JP3877789B2 - 2-Chloro-6-hydroxyisonicotinic acid derivative and plant disease control agent - Google Patents
2-Chloro-6-hydroxyisonicotinic acid derivative and plant disease control agent Download PDFInfo
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- JP3877789B2 JP3877789B2 JP01739595A JP1739595A JP3877789B2 JP 3877789 B2 JP3877789 B2 JP 3877789B2 JP 01739595 A JP01739595 A JP 01739595A JP 1739595 A JP1739595 A JP 1739595A JP 3877789 B2 JP3877789 B2 JP 3877789B2
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- LKBKBWHQEQTDOE-UHFFFAOYSA-N 2-chloro-6-oxo-1h-pyridine-4-carboxylic acid Chemical class OC(=O)C=1C=C(Cl)NC(=O)C=1 LKBKBWHQEQTDOE-UHFFFAOYSA-N 0.000 title claims description 25
- 201000010099 disease Diseases 0.000 title claims description 21
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 title claims description 21
- 239000003795 chemical substances by application Substances 0.000 title claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 57
- -1 phenyl-p-chlorophenylmethyl group Chemical group 0.000 claims description 46
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 34
- 125000000217 alkyl group Chemical group 0.000 claims description 27
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 27
- 125000004391 aryl sulfonyl group Chemical group 0.000 claims description 18
- 125000003342 alkenyl group Chemical group 0.000 claims description 17
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 14
- 125000002252 acyl group Chemical group 0.000 claims description 14
- 239000004480 active ingredient Substances 0.000 claims description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- 125000001072 heteroaryl group Chemical group 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 7
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 7
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 125000002425 furfuryl group Chemical group C(C1=CC=CO1)* 0.000 claims description 5
- 125000005842 heteroatom Chemical group 0.000 claims description 5
- 125000003107 substituted aryl group Chemical group 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims 4
- BWWHCHGMKVVIMX-UHFFFAOYSA-N 2-oxo-6-phenyl-1h-pyridine-4-carboxylic acid Chemical class OC(=O)C1=CC(O)=NC(C=2C=CC=CC=2)=C1 BWWHCHGMKVVIMX-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 52
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 30
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 24
- 239000000203 mixture Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000002904 solvent Substances 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 241000196324 Embryophyta Species 0.000 description 17
- 235000019441 ethanol Nutrition 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 8
- 125000004217 4-methoxybenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1OC([H])([H])[H])C([H])([H])* 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 239000003814 drug Substances 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 229940079593 drug Drugs 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 6
- 241000209094 Oryza Species 0.000 description 6
- 235000007164 Oryza sativa Nutrition 0.000 description 6
- 150000002170 ethers Chemical class 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 235000009566 rice Nutrition 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000008282 halocarbons Chemical class 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000010898 silica gel chromatography Methods 0.000 description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 5
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 125000006307 alkoxy benzyl group Chemical group 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 235000011181 potassium carbonates Nutrition 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 0 *c1cc(O*)nc(Cl)c1 Chemical compound *c1cc(O*)nc(Cl)c1 0.000 description 3
- SQSYNRCXIZHKAI-UHFFFAOYSA-N 2,6-dichloroisonicotinic acid Chemical compound OC(=O)C1=CC(Cl)=NC(Cl)=C1 SQSYNRCXIZHKAI-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 125000002774 3,4-dimethoxybenzyl group Chemical group [H]C1=C([H])C(=C([H])C(OC([H])([H])[H])=C1OC([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000006201 3-phenylpropyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004863 4-trifluoromethoxyphenyl group Chemical group [H]C1=C([H])C(OC(F)(F)F)=C([H])C([H])=C1* 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 231100000674 Phytotoxicity Toxicity 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 3
- 125000003435 aroyl group Chemical group 0.000 description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000007530 organic bases Chemical class 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 2
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 2
- VAJVDSVGBWFCLW-UHFFFAOYSA-N 3-Phenyl-1-propanol Chemical compound OCCCC1=CC=CC=C1 VAJVDSVGBWFCLW-UHFFFAOYSA-N 0.000 description 2
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 description 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- 125000001318 4-trifluoromethylbenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])*)C(F)(F)F 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 241001330975 Magnaporthe oryzae Species 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 241000700605 Viruses Species 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 125000005036 alkoxyphenyl group Chemical group 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- SLUNEGLMXGHOLY-UHFFFAOYSA-N benzene;hexane Chemical compound CCCCCC.C1=CC=CC=C1 SLUNEGLMXGHOLY-UHFFFAOYSA-N 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000000417 fungicide Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000007327 hydrogenolysis reaction Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Chemical class OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 description 2
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000003032 phytopathogenic effect Effects 0.000 description 2
- 125000004591 piperonyl group Chemical group C(C1=CC=2OCOC2C=C1)* 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 2
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000004563 wettable powder Substances 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- 125000004215 2,4-difluorophenyl group Chemical group [H]C1=C([H])C(*)=C(F)C([H])=C1F 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-UHFFFAOYSA-N 0.000 description 1
- 125000002927 2-methoxybenzyl group Chemical group [H]C1=C([H])C([H])=C(C(OC([H])([H])[H])=C1[H])C([H])([H])* 0.000 description 1
- WDRCPKDLZOQCFU-UHFFFAOYSA-N 2-methyl-n-phenylpropanamide Chemical compound CC(C)C(=O)NC1=CC=CC=C1 WDRCPKDLZOQCFU-UHFFFAOYSA-N 0.000 description 1
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000003852 3-chlorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C(Cl)=C1[H])C([H])([H])* 0.000 description 1
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000006283 4-chlorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1Cl)C([H])([H])* 0.000 description 1
- 125000004176 4-fluorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1F)C([H])([H])* 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- 125000006181 4-methyl benzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])C([H])([H])* 0.000 description 1
- SKDHHIUENRGTHK-UHFFFAOYSA-N 4-nitrobenzoyl chloride Chemical compound [O-][N+](=O)C1=CC=C(C(Cl)=O)C=C1 SKDHHIUENRGTHK-UHFFFAOYSA-N 0.000 description 1
- 125000006491 4-t-butyl benzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])*)C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
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- 239000005995 Aluminium silicate Substances 0.000 description 1
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- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
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- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
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- 229920001214 Polysorbate 60 Polymers 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
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- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 1
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- 239000003093 cationic surfactant Substances 0.000 description 1
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- NWSBNVVOFKKFNV-UHFFFAOYSA-N chloroform;oxolane Chemical compound ClC(Cl)Cl.C1CCOC1 NWSBNVVOFKKFNV-UHFFFAOYSA-N 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
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- ZRSDQBKGDNPFLT-UHFFFAOYSA-N ethanol;oxolane Chemical compound CCO.C1CCOC1 ZRSDQBKGDNPFLT-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
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- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical class O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
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- 229930195733 hydrocarbon Natural products 0.000 description 1
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- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
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- 238000001819 mass spectrum Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
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- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000003232 p-nitrobenzoyl group Chemical group [N+](=O)([O-])C1=CC=C(C(=O)*)C=C1 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
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- 229910052700 potassium Inorganic materials 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
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- 235000010413 sodium alginate Nutrition 0.000 description 1
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- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
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Landscapes
- Pyridine Compounds (AREA)
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Description
【０００１】
【産業上の利用分野】
本発明は、２−クロロ−６−ヒドロキシイソニコチン酸誘導体に関し、当該誘導体は、植物病害防除剤、特に水田用の植物病害防除剤として用いることができる。
【０００２】
【従来の技術】
イソニコチン酸誘導体に関する農業用殺菌剤としての生理活性の検討例としては、例えば２，６−ジハロゲン化イソニコチン酸及びそのエステル誘導体が植物病害防除剤として有効であることが知られている（特開昭６３−９３７６６号）。
【０００３】
【発明が解決しようとする課題】
しかしながら上記の化合物においては、保護すべき植物体に薬害が生ずる場合があり、植物に対してより安全な薬剤が求められていた。本発明の目的は、薬害が少なく優れた植物病害防除活性を有する新規化合物及び薬剤を提供することにある。
【０００４】
【課題を解決するための手段】
本発明者等は、かかる課題を解決するため種々検討した結果、下記一般式（１）〜（３）で表される２−クロロ−６−ヒドロキシイソニコチン酸誘導体が植物に対する薬害の心配がなく、優れた植物病害防除活性を示すことを見いだし、本発明を完成するに至った。
【０００５】
即ち、本発明は、一般式（１）
【０００６】
【化４】
［式中、Ｒ1は水素原子、アリル基、プロパルギル基、アシル基、低級アルキルスルホニル基、無置換若しくは置換基を有するベンジル基、又は無置換若しくは置換基を有するアリールスルホニル基を表し、Ｒ2は水素原子、フェニル−ｐ−クロロフェニルメチル基、又はＣＨ2Ｒ3（ここでＲ3は、水素原子、トリフルオロメチル基、シアノ基、低級アルキル基、低級アルコキシ基、低級アルケニル基、アラルキル基、又は無置換若しくは置換基を有するフェニル基である。）を表す。ただし、Ｒ1及びＲ2が同時に水素原子を表すことはなく、またＲ1及びＲ3が同時に水素原子を表すことはない。］、
一般式（２）
【０００８】
【化５】
（式中、Ｒ4は水素原子、アリル基、又は無置換若しくは置換基を有するベンジル基を表し、Ｒ5は水素原子、無置換若しくは置換基を有する低級アルキル基、又は無置換若しくは置換基を有するアラルキル基を表し、Ｒ6は水素原子、無置換若しくは置換基を有する低級アルキル基、低級アルケニル基、無置換若しくは置換基を有するアラルキル基、無置換若しくは置換基を有するアリール基、ヘテロアリール基、又は無置換若しくは置換基を有するアリールスルホニル基を表し、或いは−ＮＲ5Ｒ6は環状アミノ基を表す。）、
又は一般式（３）
【００１０】
【化６】
（式中、Ｒ７は水素原子、又はベンジル基を表し、Ｒ８は水素原子、アシル基、無置換若しくは置換基を有するアリールスルホニル基、Ｎ−アリールアミノカルボニル基、又はヘテロアリール基を表す。）、
で示される２−クロロ−６−ヒドロキシイソニコチン酸誘導体（ただし、２−クロロ−６−プロペニルオキシ−４−ピリジンカルボン酸を除く。）及びこれを有効成分とする植物病害防除剤に関する。
【００１２】
まず、本発明の一般式（１）で示される２−クロロ−６−ヒドロキシイソニコチン酸誘導体について説明する。
一般式（１）中のＲ1は、水素原子、アリル基、プロパルギル基、アシル基、低級アルキルスルホニル基、無置換若しくは置換基を有するベンジル基、又は無置換若しくは置換基を有するアリールスルホニル基を表す。
【００１３】
ここでいうアシル基としては、例えばアセチル基、プロピオニル基等のアルカノイル基、ベンゾイル基等のアロイル基等が挙げられ、好ましくはアセチル基が挙げられる。また低級アルキルスルホニル基としては、例えばメタンスルホニル基、エタンスルホニル基等の炭素数１〜４の低級アルキル基を有するスルホニル基等が挙げられ、アルキル基は直鎖状でも分枝状でも良い。好ましくは、直鎖状の炭素数１〜３の低級アルキルスルホニル基が挙げられる。より好ましくはメタンスルホニル基が挙げられる。
【００１４】
無置換若しくは置換基を有するベンジル基としては、例えばベンジル基や、４−メトキシベンジル基、２，４−ジメトキシベンジル基、３，４−ジメトキシベンジル基、２，３−ジメトキシベンジル基、ピペロニル基等のアルコキシベンジル基等が挙げられ、好ましくは、ベンジル基、メトキシベンジル基が挙げられる。無置換若しくは置換基を有するアリールスルホニル基としては、例えばベンゼンスルホニル基や、ｐ−トルエンスルホニル基等のアルキル置換アリールスルホニル基が挙げられ、好ましくはｐ−トルエンスルホニル基が挙げられる。
【００１５】
Ｒ1としては、特に水素原子、無置換若しくは置換基を有するベンジル基が好ましい。
Ｒ2は水素原子、フェニル−ｐ−クロロフェニルメチル基、又はＣＨ2Ｒ3（ここでＲ3は、水素原子、トリフルオロメチル基、シアノ基、低級アルキル基、低級アルコキシ基、低級アルケニル基、アラルキル基、又は無置換若しくは置換基を有するフェニル基である。）を表す。
【００１６】
Ｒ3で定義される低級アルキル基としては、直鎖状でも分枝状でも良く、例えばメチル基、エチル基、ｎ−プロピル基、イソプロピル基等の炭素数１〜４の低級アルキル基、好ましくはメチル基、エチル基の炭素数１〜２の低級アルキル基が挙げられ、低級アルコキシ基としては、例えばメトキシ基、エトキシ基等の炭素数１〜４の低級アルコキシ基、好ましくは炭素数１〜２の低級アルコキシ基が挙げられ、低級アルケニル基としては、例えばビニル基、アリル基等の炭素数２〜４の低級アルケニル基、好ましくはビニル基が挙げられ、アラルキル基としては、例えば２−フェニルエチル基、ベンジル基等の炭素数１〜４の低級アルキル基が置換したフェニル基、好ましくは２−フェニルエチル基が挙げられ、無置換若しくは置換基を有するフェニル基としては、例えばフェニル基や、４−メトキシフェニル基等のアルコキシフェニル基、４−クロロフェニル基等のハロゲン置換フェニル基等が挙げられ、好ましくはフェニル基、アルコキシフェニル基が挙げられる。
【００１７】
Ｒ2としては特に水素原子、ＣＨ2Ｒ3（ただし、Ｒ3は水素原子、シアノ基、低級アルケニル基、アラルキル基、又はアルコキシ基で置換されたフェニル基である）が好ましい。
【００１８】
ただし、一般式（１）において、Ｒ1及びＲ2が共に水素原子である化合物並びにＲ1及びＲ3共に水素原子である化合物は本発明の範囲外である。
Ｒ1、Ｒ2の組み合わせのうち特に好ましいものとしては、Ｒ1として水素原子、ベンジル基、４−メトキシベンジル基、３，４−ジメトキシベンジル基又はピペロニル基が、Ｒ2として水素原子、メチル基、エチル基、シアノメチル基、アリル基、４−メトキシベンジル基又は３−フェニルプロピル基が挙げられる。
【００１９】
尚、一般式（１）で示される化合物の具体的構造を例示すれば、表１の通りである。
【００２０】
【表１】
【表２】
【表３】
次に本発明の一般式（２）で示される２−クロロ−６−ヒドロキシイソニコチン酸誘導体について説明する。
一般式（２）中のＲ4は、水素原子、アリル基、又は無置換若しくは置換基を有するベンジル基を表す。
ここでいう無置換若しくは置換基を有するベンジル基としては、例えばベンジル基や、４−メトキシベンジル基等のアルコキシベンジル基、好ましくはベンジル基が挙げられる。
【００２４】
Ｒ4としては特に水素原子、無置換若しくは置換基を有するベンジル基が好ましい。
またＲ5は水素原子、無置換若しくは置換基を有する低級アルキル基、又は無置換若しくは置換基を有するアラルキル基を表す。
【００２５】
Ｒ5で定義される無置換若しくは置換基を有する低級アルキル基としては、炭素数１〜６の低級アルキル基が好ましく、例えばメチル基、エチル基、ブチル基、イソプロピル基等の直鎖状又は分岐状のアルキル基、シクロヘキシル基、シクロヘキシルメチル基等の環状アルキル基、２−メトキシエチル基、２−テトラヒドロピラニルメチル基等のアルコキシ置換アルキル基、２−シアノエチル基等のシアノ置換アルキル基等、より好ましくは直鎖状アルキル基が挙げられ、無置換若しくは置換基を有するアラルキル基としては、例えばベンジル基や、４−メトキシベンジル基等のアルコキシベンジル基、フルフリル基等のヘテロ原子を有するアラルキル基等、好ましくはアルコキシベンジル基が挙げられる。
【００２６】
Ｒ5としては特に水素原子、無置換若しくは置換基を有する低級アルキル基、無置換若しくは置換基を有するアラルキル基が好ましい。より好ましくは水素原子、アルコキシ基で置換されたアラルキル基である。
【００２７】
またＲ6は水素原子、無置換若しくは置換基を有する低級アルキル基、低級アルケニル基、無置換若しくは置換基を有するアラルキル基、無置換若しくは置換基を有するアリール基、ヘテロアリール基、又は無置換若しくは置換基を有するアリールスルホニル基を表す。
【００２８】
Ｒ6で定義される無置換若しくは置換基を有する低級アルキル基としては、炭素数１〜６のアルキル基が好ましく、例えばメチル基、エチル基、ブチル基、イソプロピル基等の直鎖状又は分枝状のアルキル基、シクロヘキシル基、シクロヘキシルメチル基等の環状アルキル基、２−メトキシエチル基、２−テトラヒドロピラニルメチル基等のアルコキシアルキル基、シアノメチル基、２−シアノエチル基等のシアノ基で置換された低級アルキル基、２，２，２−トリフルオロエチル基等のハロゲン置換低級アルキル基等が挙げられ、低級アルケニル基としては、例えばアリル基、クロチル基等の炭素数３〜４のアルケニル基が挙げられ、好ましくはアリル基が挙げられる。
【００２９】
無置換若しくは置換基を有するアラルキル基としては、例えばベンジル基等の無置換アラルキル基、４−メトキシベンジル基、２−メトキシベンジル基、３，４−ジメトキシベンジル基等のアルコキシベンジル基、４−フルオロベンジル基、４−クロロベンジル基、３−クロロベンジル基等のハロゲン置換ベンジル基、４−メチルベンジル基、４−ｔ−ブチルベンジル基、４−トリフルオロメチルベンジル基等のアルキル置換ベンジル基、１−フェニルエチル基、２−フェニルエチル基、３−フェニルプロピル基、４−フェニルブチル基、１−フェニル−１−メチルエチル基等のフェニル置換アルキル基、フルフリル基等のヘテロ原子を有するアラルキル基、１−ナフチルメチル基、４−ジメチルアミノベンジル基等が挙げられ、好ましくはフェニル置換アルキル基が挙げられる。
【００３０】
無置換若しくは置換基を有するアリ−ル基としては、例えばフェニル基、２，４−ジフルオロフェニル基、４−トリフルオロメトキシフェニル基、２−ベンゾイルフェニル基等、好ましくは、４−トリフルオロメトキシフェニル基、２−ベンゾイルフェニル基が挙げられ、ヘテロアリ−ル基としては、例えば２−ピリミジル基、３−ピリジル基等のヘテロ原子として窒素原子をもつヘテロアリール基等が挙げられ、無置換若しくは置換基を有するアリールスルホニル基としては、例えばフェニルスルホニル基等の無置換アリールスルホニル基、ｐ−トルエンスルホニル基等のアルキル置換アリールスルホニル基、２−フルオロフェニルスルホニル基等のハロゲン置換アリールスルホニル基等、好ましくはアルキル又はハロゲン置換アリールスルホニル基が挙げられる。
【００３１】
Ｒ6としては低級アルケニル基、無置換若しくは置換基を有するアラルキル基、無置換若しくは置換基を有するアリール基がより好ましく、特に低級アルケニル基、無置換のアラルキル基、フルフリル基若しくはフルオロアルキル基で置換されたアラルキル基が好ましい。
【００３２】
また、一般式（２）において−ＮＲ5Ｒ6が環状アミノ基を表す化合物も本発明に含まれる。−ＮＲ5Ｒ6で定義される環状アミノ基としては、例えばテトラヒドロイソキノリノ基、ピペリジノ基、モルホリノ基、３，５−ジメチルモルホリノ基、ベンゾモルホリノ基等、好ましくはテトラヒドロイソキノリノ基が挙げられる。
【００３３】
Ｒ4、Ｒ5、Ｒ6において特に好ましい組み合わせとしては、Ｒ4として水素原子、ベンジル基、４−メトキシベンジル基又はアリル基が、Ｒ5として水素原子又は４−メトキシベンジル基が、Ｒ6として４−フルオロベンジル基、２−フェニルエチル基、３−フェニルプロピル基、４−トリフルオロメチルベンジル基、２−ベンゾイルフェニル基、フルフリル基、アリル基、４−トリフルオロメトキシフェニル基又はシアノメチル基が、また−ＮＲ5Ｒ6が環状アミノ基としてテトラヒドロイソキノリノ基が挙げられる。
【００３４】
尚、一般式（２）で示される化合物の具体的構造を例示すれば、表２のとおりである。
【００３５】
【表４】
【表５】
【表６】
【表７】
【表８】
【表９】
【表１０】
【表１１】
最後に本発明の一般式（３）で示される２−クロロ−６−ヒドロキシイソニコチン酸誘導体について説明する。
一般式（３）中のＲ7は水素原子、又はベンジル基を表す。Ｒ7として好ましくはベンジル基である。
Ｒ8は水素原子、アシル基、無置換若しくは置換基を有するアリールスルホニル基、Ｎ−アリールアミノカルボニル基又はヘテロアリール基を表す。
【００４４】
ここでいうアシル基としては、例えばアセチル基、プロピオニル基等のアルカノイル基、ベンゾイル基、４−アミノベンゾイル基、４−ニトロベンゾイル基等のアロイル基、好ましくはアロイル基であり、より好ましくは４−ニトロベンゾイル基が挙げられる。また無置換若しくは置換基を有するアリールスルホニル基としては、例えばフェニルスルホニル基、ｐ−トルエンスルホニル基等、好ましくはｐ−トルエンスルホニル基が挙げられ、Ｎ−アリールアミノカルボニル基としては、例えばＮ−フェニルアミノカルボニル基、Ｎ−ｐ−トルイルアミノカルボニル基等が挙げられ、ヘテロアリール基としては、例えば２−ピリジル基等のヘテロ原子として窒素原子を有するヘテロアリール基が挙げられる。
【００４５】
Ｒ8として好ましくはアシル基である。
尚、一般式（３）で示される化合物の具体的構造を例示すれば、表３のとおりである。
【００４６】
【表１２】
【表１３】
本発明における一般式（１）〜（３）で示される化合物の製造法は、例えば下記の方法を挙げることができる。但し、当該化合物は、これらの製造法に限定されるものではない。尚、説明中に使用しているＲ1〜Ｒ8の定義は、特にことわりがない限り、上記で説明したＲ1〜Ｒ8の定義と同じである。
【００４９】
一般式（１）においてＲ1が水素、アリル基、プロパルギル基又は、無置換若しくは置換基を有するベンジル基である場合下記の方法で製造することができる。
Ａ法：
【００５０】
【化７】
２，６−ジクロロイソニコチン酸と、一般式（４）（Ｍはナトリウム、カリウム等の金属を表し、Ｒ1は水素、アリル基、プロパルギル基、無置換若しくは置換基を有するベンジル基を表す。）で示される水酸化物又はアルコラートとを反応させて得たカルボン酸（１Ａ）（一般式（１）においてＲ2が水素である化合物）に塩化チオニルを反応させ、酸塩化物（５）を得る。これに塩基の存在下、一般式（６）（Ｒ2は上記定義のうちで水素を除くものを表す。）で示されるアルコール類とを反応させることにより化合物（１Ｂ）、即ち一般式（１）で示される化合物を製造することができる。
Ｂ法：
【００５２】
【化８】
（１Ａ）で示されるカルボン酸を塩基の存在下、一般式（７）（式中、Ｒ2は上記定義のうちで水素を除き、Ｘはハロゲン原子を表す。）で示されるハロゲン化物と反応させることにより（１Ｂ）で示される化合物が製造できる。
【００５４】
また一般式（１）においてＲ1がアシル基、低級アルキルスルホニル基又は無置換若しくは置換基を有するアリールスルホニル基である化合物は、以下の方法で製造できる。
Ｃ法：
【００５５】
【化９】
化合物（１Ｄ）は、溶媒中、塩基の存在下、化合物（１Ｃ）（一般式（１）においてＲ1が水素である化合物）と一般式（８）（式中Ｒ1はアシル基、低級アルキルスルホニル基又は無置換若しくは置換基を有するアリールスルホニル基を表す。）で示される酸塩化物とを反応することにより製造することができる。
【００５７】
Ａ〜Ｃ法の各工程の反応を行う際、溶媒を用いるのが好ましく、例えば水、メタノール、エタノール等のアルコール類、酢酸エチル等のエステル類、クロロホルム、ジクロロエタン等のハロゲン化炭化水素類、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシド等の非プロトン性極性溶媒、アセトニトリル、プロピオニトリル等のニトリル類が挙げられ、反応に関与しないあらゆる溶媒が使用できる。塩基としては例えばトリエチルアミン、ジイソプロピルエチルアミン、ピリジン、４−ジメチルアミノピリジン、１，８−ジアザビシクロ［５，４，０］−７−ウンデセン等の有機塩基、炭酸カリウム、炭酸セシウム等の炭酸塩、水酸化カリウム、水酸化ナトリウム等の水酸化物が使用できる。反応温度については、０℃〜溶媒還流温度が好ましい。反応時間は用いる溶媒、原料等により異なるが、通常０．５〜３５時間である。
【００５８】
次に本発明における前記一般式（２）の化合物は下記の方法で製造することができる。
Ｄ法：
【００５９】
【化１０】
酸塩化物（９）を適当な溶媒中、塩基の存在下に、一般式（１０）で示されるアミンと反応させることにより（２Ａ）で示される化合物が製造できる。反応溶媒としては、例えばテトラヒドロフラン等のエーテル類、クロロホルム、ジクロロエタン等のハロゲン化炭化水素類、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシド等の非プロトン性極性溶媒が挙げられる。塩基としては例えばトリエチルアミン、ジイソプロピルエチルアミン、ピリジン、４−ジメチルアミノピリジン、１，８−ジアザビシクロ［５，４，０］−７−ウンデセン等の有機塩基、水酸化ナトリウム、水酸化カリウム等の水酸化物、炭酸カリウム、炭酸セシウム等の炭酸塩が使用できる。反応温度については、−１０〜５０℃が好ましい。更に一般式（２Ａ）においてＲ4＝ＣＨ2Ｐｈの場合、溶媒中、適当な触媒の存在下、水素化分解反応を行うことにより一般式（２）においてＲ4＝Ｈの化合物が製造できる。この反応の溶媒としては、メタノール、エタノール等のアルコール類、酢酸エチル等のエステル類、テトラヒドロフラン、ジオキサン等のエーテル類が挙げられる。触媒としてはＰｄ，ＰｔＯ2等が使用できる。反応温度としては、室温〜４０℃が好ましい。反応時間は用いる溶媒、原料等により異なるが、通常０．５〜２４時間である。
【００６１】
次に、本発明における一般式（３）の化合物は、下記の方法で製造することができる。
Ｅ法：
【００６２】
【化１１】
カルボン酸（１１）を酸触媒存在化、メタノール又はエタノール中、加熱還流すことにより式（１２）（Ｗはメチル基又はエチル基を表す。）で示されるエステルが得られる。酸触媒としては塩酸、硫酸、ｐ−トルエンスルホン酸、塩化アセチル等が使用できる。エステル（１２）とヒドラジンをエタノール中加熱還流することにより一般式（３）においてＲ8＝Ｈの化合物（３Ａ）が得られる。この化合物をピリジン中、一般式（１３）で表される酸ハロゲン化物又は酸無水物と反応させることにより一般式（３）（Ｒ8が水素であるものを除く。）の化合物が得られる。更にＲ7＝ＣＨ2Ｐｈの場合、溶媒中、触媒の存在下、水素化分解反応を行うことにより一般式（３）においてＲ7＝Ｈの化合物が得られる。この反応において溶媒としては、メタノール、エタノール等のアルコール類、酢酸エチル等のエステル類、テトラヒドロフラン、ジオキサン等のエーテル類が使用でき、触媒としてはＰｄ，ＰｔＯ2等が使用できる。反応温度としては、室温〜４０℃が好ましい。反応時間は用いる溶媒、原料等により異なるが、通常０．５〜２４時間である。
Ｆ法：
【００６４】
【化１２】
酸塩化物（１４）を溶媒中、塩基存在下、一般式（１５）で示されるヒドラジン誘導体と反応させることにより化合物（３Ｄ）が得られる。この反応において、溶媒としては例えばジクロロメタン、クロロホルム等のハロゲン化炭化水素類、テトラヒドロフラン等のエーテル類が使用でき、塩基としては例えばトリエチルアミン、ジイソプロピルエチルアミン、ピリジン、４−ジメチルアミノピリジン、１，８−ジアザビシクロ［５，４，０］−７−ウンデセン等の有機塩基、水酸化ナトリウム、水酸化カリウム等の水酸化物、炭酸カリウム、炭酸セシウム等の炭酸塩が使用できる。反応温度については、０〜５０℃が好ましい。反応時間は用いる溶媒、原料等により異なるが、通常０．５〜２４時間である。
Ｇ法：
【００６６】
【化１３】
一般式（３）においてＲ8がＮ−アリールアミノカルボニル基の場合、化合物（３Ａ）とアリールイソシアナート（１６）（式中Ａｒはアリール基を表す。）を溶媒中で反応させることにより製造することができる。この反応において、溶媒としてはテトラヒドロフラン等のエーテル類、ジクロロメタン、クロロホルム等のハロゲン化炭化水素類、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシド等の非プロトン性極性溶媒等が使用できる。反応温度については、０〜５０℃が好ましい。反応時間は用いる溶媒、原料等により異なるが、通常０．５〜２４時間である。
【００６８】
本発明はまた、上記一般式（１）〜（３）で示される２−クロロ−６−ヒドロキシイソニコチン酸誘導体を有効成分とする植物病害防除剤に関する。本発明の植物病害防除剤は、植物病原ウィルス、細菌及び糸状菌による各種の植物病害防除に適用し得るが、特にイネの主要病害であるいもち病に優れた効果を示す。
【００６９】
本薬剤は、有効成分を単独で使用することも可能であるが、通常、農薬の製剤に用いられる固体及び液体坦体、並びに分散剤、希釈剤、乳化剤、展着剤、増粘剤等の補助剤と混合して、水和剤、液剤、油剤、粉剤、粒剤、ゾル剤（フロアブル）等の剤型に製剤して使用することができる。
【００７０】
固体及び液体坦体としては、例えばタルク、クレー、ベントナイト、カオリン、けいそう土、モンモリロナイト、雲母、バーミキュライト、石膏、炭酸カルシウム、ホワイトカーボン、木粉、澱粉、アルミナ、珪酸塩、糖重合体、ワックス類、水、アルコール類（メチルアルコール、エチルアルコール、ｎ−プロピルアルコール、イソプロピルアルコール、ｎ−ブチルアルコール、エチレングリコール、ベンジルアルコール等）、石油溜分（石油エーテル、ケロシン、ソルベントナフサ等）、脂肪族又は脂環式炭化水素類（ｎ−ヘキサン、シクロヘキサン等）、芳香族炭化水素類（ベンゼン、トルエン、キシレン、エチルベンゼン、クロロベンゼン、クメン、メチルナフタレン等）、ハロゲン化炭化水素類（クロロホルム、ジクロロメタン等）、エーテル類（イソプロピルエーテル、エチレンオキシド、テトラヒドロフラン等）、ケトン類（アセトン、メチルエチルケトン、シクロヘキサノン、メチルイソブチルケトン等）、エステル類（酢酸エチル、酢酸ブチル、エチレングリコールアセタート、酢酸アミル等）、酸アミド類（ジメチルホルムアミド、ジメチルアセトアニリド等）、ニトリル類（アセトニトリル、プロピオニトリル、アクリロニトリル等）、スルホキシド類（ジメチルスルホキシド等）、アルコールエーテル類（エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル等）等が挙げられる。
【００７１】
補助剤としては、例えば非イオン型界面活性剤（ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルエステル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンソルビタンアルキルエステル、ソルビタンアルキルエステル等）、陰イオン型界面活性剤（アルキルベンゼンスルホナート、アルキルスルホサクシナート、ポリオキシエチレンアルキルスルファート、アリールスルホナート等）、陽イオン型界面活性剤（アルキルアミン類、ポリオキシエチレンアルキルアミン類、第四級アンモニウム塩類等）、両性型界面活性剤（アルキルアミノエチルグリシン、アルキルジメチルベタイン等）、ポリビニルアルコール、ヒドロキシプロピルセルロース、カルボキシメチルセルロース、アラビアゴム、トラガントガム、キサンタンガム、ポリビニルアセタート、ゼラチン、カゼイン、アルギン酸ソーダ等が挙げられる。
【００７２】
更に、本薬剤は、各種の農園芸用殺菌剤、除草剤、植物生長調節剤、殺虫剤、殺ダニ剤等の農薬や、肥料等と混合して用いることができる。
本薬剤における有効成分含有量は、製剤形態、施用方法、その他の条件によって種々異なる。通常は０．５〜９５％（重量）、好ましくは２〜７０％（重量）である。本薬剤の施用方法としては、植物への施用（茎葉散布）、植物の生育土壌への施用（土壌施用）、田面水への施用（水面施用）、種子への施用（種子処理）等が可能である。本薬剤の施用量に関しては、適用植物、適用病害等によっても異なるが、茎葉散布の場合には有効成分濃度１〜１００００ｐｐｍ、好ましくは１０〜１０００ｐｐｍの溶液を１０アール当たり５０〜３００ｌ施用するのが好ましく、土壌施用及び水面施用の場合には、有効成分量で１０アール当たり０．１〜５０００ｇ、特に好ましくは１〜１０００ｇ施用するのが好ましい。また、種子処理の場合には、種子１ｋｇに対して、０．００１〜５０ｇの有効成分を施用するのが好ましい。
【００７３】
【実施例】
次に本発明を製造例、製剤例及び試験例によって説明するが、本発明はこれらの実施例のみによって限定されるものではない。
【００７４】
（製造例１）化合物Ｎｏ．（１−１７）の合成
テトラヒドロフラン５０ｍｌに４−メトキシべンジルアルコール６．３３ｇを溶解し、水素化ナトリウム（６０％オイルサスペンジョン）１．７５ｇを加え、室温で３０分間撹拌した。この溶液を冷却しながら、２，６−ジクロロイソニコチン酸４．０ｇのテトラヒドロフラン溶液を加え、３時間加熱還流した。反応液を冷却後、減圧濃縮し、残さに水を加え、エーテルで抽出した。水層を濃塩酸で酸性とし、クロロホルムで抽出し、クロロホルム層を水洗して無水硫酸ナトリウムで乾燥した。クロロホルム層を減圧濃縮し、得られた残さを５％ＮａＯＨ水溶液１００ｍｌに溶解し、少量のクロロホルムを加えるとカルボン酸塩が沈殿した。沈殿を濾別し、エーテルで洗い、化合物Ｎｏ．（１−１７）のナトリウム塩を得た。これを１０％ＨＣｌ水１００ｍｌに溶解し、クロロホルムで抽出後、クロロホルム層を水、飽和食塩水で順次洗浄し、無水硫酸ナトリウムで乾燥した。クロロホルム層を減圧濃縮し、化合物Ｎｏ．（１−１７）３．６ｇを粉末として得た。
６０ＭＨｚ−1Ｈ−ＮＭＲ（内部標準ＴＭＳ）： 表４中に示した。
【００７５】
（製造例２）化合物Ｎｏ．（１−２１）の合成
テトラヒドロフラン１０ｍｌに化合物Ｎｏ．（１−１７）０．５０ｇを溶解し、ピリジン０．３４ｍｌを加えた。この溶液を冷却し、テトラヒドロフラン３ｍｌに溶解した塩化チオニル０．１５ｍｌを滴下し、室温で１０分間撹拌した。この溶液を冷却し、３−フェニル−１−プロパノール０．２４ｇ、トリエチルアミン０．７１ｍｌをテトラヒドロフラン５ｍｌに溶解した溶液を滴下した。反応液を室温で一晩撹拌した後、クロロホルムを加え、希塩酸、水、飽和重曹水、飽和食塩水で順次洗浄し、無水硫酸ナトリウムで乾燥した。減圧濃縮し、得られた残さをシリカゲルカラムクロマトグラフィー（ヘキサン／酢酸エチル＝５／１）で精製し、化合物Ｎｏ．（１−２１）を得た。
６０ＭＨｚ−1Ｈ−ＮＭＲ（内部標準ＴＭＳ）： 表４中に示した。
【００７６】
（製造例３）化合物Ｎｏ．（１−１９）の合成
化合物Ｎｏ．（１−１７）０．２０ｇをＮ，Ｎ−ジメチルホルムアミド７ｍｌに溶解し、トリエチルアミン０．１３ｍｌ、クロロアセトニトリル６２ｍｇを順次加え、室温で１日、５０℃で７時間撹拌した。反応液を減圧濃縮し、残さをクロロホルムに溶解し、希塩酸、水、飽和重曹水、飽和食塩水で順次洗浄し、無水硫酸ナトリウムで乾燥した。減圧濃縮して得られた残さをシリカゲルカラムクロマトグラフィー（ベンゼン／酢酸エチル＝２０／１）で精製し、化合物Ｎｏ．（１−１９）０．１９ｇを得た。
６０ＭＨｚ−1Ｈ−ＮＭＲ（内部標準ＴＭＳ）、融点： 表４中に示した。
【００７７】
（製造例４）化合物Ｎｏ．（１−３１）の合成
２−クロロ−６−ヒドロキシイソニコチン酸０．９５ｇをテトラヒドロフラン５ｍｌに溶かし、トリエチルアミン１．１１ｇ、ｐ−トルエンスルホニルクロリド１．０５ｇを加え、室温で７時間攪拌した。反応液を減圧濃縮し、残さに飽和重曹水とベンゼンを加え分液し、水層を塩酸で酸性としてベンゼンで抽出した。
ベンゼン層を硫酸ナトリウムで乾燥した後、濃縮し、残さにベンゼンを加え、濾過により不溶物をのぞき、濾液を濃縮して化合物Ｎｏ．（１−３１）０．７４ｇを得た。
６０ＭＨｚ−1Ｈ−ＮＭＲ（内部標準ＴＭＳ）、融点： 表４中に示した。
【００７８】
（製造例５）化合物Ｎｏ．（２−２２）の合成
２−クロロ−６−ヒドロキシイソニコチン酸１０．０ｇをＮ，Ｎ−ジメチルホルムアミド１５ｇに溶かし、室温で塩化チオニル１５ｍｌを滴下した。混合物を６０℃で２時間攪拌後、減圧下に塩化チオニルを留去し、２−クロロ−６−ヒドロキシイソニコチン酸塩化物のＮ，Ｎ−ジメチルホルムアミド溶液を得た。トリエチルアミン１０ｍｌ、ｐ−トリフルオロメチルベンジルアミン１．０ｇ、酸塩化物溶液２．９ｇをテトラヒドロフラン１５ｍｌに溶かし、室温で７時間攪拌した。反応液を氷−希塩酸にあけ、酢酸エチルで抽出し、有機層を水、飽和食塩水で順次洗浄し、硫酸ナトリウムで乾燥した。減圧濃縮して得られた残さをシリカゲルカラムクロマトグラフィー（クロロホルム／メタノール＝５／１）で精製し、化合物Ｎｏ．（２−２２）０．９４ｇを結晶として得た。
マススペクトル、融点： 表４中に示した。
【００７９】
（製造例６）化合物Ｎｏ．（２−５２）及び化合物Ｎｏ．（２−２８）の合成化合物Ｎｏ．（１−７）１．０ｇ、ピリジン０．６７ｍｌをテトラヒドロフラン１０ｍｌに溶かし、この溶液に氷冷下、塩化チオニル０．３３ｍｌのテトラヒドロフラン溶液を滴下し１５分間攪拌した後、４−トリフルオロメトキシアニリン０．７１ｇ、トリエチルアミン１．６ｍｌのテトラヒドロフラン溶液を滴下し、室温で２時間攪拌した。反応液を氷−希塩酸にあけ、クロロホルムで抽出し、有機層を水、飽和重曹水、水、飽和食塩水で順次洗浄し、硫酸ナトリウムで乾燥した。減圧濃縮して残さをベンゼン−ヘキサンより結晶化して化合物Ｎｏ．（２−５２）１．２５ｇを得た。
６０ＭＨｚ−1Ｈ−ＮＭＲ（内部標準ＴＭＳ）、融点： 表４中に示した。
次に化合物Ｎｏ．（２−５２）０．３０ｇをエタノール１５ｍｌ＋酢酸エチル５ｍｌに溶かし、５％Ｐｄ−Ｃ４０ｍｇを加え室温で攪拌した。ｔｌｃで反応の終了を確認した後、反応液を濾過して濾液を濃縮し、残さをクロロホルム−ヘキサンより結晶化して化合物Ｎｏ．（２−２８）１４５ｍｇを得た。
６０ＭＨｚ−1Ｈ−ＮＭＲ（内部標準ＴＭＳ）、融点： 表４中に示した。
【００８０】
（製造例７）化合物Ｎｏ．（３−７）、化合物Ｎｏ．（３−１０）、化合物Ｎｏ．（３−４）の合成
化合物Ｎｏ．（１−７）７．０ｇをエタノール３５ｍｌに溶かし、硫酸０．５ｍｌを加え、７時間還流した。放冷後、濃縮し、残さをシリカゲルカラムクロマトグラフィー（ベンゼン）により精製し、化合物Ｎｏ．（１−９）４．９ｇを得た。
６０ＭＨｚ−1Ｈ−ＮＭＲ（内部標準ＴＭＳ）： 表４中に示した。
次に化合物Ｎｏ．（１−９）１．１ｇをエタノール１５ｍｌに溶かし、無水ヒドラジン０．２６ｇを加えて２０時間還留した。反応液を濃縮し、残さをシリカゲルカラムクロマトグラフィー（ベンゼン／ヘキサン＝１／１）で精製し、化合物Ｎｏ．（３−７）０．８６ｇを得た。
６０ＭＨｚ−1Ｈ−ＮＭＲ（内部標準ＴＭＳ）： 表４中に示した。
次に化合物Ｎｏ．（３−７）０．６０ｇをピリジン５ｍｌに溶かし、４−ニトロ安息香酸塩化物０．４４ｇを加え室温で一晩攪拌した。反応液を１０％塩酸水にあけ、生じた沈殿を濾別して水、クロロホルムで洗浄し、乾燥後、エタノールより再結晶して化合物Ｎｏ．（３−１０）０．４２ｇを得た。
６０ＭＨｚ−1Ｈ−ＮＭＲ（内部標準ＴＭＳ）： 表４中に示した。
次に化合物Ｎｏ．（３−１０）０．４０ｇをエタノール−テトラヒドロフランに溶かし、１０％Ｐｄ−Ｃ９０ｍｇを加え、室温で攪拌した。ｔｌｃで原料消失を確認し、反応液を濃縮して化合物Ｎｏ．（３−４）を得た。
６０ＭＨｚ−1Ｈ−ＮＭＲ（内部標準ＴＭＳ）： 表４中に示した。
【００８１】
（製造例８）化合物Ｎｏ．（３−１２）の合成
化合物Ｎｏ．（３−７）０．３５ｇをＮ，Ｎ−ジメチルホルムアミド５ｍｌに溶かし、フェニルイソシアナート０．１８ｇを加え、室温で３時間攪拌した。反応液を濃縮し、残さをクロロホルム−テトラヒドロフランに溶かして水洗した。
有機層を硫酸ナトリウムで乾燥後、濃縮し残さをベンゼンより結晶化した。結晶をベンゼン−ヘキサンより再結晶して化合物Ｎｏ．（３−１２）０．３１ｇを得た。
６０ＭＨｚ−1Ｈ−ＮＭＲ（内部標準ＴＭＳ）、融点： 表４中に示した。
【００８２】
（製造例９）
製造実施例１〜８のいずれかの方法と同様に、表４記載の各化合物を合成した。各化合物の物性値は、表４中に示した。
【００８３】
【表１４】
【表１５】
【表１６】
【表１７】
【表１８】
【表１９】
【表２０】
【表２１】
【表２２】
【表２３】
【表２４】
【表２５】
（製剤例１）粉剤
表４に示す２−クロロ−６−ヒドロキシイソニコチン酸誘導体２重量部をそれぞれ、クレー９８重量部と混合粉砕し、粉剤とした。
【００９６】
（製剤例２）水和剤
表４に示す２−クロロ−６−ヒドロキシイソニコチン酸誘導体２０重量部をそれぞれ、クレー６８重量部、ホワイトカーボン８重量部及びポリオキシエチレンノニルフェニルエーテル４重量部と混合粉砕し、水和剤とした。
【００９７】
（製剤例３）粒剤
表４に示す２−クロロ−６−ヒドロキシイソニコチン酸誘導体５重量部をそれぞれ、ベントナイト及びタルクの等量混合物９０重量部及びアルキルベンゼンスルホン酸ナトリウム５重量部を混合粉砕し、粒剤に成型した。
【００９８】
（試験例１）イネいもち病防除試験（土壌施用）
ポット（直径６ｃｍ，高さ５．５ｃｍ）で育種した２葉期のイネ（品種：愛知旭）に、（製剤例２）記載の水和剤と同様に調製した各薬液を、各々土壌施用した（有効成分量で３ｍｇ／ポット）。１４日後にイネいもち病菌（Ｐｙｒｉｃｕｌａｒｉａ ｏｒｙｚａｅ）の胞子懸濁液を噴霧接種し、２５℃の湿室に２４時間置いた後、温室内で発病させ、胞子懸濁液接種１０日後に病斑数を調査し、下記式より防除価を算出した。対照薬剤として、２，６−ジクロロイソニコチン酸についても同様の方法で試験を行った。結果を表５に示す。
【００９９】
【数１】
【表２６】
【発明の効果】
本発明に係る２−クロロ−６−ヒドロキシイソニコチン酸誘導体を有効成分とする植物病害防除剤は、植物病原ウィルス、細菌及び糸状菌による各種の植物病害、特にイネの主要病害であるいもち病の防除に優れた効果を示すと共に薬害の心配もない。[0001]
[Industrial application fields]
The present invention relates to a 2-chloro-6-hydroxyisonicotinic acid derivative, which can be used as a plant disease control agent, particularly as a plant disease control agent for paddy fields.
[0002]
[Prior art]
As an examination example of physiological activity as an agricultural fungicide relating to isonicotinic acid derivatives, for example, 2,6-dihalogenated isonicotinic acid and its ester derivatives are known to be effective as plant disease control agents. No. 63-93766).
[0003]
[Problems to be solved by the invention]
However, the above compounds may cause phytotoxicity in plants to be protected, and a safer drug for plants has been demanded. An object of the present invention is to provide a novel compound and a drug having an excellent plant disease control activity with little phytotoxicity.
[0004]
[Means for Solving the Problems]
As a result of various studies to solve such problems, the present inventors have found that the 2-chloro-6-hydroxyisonicotinic acid derivatives represented by the following general formulas (1) to (3) have no fear of phytotoxicity to plants. The present inventors have found that it exhibits excellent plant disease control activity and has completed the present invention.
[0005]
That is, the present invention relates to the general formula (1)
[0006]
[Formula 4]
[Wherein R 1 Represents a hydrogen atom, an allyl group, a propargyl group, an acyl group, a lower alkylsulfonyl group, an unsubstituted or substituted benzyl group, or an unsubstituted or substituted arylsulfonyl group, R 2 Is a hydrogen atom, a phenyl-p-chlorophenylmethyl group, or CH 2 R Three (Where R Three Is a hydrogen atom, a trifluoromethyl group, a cyano group, a lower alkyl group, a lower alkoxy group, a lower alkenyl group, an aralkyl group, or an unsubstituted or substituted phenyl group. ). However, R 1 And R 2 Do not represent hydrogen atoms at the same time, and R 1 And R Three Do not represent hydrogen atoms at the same time. ],
General formula (2)
[0008]
[Chemical formula 5]
(Wherein R Four Represents a hydrogen atom, an allyl group, or an unsubstituted or substituted benzyl group, R Five Represents a hydrogen atom, an unsubstituted or substituted lower alkyl group, or an unsubstituted or substituted aralkyl group, R 6 Is a hydrogen atom, an unsubstituted or substituted lower alkyl group, a lower alkenyl group, an unsubstituted or substituted aralkyl group, an unsubstituted or substituted aryl group, a heteroaryl group, or an unsubstituted or substituted group. Represents an arylsulfonyl group having -NR Five R 6 Represents a cyclic amino group. ),
Or general formula (3)
[0010]
[Chemical 6]
(Wherein R 7 Represents a hydrogen atom or a benzyl group, R 8 Represents a hydrogen atom, an acyl group, an unsubstituted or substituted arylsulfonyl group, an N-arylaminocarbonyl group, or a heteroaryl group. ),
2-Chloro-6-hydroxyisonicotinic acid derivative represented by (However, 2-chloro-6-propenyloxy-4-pyridinecarboxylic acid is excluded.) And a plant disease control agent comprising this as an active ingredient.
[0012]
First, the 2-chloro-6-hydroxyisonicotinic acid derivative represented by the general formula (1) of the present invention will be described.
R in general formula (1) 1 Represents a hydrogen atom, an allyl group, a propargyl group, an acyl group, a lower alkylsulfonyl group, an unsubstituted or substituted benzyl group, or an unsubstituted or substituted arylsulfonyl group.
[0013]
As an acyl group here, alkanoyl groups, such as an acetyl group and a propionyl group, aroyl groups, such as a benzoyl group, etc. are mentioned, for example, Preferably an acetyl group is mentioned. Examples of the lower alkylsulfonyl group include a sulfonyl group having a lower alkyl group having 1 to 4 carbon atoms such as a methanesulfonyl group and an ethanesulfonyl group. The alkyl group may be linear or branched. Preferably, a linear C1-C3 lower alkylsulfonyl group is mentioned. More preferred is a methanesulfonyl group.
[0014]
Examples of the unsubstituted or substituted benzyl group include benzyl group, 4-methoxybenzyl group, 2,4-dimethoxybenzyl group, 3,4-dimethoxybenzyl group, 2,3-dimethoxybenzyl group, piperonyl group and the like. And the like, preferably a benzyl group and a methoxybenzyl group. Examples of the unsubstituted or substituted arylsulfonyl group include a benzenesulfonyl group and an alkyl-substituted arylsulfonyl group such as a p-toluenesulfonyl group, preferably a p-toluenesulfonyl group.
[0015]
R 1 In particular, a hydrogen atom, an unsubstituted or substituted benzyl group is preferable.
R 2 Is a hydrogen atom, a phenyl-p-chlorophenylmethyl group, or CH 2 R Three (Where R Three Is a hydrogen atom, a trifluoromethyl group, a cyano group, a lower alkyl group, a lower alkoxy group, a lower alkenyl group, an aralkyl group, or an unsubstituted or substituted phenyl group. ).
[0016]
R Three As the lower alkyl group defined by the formula, it may be linear or branched, for example, a lower alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, preferably a methyl group. And a lower alkyl group having 1 to 2 carbon atoms in an ethyl group. Examples of the lower alkoxy group include lower alkoxy groups having 1 to 4 carbon atoms such as methoxy group and ethoxy group, preferably lower ones having 1 to 2 carbon atoms. Examples of the lower alkenyl group include a lower alkenyl group having 2 to 4 carbon atoms such as a vinyl group and an allyl group, preferably a vinyl group. Examples of the aralkyl group include a 2-phenylethyl group, A phenyl group substituted with a lower alkyl group having 1 to 4 carbon atoms such as a benzyl group, preferably a 2-phenylethyl group, may be used. The group, for example, a phenyl group, 4-methoxyphenyl alkoxyphenyl group such as a phenyl group, and a halogen-substituted phenyl group such as 4-chlorophenyl group, preferably a phenyl group, alkoxyphenyl group.
[0017]
R 2 As especially hydrogen atom, CH 2 R Three (However, R Three Is preferably a hydrogen atom, a cyano group, a lower alkenyl group, an aralkyl group, or a phenyl group substituted with an alkoxy group.
[0018]
However, in the general formula (1), R 1 And R 2 Wherein both are hydrogen atoms and R 1 And R Three Compounds that are both hydrogen atoms are outside the scope of the present invention.
R 1 , R 2 Among these combinations, particularly preferred are R 1 As a hydrogen atom, benzyl group, 4-methoxybenzyl group, 3,4-dimethoxybenzyl group or piperonyl group, 2 Examples thereof include a hydrogen atom, a methyl group, an ethyl group, a cyanomethyl group, an allyl group, a 4-methoxybenzyl group, and a 3-phenylpropyl group.
[0019]
Examples of the specific structure of the compound represented by the general formula (1) are shown in Table 1.
[0020]
[Table 1]
[Table 2]
[Table 3]
Next, the 2-chloro-6-hydroxyisonicotinic acid derivative represented by the general formula (2) of the present invention will be described.
R in general formula (2) Four Represents a hydrogen atom, an allyl group, or an unsubstituted or substituted benzyl group.
Examples of the unsubstituted or substituted benzyl group herein include a benzyl group and an alkoxybenzyl group such as a 4-methoxybenzyl group, preferably a benzyl group.
[0024]
R Four Particularly preferred is a hydrogen atom, an unsubstituted or substituted benzyl group.
Also R Five Represents a hydrogen atom, an unsubstituted or substituted lower alkyl group, or an unsubstituted or substituted aralkyl group.
[0025]
R Five The lower alkyl group having an unsubstituted or substituted group defined by the formula (1) is preferably a lower alkyl group having 1 to 6 carbon atoms, for example, a linear or branched group such as a methyl group, an ethyl group, a butyl group, or an isopropyl group. Cyclic alkyl groups such as alkyl groups, cyclohexyl groups and cyclohexylmethyl groups, alkoxy-substituted alkyl groups such as 2-methoxyethyl groups and 2-tetrahydropyranylmethyl groups, cyano-substituted alkyl groups such as 2-cyanoethyl groups, and the like, more preferably Examples of the aralkyl group having a non-substituted or substituted group include a benzyl group, an alkoxybenzyl group such as a 4-methoxybenzyl group, and an aralkyl group having a heteroatom such as a furfuryl group. Includes an alkoxybenzyl group.
[0026]
R Five In particular, a hydrogen atom, an unsubstituted or substituted lower alkyl group, and an unsubstituted or substituted aralkyl group are preferable. More preferred is a hydrogen atom or an aralkyl group substituted with an alkoxy group.
[0027]
Also R 6 Is a hydrogen atom, an unsubstituted or substituted lower alkyl group, a lower alkenyl group, an unsubstituted or substituted aralkyl group, an unsubstituted or substituted aryl group, a heteroaryl group, or an unsubstituted or substituted group. Represents an arylsulfonyl group.
[0028]
R 6 As the unsubstituted or substituted lower alkyl group defined by the above, an alkyl group having 1 to 6 carbon atoms is preferable, for example, a linear or branched group such as a methyl group, an ethyl group, a butyl group, and an isopropyl group. Lower alkyl substituted with a cyclic alkyl group such as an alkyl group, a cyclohexyl group and a cyclohexylmethyl group, an alkoxyalkyl group such as a 2-methoxyethyl group and a 2-tetrahydropyranylmethyl group, a cyano group such as a cyanomethyl group and a 2-cyanoethyl group Examples thereof include halogen-substituted lower alkyl groups such as alkyl groups and 2,2,2-trifluoroethyl groups. Examples of lower alkenyl groups include alkenyl groups having 3 to 4 carbon atoms such as allyl groups and crotyl groups. An allyl group is preferable.
[0029]
Examples of the unsubstituted or substituted aralkyl group include an unsubstituted aralkyl group such as a benzyl group, an alkoxybenzyl group such as a 4-methoxybenzyl group, a 2-methoxybenzyl group, and a 3,4-dimethoxybenzyl group, 4-fluoro Alkyl-substituted benzyl groups such as benzyl group, 4-chlorobenzyl group, halogen-substituted benzyl group such as 3-chlorobenzyl group, 4-methylbenzyl group, 4-t-butylbenzyl group, 4-trifluoromethylbenzyl group, An aralkyl group having a hetero atom such as a phenyl-substituted alkyl group such as a phenylethyl group, a 2-phenylethyl group, a 3-phenylpropyl group, a 4-phenylbutyl group or a 1-phenyl-1-methylethyl group, a furfuryl group, 1-naphthylmethyl group, 4-dimethylaminobenzyl group and the like can be mentioned, preferably Eniru substituted alkyl group.
[0030]
Examples of the unsubstituted or substituted aryl group include a phenyl group, a 2,4-difluorophenyl group, a 4-trifluoromethoxyphenyl group, a 2-benzoylphenyl group, and the like, preferably 4-trifluoromethoxyphenyl. Group, a 2-benzoylphenyl group, and the heteroaryl group includes, for example, a heteroaryl group having a nitrogen atom as a heteroatom such as a 2-pyrimidyl group and a 3-pyridyl group, and is unsubstituted or substituted. As the arylsulfonyl group having, for example, an unsubstituted arylsulfonyl group such as a phenylsulfonyl group, an alkyl-substituted arylsulfonyl group such as a p-toluenesulfonyl group, a halogen-substituted arylsulfonyl group such as a 2-fluorophenylsulfonyl group, etc. Alkyl or halogen substituted aryls Honiru group, and the like.
[0031]
R 6 Is more preferably a lower alkenyl group, an unsubstituted or substituted aralkyl group, or an unsubstituted or substituted aryl group, particularly a lower alkenyl group, an unsubstituted aralkyl group, a furfuryl group or a fluoroalkyl group. Aralkyl groups are preferred.
[0032]
In the general formula (2), -NR Five R 6 A compound in which represents a cyclic amino group is also included in the present invention. -NR Five R 6 Examples of the cyclic amino group defined by include tetrahydroisoquinolino group, piperidino group, morpholino group, 3,5-dimethylmorpholino group, benzomorpholino group, etc., preferably tetrahydroisoquinolino group.
[0033]
R Four , R Five , R 6 Particularly preferred combinations in R are R Four As a hydrogen atom, a benzyl group, a 4-methoxybenzyl group or an allyl group, Five As a hydrogen atom or 4-methoxybenzyl group 6 4-fluorobenzyl group, 2-phenylethyl group, 3-phenylpropyl group, 4-trifluoromethylbenzyl group, 2-benzoylphenyl group, furfuryl group, allyl group, 4-trifluoromethoxyphenyl group or cyanomethyl group And -NR Five R 6 Includes a tetrahydroisoquinolino group as the cyclic amino group.
[0034]
Examples of the specific structure of the compound represented by the general formula (2) are as shown in Table 2.
[0035]
[Table 4]
[Table 5]
[Table 6]
[Table 7]
[Table 8]
[Table 9]
[Table 10]
[Table 11]
Finally, the 2-chloro-6-hydroxyisonicotinic acid derivative represented by the general formula (3) of the present invention will be described.
R in general formula (3) 7 Represents a hydrogen atom or a benzyl group. R 7 As preferred, it is a benzyl group.
R 8 Represents a hydrogen atom, an acyl group, an unsubstituted or substituted arylsulfonyl group, an N-arylaminocarbonyl group or a heteroaryl group.
[0044]
The acyl group here is, for example, an alkanoyl group such as an acetyl group or a propionyl group, an aroyl group such as a benzoyl group, a 4-aminobenzoyl group, or a 4-nitrobenzoyl group, preferably an aroyl group, more preferably 4- A nitrobenzoyl group is mentioned. Examples of the unsubstituted or substituted arylsulfonyl group include a phenylsulfonyl group and a p-toluenesulfonyl group, preferably a p-toluenesulfonyl group, and the N-arylaminocarbonyl group includes, for example, N-phenyl. An aminocarbonyl group, Np-toluylaminocarbonyl group, etc. are mentioned, As a heteroaryl group, the heteroaryl group which has a nitrogen atom as heteroatoms, such as 2-pyridyl group, is mentioned, for example.
[0045]
R 8 Preferred is an acyl group.
Examples of the specific structure of the compound represented by the general formula (3) are shown in Table 3.
[0046]
[Table 12]
[Table 13]
Examples of the method for producing the compounds represented by the general formulas (1) to (3) in the present invention include the following methods. However, the compound is not limited to these production methods. R used in the explanation 1 ~ R 8 The definition of R is as described above unless otherwise specified. 1 ~ R 8 The definition is the same as
[0049]
In the general formula (1), R 1 Is hydrogen, allyl group, propargyl group, or unsubstituted or substituted benzyl group, it can be produced by the following method.
Method A:
[0050]
[Chemical 7]
2,6-dichloroisonicotinic acid and general formula (4) (M represents a metal such as sodium or potassium, R 1 Represents hydrogen, allyl group, propargyl group, unsubstituted or substituted benzyl group. Carboxylic acid (1A) obtained by reacting with a hydroxide or alcoholate represented by formula (1) (in formula (1), R 2 The compound wherein is hydrogen is reacted with thionyl chloride to give the acid chloride (5). In the presence of a base, general formula (6) (R 2 Represents the above definition excluding hydrogen. The compound (1B), that is, the compound represented by the general formula (1) can be produced by reacting with an alcohol represented by
Method B:
[0052]
[Chemical 8]
In the presence of a base, the carboxylic acid represented by (1A) is represented by the general formula (7) (wherein R 2 In the above definition, except for hydrogen, X represents a halogen atom. The compound shown by (1B) can be manufactured by making it react with the halide shown by.
[0054]
In the general formula (1), R 1 A compound in which is an acyl group, a lower alkylsulfonyl group or an unsubstituted or substituted arylsulfonyl group can be produced by the following method.
Method C:
[0055]
[Chemical 9]
Compound (1D) is compound (1C) (in formula (1), R in the presence of a base in a solvent). 1 In which R is hydrogen) and general formula (8) (wherein R 1 Represents an acyl group, a lower alkylsulfonyl group, or an arylsulfonyl group that is unsubstituted or substituted. It can manufacture by reacting with the acid chloride shown by.
[0057]
It is preferable to use a solvent when performing the reaction in each step of methods A to C. For example, water, alcohols such as methanol and ethanol, esters such as ethyl acetate, halogenated hydrocarbons such as chloroform and dichloroethane, N , N-dimethylformamide, aprotic polar solvents such as dimethyl sulfoxide, and nitriles such as acetonitrile and propionitrile, and any solvent that does not participate in the reaction can be used. Examples of the base include triethylamine, diisopropylethylamine, pyridine, 4-dimethylaminopyridine, organic bases such as 1,8-diazabicyclo [5,4,0] -7-undecene, carbonates such as potassium carbonate and cesium carbonate, hydroxide Hydroxides such as potassium and sodium hydroxide can be used. About reaction temperature, 0 degreeC-solvent recirculation | reflux temperature is preferable. While the reaction time varies depending on the solvent and raw materials used, it is generally 0.5 to 35 hours.
[0058]
Next, the compound of the general formula (2) in the present invention can be produced by the following method.
Method D:
[0059]
[Chemical Formula 10]
The compound represented by (2A) can be produced by reacting the acid chloride (9) with an amine represented by the general formula (10) in an appropriate solvent in the presence of a base. Examples of the reaction solvent include ethers such as tetrahydrofuran, halogenated hydrocarbons such as chloroform and dichloroethane, and aprotic polar solvents such as N, N-dimethylformamide and dimethyl sulfoxide. Examples of the base include triethylamine, diisopropylethylamine, pyridine, 4-dimethylaminopyridine, organic bases such as 1,8-diazabicyclo [5,4,0] -7-undecene, and hydroxides such as sodium hydroxide and potassium hydroxide. Carbonates such as potassium carbonate and cesium carbonate can be used. About reaction temperature, -10-50 degreeC is preferable. Further, in the general formula (2A), R Four = CH 2 In the case of Ph, R in the general formula (2) is obtained by performing a hydrogenolysis reaction in a solvent in the presence of an appropriate catalyst. Four = H can be produced. Examples of the solvent for this reaction include alcohols such as methanol and ethanol, esters such as ethyl acetate, and ethers such as tetrahydrofuran and dioxane. Pd, PtO as catalyst 2 Etc. can be used. The reaction temperature is preferably room temperature to 40 ° C. While the reaction time varies depending on the solvent and raw materials used, it is generally 0.5 to 24 hours.
[0061]
Next, the compound of the general formula (3) in the present invention can be produced by the following method.
Method E:
[0062]
Embedded image
An ester represented by the formula (12) (W represents a methyl group or an ethyl group) is obtained by heating and refluxing the carboxylic acid (11) in the presence of an acid catalyst in methanol or ethanol. As the acid catalyst, hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, acetyl chloride and the like can be used. The ester (12) and hydrazine are heated to reflux in ethanol to give R in general formula (3). 8 Compound (3A) with = H is obtained. By reacting this compound with an acid halide or acid anhydride represented by the general formula (13) in pyridine, the general formula (3) (R 8 Except where is hydrogen. ) Is obtained. R 7 = CH 2 In the case of Ph, R in formula (3) is obtained by performing a hydrogenolysis reaction in a solvent in the presence of a catalyst. 7 A compound of = H is obtained. In this reaction, alcohols such as methanol and ethanol, esters such as ethyl acetate, ethers such as tetrahydrofuran and dioxane can be used as the solvent, and Pd, PtO as the catalyst. 2 Etc. can be used. The reaction temperature is preferably room temperature to 40 ° C. While the reaction time varies depending on the solvent and raw materials used, it is generally 0.5 to 24 hours.
Method F:
[0064]
Embedded image
The compound (3D) is obtained by reacting the acid chloride (14) with a hydrazine derivative represented by the general formula (15) in the presence of a base in a solvent. In this reaction, for example, halogenated hydrocarbons such as dichloromethane and chloroform and ethers such as tetrahydrofuran can be used as the solvent, and examples of the base include triethylamine, diisopropylethylamine, pyridine, 4-dimethylaminopyridine, 1,8-diazabicyclo. Organic bases such as [5,4,0] -7-undecene, hydroxides such as sodium hydroxide and potassium hydroxide, and carbonates such as potassium carbonate and cesium carbonate can be used. About reaction temperature, 0-50 degreeC is preferable. While the reaction time varies depending on the solvent and raw materials used, it is generally 0.5 to 24 hours.
Method G:
[0066]
Embedded image
In the general formula (3), R 8 When N is an N-arylaminocarbonyl group, it can be produced by reacting compound (3A) with aryl isocyanate (16) (wherein Ar represents an aryl group) in a solvent. In this reaction, ethers such as tetrahydrofuran, halogenated hydrocarbons such as dichloromethane and chloroform, aprotic polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide, and the like can be used as the solvent. About reaction temperature, 0-50 degreeC is preferable. While the reaction time varies depending on the solvent and raw materials used, it is generally 0.5 to 24 hours.
[0068]
The present invention also relates to a plant disease control agent comprising a 2-chloro-6-hydroxyisonicotinic acid derivative represented by the general formulas (1) to (3) as an active ingredient. The plant disease control agent of the present invention can be applied to various plant disease control by phytopathogenic viruses, bacteria, and filamentous fungi, and exhibits an excellent effect particularly on rice blast, which is the main disease of rice.
[0069]
This drug can be used alone as an active ingredient, but usually solid and liquid carriers used in agrochemical formulations, as well as dispersants, diluents, emulsifiers, spreading agents, thickeners, etc. It can be mixed with an auxiliary agent and formulated into dosage forms such as wettable powders, liquids, oils, powders, granules, sols (flowables) and the like.
[0070]
Examples of solid and liquid carriers include talc, clay, bentonite, kaolin, diatomaceous earth, montmorillonite, mica, vermiculite, gypsum, calcium carbonate, white carbon, wood flour, starch, alumina, silicate, sugar polymer, wax , Water, alcohols (methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, ethylene glycol, benzyl alcohol, etc.), petroleum fractions (petroleum ether, kerosene, solvent naphtha, etc.), aliphatic Or alicyclic hydrocarbons (n-hexane, cyclohexane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, chlorobenzene, cumene, methylnaphthalene, etc.), halogenated hydrocarbons (chloroform, dichloromethane, etc.) , Ethers (isopropyl ether, ethylene oxide, tetrahydrofuran, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, etc.), esters (ethyl acetate, butyl acetate, ethylene glycol acetate, amyl acetate, etc.), acid amides (Dimethylformamide, dimethylacetanilide, etc.), nitriles (acetonitrile, propionitrile, acrylonitrile, etc.), sulfoxides (dimethylsulfoxide, etc.), alcohol ethers (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.), etc. .
[0071]
Examples of auxiliary agents include nonionic surfactants (polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkyl phenyl ether, polyoxyethylene sorbitan alkyl ester, sorbitan alkyl ester, etc.), anionic surfactant Agents (alkylbenzene sulfonate, alkylsulfosuccinate, polyoxyethylene alkylsulfate, arylsulfonate, etc.), cationic surfactants (alkylamines, polyoxyethylene alkylamines, quaternary ammonium salts, etc.), Amphoteric surfactants (alkylaminoethylglycine, alkyldimethylbetaine, etc.), polyvinyl alcohol, hydroxypropylcellulose, carboxymethylcellulose, gum arabic, traga Togamu, xanthan gum, polyvinyl acetate, gelatin, casein, sodium alginate, and the like.
[0072]
Furthermore, this medicine can be used by mixing with various agricultural and horticultural fungicides, herbicides, plant growth regulators, pesticides such as insecticides and acaricides, fertilizers and the like.
The active ingredient content in this drug varies depending on the preparation form, application method, and other conditions. Usually, it is 0.5 to 95% (weight), preferably 2 to 70% (weight). Application methods of this drug include plant application (stem and foliage application), plant application to growing soil (soil application), paddy water application (water surface application), seed application (seed treatment), etc. It is. The application amount of this drug varies depending on the applied plant, the applied disease, etc., but in the case of foliage spraying, a solution having an active ingredient concentration of 1 to 10000 ppm, preferably 10 to 1000 ppm, is applied at 50 to 300 l per 10 ares. Preferably, in the case of soil application and water surface application, it is preferable to apply 0.1 to 5000 g, particularly preferably 1 to 1000 g per 10 ares in terms of the active ingredient amount. In the case of seed treatment, it is preferable to apply 0.001 to 50 g of an active ingredient per 1 kg of seed.
[0073]
【Example】
Next, the present invention will be described with reference to Production Examples, Formulation Examples, and Test Examples, but the present invention is not limited only to these Examples.
[0074]
(Production Example 1) Compound No. Synthesis of (1-17)
In 50 ml of tetrahydrofuran, 6.33 g of 4-methoxybenzyl alcohol was dissolved, 1.75 g of sodium hydride (60% oil suspension) was added, and the mixture was stirred at room temperature for 30 minutes. While this solution was cooled, a tetrahydrofuran solution of 4.0 g of 2,6-dichloroisonicotinic acid was added and heated to reflux for 3 hours. The reaction mixture was cooled and concentrated under reduced pressure, water was added to the residue, and the mixture was extracted with ether. The aqueous layer was acidified with concentrated hydrochloric acid and extracted with chloroform. The chloroform layer was washed with water and dried over anhydrous sodium sulfate. The chloroform layer was concentrated under reduced pressure, and the resulting residue was dissolved in 100 ml of 5% NaOH aqueous solution, and a small amount of chloroform was added to precipitate a carboxylate. The precipitate was filtered off and washed with ether. The sodium salt of (1-17) was obtained. This was dissolved in 100 ml of 10% aqueous HCl and extracted with chloroform, and then the chloroform layer was washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The chloroform layer was concentrated under reduced pressure. 3.6 g of (1-17) was obtained as a powder.
60MHz- 1 1 H-NMR (internal standard TMS): Shown in Table 4.
[0075]
(Production Example 2) Compound No. Synthesis of (1-21)
Compound No. 1 was added to 10 ml of tetrahydrofuran. (1-17) 0.50 g was dissolved, and 0.34 ml of pyridine was added. The solution was cooled, 0.15 ml of thionyl chloride dissolved in 3 ml of tetrahydrofuran was added dropwise, and the mixture was stirred at room temperature for 10 minutes. The solution was cooled, and a solution prepared by dissolving 0.24 g of 3-phenyl-1-propanol and 0.71 ml of triethylamine in 5 ml of tetrahydrofuran was added dropwise. The reaction mixture was stirred at room temperature overnight, chloroform was added, and the mixture was washed successively with diluted hydrochloric acid, water, saturated aqueous sodium hydrogen carbonate, and saturated brine, and dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (hexane / ethyl acetate = 5/1). (1-21) was obtained.
60MHz- 1 1 H-NMR (internal standard TMS): Shown in Table 4.
[0076]
(Production Example 3) Compound No. Synthesis of (1-19)
Compound No. (1-17) 0.20 g was dissolved in N, N-dimethylformamide (7 ml), triethylamine (0.13 ml) and chloroacetonitrile (62 mg) were successively added, and the mixture was stirred at room temperature for 1 day and at 50 ° C. for 7 hours. The reaction solution was concentrated under reduced pressure, the residue was dissolved in chloroform, washed successively with dilute hydrochloric acid, water, saturated aqueous sodium hydrogen carbonate, and saturated brine, and dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (benzene / ethyl acetate = 20/1). (1-19) 0.19 g was obtained.
60MHz- 1 1 H-NMR (internal standard TMS), melting point: Shown in Table 4.
[0077]
(Production Example 4) Compound No. Synthesis of (1-31)
0.95 g of 2-chloro-6-hydroxyisonicotinic acid was dissolved in 5 ml of tetrahydrofuran, 1.11 g of triethylamine and 1.05 g of p-toluenesulfonyl chloride were added, and the mixture was stirred at room temperature for 7 hours. The reaction mixture was concentrated under reduced pressure, saturated aqueous sodium hydrogen carbonate and benzene were added to the residue and the phases were separated, and the aqueous layer was acidified with hydrochloric acid and extracted with benzene.
The benzene layer was dried over sodium sulfate and then concentrated, benzene was added to the residue, the insoluble matter was removed by filtration, the filtrate was concentrated, and the compound no. 0.73 g of (1-31) was obtained.
60MHz- 1 1 H-NMR (internal standard TMS), melting point: Shown in Table 4.
[0078]
(Production Example 5) Compound No. Synthesis of (2-22)
10.0 g of 2-chloro-6-hydroxyisonicotinic acid was dissolved in 15 g of N, N-dimethylformamide, and 15 ml of thionyl chloride was added dropwise at room temperature. After the mixture was stirred at 60 ° C. for 2 hours, thionyl chloride was distilled off under reduced pressure to obtain an N, N-dimethylformamide solution of 2-chloro-6-hydroxyisonicotinic acid chloride. 10 ml of triethylamine, 1.0 g of p-trifluoromethylbenzylamine and 2.9 g of an acid chloride solution were dissolved in 15 ml of tetrahydrofuran and stirred at room temperature for 7 hours. The reaction mixture was poured into ice-dilute hydrochloric acid and extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, and dried over sodium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (chloroform / methanol = 5/1). (2-22) 0.94 g was obtained as crystals.
Mass spectrum, melting point: Shown in Table 4.
[0079]
(Production Example 6) Compound No. (2-52) and compound no. Synthetic compound No. (2-28) (1-7) 1.0 g and 0.67 ml of pyridine were dissolved in 10 ml of tetrahydrofuran. To this solution was added dropwise a solution of 0.33 ml of thionyl chloride under ice-cooling and stirred for 15 minutes. A solution of 0.71 g of tetrahydrofuran and 1.6 ml of triethylamine was added dropwise, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was poured into ice-dilute hydrochloric acid and extracted with chloroform. The organic layer was washed successively with water, saturated aqueous sodium hydrogen carbonate, water and saturated brine, and dried over sodium sulfate. After concentration under reduced pressure, the residue was crystallized from benzene-hexane to give compound no. (2-52) 1.25 g was obtained.
60MHz- 1 1 H-NMR (internal standard TMS), melting point: Shown in Table 4.
Next, Compound No. (2-52) 0.30 g was dissolved in ethanol 15 ml + ethyl acetate 5 ml, 5% Pd-C 40 mg was added and stirred at room temperature. After confirming the completion of the reaction with tlc, the reaction solution was filtered and the filtrate was concentrated, and the residue was crystallized from chloroform-hexane to give Compound No. (2-28) 145 mg was obtained.
60MHz- 1 1 H-NMR (internal standard TMS), melting point: Shown in Table 4.
[0080]
(Production Example 7) Compound No. (3-7), Compound No. (3-10), Compound No. Synthesis of (3-4)
Compound No. (1-7) 7.0 g was dissolved in ethanol 35 ml, sulfuric acid 0.5 ml was added, and the mixture was refluxed for 7 hours. After allowing to cool, the mixture was concentrated, and the residue was purified by silica gel column chromatography (benzene). (1-9) 4.9 g was obtained.
60MHz- 1 1 H-NMR (internal standard TMS): Shown in Table 4.
Next, Compound No. 1.1 g of (1-9) was dissolved in 15 ml of ethanol, 0.26 g of anhydrous hydrazine was added, and the mixture was refluxed for 20 hours. The reaction solution was concentrated, and the residue was purified by silica gel column chromatography (benzene / hexane = 1/1). (3-7) 0.86 g was obtained.
60MHz- 1 1 H-NMR (internal standard TMS): Shown in Table 4.
Next, Compound No. (3-7) 0.60 g was dissolved in 5 ml of pyridine, 0.44 g of 4-nitrobenzoic acid chloride was added, and the mixture was stirred overnight at room temperature. The reaction solution was poured into 10% aqueous hydrochloric acid, and the resulting precipitate was filtered off, washed with water and chloroform, dried, recrystallized from ethanol, and then compound no. (3-10) 0.42 g was obtained.
60MHz- 1 1 H-NMR (internal standard TMS): Shown in Table 4.
Next, Compound No. (3-10) 0.40 g was dissolved in ethanol-tetrahydrofuran, 90% of 10% Pd-C was added, and the mixture was stirred at room temperature. The disappearance of the raw material was confirmed by tlc, and the reaction solution was concentrated to give compound no. (3-4) was obtained.
60MHz- 1 1 H-NMR (internal standard TMS): Shown in Table 4.
[0081]
(Production Example 8) Compound No. Synthesis of (3-12)
Compound No. (3-7) 0.35 g was dissolved in 5 ml of N, N-dimethylformamide, 0.18 g of phenyl isocyanate was added, and the mixture was stirred at room temperature for 3 hours. The reaction solution was concentrated, and the residue was dissolved in chloroform-tetrahydrofuran and washed with water.
The organic layer was dried over sodium sulfate and concentrated, and the residue was crystallized from benzene. The crystals were recrystallized from benzene-hexane to give compound no. (3-12) 0.31 g was obtained.
60MHz- 1 1 H-NMR (internal standard TMS), melting point: Shown in Table 4.
[0082]
(Production Example 9)
In the same manner as in any one of Production Examples 1 to 8, each compound shown in Table 4 was synthesized. The physical property values of each compound are shown in Table 4.
[0083]
[Table 14]
[Table 15]
[Table 16]
[Table 17]
[Table 18]
[Table 19]
[Table 20]
[Table 21]
[Table 22]
[Table 23]
[Table 24]
[Table 25]
(Formulation Example 1) Powder
2 parts by weight of 2-chloro-6-hydroxyisonicotinic acid derivative shown in Table 4 was mixed and ground with 98 parts by weight of clay to prepare powder.
[0096]
(Formulation example 2) wettable powder
20 parts by weight of 2-chloro-6-hydroxyisonicotinic acid derivative shown in Table 4 was mixed and ground with 68 parts by weight of clay, 8 parts by weight of white carbon and 4 parts by weight of polyoxyethylene nonylphenyl ether, respectively, did.
[0097]
(Formulation example 3) Granules
5 parts by weight of 2-chloro-6-hydroxyisonicotinic acid derivative shown in Table 4 was mixed and ground with 90 parts by weight of an equal mixture of bentonite and talc and 5 parts by weight of sodium alkylbenzenesulfonate, and formed into granules.
[0098]
(Test Example 1) Rice blast control test (soil application)
Each medicinal solution prepared in the same manner as the wettable powder described in (Formulation Example 2) was applied to each of the two-leaved rice (variety: Aichi Asahi) bred in a pot (diameter 6 cm, height 5.5 cm). (The active ingredient amount is 3 mg / pot). 14 days later, a spore suspension of rice blast fungus (Pyricularia oryzae) was spray-inoculated, placed in a humid room at 25 ° C. for 24 hours, then caused to develop disease in a greenhouse, and 10 days after inoculation of the spore suspension, The control value was calculated from the following formula. As a control drug, 2,6-dichloroisonicotinic acid was also tested in the same manner. The results are shown in Table 5.
[0099]
[Expression 1]
[Table 26]
【The invention's effect】
The plant disease control agent comprising the 2-chloro-6-hydroxyisonicotinic acid derivative according to the present invention as an active ingredient is used for various plant diseases caused by phytopathogenic viruses, bacteria and filamentous fungi, particularly rice blast which is a major disease of rice. It has excellent control effects and is free from chemical damage.
Claims (14)
で示される２−クロロ−６−ヒドロキシイソニコチン酸誘導体（ただし、２−クロロ−６−プロペニルオキシ−４−ピリジンカルボン酸を除く。）。General formula (1)
2-chloro-6-hydroxyisonicotinic acid derivatives (excluding 2-chloro-6-propenyloxy-4-pyridinecarboxylic acid) .
で示される２−クロロ−６−ヒドロキシイソニコチン酸誘導体。General formula (2)
A 2-chloro-6-hydroxyisonicotinic acid derivative represented by
で示される２−クロロ−６−ヒドロキシイソニコチン酸誘導体。General formula (3)
A 2-chloro-6-hydroxyisonicotinic acid derivative represented by
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01739595A JP3877789B2 (en) | 1995-02-06 | 1995-02-06 | 2-Chloro-6-hydroxyisonicotinic acid derivative and plant disease control agent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01739595A JP3877789B2 (en) | 1995-02-06 | 1995-02-06 | 2-Chloro-6-hydroxyisonicotinic acid derivative and plant disease control agent |
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| Publication Number | Publication Date |
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| JPH08208613A JPH08208613A (en) | 1996-08-13 |
| JP3877789B2 true JP3877789B2 (en) | 2007-02-07 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB9919588D0 (en) * | 1999-08-18 | 1999-10-20 | Hoechst Schering Agrevo Gmbh | Fungicidal compounds |
| WO2003043578A2 (en) * | 2001-11-19 | 2003-05-30 | Iconix Pharmaceuticals, Inc. | Modulators of rho c activity |
| WO2009083553A1 (en) * | 2007-12-31 | 2009-07-09 | Rheoscience A/S | Azine compounds as glucokinase activators |
| GB201913110D0 (en) * | 2019-09-11 | 2019-10-23 | Benevolentai Bio Ltd | New compounds and methods |
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