculturally useful crops. The (+)-triazolyl alcohol derivative of the present invention can be produced by a method commonly used to obtain an optically active substance, that is, by asymmetric reduction, or by using a racemic compound and an optically active reactive compound. Examples include a method of dividing diastereomers. They will be explained in order below. (1) Production method by asymmetric reduction The racemic form of the compound represented by the general formula () is
It can be obtained by reducing the ketone compound represented by the general formula () with a metal hydrogen complex compound such as lithium aluminum hydride (LiAlH 4 ) or sodium borohydride (NaBH 4 ) (Unexamined Japanese Patent Application Publication No. 1989-1998-
Publication No. 124771). [In the formula, X represents a hydrogen atom or a chlorine atom. ]
As a method for asymmetric reduction, it is usual to utilize the fact that an enantioplane discrimination reaction occurs when a ketone compound (), which is a chiral metal hydrogen complex compound, is reduced, and some of the methods will be described below. (a) As a chiral metal-hydrogen complex compound, a chiral modified lithium aluminum hydride-based reducing agent obtained by partially decomposing lithium aluminum hydride with an optically active alcohol is generally used [Reference; Tetrahedron, Vol. 29 , 913 (1973);
Bull.Soc.Chim.Fr., 1968, 3795; J.Org.
Chem., 38(10), 1973, Tetrahedron,
Letters, Vol. 36, 3165 (1976), etc.]. In the present invention, examples of optically active alcohols used as chiral sources include (-)-menthol, (-)-borneol, (-)-N-methylefedrine, (-)-2-N,N- Dimethylamino-1-phenylethanol is mentioned, but of course other optically active alcohols such as quinine, cis-myrtenol, 2-N-
Benzyl-N-methylamino-1-phenylethanol, 4-dimethylamino-3-methyl-
Optically active forms of alkaloids, carbohydrates, or amino alcohols such as 1,2-diphenyl-2-butanol can be used. To prepare a chiral modified lithium aluminum hydride reducing agent with an optically active alcohol as an asymmetric source, it was suspended in a suitable solvent.
What is necessary is to add 1 to 3 equivalent ratios of optically active alcohol to 1 equivalent ratio of LiAlH 4 . Ethers such as diethyl ether, THF, and dioxane are most commonly used as solvents, but aromatic hydrocarbons such as benzene and toluene, and aliphatic hydrocarbons such as n-hexane and n-pentane are also used. can. (b) Optically active alcohol 1 equivalent ratio and general formula () as a chiral metal hydrogen complex compound [In the formula, R 2 represents a lower alkyl group or a phenyl group. ] It may be advantageous to use a chiral modified lithium aluminum hydride reducing agent obtained by reacting a 2-equivalent ratio of N-substituted aniline represented by 1-equivalent ratio of lithium aluminum hydride [Literature;
Tetrahedron Letters, Vol. 21, 2753 (1980)]. Examples of the optically active alcohol used as an asymmetric source in the present invention include (-)-N-methylefedrin or (-)-2-N,N-
It is one of the optically active forms of optically active amino alcohols such as dimethylamino-1-phenylethanol. As the N-substituted aniline, lower alkyl-substituted anilines such as N-methylaniline and N-ethylaniline, diphenylamine, etc. give good results. To prepare this chiral modified lithium aluminum hydride reducing agent, suspend 1 equivalent ratio of LiAlH 4 in a suitable solvent, add 1 equivalent ratio of optically active alcohol, and then add 2 equivalent ratio of N-substituted aniline. If desired, the solvents mentioned in section (a) can be similarly used. Asymmetric reduction is carried out by adding a ketone compound () dissolved in an appropriate solvent to the chiral modified lithium aluminum hydride thus prepared in (a) or (b). As the solvent, those mentioned in section (a) can be used. The reaction temperature at this time can range from -80°C to the boiling point of the solvent, but it is preferably carried out at 0°C or lower. After the reaction is completed, a dilute acidic aqueous solution is added to decompose the complex compound, and then the desired product is obtained by extraction, silica gel column chromatography, or recrystallization. (2) Method of resolving diastereomers A method of resolving optical isomers using diastereomeric esters obtained from a racemic alcohol compound and a reactive optically active compound is known (Reference; Org. Reaction Vol. 2, 380 ). A mixture of diastereomeric esters (2) is obtained by reacting a racemic triazolyl alcohol (2) with a reactive derivative of an optically active carboxylic acid in the presence of a base. This is separated into (+)-triazolyl alcohol ester and (-)-triazolyl alcohol ester by chromatography or fractional crystallization, and then (+)-
By decomposing the ester of triazolyl alcohol, a (+)-triazolyl alcohol derivative () is obtained. [In the formula, X and * are as described above.] ]
【表】
ル
トリアゾリルアルコール（）のラセミ体エス
テル化に用いられる光学活性カルボン酸の一例を
あげるならば、（−）−メントキシ酢酸（＋）また
は（−）−Ｎ−トリフルオロアセチルプロリン、
（＋）−カンホ酸、（＋）または（−）−マンデル
酸、（＋）または（−）−２−フエニルプロピオン
酸、（＋）または（−）−２−イソプロピル−4′−
クロロフエニル酢酸、（＋）または（−）−α−メ
トキシ−α−トリフルオロメチルフエニル酢酸、
（＋）または（−）−シス菊酸、（＋）または（−）
トランス菊酸などがある。これらの光学活性カル
ボン酸の反応性誘導体としては、その酸ハライド
あるいは酸無水物があるが一般には常法により酸
ハロゲン化物とした後、トリアゾリルアルコール
（）のラセミ体と反応させることによりエステ
ル化を行なう。反応は一般の不活性溶媒中で行な
われ（たとえばアセトン、アセトニトリル、テト
ラヒドロフラン、酢酸エチル、ベンゼン、トルエ
ン、ジクロロメタン、クロロホルム、四塩化炭素
等）、脱ハロゲン化水素剤（たとえばトリエチル
アミン、Ｎ，Ｎ−ジメチルアニリン、ピリジン
等）を用いることにより反応は達成される。
一般にトリアゾリルアルコール（）のラセミ
体に対して１〜５倍モルの酸ハロゲン化物と脱ハ
ロゲン化水素剤が用いられる。ピリジンまたは溶
媒として用いることもでき、この場合は（）に
対して過剰量が使用される。反応温度は室温から
溶媒の沸点までの範囲で行なわれる。
むろん前述光学活性カルボン酸の酸無水物を用
いてエステル化することも可能である。
このようにして得られたトリアゾリルアルコー
ルのジアステレオマーエステル混合物（）が結
晶化する場合には分別結晶を繰返すことにより、
油状物の場合にはカラムクロマトグラフイーある
いは高速液体クロマトグラフイーにより分割す
る。
こうして得られた（＋）−トリアゾリルアルコ
ールのエステルを水酸化ナトリウムあるいは水酸
化カリウム等の塩基の存在下に、適当な溶媒、す
なわち水あるいは含水有機溶媒（メタノールある
いはエタノールを用いるのが一般的である）等中
で分解することにより（＋）−トリアゾリルアル
コール誘導体（）を得る。
このようにして得られた該誘導体を実際に施用
する際には、他成分を何ら加えずに使用できる
し、植物生長調節剤として使いやすくするため担
体と混合して施用することができ、通常使用され
る形態、たとえば粉剤、水和剤、油剤、乳剤、錠
剤、粒剤、微粒剤、エアゾール、フロアブルなど
のいずれとしても使用できる。
前記製剤中には一般に活性化合物（混合成分を
含めて）を重量にして0.1〜95.0％、好ましくは
0.2〜90.0％を含み、通常10アールあたり２〜500
ｇの施用量が適当である。
さらにその施用濃度は、0.001〜1.0％の範囲が
望ましいが、これらの施用量および施用濃度は剤
型、施用時期、方法、場所、対象病害、対象作物
等によつても異なるため前記範囲に拘わることな
く増減することは何ら差し支えない。
さらに他の植物生長調節剤および除草剤たとえ
ば、２，４−ジクロロフエノキシ酢酸、２−メチ
ル−４−クロロフエノキシ酪酸、２−メチル−４
−クロロフエノキシ酢酸（エステル、塩類を含
む）等のフエノキシ系除草剤、２，４−ジクロロ
フエニル4′−ニトロフエニルエーテル、２，４，
６−トリクロロフエニル4′−ニトロフエニルエー
テル、２−クロロ−４−トリフルオロメチルフエ
ニル3′−エトキシ−4′−ニトロフエニルエーテ
ル、２，４−ジクロロフエニル4′−ニトロ−3′−
メトキシフエニルエーテル、２，４−ジクロロフ
エニル3′−メトキシカルボニル−4′−ニトロフエ
ニルエーテル等のジフエニルエーテル系除草剤、
２−クロロ−４，６−ビスエチルアミノ−１，
３，５−トリアジン、２−クロロ−４−エチルア
ミノ−６−イソプロピルアミノ−１，３，５−ト
リアジン、２−メチルチオ−４，６−ビスエチル
アミノ−１，３，５−トリアジン、２−メチルチ
オ−４，６−ビスイソプロピルアミノ−１，３，
５−トリアジン等のトリアジン系除草剤、３−
（３，４−ジクロロフエニル）−１，１−ジメチル
ウレア、３−（３，４−ジクロロフエニル）−１−
メトキシ−１−メチルウレア、１−（α，α−ジ
メチルベンジル）−３−ｐ−トリルウレア、１−
（２−ベンゾチアゾリル）−１，３−ジメチルウレ
ア等の尿素系除草剤、イソプロピルＮ−（３−ク
ロロフエニル）カーバメート、メチルＮ−（３，
４−ジクロロフエニル）カーバメート等のカーバ
メート系除草剤、Ｓ−（４−クロロベンジル）Ｎ，
Ｎ−ジエチルチオールカーバメート、Ｓ−エチル
Ｎ，Ｎ−ヘキサメチレンチオールカーバメート等
のチオールカーバメート系除草剤、３，４−ジク
ロロプロピオンアニリド、２−クロロ−Ｎ−メト
キシメチル−2′，6′−ジエチルアセトアニリド、
２−クロロ−2′，6′−ジエチル−Ｎ−（ブトキシ
メチル）−アセトアニリド、２−クロロ−2′，
6′−ジエチル−Ｎ−（ｎ−プロポキシエチル）ア
セトアニリド、Ｎ−クロロアセチル−Ｎ−（２，
６−ジエチルフエニル）グリシンエチルエステル
等の酸アニリド系除草剤、５−ブロモ−３−sec
−ブチル−６−メチルウラシル、３−シクロヘキ
シル−５，６−トリメチレンウラシル等のウラシ
ル系除草剤、１，1′−ジメチル−４，4′−ビピリ
ジニウムクロリド等のピリジニウム塩系除草剤、
Ｎ−（ホスホノメチル）グリシン、Ｎ−Ｎ−ビス
（ホスホノメチル）グリシン、Ｏ−エチルＯ−（２
−ニトロ−５−メチルフエニル）Ｎ−sec−ブチ
ルホスホロアミドチオエート、Ｓ−（２−メチル
−１−ピペリジルカルボニルメチル）Ｏ，Ｏ−ジ
−ｎ−プロピルジチオホスフエート、Ｓ−（２−
メチル−１−ピペリジルカルボニルメチル）Ｏ，
Ｏ−ジフエニルジチオホスフエート等のリン系除
草剤、α，α，α−トリフルオロ−２，６−ジニ
トロ−Ｎ，Ｎ−ジプロピル−ｐ−トルイジン等の
トルイジン系除草剤、５−ｔ−ブチル−３−（２，
４−ジクロロ−５−イソプロポキシフエニル）−
１，３，４−オキサジアゾリン−２−オン、３−
イソプロピル−（1H）−２，１，３−ベンゾチア
ジアジン−（3H）−オン−２，２−ジオキシド、
α−（β−ナフトキシ）プロピオンアニリド、４
−（２，４−ジクロロベンゾイル）１，３−ジメ
チルピラゾール−５−イルｐ−トルエンスルホネ
ート、３−（メトキシカルボニルアミノ）フエニ
ル３−メチルフエニルカーバメート、４−アミノ
−３−メチル−６−フエニル−１，２，４−トリ
アジンなどと混合して使用でき、いずれも各単剤
の防除効果を減ずることはなく、混合による相乗
効果も期待されるものである。また本発明化合物
は、殺菌剤、殺虫剤等と混合して使用することが
でき、たとえばＮ−（３，５−ジクロロフエニル）
−１，２−ジメチルシクロプロパン−１，２−ジ
カルボキシイミド、Ｓ−ｎ−ブチルＳ−ｐ−ｔ−
ブチルベンジルジチオカーボンイミデート、０，
０−ジメチル０−（２，６−ジクロロ−４−メチ
ルフエニル）ホスホロチオエート、メチル１−ブ
チルカルバモイル−1H−ベンズイミダゾール−
２−イルカーバメート、Ｎ−トリクロロメチルチ
オ−４−シクロヘキセン−１，２−ジカルボキシ
イミド、シス−Ｎ−（１，１，２，２−テトラク
ロロエチルチオ）−４−シクロヘキセン−１，２
−ジカルボキシイミド、ポリオキシン、ストレプ
トマイシン、ジンクエチレンビスジチオカーバメ
ート、ジンクジメチルチオカーバメート、マンガ
ンエチレンビスジチオカーバメート、ビス（Ｎ，
Ｎ−ジメチルチオカルバモイル）ジスルフイド、
テトラクロロイソフタロニトリル、８−ヒドロキ
シキノリン、ドデシルグアニジンアセテート、
５，６−ジヒドロ−２−メチル−１，４−オキサ
チイン−３−カルボキサニリド、N′−ジクロロ
フルオロメチルチオ−Ｎ−，Ｎ−ジメチル−
N′−フエニルスルフアミド、１−（４−クロロフ
エノキシ）−３，３−ジメチル−１−（１，２，４
−トリアゾール−１−イル）−２−ブタノン、１，
２−ビス（３−メトキシカルボニル−２−チオウ
レイド）ベンゼン、メチルＮ−（２，６−ジメチ
ルフエニル）−Ｎ−メトキシアセチル−２−メチ
ルグリシネート、アルミニウムエチルホスフアイ
ト等の殺菌剤、０，０−ジメチル０−（４−ニト
ロ−３−メチルフエニル）ホスホロチオエート、
０−（４−シアノフエニル）０，０−ジメチルホ
スホロチオエート、０−（４−シアノフエニル）
０−エチルフエニルホスホノチオエート、０，０
−ジメチルＳ−（Ｎ−メチルカルバモイルメチル）
ホスホロジチオエート、２−メトキシ−4H−１，
３，２−ベンゾジオキサホスホリン−２−スルフ
イド、０，０−ジメチルＳ−（１−エトキシカル
ボニル−１−フエニルメチル）ホスホロジチオエ
ート等の有機リン系殺菌剤、α−シアノ−３−フ
エノキシベンジル−２−（４−クロロフエニル）
イソバレレート、３−フエノキシベンジル２，２
−ジメチル−３−（２，２−ジクロロビニル）シ
クロプロパンカルボキシレート、α−シアノ−３
−フエノキシベンジル2′，2′−ジメチル−3′−
（２，２−ジブロモビニル）シクロプロパンカル
ボキシレート等のピレスロイド系殺菌剤等と混合
して使用することができ、さらに混合による相乗
効果も期待されるものである。
次に参考例をあげて本発明に関する化合物の製
法を詳しく述べる。
参考例 １
（＋）−（Ｅ）−１−（４−クロロフエニル）−２
−（１，２，４−トリアゾール−１−イル）−
４，４−ジメチル−１−ペンテン−３−オール
の不斉還元による合成
LiAlH41.25ｇ（0.033モル）、エチルエーテル、
（40c.c.）中へ氷冷下（−）−Ｎ−メチルエフエドリ
ン6.1ｇ（0.034モル）のエチルエーテル（100c.c.）
溶液を30分間で滴下した。滴下後15分保温撹拌
し、ついでＮ−エチルアニリン8.24ｇ（0.068モ
ル）のエチルエーテル（45c.c.）溶液を30分間で滴
下した。滴下後室温で３時間撹拌した。続いて
（Ｅ）−１−（１−クロロフエニル）−２−（１，２，
４−トリアゾール−１−イル）−４，４−ジメチ
ル−１−ペンテン−３−オン2.9ｇ（0.01モル）
のエチルエーテル（60c.c.）溶液を−70〜−67℃で
12分間で加え、−73℃で３時間保温撹拌した。室
温で一夜放置し、2N塩酸（110c.c.）を加え分解
し、分取した有機層を飽和炭酸水素ナトリウム水
溶液（100c.c.）、ついで氷水（100c.c.）で洗浄し、
芒硝で乾燥後減圧濃縮し、3.0ｇのトリアゾリル
アルコール体を結晶として得た；〔α〕24 D＋9.0゜（Ｃ
＝1.0、CHCl3）得られた結晶の2.5ｇをシクロヘ
キサンとジオキサンの混合溶媒から２回再結晶を
繰返すことにより0.81ｇの（＋）−（Ｅ）−１−（４
−クロロフエニル）−２−（１，２，４−トリアゾ
ール−１−イル）−４，４−ジメチル−１−ペン
テン−３−オールを得た。
〔α〕24 D＋15.7゜（Ｃ＝1.0、CHCl3）mp169〜170
℃
NMRスペクトルは参考例13に示したラセミ体
と同一であつた。
参考例 ２
（＋）−（Ｅ）−１−（２，４−ジクロロフエニ
ル）−２−（１，２，４−トリアゾール−１−イ
ル）−４，４−ジメチル−１−ペンテン−３−
オールの不斉還元による合成
参考例１と同様の手順によりLiAlH40.63ｇエ
チルエーテル（20c.c.）にＮ−メチルエフエドリン
3.05ｇのエチルエーテル（50c.c.）溶液を加え、つ
いでＮ−エチルアニリン4.12ｇのエチルエーテル
（20c.c.）溶液を加え、キラルな金属水素錯化合物
を調整した。続いて−70℃で（Ｅ）−１−（２，４
−ジクロロフエニル）−２−（１，２，４−トリア
ゾール−１−イル）−４，４−ジメチル−１−ペ
ンテン−３−オン1.62ｇのエチルエーテル（30
c.c.）溶液を加え、−73℃で５時間保温撹拌した。
室温で一晩放置したのち、2N塩酸（60c.c.）で分
解し、有機層を飽和炭酸水素ナトリウム水溶液
（100c.c.）、氷冷水（100c.c.）で洗浄し、芒硝で乾燥
後、減圧濃縮して1.82ｇの粗結晶を得た。シクロ
ヘキサン−メタノールの混合溶媒から３回再結晶
を繰返すことにより0.41ｇの（＋）−（Ｅ）−１−
（２，４−ジクロロフエニル）−２−１，２，４−
トリアゾール−１−イル）−４，４−ジメチル−
１−ペンテン３−オールを得た。
〔α〕24 D＋29.2゜（Ｃ＝1.0、CHCl3）mp160〜161
℃
NMRスペクトルは参考例14に示したラセミ体
と同一であつた。
参考例 ３
ジアステレオマーエステルの分割による（−）
および（＋）−（Ｅ）−１−（４−クロロフエニ
ル）−２−（１，２，４−トリアゾール−１−イ
ル）−４，４−ジメチル−１−ペンテン−３−
オールの合成
（±）−（Ｅ）−１−（４−クロロフエニル）−２
−（１，２，４−トリアゾール−１−イル）−４，
４−ジメチル−１−ペンテン−３−オール4.3ｇ
と（−）−メントキシアセチルクロライド８ｇと
をピリジン50c.c.中で70℃に７時間撹拌した。反応
混合物を氷水200c.c.中に注ぎ、酢酸エチル400c.c.で
抽出したのち有機層を0.5N塩酸200c.c.、飽和炭酸
水素ナトリウム水200c.c.、氷冷水200c.c.で順次洗浄
し、芒硝で乾燥後減圧濃縮して粗製油状物を得
た。これをシリカゲルカラムクロマトグラフイー
（シリカゲル150ｇ、展開溶媒ｎ−ヘキサン：アセ
トン＝30：１）により精製し、（±）、〔（Ｅ）−１
−（４−クロロフエニル）−２−（１，２，４）−ト
リアーゾル−１−イル）−４，４−ジメチル−１
−ペンテン−３−イル〕−（−）−メントキシアセ
テート7.4ｇを得た。得られたジアステレオマー
エステルの混合物を再度シリカゲルカラムクロマ
トグラフイー（シリカゲル250ｇ、展開溶媒ｎ−
ヘキサン：ベンゼン：アセトン＝20：20：１）に
かけると、先ず（−）−〔（Ｅ）−１−（４−クロロ
フエニル）−２−（１，２，４−トリアゾール−１
−イル）−４，４−ジメチル−１−ペンテン−３
−イル〕−（−）メントキシアセテート2.6ｇ（n25 D
1.5265）が溶出し、ついでジアステレオマーエス
テルの混合物が３ｇ溶出し、最後に（＋）−〔（Ｅ）
−１−（４−クロロフエニル）２−（１，２，４−
トリアゾール−１−イル）−４，４−ジメチル−
１−ペンテン−３−イル〕−（−）−メントキシア
セテート1.2ｇ（n25 D1.5281）が溶出した。
（−）−〔（Ｅ）−１−（４−クロロフエニル）−２
−（１，２，４−トリアゾール−１−イル）−４，
４−ジメチル−１−ペンテン−３−イル〕−（−）
−メントキシアセテート2.6ｇにKOH0.4ｇの95％
含水エタノール溶液40c.c.を加え30℃で１時間撹拌
したのち反応混合物を氷水200c.c.中に注ぎ、酢酸
エチル300c.c.で抽出し、有機層を芒硝で乾燥後、
減圧濃縮し、得られた粗結晶を四塩化炭素−ｎ−
ヘキサンの混合溶媒から再結晶し、1.2ｇの（−）
−（Ｅ）−１−（４−クロロフエニル）−２−（１，
２，４−トリアゾール−１−イル）−４，４−ジ
メチル−１−ペンテン−３−オールを得た。〔α〕
24 D−16.0℃（Ｃ＝１，CHCl3）mp170〜171℃
NMRスペクトルは参考例13に示したラセミ体
と同一であつた。
同様に（＋）−〔（Ｅ）−１−（４−クロロフエニ
ル）−２−（１，２，４−トリアゾール−１−イ
ル）−４，４−ジメチル−１−ペンテン−３−イ
ル〕−（−）−メントキシアセテート1.2ｇを
KOH0.2ｇの95％含水エタノール溶液20c.c.で処理
して得られた粗結晶を四塩化炭素−ｎ−ヘキサン
の混合溶液から再結晶し、0.5ｇの（＋）−（Ｅ）−
１−（４−クロロフエニル）−２−（１，２，４−
トリアゾール−１−イル）−４，４−ジメチル−
１−ペンテン−３−オールを得た。〔α〕24 D＋14.0゜
（Ｃ＝1.0，CHCl3）mp169〜170℃
参考例 ４
ジアステレオマーエステルの分割による（−）
および（＋）−（Ｅ）−１−（２，４−クロロフエ
ニル）−２−（１，２，４−トリアゾール−１−
イル）−４，４−ジメチル−１−ペンテン−３
−オールの合成
（±）−（Ｅ）−１−（２，４−ジクロロフエニ
ル）−２−（１，２，４−トリアゾール−１−イ
ル）−４，４−ジメチル−１−ペンテン−３−オ
ール４ｇと（−）−メントキシアセチルクロライ
ド８ｇをピリジン50c.c.中で70℃に７時間撹拌し
た。以後参考例３と同様の処理をし、粗製油状物
をシリカゲルカラムクロマトグラフイー（シリカ
ゲル150ｇ、展開溶媒ｎ−ヘキサン：アセトン＝
30：１）により精製することにより、（±）−
〔（Ｅ）−１−（２，４−ジクロロフエニル）−２−
（１，２，４−トリアゾール−１−イル）−４，４
−ジメチル−１−ペンテン−３−イル〕−（−）−
メントキシアセテート５ｇを得た。このジアステ
レオマーエステルの混合物を再度シリカゲルカラ
ムクロマトグラフイー（シリカゲル250ｇ、展開
溶媒ｎ−ヘキサン：ベンゼン：アセトン＝20：
20：１）にかけると、先ず（−）−〔（Ｅ）−１−
（２，４−ジクロロフエニル）−２−（１，２，４
−トリアゾール−１−イル）−４，４−ジメチル
−１−ペンテン−３−イル〕−（−）−メントキシ
アセテート1.6ｇ（n28 D1.5172）が溶出し、ついで
ジアステレオマーエステルの混合物が２ｇ溶出
し、最後に（＋）−〔（Ｅ）−１−（２，４−ジクロ
ロフエニル）−２−（１，２，４−トリアゾール−
１−イル）−４，４−ジメチル−１−ペンテン−
３−イル〕−（−）−メントキシアセテート0.7（n28 D
1.5102）が溶出した。
（−）−〔（Ｅ）−１−（２，４−ジクロロフエニ
ル）−２−（１，２，４−トリアゾール−１−イ
ル）−４，４−ジメチル−１−ペンテン−３−イ
ル〕−（−）−メントキシアセテート1.6ｇに
KOH0.2ｇの95％含水エタノール溶液（30c.c.）を
加え、25℃で１時間撹拌したのち、反応混合物を
氷水200c.c.中に注ぎ酢酸エチル300c.c.で抽出し、有
機層を芒硝で乾燥後、減圧濃縮し、得られた粗結
晶を四塩化炭素−ｎ−ヘキサンの混合溶媒から再
結晶して0.8ｇの（−）−（Ｅ）−１−（２，４−ジ
クロロフエニル）−２−（１，２，４−トリアゾー
ル−１−イル）−４，４−ジメチル−１−ペンテ
ン−３−オールを得た。
〔α〕24 D−31.7゜（Ｃ＝1.0，CHCl3）mp160〜161
℃
NMRスペクトルは参考例14で示したラセミ体
と同一であつた。
同様に（＋）−〔（Ｅ）−１−（２，４−ジクロロ
フエニル）−２−（１，２，４−トリアゾール−１
−イル）−４，４−ジメチル−１−ペンテン−３
−イル〕−（−）−メントキシアセテート0.7ｇを
KOH0.1ｇの90％含水エタノール溶液（20c.c.）で
処理して得られた粗結晶を四塩化炭素−ｎ−ヘキ
サンの混合溶媒から再結晶して、0.3ｇの（＋）−
（Ｅ）−１−（２，４−ジクロロフエニル）−２−
（１，２，４−トリアゾール−１−イル）−４，４
−ジメチル−１−ペンテン−３−オールを得た。
〔α〕24 D＋26.0°（Ｃ＝1.0，CHCl3）mp160〜161℃
参考例 ５
（−）−メントールを用いた不斉還元
LiAlH40.4ｇ（0.01モル）、THF30c.c.の中に
（−）−メントール4.4ｇ（0.028モル）のTHF30c.c.
溶液を10℃で加えたのち室温で30分撹拌した。続
いて１−（４−クロロフエニル）−２−（１，２，
４−トリアゾール−１−イル）−４，４−ジメチ
ル−１−ペンテン−３−オン2.0ｇ（0.007モル）
のTHF（50c.c.）の溶液を一30℃で加え、−５℃に
２時間保温撹拌した。1N塩酸５c.c.を加えたのち
不溶物を濾去し、濾液を氷水300c.c.中に注ぎエチ
ルエーテル500c.c.で抽出した。有機層を飽和炭酸
水素ナトリウム水溶液200c.c.と氷冷水200c.c.で洗浄
し、芒硝で乾燥したのち減圧濃縮し、粗生成物を
油状物として得た。得られた粗生成物をシリカゲ
ルカラムクロマトグラフイー（シリカゲル100ｇ、
展開溶媒ｎ−ヘキサン：アセトン＝30：１）によ
り分離精製し、未反応原料ケトン体0.5ｇを回収
し、（＋）−（Ｅ）−１−（４−クロロフエニル）−２
−（１，２，４−トリアゾール−１−イル）−４，
４−ジメチル−１−ペンテン−３−オールの結晶
（四塩化炭素とｎ−ヘキサンの混合溶媒から結晶
化）1.3ｇを得た；〔α〕26 D＋5.0゜（Ｃ＝１，CHCl3）
参考例 ６
（−）−ボルネオールを用いた不斉還元
LiAlH40.2ｇ（0.0053モル）、THF30c.c.中に
（−）−ボルネオール2.4ｇ（0.0155モル）のTHF
溶液30c.c.を０℃で加えたのち室温で50分間撹拌し
た。続いて（Ｅ）−１−（４−クロロフエニル）−
２−（１，２，４−トリアゾール−１−イル）−
４，４−ジメチル−１−ペンテン−３−オン1.0
ｇ（0.0034モル）をのTHF溶液30c.c.を０℃で加
え、室温で３時間撹拌した。IN塩酸0.5c.c.を加
え、不溶物を濾去し、濾液を氷冷水300c.c.中に注
ぎ、エチルエーテル500c.c.で抽出し、有機層を飽
和炭酸水素ナトリウム200c.c.、氷冷水200c.c.で洗浄
し、芒硝で乾燥後、減圧濃縮し得られた粗製油状
物をシリカゲルカラムクロマトグラフイー（シリ
カゲル100ｇ、展開溶媒ｎ−ヘキサン：アセトン
＝30：１）で分離精製し未反応原料ケトン体0.4
ｇを回収し、（＋）−（Ｅ）−１−（４−クロロフエ
ニル）−２−（１，２，４−トリアゾール−１−イ
ル）−４，４−ジメチル−１−ペンテン−３−オ
ールの結晶（四塩化炭素とｎ−ヘキサンの混合溶
媒から結晶化）0.45ｇを得た；〔α〕24 D＋32℃（Ｃ
＝１，CHCl3）
参考例 ７
（＋）−２−Ｎ−ベンジル−Ｎ−メチルアミノ
−１−フエニルエタノールを用いた不斉還元
LiAlH40.114ｇ（3.0ミリモル）エチルエーテル
４mlに室温下、（−）−２−Ｎ−ベンジル−Ｎ−メ
チルアミノ−１−フエニルエタノール0.78ｇ
（3.23ミリモル）のアミノエーテル５ml溶液を15
分間で滴下した。滴下後室温で30分間撹拌し、つ
いでＮ−メチルアニリン0.64ｇ（6.0ミリモル）
のエチルエーテル３ml溶液を15分間で滴下した。
滴下後35℃で1.75時間撹拌したのち−78℃に冷却
し、（Ｅ）−１−（４−クロロフエニル）−２−（１，
２，４−トリアゾール−１−イル）−４，４−ジ
メチル−１−ペンテン−３−オン0.29ｇ（1.0ミ
リモル）のエチルエーテル６ml溶液を滴下した。
３時間保温撹拌後、室温で１時間撹拌し2N塩酸
８mlを加えて分解した。有機層を分液し、飽和炭
酸水素ナトリウム水溶液10ml、氷冷水10mlで洗浄
後、芒硝乾燥、減圧濃縮し、0.28ｇの粗（＋）−
（Ｅ）−１−（４−クロロフエニル）−２−（１，２，
４−トリアゾール−１−イル）−４，４−ジメチ
ル−１−ペンテン−３−オールを得た。〔α〕24 D＋
14.6゜（Ｃ＝1.0，CHCl3）
参考例 ８
（−）−２−Ｎ−ベンジル−Ｎ−メチルアミノ
−１−フエニルエタノールを用いた不斉還元
LiAlH40.114ｇ（3.0ミリモル）エチルエーテル
４mlに氷冷下、（−）−２−Ｎ−ベンジル−Ｎ−メ
チルアミノ−１−フエニルエタノール0.78ｇ
（3.23ミリモル）のエチルエーテル５ml溶液を15
分間滴下した。滴下後30分間保温撹拌し、ついで
Ｎ−メチルアニリン0.64ｇ（6.0ミリモル）のエ
チルエーテル３ml溶液を15分間で滴下した。滴下
後室温で３時間撹拌したのち−78℃に冷却し、
（Ｅ）−１−（２，４−ジクロロフエニル）−２−
（１，２，４−トリアゾール−１−イル）−４，４
−ジメチル−１−ペンテン−３−オン0.32ｇ
（1.0ミリモル）のエチルエーテル５ml溶液を滴下
した。３時間保温撹拌後、室温で一夜放置し、
2N塩酸８mlを加えて分解した。有機層を分液し、
飽和炭酸水素ナトリウム水溶液10ml氷冷水10mlで
洗浄後、芒硝で乾燥した。減圧濃縮すると0.33ｇ
の粗（＋）−〔Ｅ）−１−（２，４−ジクロロフエニ
ル）−２−（１，２，４−トリアゾール−１−イ
ル）−４，４−ジメチル−１−ペンテン−３−オ
ールを得た。〔α〕24 D＋26.1゜（Ｃ＝1.0，CHCl3）
参考例９〜12
参考例８において、（−）−２−Ｎ−ベンジル−
Ｎ−メチルアミノ−１−フエニルエタノールに代
えて下記光学活性アミノアルコールを用いた以外
は参考例８に準じて行ない粗（＋）−（Ｅ）−１−
（２，４−ジクロロフエニル）−２−（１，２，４
−トリアゾール−１−イル）−４，４−ジメチル
−１−ペンテン−３−オールを得た。その結果を
第１表に示す。[Table] Le
Examples of optically active carboxylic acids used for racemic esterification of triazolyl alcohol () are (-)-menthoxyacetic acid (+) or (-)-N-trifluoroacetylproline,
(+)-Camphoic acid, (+) or (-)-Mandelic acid, (+) or (-)-2-phenylpropionic acid, (+) or (-)-2-isopropyl-4'-
Chlorophenyl acetic acid, (+) or (-)-α-methoxy-α-trifluoromethylphenylacetic acid,
(+) or (-)-cis chrysanthemum acid, (+) or (-)
Examples include trans chrysanthemum acid. Reactive derivatives of these optically active carboxylic acids include their acid halides and acid anhydrides, but in general, they are converted into acid halides by conventional methods, and then esters are obtained by reacting with a racemic form of triazolyl alcohol (). . The reaction is carried out in a common inert solvent (e.g. acetone, acetonitrile, tetrahydrofuran, ethyl acetate, benzene, toluene, dichloromethane, chloroform, carbon tetrachloride, etc.) and a dehydrohalogenating agent (e.g. triethylamine, N,N-dimethyl Aniline, pyridine, etc.). Generally, an acid halide and a dehydrohalogenating agent are used in an amount of 1 to 5 times the molar amount relative to the racemic form of triazolyl alcohol (2). It can also be used as pyridine or as a solvent, in which case an excess amount relative to () is used. The reaction temperature ranges from room temperature to the boiling point of the solvent. Of course, it is also possible to carry out esterification using the acid anhydride of the optically active carboxylic acid mentioned above. When the diastereomeric ester mixture () of triazolyl alcohol obtained in this way crystallizes, by repeating the fractional crystallization,
In the case of oil, it is separated by column chromatography or high performance liquid chromatography. The ester of (+)-triazolyl alcohol thus obtained is treated in the presence of a base such as sodium hydroxide or potassium hydroxide with a suitable solvent, that is, water or a water-containing organic solvent (methanol or ethanol is generally used). (+)-Triazolyl alcohol derivative () is obtained by decomposing the compound in (+)-triazolyl alcohol derivative (). When actually applying the derivative obtained in this way, it can be used without adding any other ingredients, or it can be mixed with a carrier to make it easier to use as a plant growth regulator. It can be used in any form, such as powders, wettable powders, oils, emulsions, tablets, granules, fine granules, aerosols, flowables, etc. The formulations generally contain from 0.1 to 95.0% by weight of active compound (including mixed ingredients), preferably
Contains 0.2-90.0%, usually 2-500 per 10 ares
An application amount of 1.5 g is appropriate. Furthermore, the application concentration is preferably in the range of 0.001 to 1.0%, but these application amounts and concentrations vary depending on the dosage form, application time, method, location, target disease, target crop, etc., so they are not limited to the above range. There is no problem in increasing or decreasing it without any problem. Still other plant growth regulators and herbicides such as 2,4-dichlorophenoxyacetic acid, 2-methyl-4-chlorophenoxybutyric acid, 2-methyl-4
- Phenoxy herbicides such as chlorophenoxyacetic acid (including esters and salts), 2,4-dichlorophenyl 4'-nitrophenyl ether, 2,4,
6-Trichlorophenyl 4'-nitrophenyl ether, 2-chloro-4-trifluoromethylphenyl 3'-ethoxy-4'-nitrophenyl ether, 2,4-dichlorophenyl 4'-nitro-3 ′−
Diphenyl ether herbicides such as methoxyphenyl ether, 2,4-dichlorophenyl 3'-methoxycarbonyl-4'-nitrophenyl ether,
2-chloro-4,6-bisethylamino-1,
3,5-triazine, 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine, 2-methylthio-4,6-bisethylamino-1,3,5-triazine, 2- Methylthio-4,6-bisisopropylamino-1,3,
5- Triazine herbicides such as triazine, 3-
(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1-
Methoxy-1-methylurea, 1-(α,α-dimethylbenzyl)-3-p-tolylurea, 1-
Urea herbicides such as (2-benzothiazolyl)-1,3-dimethylurea, isopropyl N-(3-chlorophenyl) carbamate, methyl N-(3,
Carbamate herbicides such as 4-dichlorophenyl)carbamate, S-(4-chlorobenzyl)N,
Thiol carbamate herbicides such as N-diethylthiol carbamate and S-ethyl N,N-hexamethylenethiol carbamate, 3,4-dichloropropionanilide, 2-chloro-N-methoxymethyl-2',6'-diethylacetanilide ,
2-chloro-2',6'-diethyl-N-(butoxymethyl)-acetanilide, 2-chloro-2',
6'-diethyl-N-(n-propoxyethyl)acetanilide, N-chloroacetyl-N-(2,
Acid anilide herbicides such as 6-diethyl phenyl) glycine ethyl ester, 5-bromo-3-sec
- Uracil herbicides such as butyl-6-methyluracil and 3-cyclohexyl-5,6-trimethyleneuracil, pyridinium salt herbicides such as 1,1'-dimethyl-4,4'-bipyridinium chloride,
N-(phosphonomethyl)glycine, N-N-bis(phosphonomethyl)glycine, O-ethyl O-(2
-Nitro-5-methylphenyl)N-sec-butylphosphoramidothioate, S-(2-methyl-1-piperidylcarbonylmethyl)O,O-di-n-propyldithiophosphate, S-(2-
methyl-1-piperidylcarbonylmethyl)O,
Phosphorus herbicides such as O-diphenyldithiophosphate, toluidine herbicides such as α,α,α-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine, 5-t-butyl -3-(2,
4-dichloro-5-isopropoxyphenyl)-
1,3,4-oxadiazolin-2-one, 3-
isopropyl-(1H)-2,1,3-benzothiadiazin-(3H)-one-2,2-dioxide,
α-(β-naphthoxy)propionanilide, 4
-(2,4-dichlorobenzoyl)1,3-dimethylpyrazol-5-yl p-toluenesulfonate, 3-(methoxycarbonylamino)phenyl 3-methylphenyl carbamate, 4-amino-3-methyl-6-phenyl It can be used in combination with -1,2,4-triazine, etc., and neither of them will reduce the pesticidal effect of each single agent, and a synergistic effect by mixing is expected. Furthermore, the compound of the present invention can be used in combination with fungicides, insecticides, etc., such as N-(3,5-dichlorophenyl).
-1,2-dimethylcyclopropane-1,2-dicarboximide, S-n-butyl S-pt-
Butylbenzyldithiocarbonimidate, 0,
0-Dimethyl 0-(2,6-dichloro-4-methylphenyl)phosphorothioate, methyl 1-butylcarbamoyl-1H-benzimidazole-
2-ylcarbamate, N-trichloromethylthio-4-cyclohexene-1,2-dicarboximide, cis-N-(1,1,2,2-tetrachloroethylthio)-4-cyclohexene-1,2
- dicarboximide, polyoxin, streptomycin, zinc ethylene bisdithiocarbamate, zinc dimethylthiocarbamate, manganese ethylene bisdithiocarbamate, bis(N,
N-dimethylthiocarbamoyl) disulfide,
Tetrachloroisophthalonitrile, 8-hydroxyquinoline, dodecylguanidine acetate,
5,6-dihydro-2-methyl-1,4-oxathiin-3-carboxanilide, N'-dichlorofluoromethylthio-N-,N-dimethyl-
N'-Phenylsulfamide, 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4
-triazol-1-yl)-2-butanone, 1,
Bactericidal agents such as 2-bis(3-methoxycarbonyl-2-thioureido)benzene, methyl N-(2,6-dimethylphenyl)-N-methoxyacetyl-2-methylglycinate, aluminum ethyl phosphite, 0, 0-dimethyl 0-(4-nitro-3-methylphenyl) phosphorothioate,
0-(4-cyanophenyl)0,0-dimethylphosphorothioate, 0-(4-cyanophenyl)
0-ethylphenylphosphonothioate, 0,0
-dimethyl S-(N-methylcarbamoylmethyl)
Phosphorodithioate, 2-methoxy-4H-1,
Organophosphorus fungicides such as 3,2-benzodioxaphosphorine-2-sulfide, 0,0-dimethyl S-(1-ethoxycarbonyl-1-phenylmethyl)phosphorodithioate, α-cyano-3-phenyl Enoxybenzyl-2-(4-chlorophenyl)
Isovalerate, 3-phenoxybenzyl 2,2
-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate, α-cyano-3
-Phenoxybenzyl 2',2'-dimethyl-3'-
It can be used in combination with a pyrethroid fungicide such as (2,2-dibromovinyl)cyclopropanecarboxylate, and a synergistic effect is also expected by mixing. Next, the method for producing the compound related to the present invention will be described in detail by giving reference examples. Reference example 1 (+)-(E)-1-(4-chlorophenyl)-2
-(1,2,4-triazol-1-yl)-
Synthesis by asymmetric reduction of 4,4-dimethyl-1-penten-3-ol LiAlH 4 1.25 g (0.033 mol), ethyl ether,
(40 c.c.) under ice-cooling (-)-N-methylefedrine 6.1 g (0.034 mol) in ethyl ether (100 c.c.)
The solution was added dropwise over 30 minutes. After the dropwise addition, the mixture was stirred while keeping it warm for 15 minutes, and then a solution of 8.24 g (0.068 mol) of N-ethylaniline in ethyl ether (45 c.c.) was added dropwise over 30 minutes. After the addition, the mixture was stirred at room temperature for 3 hours. Then (E)-1-(1-chlorophenyl)-2-(1,2,
2.9 g (0.01 mol) of 4-triazol-1-yl)-4,4-dimethyl-1-penten-3-one
in ethyl ether (60 c.c.) at -70 to -67°C.
The mixture was added over 12 minutes and stirred at -73°C for 3 hours. The mixture was left at room temperature overnight, decomposed by adding 2N hydrochloric acid (110 c.c.), and the separated organic layer was washed with a saturated aqueous sodium bicarbonate solution (100 c.c.) and then with ice water (100 c.c.).
After drying with Glauber's salt, it was concentrated under reduced pressure to obtain 3.0 g of triazolyl alcohol as crystals; [α] 24 D +9.0° (C
= 1.0, CHCl 3 ) 0.81 g of (+)-(E)-1-(4
-chlorophenyl)-2-(1,2,4-triazol-1-yl)-4,4-dimethyl-1-penten-3-ol was obtained. [α] 24 D +15.7゜(C=1.0, CHCl3 ) mp169~170
The C NMR spectrum was the same as that of the racemate shown in Reference Example 13. Reference example 2 (+)-(E)-1-(2,4-dichlorophenyl)-2-(1,2,4-triazol-1-yl)-4,4-dimethyl-1-penten-3 −
Synthesis by asymmetric reduction of ol N-methyl ephedrine was added to 0.63 g of LiAlH 4 ethyl ether (20 c.c.) using the same procedure as in Reference Example 1.
A chiral metal hydrogen complex was prepared by adding a solution of 3.05 g of ethyl ether (50 c.c.) followed by a solution of 4.12 g of N-ethylaniline in ethyl ether (20 c.c.). Subsequently, (E)-1-(2,4
-dichlorophenyl)-2-(1,2,4-triazol-1-yl)-4,4-dimethyl-1-penten-3-one 1.62 g of ethyl ether (30
cc) solution was added and stirred at -73°C for 5 hours.
After standing overnight at room temperature, decompose with 2N hydrochloric acid (60 c.c.), wash the organic layer with saturated aqueous sodium bicarbonate solution (100 c.c.), ice-cold water (100 c.c.), and dry with Glauber's salt. Thereafter, it was concentrated under reduced pressure to obtain 1.82 g of crude crystals. By repeating recrystallization three times from a mixed solvent of cyclohexane-methanol, 0.41 g of (+)-(E)-1-
(2,4-dichlorophenyl)-2-1,2,4-
triazol-1-yl)-4,4-dimethyl-
1-penten-3-ol was obtained. [α] 24 D +29.2゜(C=1.0, CHCl3 ) mp160~161
The C NMR spectrum was the same as that of the racemate shown in Reference Example 14. Reference example 3 (-) by resolution of diastereomeric esters
and (+)-(E)-1-(4-chlorophenyl)-2-(1,2,4-triazol-1-yl)-4,4-dimethyl-1-penten-3-
Synthesis of ol (±)-(E)-1-(4-chlorophenyl)-2
-(1,2,4-triazol-1-yl)-4,
4-dimethyl-1-penten-3-ol 4.3g
and 8 g of (-)-menthoxyacetyl chloride were stirred in 50 c.c. of pyridine at 70°C for 7 hours. The reaction mixture was poured into 200 c.c. of ice water, extracted with 400 c.c. of ethyl acetate, and the organic layer was extracted with 200 c.c. of 0.5N hydrochloric acid, 200 c.c. of saturated sodium bicarbonate water, and 200 c.c. of ice-cold water. The mixture was washed sequentially, dried over Glauber's salt, and concentrated under reduced pressure to obtain a crude oil. This was purified by silica gel column chromatography (150 g of silica gel, developing solvent n-hexane:acetone = 30:1), (±), [(E)-1
-(4-chlorophenyl)-2-(1,2,4)-triazol-1-yl)-4,4-dimethyl-1
7.4 g of -penten-3-yl]-(-)-menthoxy acetate were obtained. The resulting diastereomer ester mixture was again subjected to silica gel column chromatography (silica gel 250g, developing solvent n-
When applied to hexane:benzene:acetone=20:20:1), first, (-)-[(E)-1-(4-chlorophenyl)-2-(1,2,4-triazole-1
-yl)-4,4-dimethyl-1-pentene-3
-yl]-(-)menthoxy acetate 2.6g (n 25 D
1.5265) elutes, then 3 g of a mixture of diastereomeric esters elutes, and finally (+)-[(E)
-1-(4-chlorophenyl)2-(1,2,4-
triazol-1-yl)-4,4-dimethyl-
1.2 g (n 25 D 1.5281) of 1-penten-3-yl]-(-)-menthoxy acetate was eluted. (-)-[(E)-1-(4-chlorophenyl)-2
-(1,2,4-triazol-1-yl)-4,
4-dimethyl-1-penten-3-yl]-(-)
- 95% of 0.4g of KOH in 2.6g of menthoxyacetate
After adding 40 c.c. of aqueous ethanol solution and stirring at 30°C for 1 hour, the reaction mixture was poured into 200 c.c. of ice water, extracted with 300 c.c. of ethyl acetate, and the organic layer was dried with Glauber's salt.
After concentration under reduced pressure, the obtained crude crystals were dissolved in carbon tetrachloride-n-
Recrystallized from a mixed solvent of hexane, 1.2 g of (-)
-(E)-1-(4-chlorophenyl)-2-(1,
2,4-triazol-1-yl)-4,4-dimethyl-1-penten-3-ol was obtained. [α]
24D -16.0 °C (C=1, CHCl3 ) mp170-171°C NMR spectrum was the same as that of the racemate shown in Reference Example 13. Similarly, (+)-[(E)-1-(4-chlorophenyl)-2-(1,2,4-triazol-1-yl)-4,4-dimethyl-1-penten-3-yl]- (-)-menthoxy acetate 1.2g
The crude crystals obtained by treatment with 20 c.c. of a 95% aqueous ethanol solution of 0.2 g of KOH were recrystallized from a mixed solution of carbon tetrachloride-n-hexane, and 0.5 g of (+)-(E)-
1-(4-chlorophenyl)-2-(1,2,4-
triazol-1-yl)-4,4-dimethyl-
1-penten-3-ol was obtained. [α] 24 D +14.0° (C = 1.0, CHCl 3 ) mp169-170°C Reference example 4 (-) by resolution of diastereomeric esters
and (+)-(E)-1-(2,4-chlorophenyl)-2-(1,2,4-triazole-1-
yl)-4,4-dimethyl-1-pentene-3
-Synthesis of -ol (±)-(E)-1-(2,4-dichlorophenyl)-2-(1,2,4-triazol-1-yl)-4,4-dimethyl-1-penten- 4 g of 3-ol and 8 g of (-)-menthoxyacetyl chloride were stirred in 50 c.c. of pyridine at 70°C for 7 hours. Thereafter, the same treatment as in Reference Example 3 was carried out, and the crude oil was subjected to silica gel column chromatography (150 g of silica gel, developing solvent n-hexane: acetone =
(±)-
[(E)-1-(2,4-dichlorophenyl)-2-
(1,2,4-triazol-1-yl)-4,4
-dimethyl-1-penten-3-yl]-(-)-
5 g of menthoxy acetate was obtained. This mixture of diastereomeric esters was subjected to silica gel column chromatography again (250 g of silica gel, developing solvent n-hexane:benzene:acetone = 20:
20:1), first (-)-[(E)-1-
(2,4-dichlorophenyl)-2-(1,2,4
1.6 g (n 28 D 1.5172) of -triazol-1-yl)-4,4-dimethyl-1-penten-3-yl]-(-)-menthoxy acetate elute, followed by a mixture of diastereomeric esters. 2g elute, and finally (+)-[(E)-1-(2,4-dichlorophenyl)-2-(1,2,4-triazole-
1-yl)-4,4-dimethyl-1-pentene-
3-yl]-(-)-menthoxy acetate 0.7 (n 28 D
1.5102) was eluted. (-)-[(E)-1-(2,4-dichlorophenyl)-2-(1,2,4-triazol-1-yl)-4,4-dimethyl-1-penten-3-yl ]-(-)-menthoxy acetate 1.6g
A 95% aqueous ethanol solution (30 c.c.) containing 0.2 g of KOH was added and stirred at 25°C for 1 hour. The reaction mixture was poured into 200 c.c. of ice water and extracted with 300 c.c. of ethyl acetate. was dried with Glauber's salt, concentrated under reduced pressure, and the obtained crude crystals were recrystallized from a mixed solvent of carbon tetrachloride-n-hexane to give 0.8 g of (-)-(E)-1-(2,4-dichloro Phenyl)-2-(1,2,4-triazol-1-yl)-4,4-dimethyl-1-penten-3-ol was obtained. [α] 24 D −31.7゜(C=1.0, CHCl3 ) mp160～161
The C NMR spectrum was the same as that of the racemate shown in Reference Example 14. Similarly, (+)-[(E)-1-(2,4-dichlorophenyl)-2-(1,2,4-triazole-1
-yl)-4,4-dimethyl-1-pentene-3
-yl]-(-)-menthoxy acetate 0.7g
The crude crystals obtained by treating 0.1 g of KOH with a 90% aqueous ethanol solution (20 c.c.) were recrystallized from a mixed solvent of carbon tetrachloride-n-hexane, and 0.3 g of (+)-
(E)-1-(2,4-dichlorophenyl)-2-
(1,2,4-triazol-1-yl)-4,4
-dimethyl-1-penten-3-ol was obtained.
[α] 24 D +26.0° (C = 1.0, CHCl 3 ) mp160-161°C Reference example 5 Asymmetric reduction using (-)-menthol LiAlH 4 0.4g (0.01 mol) in THF30c.c. (-)-menthol 4.4g (0.028mol) THF30c.c.
The solution was added at 10°C and then stirred at room temperature for 30 minutes. Subsequently, 1-(4-chlorophenyl)-2-(1,2,
2.0 g (0.007 mol) of 4-triazol-1-yl)-4,4-dimethyl-1-penten-3-one
A solution of THF (50 c.c.) was added at -30°C, and the mixture was stirred and kept at -5°C for 2 hours. After adding 5 c.c. of 1N hydrochloric acid, insoluble materials were filtered off, and the filtrate was poured into 300 c.c. of ice water and extracted with 500 c.c. of ethyl ether. The organic layer was washed with 200 c.c. of saturated aqueous sodium hydrogen carbonate solution and 200 c.c. of ice-cold water, dried over Glauber's salt, and concentrated under reduced pressure to obtain a crude product as an oil. The obtained crude product was subjected to silica gel column chromatography (100 g of silica gel,
Separation and purification was performed using a developing solvent (n-hexane:acetone = 30:1) to recover 0.5 g of unreacted raw material ketone body, and (+)-(E)-1-(4-chlorophenyl)-2
-(1,2,4-triazol-1-yl)-4,
1.3 g of crystals of 4-dimethyl-1-penten-3-ol (crystallized from a mixed solvent of carbon tetrachloride and n-hexane) were obtained; [α] 26 D +5.0° (C = 1, CHCl 3 ) Reference Example 6 Asymmetric reduction using (-)-borneol 0.2 g (0.0053 mol) of LiAlH 4 and 2.4 g (0.0155 mol) of (-)-borneol in THF 30 c.c.
After adding 30 c.c. of the solution at 0°C, the mixture was stirred at room temperature for 50 minutes. followed by (E)-1-(4-chlorophenyl)-
2-(1,2,4-triazol-1-yl)-
4,4-dimethyl-1-penten-3-one 1.0
g (0.0034 mol) of a THF solution was added at 0°C, and the mixture was stirred at room temperature for 3 hours. Add 0.5 cc of IN hydrochloric acid, remove insoluble matter by filtration, pour the filtrate into 300 c.c. of ice-cold water, extract with 500 c.c. of ethyl ether, and extract the organic layer with 200 c.c. of saturated sodium hydrogen carbonate and 200 c.c. of ice-cold water. After washing with 200 c.c., drying with Glauber's salt, and concentrating under reduced pressure, the resulting crude oil was separated and purified using silica gel column chromatography (silica gel 100 g, developing solvent n-hexane:acetone = 30:1) to remove any unreacted substances. Raw material ketone bodies 0.4
(+)-(E)-1-(4-chlorophenyl)-2-(1,2,4-triazol-1-yl)-4,4-dimethyl-1-penten-3-ol 0.45 g of crystals (crystallized from a mixed solvent of carbon tetrachloride and n-hexane) were obtained; [α] 24 D +32°C (C
= 1, CHCl 3 ) Reference Example 7 Asymmetric reduction using (+)-2-N-benzyl-N-methylamino-1-phenylethanol 0.114 g (3.0 mmol) of LiAlH 4 was added to 4 ml of ethyl ether at room temperature. (-)-2-N-benzyl-N-methylamino-1-phenylethanol 0.78g
(3.23 mmol) in 5 ml of amino ether solution
It was dripped in minutes. After dropping, stir at room temperature for 30 minutes, then add 0.64 g (6.0 mmol) of N-methylaniline.
A solution of 3 ml of ethyl ether was added dropwise over 15 minutes.
After the dropwise addition, the mixture was stirred at 35°C for 1.75 hours and then cooled to -78°C to give (E)-1-(4-chlorophenyl)-2-(1,
A solution of 0.29 g (1.0 mmol) of 2,4-triazol-1-yl)-4,4-dimethyl-1-penten-3-one in 6 ml of ethyl ether was added dropwise.
After stirring while keeping warm for 3 hours, the mixture was stirred at room temperature for 1 hour and decomposed by adding 8 ml of 2N hydrochloric acid. The organic layer was separated, washed with 10 ml of saturated aqueous sodium bicarbonate solution and 10 ml of ice-cold water, dried with sodium sulfate, and concentrated under reduced pressure to give 0.28 g of crude (+)-
(E)-1-(4-chlorophenyl)-2-(1,2,
4-triazol-1-yl)-4,4-dimethyl-1-penten-3-ol was obtained. [α] 24 D +
14.6゜(C=1.0, CHCl 3 ) Reference example 8 Asymmetric reduction using (-)-2-N-benzyl-N-methylamino-1-phenylethanol LiAlH 4 0.114 g (3.0 mmol) ethyl ether 4 ml 0.78 g of (-)-2-N-benzyl-N-methylamino-1-phenylethanol under ice cooling.
(3.23 mmol) in 5 ml of ethyl ether
dripped for minutes. After the addition, the mixture was stirred for 30 minutes while being kept warm, and then a solution of 0.64 g (6.0 mmol) of N-methylaniline in 3 ml of ethyl ether was added dropwise over 15 minutes. After the dropwise addition, the mixture was stirred at room temperature for 3 hours, and then cooled to -78°C.
(E)-1-(2,4-dichlorophenyl)-2-
(1,2,4-triazol-1-yl)-4,4
-dimethyl-1-penten-3-one 0.32g
(1.0 mmol) in 5 ml of ethyl ether was added dropwise. After stirring while keeping warm for 3 hours, leave it at room temperature overnight.
It was decomposed by adding 8 ml of 2N hydrochloric acid. Separate the organic layer,
After washing with 10 ml of a saturated aqueous sodium bicarbonate solution and 10 ml of ice-cold water, it was dried with Glauber's salt. 0.33g when concentrated under reduced pressure
Crude (+)-[E)-1-(2,4-dichlorophenyl)-2-(1,2,4-triazol-1-yl)-4,4-dimethyl-1-penten-3- Got the oars. [α] 24 D +26.1° (C = 1.0, CHCl 3 ) Reference Examples 9 to 12 In Reference Example 8, (-)-2-N-benzyl-
Crude (+)-(E)-1-
(2,4-dichlorophenyl)-2-(1,2,4
-triazol-1-yl)-4,4-dimethyl-1-penten-3-ol was obtained. The results are shown in Table 1.
【表】【table】
【表】
参考例 13
（Ｅ）−１−（４−クロロフエニル）−２−（１，
２，４−トリアゾール−１−イル）−４，４−
ジメチル−１−ペンテン−３−オールのラセミ
体の合成
下記MNRスペクトルで特徴付けられる（Ｅ）
−１−（４−クロロフエニル）−２−（１，２，４
−トリアゾール−１−イル）−４，４−ジメチル
−１−ペンテン−３−オン（融点108〜109℃）
2.9ｇ（0.01モル）をメタノール50mlに溶解した。
これを氷冷し反応液温度を20℃以下に保ちつつ、
水素化ホウ素ナトリウム0.38ｇ（0.01モル）を加
えた。
20℃に３時間保つたのち水100ml、酢酸１mlを
加えて分解し、有機層を酢酸エチル100mlで抽出
した。５％重曹水50mlで洗浄後、無水硫酸ソーダ
で乾燥した。溶媒を減圧下に留去し、残渣をｎ−
ヘキサンから再結晶して融点153〜155℃の標題化
合物2.0ｇ（収率69％）を得た。各化合物の元素
分析値および重クロロホルム中のNMRスペクト
ルの結果を示す（δ値）。
（Ｅ）−１−（４−クロロフエニル）−２−（１，
２，４−トリアゾール−１−イル）−４，４−ジ
メチル−１−ペンテン−３−オン；
元素分析 Ｃ（％） Ｈ（％） Ｎ（％） Cl
（％）
計算値 62.17 5.58 14.50 12.23
（C15H16N3OClとして）
分析値 62.32 5.60 14.41 12.20
NMRスペクトル
8.11（1H、シングレツト、トリアゾールプロト
ン）、7.90（1H、シングレツト、トリアゾールプ
ロトン）、7.15（4H、シングレツト、フエニルプ
ロトン）、6.99（1H、シングレツト、オレフイン
プロトン）、0.99（9H、シングレツト、ブチルプ
ロトン）
（Ｅ）−１−（４−クロロフエニル）−２−（１，
２，４−トリアゾール−１−イル）−４，４−ジ
メチル−１−ペンテン−３−オール；
元素分析 Ｃ（％） Ｈ（％） Ｎ（％） Cl
（％）
計算値 61.74 6.23 14.40 12.15
（C15H16N3OClとして）
分析値 61.82 6.33 14.38 12.15
NMRスペクトル
8.52（1H、シングレツト、トリアゾールプロト
ン）、7.98（1H、シングレツト、トリアゾールプ
ロトン）、7.30（4H、シングレツト、フエニルプ
ロトン）、6.91（1H、シングレツト、オレフイン
プロトン）、4.56（2H、幅広なシングレツト、水
酸基および水酸基のついているメチンプロトン）、
0.66（9H、シングレツト、ブチルプロトン）
参考例 14
（Ｅ）−１−（４−ジクロロフエニル）−２−
（１，２，４−トリアゾール−１−イル）−４，
４−ジメチル−１−ペンテン−３−オールのラ
セミ体の合成
下記NMRスペクトルで特徴付けられる（Ｅ）
−１−（２，４−ジクロロフエニル）−２−（１，
２，４−トリアゾール−１−イル）−４，４−ジ
メチル−１−ペンテン−３−オン融点92〜93℃）
3.2ｇのメタノール溶液（50c.c.）に氷冷下水素化
ホウ素ナトリウム0.5ｇを加え、室温に３時間撹
拌したのち参考例13と同様の後処理により融点
148〜149℃の標題化合物2.6ｇを得た。
以下にNMRスペクトル（重クロロホルム中δ
値）を示す。
（Ｅ）−１−（２，４−ジクロロフエニル）−２
−（１，２，４−トリアゾール−１−イル）−４，
４−ジメチル−１−ペンテン−３−オン；8.30
（1H、シングレツト、トリアゾールプロトン）、
8.04（1H、シングレツト、トリアゾールプロト
ン、7.45（1H、マルチプレツト、フエニルプロト
ン）、7.26（2H、マルチプレツト、フエニルプロ
トン）、7.22（1H、シングレツト、オレフインプ
ロトン）、0.97（9H、シングレツト、ブチルプロ
トン）、
（Ｅ）−１−（２，４−ジクロロフエニル）−２
−（１，２，４−トリアゾール−１−イル）−４，
４−ジメチル−１−ペンテン−３−オール8.45
（1H、シングレツト、トリアゾールプロトン）、
7.97（1H、シングレツト、トリアゾールプロト
ン）7.30（3H、マルチプレツトフエニルプロト
ン）、6.80（1H、シングレツト、オレフインプロ
トン）、4.35（2H、幅広のシングレツト、水酸基
のプロトンおよび水酸基の付いているメチンプロ
トン）、0.63（9H、シングレツト、ｔ−ブチルプ
ロトン）
参考例 15
（−）−２−アミノ−１−フエニルエタノール
の合成
Ｄ−（−）−マンデル酸24.0ｇ、無水エタノール
200mlおよび濃硫酸0.18mlで７時間加熱撹拌した
のち、冷却し、減圧濃縮した。
残渣に140mlのジエチルエーテルを加えて溶解
したのち、飽和炭酸水素ナトリウム水溶液で中和
し、水洗、芒硝乾燥、つづいて減圧濃縮すると
23.6ｇの（−）−マンデル酸エチルエステルが得
られた。〔α〕24 D−132.9゜（ｃ＝1.07，CHCl3）
（−）−マンデル酸エチルエステル23.0ｇのメ
タノール160ml溶液を氷冷下、過剰のアンモニア
ガスを吹き込み室温で５時間撹拌したのち減圧濃
縮すると19.1ｇの粗（−）−マンデル酸アミドが
得られた。シクロヘキサン−イソプロパノールの
混合溶媒で再結晶すると、11.41ｇの（−）−マン
デル酸アミドが得られた。〔α〕24 D−72.7゜（ｃ＝
1.12，CH3OH）
（−）−マンデル酸アミド11.20ｇを水素化アル
ミニウムリチウム7.10ｇのテトラヒドロフラン
280ml懸濁液に加え７時間還流撹拌した。冷時、
酒石酸ナトリウムカリウムの飽和水溶液80mlを加
えて分解し、濾過、減圧濃縮すると9.93ｇの
（−）−２−アミノ−１−フエニルエタノールの結
果が得られた。
〔α〕24 D−42.5゜（ｃ＝1.10，C2H5OH）
参考例 16
（−）−２−Ｎ−ベンジルアミノ−１−フエニ
ルエタノールの合成
参考例15で得られた（−）−２−アミノ−１−
フエニルエタノール9.80ｇのエタノール150ml溶
液にベンズアルデヒド8.0ｇを加え２時間加熱撹
拌した。次に冷時、水素化ホウ素ナトリウム2.70
ｇを加え室温で２時間撹拌したのち、50〜60℃で
２時間撹拌した。エタノールを減圧留去し、2N
塩酸100mlを加えて溶解、ジエチルエーテルで洗
浄した。水層を20％水酸化ナトリウム水溶液で中
和し、クロロホルムで抽出すると10.8ｇの（−）
−２−Ｎ−ベンジルアミノ−１−フエニルエタノ
ールが得られた。
〔α〕24 D−51.5゜（ｃ＝1.0，CHCl3）mp111〜113
℃
NMRスペクトル（CDCl3）δ（ppm）
2.51（ｓ，1H），2.58（ｓ，1H），2.68〜2.96（ｍ，
2H），3.79（ｓ，2H），4.53〜4.85（ｍ，1H），
7.21（ｄ，10H）
参考例 17
（−）−２−Ｎ−ベンジル−Ｎ−メチルアミノ
−１−フエニルエタノールの合成
参考例16で得られた（−）−２−Ｎ−ベンジル
アミノ−１−フエニルエタノール10.0ｇにギ酸
8.1mlと37％ホルマリン水溶液6.9mlを加えて100
℃で3.5時間加熱撹拌したのち、減圧濃縮し、水
50mlを加えて溶解した。次に20％水酸化ナトリウ
ム水溶液で中和し、ジエチルエーテルで抽出後水
洗、芒硝乾燥、つづいて濃縮を行つてから蒸留す
るとbp144℃／0.3Torrで（−）−２−Ｎ−ベンジ
ル−Ｎ−メチルアミノ−１−フエニルエタノール
9.70ｇが得られた。
〔α〕24 D−112.2゜（ｃ＝1.0，CHCl3）
NMRスペクトル（CDCl3：δ（ppm）
2.30（ｓ，3H），2.5〜2.7（2H），3.62（ｄ，2H），
3.92（ｓ，1H），4.65〜4.9（ｍ，Ｈ），7.26（ｓ，
10H）
参考例 18
（−）−２−Ｎ，Ｎ−ジメチルアミノ−１−フ
エニルエタノールの合成
ギ酸8.8ｇと無水酢酸19.2ｇを3.5時間室温で撹
拌したのち（−）−２−アミノ−１−フエニルエ
タノール4.86ｇを加え、室温で7.5時間撹拌した。
反応溶液を減圧濃縮し、クロロホルム50mlを加え
て溶解後、飽和炭酸水素ナトリウム水溶液で中和
洗浄、水洗、芒硝乾燥つづいて減圧濃縮すると
5.61ｇの２−Ｎ−ホルミルアミノ−１−フエニル
エタノールが得られた。次に、水素化アルミニウ
ムリチウム1.84ｇのテトラヒドロフラン80ml液に
２−Ｎ−ホルミルアミノ−１−フエニルエタノー
ル5.60ｇを加えて4.5時間加熱撹拌し、冷時水1.84
mlで分解し、酒石酸カリウムナトリウムの飽和水
溶液18.4mlを加えて生成する沈澱物を濾去後減圧
濃縮すると２−Ｎ−メチルアミノ−１−フエニル
エタノールが得られた。得られた２−Ｎ−メチル
アミノ−１−フエニルエタノールにギ酸4.80ｇと
37％ホルマリン水溶液4.8mlを加えて100℃で３時
間加熱撹拌したのち、減圧濃縮し、2N水酸化ナ
トリウム水溶液で中和後、塩化メチレンで抽出
し、水洗、芒硝乾燥つづいて減圧濃縮を行つてか
ら蒸留するとbp66〜67℃／0.3Torrで3.50ｇの
（−）−２−Ｎ，Ｎ−ジメチルアミノ−１−フエニ
ルエタノールが得られた。
〔α〕24 D−56.0゜（neat，1dm）
参考例19〜24
光学活性アミノアルコールの合成
参考例16において、ベンズアルデヒドに代えて
ｏ−エトキシベンズアルデヒド、ｐ−メチルベン
ズアルデヒド、ｏ−メチルベンズアルデヒドを用
いて、参考例16および参考例17に準じて下記光学
活性アミノアルコールを合成した。それらの物理
定数を第２表に示す。[Table] Reference example 13 (E)-1-(4-chlorophenyl)-2-(1,
2,4-triazol-1-yl)-4,4-
Synthesis of racemic dimethyl-1-penten-3-ol Characterized by the following MNR spectrum (E)
-1-(4-chlorophenyl)-2-(1,2,4
-triazol-1-yl)-4,4-dimethyl-1-penten-3-one (melting point 108-109°C)
2.9 g (0.01 mol) was dissolved in 50 ml of methanol.
While cooling this with ice and keeping the reaction liquid temperature below 20℃,
0.38 g (0.01 mole) of sodium borohydride was added. After keeping at 20°C for 3 hours, 100ml of water and 1ml of acetic acid were added to decompose, and the organic layer was extracted with 100ml of ethyl acetate. After washing with 50 ml of 5% sodium bicarbonate solution, it was dried with anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was
Recrystallization from hexane gave 2.0 g (yield 69%) of the title compound having a melting point of 153-155°C. Elemental analysis values and NMR spectrum results in deuterated chloroform for each compound are shown (δ value). (E)-1-(4-chlorophenyl)-2-(1,
2,4-triazol-1-yl)-4,4-dimethyl-1-penten-3-one; Elemental analysis C (%) H (%) N (%) Cl
(%) Calculated value 62.17 5.58 14.50 12.23 (as C 15 H 16 N 3 OCl) Analytical value 62.32 5.60 14.41 12.20 NMR spectrum 8.11 (1H, singlet, triazole proton), 7.90 (1H, singlet, triazole proton), 7.15 (4H , singlet, phenyl proton), 6.99 (1H, singlet, olefin proton), 0.99 (9H, singlet, butyl proton) (E)-1-(4-chlorophenyl)-2-(1,
2,4-triazol-1-yl)-4,4-dimethyl-1-penten-3-ol; Elemental analysis C (%) H (%) N (%) Cl
(%) Calculated value 61.74 6.23 14.40 12.15 (as C 15 H 16 N 3 OCl) Analytical value 61.82 6.33 14.38 12.15 NMR spectrum 8.52 (1H, singlet, triazole proton), 7.98 (1H, singlet, triazole proton), 7.30 (4H , singlet, phenyl proton), 6.91 (1H, singlet, olefin proton), 4.56 (2H, wide singlet, hydroxyl and methine proton with hydroxyl group),
0.66 (9H, singlet, butyl proton) Reference example 14 (E)-1-(4-dichlorophenyl)-2-
(1,2,4-triazol-1-yl)-4,
Synthesis of racemic form of 4-dimethyl-1-penten-3-ol Characterized by the following NMR spectrum (E)
-1-(2,4-dichlorophenyl)-2-(1,
2,4-triazol-1-yl)-4,4-dimethyl-1-penten-3-one (melting point 92-93°C)
0.5 g of sodium borohydride was added to 3.2 g of methanol solution (50 c.c.) under ice-cooling, and after stirring at room temperature for 3 hours, the melting point was determined by the same post-treatment as in Reference Example 13.
2.6 g of the title compound was obtained at 148-149°C. Below is the NMR spectrum (δ in deuterochloroform)
value). (E)-1-(2,4-dichlorophenyl)-2
-(1,2,4-triazol-1-yl)-4,
4-dimethyl-1-penten-3-one; 8.30
(1H, singlet, triazole proton),
8.04 (1H, singlet, triazole proton), 7.45 (1H, multiplet, phenyl proton), 7.26 (2H, multiplet, phenyl proton), 7.22 (1H, singlet, olefin proton), 0.97 (9H, singlet, butyl proton), (E)-1-(2,4-dichlorophenyl)-2
-(1,2,4-triazol-1-yl)-4,
4-dimethyl-1-penten-3-ol 8.45
(1H, singlet, triazole proton),
7.97 (1H, singlet, triazole proton) 7.30 (3H, multiple phenyl proton), 6.80 (1H, singlet, olefin proton), 4.35 (2H, wide singlet, hydroxyl proton and methine proton with hydroxyl group), 0.63 (9H, singlet, t-butyl proton) Reference example 15 Synthesis of (-)-2-amino-1-phenylethanol D-(-)-mandelic acid 24.0 g, anhydrous ethanol
After heating and stirring for 7 hours with 200 ml and 0.18 ml of concentrated sulfuric acid, the mixture was cooled and concentrated under reduced pressure. After adding 140 ml of diethyl ether to the residue and dissolving it, it was neutralized with a saturated aqueous sodium bicarbonate solution, washed with water, dried with sodium sulfate, and then concentrated under reduced pressure.
23.6 g of (-)-mandelic acid ethyl ester were obtained. [α] 24 D -132.9° (c = 1.07, CHCl 3 ) A solution of 23.0 g of (-)-mandelic acid ethyl ester in 160 ml of methanol was bubbled with excess ammonia gas under ice cooling, stirred at room temperature for 5 hours, and then concentrated under reduced pressure. Then, 19.1 g of crude (-)-mandelic acid amide was obtained. Recrystallization from a mixed solvent of cyclohexane-isopropanol yielded 11.41 g of (-)-mandelic acid amide. [α] 24 D −72.7゜(c=
1.12, CH 3 OH) (−)-Mandelamide (11.20 g) was dissolved in 7.10 g of lithium aluminum hydride in tetrahydrofuran.
The mixture was added to 280 ml of suspension and stirred under reflux for 7 hours. When cold,
The mixture was decomposed by adding 80 ml of a saturated aqueous solution of sodium potassium tartrate, filtered, and concentrated under reduced pressure to obtain 9.93 g of (-)-2-amino-1-phenylethanol. [α] 24 D −42.5° (c=1.10, C 2 H 5 OH) Reference example 16 Synthesis of (−)-2-N-benzylamino-1-phenylethanol (−) obtained in Reference example 15 -2-amino-1-
8.0 g of benzaldehyde was added to a solution of 9.80 g of phenylethanol in 150 ml of ethanol, and the mixture was heated and stirred for 2 hours. Then when cold, sodium borohydride 2.70
After stirring at room temperature for 2 hours, the mixture was stirred at 50 to 60°C for 2 hours. Distill ethanol under reduced pressure and add 2N
100 ml of hydrochloric acid was added to dissolve, and the mixture was washed with diethyl ether. The aqueous layer was neutralized with a 20% aqueous sodium hydroxide solution and extracted with chloroform, resulting in 10.8 g of (-)
-2-N-benzylamino-1-phenylethanol was obtained. [α] 24 D −51.5° (c=1.0, CHCl 3 ) mp111~113
°C NMR spectrum (CDCl 3 ) δ (ppm) 2.51 (s, 1H), 2.58 (s, 1H), 2.68-2.96 (m,
2H), 3.79 (s, 2H), 4.53-4.85 (m, 1H),
7.21 (d, 10H) Reference Example 17 Synthesis of (-)-2-N-benzyl-N-methylamino-1-phenylethanol (-)-2-N-benzylamino-1 obtained in Reference Example 16 -Formic acid in 10.0g of phenylethanol
Add 8.1 ml and 6.9 ml of 37% formalin aqueous solution to 100
After heating and stirring at ℃ for 3.5 hours, it was concentrated under reduced pressure and diluted with water.
50ml was added and dissolved. Next, it was neutralized with a 20% aqueous sodium hydroxide solution, extracted with diethyl ether, washed with water, dried with sodium sulfate, concentrated, and distilled at bp 144°C/0.3 Torr (-)-2-N-benzyl-N- Methylamino-1-phenylethanol
9.70g was obtained. [α] 24 D −112.2° (c = 1.0, CHCl 3 ) NMR spectrum (CDCl 3 : δ (ppm) 2.30 (s, 3H), 2.5-2.7 (2H), 3.62 (d, 2H),
3.92 (s, 1H), 4.65-4.9 (m, H), 7.26 (s,
10H) Reference Example 18 Synthesis of (-)-2-N,N-dimethylamino-1-phenylethanol After stirring 8.8 g of formic acid and 19.2 g of acetic anhydride at room temperature for 3.5 hours, (-)-2-amino-1 was synthesized. - 4.86 g of phenylethanol was added and stirred at room temperature for 7.5 hours.
The reaction solution was concentrated under reduced pressure, dissolved by adding 50 ml of chloroform, neutralized and washed with a saturated aqueous sodium bicarbonate solution, washed with water, dried with sodium sulfate, and then concentrated under reduced pressure.
5.61 g of 2-N-formylamino-1-phenylethanol was obtained. Next, 5.60 g of 2-N-formylamino-1-phenylethanol was added to a solution of 1.84 g of lithium aluminum hydride in 80 ml of tetrahydrofuran, and the mixture was heated and stirred for 4.5 hours.
18.4 ml of a saturated aqueous solution of potassium sodium tartrate was added, and the resulting precipitate was filtered off and concentrated under reduced pressure to obtain 2-N-methylamino-1-phenylethanol. 4.80 g of formic acid was added to the obtained 2-N-methylamino-1-phenylethanol.
After adding 4.8 ml of 37% formalin aqueous solution and heating and stirring at 100°C for 3 hours, the mixture was concentrated under reduced pressure, neutralized with 2N aqueous sodium hydroxide solution, extracted with methylene chloride, washed with water, dried with mirabilite, and concentrated under reduced pressure. 3.50 g of (-)-2-N,N-dimethylamino-1-phenylethanol was obtained at bp 66-67° C./0.3 Torr. [α] 24 D −56.0° (neat, 1dm) Reference Examples 19 to 24 Synthesis of optically active amino alcohol In Reference Example 16, o-ethoxybenzaldehyde, p-methylbenzaldehyde, and o-methylbenzaldehyde were used instead of benzaldehyde. The following optically active amino alcohol was synthesized according to Reference Example 16 and Reference Example 17. Their physical constants are shown in Table 2.
【表】【table】
【表】
参考例 25
（−）−２−Ｎ−ベンジル−Ｎ−メチルアミノ
−１−フエニルエタノールで修飾された不斉修
飾水素化アルミニウムリチウム系還元剤
窒素雰囲気下、水素化アルミニウムリチウム
0.152ｇ（4.0ミリモル）のジエチルエーテル10ml
液中に氷冷下（−）−２−Ｎ−ベンジル−Ｎ−メ
チルアミノ−１−フエニルエタノール0.994ｇ
（4.12ミリモル）のジエチルエーテル10ml溶液を
15分間で滴下し、30分間保温撹拌後、Ｎ−メチル
アニリン0.883ｇ（8.24ミリモル）のジエチルエ
ーテル10ml溶液を15分間で加え、室温で2.5時間
撹拌すると次の物理的性質を有する不斉修飾水素
化アルミニウムリチウム系還元剤のジエチルエー
テル溶液が得られた。
赤外吸収スペクト（neat）：ν（cm-1）；
3419，2812，1604，1510，
1452，1322，872，750，
695
参考例１で得られた（＋）−（Ｅ）−１−（４−ク
ロロフエニル）−２−（１，２，４−トリアゾール
−１−イル）−４，４−ジメチル−１−ペンテン
−３−オール〔化合物番号１〕、参考例２で得ら
れた（＋）−（Ｅ）−１−（２，４−ジクロロフエニ
ル）−２−（１，２，４−トリアゾール−１−イ
ル）−４，４−ジメチル−１−ペンテン−３−オ
ール〔化合物番号２〕と、これに対応する参考例
３および４で得られた（−）−トリアゾリルアル
コール誘導体〔それぞれ化合物番号３および４〕
ならびに参考例13および14で得られたラセミ体
〔それぞれ化合物番号５および６〕を比較対照化
合物として行つたいくつかの試験例を次にあげて
本発明の（＋）−トリアゾリルアルコール誘導体
の優れた性質を具体的に述べる。
試験例 １
ポツトマムの矮化試験
素焼の４寸鉢に海砂と山土とピートからなる合
成土壌500ｇをつめてポツトマム（品種：パラゴ
ン）を栽培し、定植後２週間目にピンチを行い、
３本仕立として新芽が伸びてからピンチ２週間後
に、本発明化合物の所定濃度希釈液を施用し、薬
剤処理後42日目に生長抑制効果を調査した。その
結果を第３表に示す。
なお、効果の評価は薬剤処理時のポツトマムの
草丈をあらかじめ測定しておき処理後42日目の草
丈との差からこの間の伸丈を算出し、無処理区の
伸丈を100としたときの伸丈指数で表示した。値
は３連の平均値を示す。
いずれの化合物も節間伸長が抑制され、草丈の
低下がみられたがネクロシスやクロロシスの薬害
は認められず、葉の濃緑化が観察された。（＋）−
トリアゾリルアルコール誘導体（化合物番号１，
２）は（−）−トリアゾリルアルコール誘導体
（化合物番号３，４）に比べてはるかに高い矮化
効果を示し、ラセミ体（化合物番号５，６）に比
べても高い効果を示した。[Table] Reference example 25 Asymmetrically modified lithium aluminum hydride-based reducing agent modified with (-)-2-N-benzyl-N-methylamino-1-phenylethanol Lithium aluminum hydride in a nitrogen atmosphere
0.152 g (4.0 mmol) diethyl ether 10 ml
Add 0.994 g of (-)-2-N-benzyl-N-methylamino-1-phenylethanol to the liquid under ice cooling.
(4.12 mmol) in 10 ml of diethyl ether solution
After adding dropwise over 15 minutes and stirring while keeping warm for 30 minutes, a solution of 0.883 g (8.24 mmol) of N-methylaniline in 10 ml of diethyl ether was added over 15 minutes and stirred at room temperature for 2.5 hours, resulting in asymmetrically modified hydrogen having the following physical properties. A diethyl ether solution of a lithium aluminum oxide reducing agent was obtained. Infrared absorption spectrum (neat): ν (cm -1 ); 3419, 2812, 1604, 1510, 1452, 1322, 872, 750, 695 (+)-(E)-1-( obtained in Reference Example 1) 4-chlorophenyl)-2-(1,2,4-triazol-1-yl)-4,4-dimethyl-1-penten-3-ol [Compound No. 1], obtained in Reference Example 2 (+) -(E)-1-(2,4-dichlorophenyl)-2-(1,2,4-triazol-1-yl)-4,4-dimethyl-1-penten-3-ol [Compound No. 2 ] and the corresponding (-)-triazolyl alcohol derivatives obtained in Reference Examples 3 and 4 [Compound Nos. 3 and 4, respectively]
The following are some test examples in which the racemates obtained in Reference Examples 13 and 14 [Compound Nos. 5 and 6, respectively] were used as comparative compounds. Describe your excellent qualities in detail. Test example 1 Dwarfing test of pottomum Pottomum (variety: Paragon) was cultivated in a 4-inch unglazed pot filled with 500 g of synthetic soil consisting of sea sand, mountain soil, and peat, and pinched two weeks after planting.
A diluted solution of the compound of the present invention at a predetermined concentration was applied two weeks after pinching after three shoots had grown, and the growth inhibitory effect was investigated on the 42nd day after the chemical treatment. The results are shown in Table 3. In addition, to evaluate the effect, measure the plant height of potumum plants in advance during the chemical treatment, calculate the length growth during this period from the difference with the plant height 42 days after treatment, and take the growth height of the untreated plot as 100. Expressed as elongation index. Values represent the average of triplicate. All compounds suppressed internodal elongation and reduced plant height, but no necrosis or chlorosis damage was observed, and dark greening of leaves was observed. (+)−
Triazolyl alcohol derivative (compound number 1,
2) showed a much higher dwarfing effect than the (-)-triazolyl alcohol derivatives (compound numbers 3 and 4), and also showed a higher effect than the racemate (compound numbers 5 and 6).
【表】
試験例 ２
リンゴの新梢伸長抑制試験
直径18cmの素焼鉢に植えたリンゴ苗（品種：ゴ
ールデンデリシヤス）を剪定後、温室内で栽培
し、新梢の発生がみられた３週間後に所定濃度の
薬液をハンドスプレヤーで地上部全体に処理し
た。処理後14日目に新梢の長さを測定し、処理時
の新梢長との差より伸長量を算出した。１処理２
鉢を用い、測定は４〜６本の新梢について行い、
結果の平均値を第４表に示した。
（＋）−トリアゾリルアルコール誘導体は（−）
−トリアゾリルアルコール誘導体およびラセミ体
と比較してはるかに高い伸長抑制効果を示した。[Table] Test example 2 Apple new shoot growth inhibition test After pruning apple seedlings (variety: Golden Delicious) planted in clay pots with a diameter of 18 cm, they were cultivated in a greenhouse, and new shoots appeared.3 After a week, the entire above-ground part was treated with a chemical solution of a predetermined concentration using a hand sprayer. The length of new shoots was measured on the 14th day after treatment, and the amount of elongation was calculated from the difference from the length of new shoots at the time of treatment. 1 processing 2
Using a pot, measurements were taken on 4 to 6 new shoots.
The average values of the results are shown in Table 4. (+)-Triazolyl alcohol derivative is (-)
-It exhibited a much higher elongation inhibitory effect compared to triazolyl alcohol derivatives and racemates.
【表】
試験例 ３
芝草の生長抑制試験
1/5000アールワグネルポツトに畑土壌を充填
し、表面に芝草種子（シーサイドベントグラス）
を播種し、覆土後温室内で栽培した。１ケ月後地
際より１cmの高さで刈り取り、所定量の薬剤をハ
ンドスプレヤーで茎葉兼土壌処理した。処理後２
週目に伸長量を調査後再び刈り取つてさらに４週
間栽培を継続した。
第５表に処理後２週目（第１回）と６週目（第
２回）との調査結果を示した。
（＋）−トリアゾリルアルコール誘導体は（−）
−トリアゾリルアルコール誘導体およびラセミ体
に比べてはるかに高い効力を示した。[Table] Test Example 3 Turfgrass Growth Suppression Test A 1/5000 Earl Wagner pot was filled with field soil, and turfgrass seeds (seaside bentgrass) were placed on the surface.
The seeds were sown, covered with soil, and then cultivated in a greenhouse. One month later, the plants were cut at a height of 1 cm from the ground, and a prescribed amount of the chemical was applied to the leaves and the soil using a hand sprayer. After processing 2
After checking the amount of elongation each week, the plants were harvested again and cultivation was continued for another 4 weeks. Table 5 shows the results of the investigation two weeks after treatment (first time) and six weeks after treatment (second time). (+)-Triazolyl alcohol derivative is (-)
- It showed much higher potency compared to triazolyl alcohol derivatives and racemates.
【表】
試験例 ４
ハダカムギのポツト試験
1/2000アールワグネルポツトに1.5cm角孔の金
網でふるつた水田作土をつめ、元肥として尿素化
成肥料をＮ：P2O5：K2O＝1.3：1.3：1.3ｇ／pot
施肥したハダカムギ（品種：ヒノデハダカ）12粒
を播種した（12月５日）。温室内で栽培し発芽後
数cmに伸長したとき間引きして６株／potにした。
節間伸長開始期（２月15日）に所定量の薬剤を土
壌表面に灌注施用し、さらに栽培を継続し収穫時
（５月21日）における草丈、穂数および玄麦重を
測定した。調査結果を第６表に示す。供試化合物
は強い草丈抑制と分けつ促進効果を示すと同時に
増収効果を示したが、（＋）−トリアゾリルアルコ
ール誘導体は（−）−トリアゾリルアルコール誘
導体に比べてはるかに高い効果を示し、ラセミ体
と比べても強い草丈抑制効果を示した。[Table] Test example 4 Pot test of naked barley Fill a 1/2000 Ahl Wagner pot with paddy soil mixed with a wire mesh with 1.5 cm square holes, and apply urea chemical fertilizer as a starter fertilizer N: P 2 O 5 : K 2 O = 1.3 :1.3:1.3g/pot
Twelve seeds of fertilized Hadakamushi (variety: Hinode Hadaka) were sown (December 5th). The seeds were cultivated in a greenhouse, and when they grew to several centimeters after germination, they were thinned to 6 plants/pot.
At the start of internodal elongation (February 15th), a predetermined amount of the chemical was applied to the soil surface by irrigation, cultivation was continued, and plant height, number of panicles, and grain weight were measured at the time of harvest (May 21st). The survey results are shown in Table 6. The test compounds showed a strong effect on suppressing plant height and promoting tillering, while also increasing yield, but (+)-triazolyl alcohol derivatives showed a much higher effect than (-)-triazolyl alcohol derivatives. , showed a stronger effect on suppressing plant height than the racemate.
【表】
次に本発明に係る化合物の殺菌活性を調べた結
果を参考までにあげる。殺菌活性の強さは（＋）
−トリアゾリルアルコール誘導体に比べて（−）
−トリアゾリルアルコール誘導体およびラセミ体
の方がはるかに高い活性を示した。
参考試験例 １
菌生育阻止効果
水１あたりポリペプトン５ｇ、麦芽エキス20
ｇ、シヨ糖20ｇおよび寒天20ｇを含む培地を加熱
溶解し、これに乳剤形態の供試化合物の水希釈液
を所定量添加し、培地中の供試化合物濃度を所定
濃度とした。つづいて培地をよく撹拌したのちペ
トリ皿に流し込んで寒天平板とした。寒天が固化
したのち、供試菌の菌叢デイスクまたは分生胞子
懸濁液を接種した。供試菌名および接種後観察ま
での培養期間は第８表のとおりである。
なお、培養温度はリンゴ黒星病の場合は20℃、
他の菌の場合は28℃とした。[Table] Next, the results of examining the bactericidal activity of the compounds according to the present invention are listed for reference. The strength of bactericidal activity is (+)
- compared to triazolyl alcohol derivatives (-)
-Triazolyl alcohol derivatives and racemates showed much higher activity. Reference test example 1 Bacterial growth inhibition effect: 5 g of polypeptone, 20 g of malt extract per 1 water
A medium containing g, 20 g of sucrose, and 20 g of agar was dissolved by heating, and a predetermined amount of a water diluted solution of the test compound in the form of an emulsion was added thereto to adjust the concentration of the test compound in the medium to a predetermined concentration. Subsequently, the medium was thoroughly stirred and then poured into a Petri dish to form an agar plate. After the agar had solidified, a bacterial flora disk or conidial suspension of the test bacteria was inoculated. The names of the test bacteria and the culture period from inoculation to observation are shown in Table 8. The culture temperature is 20℃ for apple scab;
For other bacteria, the temperature was 28°C.
【表】【table】
【表】
供試化合物の菌生育阻害度は90％菌糸生育を阻
害する濃度（ED90）で評価した。その結果第８
表のように本発明化合物（＋）−トリアゾリルア
ルコール誘導体（化合物番号１，２）に比べて
（−）−トリアゾリルアルコール誘導体（化合物番
号３，４）およびラセミ体（化合物番号５，６）
著しく強い抗菌スペクトルを示すことが判明し
た。[Table] The fungal growth inhibition degree of the test compound was evaluated at the concentration that inhibits 90% mycelial growth (ED90). As a result, the 8th
As shown in the table, the compounds of the present invention (-)-triazolyl alcohol derivatives (compound numbers 3, 4) and racemates (compound numbers 5, 6)
It was found that it exhibited an extremely strong antibacterial spectrum.
【表】
次に配合例を示す。なお、部は重量部を表わ
す。
配合例 １
粉 剤
化合物１ ２部、クレー88部およびタルク10部
をよく粉砕混合すれば主剤含有量２％の粉剤を得
る。
配合例 ２
粉 剤
化合物２ ３部、クレー67部およびタルク30部
をよく粉砕混合すれば主剤含有量３％の粉剤を得
る。
配合例 ３
水和剤
化合物１ 30部、珪藻45部、ホワイトカーボン
20部、湿潤剤（ラウリル硫酸ソーダ）３部および
分散剤（リグニンスルホン酸カルシウム）２部を
よく粉砕混合すれば主剤含有量30％の水和剤を得
る。
配合例 ４
水和剤
化合物２ 50部、珪藻土45部、湿潤剤（アルキ
ルベンゼンスルホン酸カルシウム）2.5部および
分散剤（リグニンスルホン酸カルシウム）2.5部
をよく粉砕混合すれば主剤含有量50％の水和剤を
得る。
配合例 ５
乳 剤
化合物１ 10部、シクロヘキサノン80部および
乳化剤（ポリオキシエチレンアルキルアリルエー
テル）10部を混合すれば主剤含有量10％の乳剤を
得る。
配合例 ６
粒 剤
化合物２ ５部、ベントナイト40部、クレー50
部およびリグニンスルホン酸リトリウム５部をよ
く粉砕混合し、水を加えてよく練り合わせた後、
造粒乾燥して粒剤を得る。
配合例 ７
液 剤
化合物１ 0.05部、ハイマール1009（松本油脂
製界面活性剤）１部、ニユーコール560（ノニオン
系乳化剤）１部、シクロヘキサノン2.5部、水、
95.45部を混合すれば0.05％の液剤を得る。[Table] Next, a formulation example is shown. Note that parts represent parts by weight. Formulation Example 1 Powder 2 parts of Compound 1, 88 parts of clay, and 10 parts of talc are thoroughly ground and mixed to obtain a powder with a base ingredient content of 2%. Formulation Example 2 Powder 3 parts of Compound 2, 67 parts of clay, and 30 parts of talc are thoroughly ground and mixed to obtain a powder with a base ingredient content of 3%. Formulation example 3 Wettable powder Compound 1 30 parts, diatom 45 parts, white carbon
20 parts, 3 parts of a wetting agent (sodium lauryl sulfate), and 2 parts of a dispersing agent (calcium lignin sulfonate) are thoroughly ground and mixed to obtain a wettable powder with a base ingredient content of 30%. Formulation example 4 Hydrating agent Compound 2 50 parts, diatomaceous earth 45 parts, wetting agent (calcium alkylbenzene sulfonate) 2.5 parts and dispersing agent (calcium lignin sulfonate) 2.5 parts can be thoroughly ground and mixed to achieve hydration with a base ingredient content of 50%. get the agent. Formulation Example 5 Emulsion By mixing 10 parts of Compound 1, 80 parts of cyclohexanone, and 10 parts of an emulsifier (polyoxyethylene alkyl allyl ether), an emulsion with a base ingredient content of 10% is obtained. Formulation example 6 Granules Compound 2 5 parts, bentonite 40 parts, clay 50
1 part and 5 parts of lithium ligninsulfonate were thoroughly ground and mixed, and after adding water and kneading well,
Granulate and dry to obtain granules. Formulation example 7 Liquid agent Compound 1 0.05 parts, Hymar 1009 (Matsumoto Yushi surfactant) 1 part, Newcor 560 (nonionic emulsifier) 1 part, cyclohexanone 2.5 parts, water,
Mixing 95.45 parts yields a 0.05% solution.
Claims (1)
＊印は不斉炭素原子を意味する。〕 で示され、かつ光学活性が（＋）であるトリアゾ
リルアルコール誘導体を有効成分として含有する
ことを特徴とする植物生長調節剤。[Claims] 1. General formula [In the formula, X represents a hydrogen atom or a chlorine atom,
* indicates an asymmetric carbon atom. ] A plant growth regulator characterized by containing as an active ingredient a triazolyl alcohol derivative represented by the following formula and having an optical activity of (+).
Priority Applications (31)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18240780A JPS57106669A (en) | 1980-12-22 | 1980-12-22 | Optically active triazolyl alcohol derivative, its preparation, and plant growth regulator and herbicide containing said derivative as active component |
| AU77925/81A AU544099B2 (en) | 1980-12-15 | 1981-11-26 | Triazolylpentenols |
| CA000391391A CA1172641A (en) | 1980-12-15 | 1981-12-02 | Optical isomer of triazolylpentenols, and their production and use as fungicide, herbicide and/or plant growth regulant |
| NZ199185A NZ199185A (en) | 1980-12-15 | 1981-12-07 | Optical isomers of cis and trans geometric isomers of 1-(44-chloro or 2,4-dichloro)phenyl)-2(1,2,4-triazol-1-yl)-4,4-dimethylpent-1-en-3-ols |
| US06/328,191 US4435203A (en) | 1980-12-15 | 1981-12-07 | Optical isomer of triazolylpentenols, and their production and use as fungicide, herbicide and/or plant growth regulant |
| IL64481A IL64481A0 (en) | 1980-12-15 | 1981-12-08 | Optical isomers of triazolylpentenols,methods for their production and fungicidal,herbicidal and/or plant growth regulant compositions containing them |
| EG71881A EG15461A (en) | 1980-12-22 | 1981-12-08 | Optical isomer of triazolylpentnols,and their production and use as fungicides,herbicide and plant growth regulant |
| RO105975A RO84279B (en) | 1980-12-15 | 1981-12-11 | Process for preparing optically active triazolyl-alcohol derivatives |
| RO110153A RO86318B (en) | 1980-12-15 | 1981-12-11 | Solid fungicidal, herbicidal composition controlling plant growth |
| ES507883A ES8207159A1 (en) | 1980-12-15 | 1981-12-11 | Optical isomer of a triazolylpentenol, and its production and use as fungicide. |
| RO81116061A RO89367A (en) | 1980-12-15 | 1981-12-11 | LIQUID COMPOSITION HERBICIDE, FUNGICIDE AND PLANT GROWTH ADJUSTMENT |
| HU813755A HU187385B (en) | 1980-12-15 | 1981-12-14 | Fungicides, herbicides and plant growth regulating compositions, as well as process for the preparation of optically active triazolyl-alcohol derivatives which can be used as active ingredients of sid compositions |
| SI8112922A SI8112922A8 (en) | 1980-12-15 | 1981-12-14 | Process for producing triazolyl alcohol derivatives |
| DK553881A DK160301C (en) | 1980-12-15 | 1981-12-14 | (-) - (E) -TRIZOLYL PENTENOLS, FUNGICIDES THEREOF AND PROCEDURES FOR COMBATING FUNGI |
| SU813366002A SU1582987A3 (en) | 1980-12-15 | 1981-12-14 | Method of producing (+) or (-) derivatives of triazolyl alcohol |
| EP81305873A EP0054431B1 (en) | 1980-12-15 | 1981-12-14 | Optical isomer of a triazolylpentenol, and its production and use as fungicide |
| BR8108116A BR8108116A (en) | 1980-12-15 | 1981-12-14 | DERIVATIVE OF TRIAZOLYL ALCOHOL, PROCESS TO PRODUCE THE SAME, FUNGICIDE COMPOSITION, HERBICIDE AND REGULATORY COMPOSITION OF PLANT GROWTH AND PROCESS TO KILL A FUNGUS, PROCESS TO CONTROL THE GROWTH OF PLANTS AND PROCESS TO KILL WEED |
| EP90121117A EP0427168B1 (en) | 1980-12-15 | 1981-12-14 | Optical isomer of triazolylpentenols, and their production and use as fungicide, herbicide and/or plant growth regulant |
| EP85111505A EP0175278A3 (en) | 1980-12-15 | 1981-12-14 | Optical isomer of triazolylpentenols, and their production and use as fungicide herbicide and/or plant growth regulant |
| EP19840200456 EP0121284B1 (en) | 1980-12-15 | 1981-12-14 | (+)-triazolylpentenol derivative, its production and use as herbicide and/or plant growth regulant |
| DE3177314T DE3177314T2 (en) | 1980-12-15 | 1981-12-14 | Optically isomeric triazolyl pentenol. Process for the preparation and use as a fungicide, herbicide and / or growth regulator |
| DE8181305873T DE3175949D1 (en) | 1980-12-15 | 1981-12-14 | Optical isomer of a triazolylpentenol, and its production and use as fungicide |
| DE8484200456T DE3177274D1 (en) | 1980-12-15 | 1981-12-14 | (+) - TRIAZOLYL PENTENOL DERIVATIVE, ITS PRODUCTION AND USE AS AN HERBICIDE AND / OR PLANT GROWTH REGULATOR. |
| YU2922/81A YU43055B (en) | 1980-12-15 | 1981-12-14 | Process for producing triazolyl alcohol derivatives |
| KR1019810004924A KR870001792B1 (en) | 1980-12-15 | 1981-12-15 | Process for preparing optical isomer of triazolylpentenols |
| MYPI87002423A MY102225A (en) | 1980-12-15 | 1987-09-30 | Optical isomer of triazolylpentenols, and their production and use as fungicide, herbicide and/or plant regulant. |
| MYPI87002389A MY102222A (en) | 1980-12-15 | 1987-09-30 | Optical isomer of triazolylpentenols, and their production and use as fungicide, herbicide and/or plant growth regulant. |
| SU4613542 RU2017423C1 (en) | 1980-12-22 | 1989-03-01 | Growth-regulating composition |
| DK102190A DK162223C (en) | 1980-12-15 | 1990-04-25 | (+) - (E) -TRIZOLYL PENTENOLES AND HERBICIDE AND / OR PLANT GROWTH REGULATING AGENTS AND PROCEDURES FOR REGULATING PLANT GROWTH AND PREVENTION OF WEEDS |
| SU5011447 RU2051911C1 (en) | 1980-12-22 | 1992-04-10 | (+) optically active derivative of triazolyl alcohol |
| HRP-2922/81A HRP931272B1 (en) | 1980-12-15 | 1993-10-06 | Process for the preparation of triazolyl alchocole |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18240780A JPS57106669A (en) | 1980-12-22 | 1980-12-22 | Optically active triazolyl alcohol derivative, its preparation, and plant growth regulator and herbicide containing said derivative as active component |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63285303A Division JPH0613533B2 (en) | 1988-11-10 | 1988-11-10 | Lithium aluminum hydride asymmetric reducing agent |
| JP11262290A Division JPH02288809A (en) | 1990-04-26 | 1990-04-26 | Herbicide containing optically active triazolyl alcohol derivative as active ingredient |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57106669A JPS57106669A (en) | 1982-07-02 |
| JPH0242801B2 true JPH0242801B2 (en) | 1990-09-26 |
Family
ID=16117754
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18240780A Granted JPS57106669A (en) | 1980-12-15 | 1980-12-22 | Optically active triazolyl alcohol derivative, its preparation, and plant growth regulator and herbicide containing said derivative as active component |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS57106669A (en) |
| EG (1) | EG15461A (en) |
| RU (2) | RU2017423C1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60174772A (en) * | 1984-02-20 | 1985-09-09 | Sumitomo Chem Co Ltd | Preparation of optically active alcohol derivative |
| JPS59184168A (en) * | 1983-04-04 | 1984-10-19 | Sumitomo Chem Co Ltd | Production of optically active alcohol derivative |
| JPS59166527U (en) * | 1983-04-20 | 1984-11-08 | 松下電器産業株式会社 | SSB transmitter |
| EP0178325B1 (en) * | 1984-04-03 | 1992-04-22 | Sumitomo Chemical Company, Limited | Boron hydride type compounds and their use in a method for producing optically active alpha,beta unsaturated alcohols |
| JPS6118790A (en) * | 1984-07-05 | 1986-01-27 | Sumitomo Chem Co Ltd | Optically active borane complex, preparation thereof, and preparation of optically active alcohol derivative using same |
| DE3440112A1 (en) * | 1984-11-02 | 1986-05-07 | Bayer Ag, 5090 Leverkusen | Process for the preparation of optically active azolylcarbinol derivatives |
| US5698742A (en) * | 1984-11-21 | 1997-12-16 | Sumitomo Chemical Company, Limited | Method for producing an optically active azolyl-α, β-unsaturated alcohol |
| JPH0613533B2 (en) * | 1988-11-10 | 1994-02-23 | 住友化学工業株式会社 | Lithium aluminum hydride asymmetric reducing agent |
| WO2008068307A2 (en) * | 2006-12-07 | 2008-06-12 | Basf Se | Compositions and kits comprising a fungicidal triazole and an alkoxylated alcohol, and their uses |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5441875A (en) * | 1977-09-07 | 1979-04-03 | Sumitomo Chem Co Ltd | Azole homolog, its preparation and bactericidal agent containing the same |
| JPS55124771A (en) * | 1979-03-20 | 1980-09-26 | Sumitomo Chem Co Ltd | Triazole-based geometrical isomerism compound or its salt, its preparation, and fungicide for agriculture and gardening comprising it as active ingredient |
-
1980
- 1980-12-22 JP JP18240780A patent/JPS57106669A/en active Granted
-
1981
- 1981-12-08 EG EG71881A patent/EG15461A/en active
-
1989
- 1989-03-01 RU SU4613542 patent/RU2017423C1/en active
-
1992
- 1992-04-10 RU SU5011447 patent/RU2051911C1/en active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5441875A (en) * | 1977-09-07 | 1979-04-03 | Sumitomo Chem Co Ltd | Azole homolog, its preparation and bactericidal agent containing the same |
| JPS55124771A (en) * | 1979-03-20 | 1980-09-26 | Sumitomo Chem Co Ltd | Triazole-based geometrical isomerism compound or its salt, its preparation, and fungicide for agriculture and gardening comprising it as active ingredient |
Also Published As
| Publication number | Publication date |
|---|---|
| RU2051911C1 (en) | 1996-01-10 |
| JPS57106669A (en) | 1982-07-02 |
| RU2017423C1 (en) | 1994-08-15 |
| EG15461A (en) | 1987-05-30 |
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