JPS63264478A - Pyridylpyrimidine derivative, production thereof and plant blight controller comprising said derivative as active ingredient - Google Patents
Pyridylpyrimidine derivative, production thereof and plant blight controller comprising said derivative as active ingredientInfo
- Publication number
- JPS63264478A JPS63264478A JP29904487A JP29904487A JPS63264478A JP S63264478 A JPS63264478 A JP S63264478A JP 29904487 A JP29904487 A JP 29904487A JP 29904487 A JP29904487 A JP 29904487A JP S63264478 A JPS63264478 A JP S63264478A
- Authority
- JP
- Japan
- Prior art keywords
- lower alkyl
- group
- alkyl group
- general formula
- formula
- 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.)
- Granted
Links
- YJVKLLJCUMQBHN-UHFFFAOYSA-N 2-pyridin-2-ylpyrimidine Chemical class N1=CC=CC=C1C1=NC=CC=N1 YJVKLLJCUMQBHN-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- 239000004480 active ingredient Substances 0.000 title claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 35
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 15
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 15
- 150000005694 halopyrimidines Chemical class 0.000 claims abstract description 14
- 125000005843 halogen group Chemical group 0.000 claims abstract description 12
- 150000001340 alkali metals Chemical group 0.000 claims abstract description 8
- 125000003302 alkenyloxy group Chemical group 0.000 claims abstract description 8
- 125000004414 alkyl thio group Chemical group 0.000 claims abstract description 7
- 125000001188 haloalkyl group Chemical group 0.000 claims abstract description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- -1 malonic acid diester Chemical class 0.000 claims description 34
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 21
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 claims description 18
- 201000010099 disease Diseases 0.000 claims description 17
- 239000002585 base Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- KNXKVYCVGXFLES-UHFFFAOYSA-N pyridine-2-carboximidamide Chemical class NC(=N)C1=CC=CC=N1 KNXKVYCVGXFLES-UHFFFAOYSA-N 0.000 claims description 11
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 238000006114 decarboxylation reaction Methods 0.000 claims description 3
- 150000002081 enamines Chemical class 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 49
- 241000196324 Embryophyta Species 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 3
- 229910052736 halogen Inorganic materials 0.000 abstract 2
- 241000371644 Curvularia ravenelii Species 0.000 abstract 1
- 241001617088 Thanatephorus sasakii Species 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 62
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 43
- 239000000203 mixture Substances 0.000 description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
- 239000000243 solution Substances 0.000 description 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 238000009472 formulation Methods 0.000 description 20
- 239000002904 solvent Substances 0.000 description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 17
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 241000209140 Triticum Species 0.000 description 13
- 235000021307 Triticum Nutrition 0.000 description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 13
- 239000000725 suspension Substances 0.000 description 13
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 12
- 239000003814 drug Substances 0.000 description 11
- 238000005507 spraying Methods 0.000 description 11
- 240000007594 Oryza sativa Species 0.000 description 10
- 235000007164 Oryza sativa Nutrition 0.000 description 10
- 229940079593 drug Drugs 0.000 description 10
- 229920003023 plastic Polymers 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 235000009566 rice Nutrition 0.000 description 10
- 238000011282 treatment Methods 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 240000008067 Cucumis sativus Species 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 150000001298 alcohols Chemical class 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 241000221785 Erysiphales Species 0.000 description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 description 7
- VTGOHKSTWXHQJK-UHFFFAOYSA-N pyrimidin-2-ol Chemical compound OC1=NC=CC=N1 VTGOHKSTWXHQJK-UHFFFAOYSA-N 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- 238000011081 inoculation Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 230000003449 preventive effect Effects 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 5
- 241000233866 Fungi Species 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 5
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N Vilsmeier-Haack reagent Natural products CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 150000004703 alkoxides Chemical class 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 5
- 239000004927 clay Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 150000002463 imidates Chemical class 0.000 description 5
- 230000000361 pesticidal effect Effects 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
- 230000001225 therapeutic effect Effects 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000007810 chemical reaction solvent Substances 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- SUBJHSREKVAVAR-UHFFFAOYSA-N sodium;methanol;methanolate Chemical compound [Na+].OC.[O-]C SUBJHSREKVAVAR-UHFFFAOYSA-N 0.000 description 4
- BNIMQGKKURUQOH-UHFFFAOYSA-N 6-methylpyridine-2-carboximidamide;hydrochloride Chemical compound Cl.CC1=CC=CC(C(N)=N)=N1 BNIMQGKKURUQOH-UHFFFAOYSA-N 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 3
- 241001465180 Botrytis Species 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 244000081841 Malus domestica Species 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 206010039509 Scab Diseases 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 230000000887 hydrating effect Effects 0.000 description 3
- 150000007529 inorganic bases Chemical class 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000007530 organic bases Chemical class 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 239000012312 sodium hydride Substances 0.000 description 3
- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- 238000002255 vaccination Methods 0.000 description 3
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- FFNVQNRYTPFDDP-UHFFFAOYSA-N 2-cyanopyridine Chemical class N#CC1=CC=CC=N1 FFNVQNRYTPFDDP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 235000009849 Cucumis sativus Nutrition 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 241000220225 Malus Species 0.000 description 2
- 206010027146 Melanoderma Diseases 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 241000579741 Sphaerotheca <fungi> Species 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 241000317942 Venturia <ichneumonid wasp> Species 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000001580 bacterial effect Effects 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
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000417 fungicide Substances 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 230000002140 halogenating effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Chemical class OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 239000004563 wettable powder Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- FUJZJBCWPIOHHN-QHHAFSJGSA-N (e)-1-phenylbut-2-en-1-one Chemical compound C\C=C\C(=O)C1=CC=CC=C1 FUJZJBCWPIOHHN-QHHAFSJGSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-N 2,2-diethylpropanedioic acid Chemical compound CCC(CC)(C(O)=O)C(O)=O LTMRRSWNXVJMBA-UHFFFAOYSA-N 0.000 description 1
- VUOAVXKLOHHZHC-UHFFFAOYSA-N 2-(6-methylpyridin-2-yl)pyrimidine Chemical compound CC1=CC=CC(C=2N=CC=CN=2)=N1 VUOAVXKLOHHZHC-UHFFFAOYSA-N 0.000 description 1
- QRBLKGHRWFGINE-UGWAGOLRSA-N 2-[2-[2-[[2-[[4-[[2-[[6-amino-2-[3-amino-1-[(2,3-diamino-3-oxopropyl)amino]-3-oxopropyl]-5-methylpyrimidine-4-carbonyl]amino]-3-[(2r,3s,4s,5s,6s)-3-[(2s,3r,4r,5s)-4-carbamoyl-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy-4,5-dihydroxy-6-(hydroxymethyl)- Chemical compound N=1C(C=2SC=C(N=2)C(N)=O)CSC=1CCNC(=O)C(C(C)=O)NC(=O)C(C)C(O)C(C)NC(=O)C(C(O[C@H]1[C@@]([C@@H](O)[C@H](O)[C@H](CO)O1)(C)O[C@H]1[C@@H]([C@](O)([C@@H](O)C(CO)O1)C(N)=O)O)C=1NC=NC=1)NC(=O)C1=NC(C(CC(N)=O)NCC(N)C(N)=O)=NC(N)=C1C QRBLKGHRWFGINE-UGWAGOLRSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical group C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- JVKRKMWZYMKVTQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical group C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JVKRKMWZYMKVTQ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- LLCYXFYLGPOKQO-UHFFFAOYSA-N 2-methyl-6-pyridin-2-ylpyridine Chemical compound CC1=CC=CC(C=2N=CC=CC=2)=N1 LLCYXFYLGPOKQO-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical class COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- WVGFLFANRMFICF-UHFFFAOYSA-N 4-chloro-6-(2-methylphenyl)-2-(6-methylpyridin-2-yl)pyrimidine Chemical compound CC1=CC=CC(C=2N=C(C=C(Cl)N=2)C=2C(=CC=CC=2)C)=N1 WVGFLFANRMFICF-UHFFFAOYSA-N 0.000 description 1
- QZDHLMKDPJYQPG-UHFFFAOYSA-N 4-methyl-2-pyridin-2-ylpyrimidine Chemical compound CC1=CC=NC(C=2N=CC=CC=2)=N1 QZDHLMKDPJYQPG-UHFFFAOYSA-N 0.000 description 1
- IZWXAUDXBDYDFE-UHFFFAOYSA-N 4-phenyl-2-pyridin-2-ylpyrimidine Chemical compound C1=CC=CC=C1C1=CC=NC(C=2N=CC=CC=2)=N1 IZWXAUDXBDYDFE-UHFFFAOYSA-N 0.000 description 1
- UHPMCKVQTMMPCG-UHFFFAOYSA-N 5,8-dihydroxy-2-methoxy-6-methyl-7-(2-oxopropyl)naphthalene-1,4-dione Chemical compound CC1=C(CC(C)=O)C(O)=C2C(=O)C(OC)=CC(=O)C2=C1O UHPMCKVQTMMPCG-UHFFFAOYSA-N 0.000 description 1
- CMADFEQMYFNYCF-UHFFFAOYSA-N 6-methylpyridine-2-carbonitrile Chemical compound CC1=CC=CC(C#N)=N1 CMADFEQMYFNYCF-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 244000291564 Allium cepa Species 0.000 description 1
- 235000002732 Allium cepa var. cepa Nutrition 0.000 description 1
- 241000223600 Alternaria Species 0.000 description 1
- 241000412366 Alternaria mali Species 0.000 description 1
- 244000144730 Amygdalus persica Species 0.000 description 1
- 235000003276 Apios tuberosa Nutrition 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000010744 Arachis villosulicarpa Nutrition 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000219310 Beta vulgaris subsp. vulgaris Species 0.000 description 1
- 235000005039 Brassica rapa var. dichotoma Nutrition 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
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- 235000009496 Juglans regia Nutrition 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
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- 241001330975 Magnaporthe oryzae Species 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 101100289255 Mycolicibacterium smegmatis (strain ATCC 700084 / mc(2)155) lnt gene Proteins 0.000 description 1
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- 101100208473 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) lcm-2 gene Proteins 0.000 description 1
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- 229910019142 PO4 Inorganic materials 0.000 description 1
- 101150087495 PPM2 gene Proteins 0.000 description 1
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- 108010035235 Phleomycins Proteins 0.000 description 1
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- 235000003434 Sesamum indicum Nutrition 0.000 description 1
- 244000040738 Sesamum orientale Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 244000061458 Solanum melongena Species 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 235000021536 Sugar beet Nutrition 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 241000270708 Testudinidae Species 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 1
- KZNMRPQBBZBTSW-UHFFFAOYSA-N [Au]=O Chemical compound [Au]=O KZNMRPQBBZBTSW-UHFFFAOYSA-N 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 206010000496 acne Diseases 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 244000130745 brown sarson Species 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- OOCMUZJPDXYRFD-UHFFFAOYSA-L calcium;2-dodecylbenzenesulfonate Chemical compound [Ca+2].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O OOCMUZJPDXYRFD-UHFFFAOYSA-L 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 235000020971 citrus fruits Nutrition 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- BNIXMGBGYGZYND-UHFFFAOYSA-N ethyl 2,2-dimethyl-3-oxo-3-phenylpropanoate Chemical compound CCOC(=O)C(C)(C)C(=O)C1=CC=CC=C1 BNIXMGBGYGZYND-UHFFFAOYSA-N 0.000 description 1
- 210000000744 eyelid Anatomy 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001922 gold oxide Inorganic materials 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 230000000968 intestinal effect Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- WSBUTZAETFXDTQ-UHFFFAOYSA-N methyl 6-methylpyridine-2-carboximidate Chemical compound COC(=N)C1=CC=CC(C)=N1 WSBUTZAETFXDTQ-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- 239000005645 nematicide Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- UXCDUFKZSUBXGM-UHFFFAOYSA-N phosphoric tribromide Chemical compound BrP(Br)(Br)=O UXCDUFKZSUBXGM-UHFFFAOYSA-N 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
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- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
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- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- SSOLNOMRVKKSON-UHFFFAOYSA-N proguanil Chemical compound CC(C)\N=C(/N)N=C(N)NC1=CC=C(Cl)C=C1 SSOLNOMRVKKSON-UHFFFAOYSA-N 0.000 description 1
- 230000000069 prophylactic effect Effects 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 125000004436 sodium atom Chemical group 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
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- 239000007921 spray Substances 0.000 description 1
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- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
Landscapes
- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は新規なピリジルピリミジン誘導体、その製造法
およびそれを有効成分とする植物病害防除剤に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel pyridylpyrimidine derivative, a method for producing the same, and a plant disease control agent containing the same as an active ingredient.
〈従来の技術〉
これまで、ピリジルピリミジン誘導体としては、例えば
4−メチル−2−(2−ピリジル)ピリミジン、4−フ
ェニル−2−(2−ピリジル)ピリミジンの合成例がJ
* Org a Cherna、 82 。<Prior art> As pyridylpyrimidine derivatives, examples of synthesis of 4-methyl-2-(2-pyridyl)pyrimidine and 4-phenyl-2-(2-pyridyl)pyrimidine have been reported in J.
*Orga Cherna, 82.
1591(1967)に記載されており、N。1591 (1967), N.
N−ジメチル−2−(6−メチル−2−ピリジル−ピリ
ミジン−4−イルチオ)エチルアミンがフレオマイシン
(医薬)の増強剤として用いられることがAu5L J
、 Chem、 、 85 、 1208(1982
)に記載されている。Au5L J that N-dimethyl-2-(6-methyl-2-pyridyl-pyrimidin-4-ylthio)ethylamine is used as a potentiator for phleomycin (medicine).
, Chem, , 85, 1208 (1982
)It is described in.
しかしながら、上記誘導体が殺菌活性を示すことは何ら
知られていない。However, it is not known that the above derivatives exhibit bactericidal activity.
〈発明が解決しようとする問題点〉
本発明は、多くの植物病害に対して予防的あるいは治療
的に防除効力を有する化合物の開発を目的とするもので
あろう
〈問題点を解決するための手段〉
本発明者らは、上記目的を達成するために、鋭意検討を
重ねた結果、一般式
〔式中、亀は低級アルキル基を表わし、R2およびR3
は同一または相異なり水素原子またはメチル基を表わし
、nは0〜5の整数を表わし、R4は同一または相異な
り、低級アルキル基、低級アルコキシ基、低殺ハロアル
キル基またはハロゲン原子を表わし、融は水素原子また
は低級アルキル基を表わし、へは水素原子、低級アルキ
ル基、低級アルコキシ基、低級アルケニルオキシ基また
は低級アルキルチオ基を表わすウ 〕
で示されるピルジルピリミジン誘導体(以下、本発明化
合物を記す。)が、優れた殺菌活性を有することを見出
し、本発明に至った。<Problems to be solved by the invention> The purpose of the present invention is to develop compounds that have prophylactic or therapeutic effects on many plant diseases. Means> In order to achieve the above object, the present inventors have made intensive studies and found that the general formula [wherein the tortoise represents a lower alkyl group, R2 and R3
are the same or different and represent a hydrogen atom or a methyl group, n represents an integer of 0 to 5, R4 is the same or different and represents a lower alkyl group, a lower alkoxy group, a low haloalkyl group, or a halogen atom; represents a hydrogen atom or a lower alkyl group, and represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower alkenyloxy group, or a lower alkylthio group.] Pyrzylpyrimidine derivatives (hereinafter referred to as compounds of the present invention). ) was found to have excellent bactericidal activity, leading to the present invention.
本発明化合物によって防除できる植物病害としては、イ
ネのいもち病(Pyricularia oryzae
)、ごま葉枯病(Cochliobolus m1ya
beanus)、紋枯病(Rhizoctonia 5
olani)、ムギ類のうどんこ病(Puccinia
striiformis、P、graminisXP
*rJ(1−ita P、hordei)、アイスポッ
ト(Pseudocercos−porella he
rpotrichoides)、雲形病(Rhynch
osporium 5ecalis)、葉枯病(Sep
toria tritici)%ふ枯病(Leptos
phaeria nodorum)、カンキツの黒点病
(Diaporthe citri) 、そうか病(E
lsinoefawcetti)、リンゴのうどんこ病
(Podosphaeraleucotricha)、
斑点落葉病(Al ternaria mal i )
、黒星病(Venturia 1naequalis)
、ナシの黒星病(Venturia nashicol
a)、黒斑病(Al ternariakikuchi
ana)、モモの灰層病(Sllerotinia c
i −nerea)、ブドウの黒とう病(Elsino
e ampelina)、晩腐病(Glomorell
a cingulata)、うどんこ病(Uncinv
la necator)、ウリ類の炭そ病(Coll−
etotrichum lagenarium)、うど
んこ病(Spha−erotheca fuligin
ea)、 ) vトの輪紋病(Al ter−nari
a 5olani\疫病(Phytophthora
1nfestans)、ナスの褐紋病(Phomops
i s vexans )、アブラナ科野菜の黒斑病
(Alternbria japonica)、白斑病
(Gercosporella brassicae)
、ネギのさび病(Puccinia allii)、ダ
イズの紫斑病(Cercosporakikuchi
i )、黒とう病(Elsinoe glycines
)、インゲンの炭そ病(Colletotrichum
lindemu−thianum) 、ラッカセイの
黒渋病(Mycosphaere−11a perso
natum)、褐斑病(Cercospora ara
chi −dicola)、エントウのうどんこ病(E
rys 1phep i s i )、ジャガイモの夏
疫病(Alternaria 5olani)、テンサ
イの褐斑病(Cercospora beticola
)、バラの黒星病(Diplocarpon rosa
e)、うどんこ病(Sphaerotheca pan
nosa)、種々の作物の灰色かび病(Botryti
s cinerea)、菌核病(Scler−otin
ia sclerotiorum)等があげられる。Plant diseases that can be controlled by the compounds of the present invention include rice blast (Pyricularia oryzae).
), sesame leaf blight (Cochliobolus m1ya
beanus), sheath blight (Rhizoctonia 5)
olani), powdery mildew of wheat (Puccinia
striiformis, P. graminis XP
*rJ (1-ita P, hordei), eye spot (Pseudocercos-porella he
rpotrichoides), Rhynch
osporium 5ecalis), leaf blight (Sep.
toria tritici)% Blight (Leptos
phaeria nodorum), citrus black spot (Diaporthe citri), scab disease (E
lsinoefawcetti), apple powdery mildew (Podosphaeraleucotricha),
Leaf spot disease (Alternaria mali)
, Venturia 1naequalis
, Venturia nashicol
a), Al ternariakikuchi
ana), peach gray layer disease (Sllerotinia c
i-nerea), grape blackhead (Elsino
e ampelina), late rot disease (Glomorell)
a cingulata), powdery mildew (Uncinv
la necator), cucurbit anthracnose (Coll-
etotrichum lagenarium), powdery mildew (Spha-erotheca fuligin)
ea), ) vt Alter-nari
a 5olani\plague (Phytophthora
1nfestans), eggplant brown spot disease (Phomops
i s vexans), black spot of cruciferous vegetables (Alternbria japonica), white spot (Gercosporella brassicae)
, green onion rust (Puccinia allii), soybean purpura (Cercosporakikuchi)
i), Elsinoe glycines
), kidney bean anthracnose (Colletotrichum
lindemu-thianum), groundnut black astringent disease (Mycosphaere-11a perso
natum), Cercospora ara
chi-dicola), powdery mildew of pea (E.
rys 1phepis i), summer blight of potato (Alternaria 5olani), brown spot of sugar beet (Cercospora beticola)
), Diplocarpon rosa
e), powdery mildew (Sphaerotheca pan)
nosa), botrytis (Botryti) of various crops
S cinerea), Sclerotinia
ia sclerotiorum).
次に本発明化合物の製造法について詳しく説明するっ
□
本発明化合物のうち一般式
〔式中、R,、R2、Rs、IL4、R5およびnは前
記と同じ意味を表わし、λiは水素原子を表わすっ 〕
で示されるピリジルピリミジン誘導体は、一般式
〔式中、K1、R2、R3、R4、R5およびnは前記
と同じ意味を表わし、Xはハロゲン原子を表わす。〕
で示されるハロピリミジン誘導体を還元するこロピリミ
ジン誘導体を溶媒中、触媒存在下、水素ガスと常圧あ名
いは、加圧下、室温〜50’C!。Next, the method for producing the compound of the present invention will be explained in detail.
□ Among the compounds of the present invention, pyridylpyrimidine derivatives represented by the general formula [wherein R,, R2, Rs, IL4, R5 and n represent the same meanings as above, and λi represents a hydrogen atom] are represented by the general formula [In the formula, K1, R2, R3, R4, R5 and n represent the same meanings as above, and X represents a halogen atom. ] The halopyrimidine derivative represented by is reduced in a solvent in the presence of a catalyst with hydrogen gas at normal pressure under pressure at room temperature to 50'C! .
0、5〜8時間接触させることにより上記一般式〔曹〕
で示されるピリジルピリミジン誘導体を得ることができ
る。By contacting for 0.5 to 8 hours, the above general formula [sulfur]
A pyridylpyrimidine derivative represented by can be obtained.
上記反応に用いうる溶媒としては、メタノール、エタノ
ール等の低級アルコール類、ジオキサン、酢酸エチル等
のエステル類、トルエン等の芳香族炭化水素類、水およ
びそれらの混合物等があげられる。触媒としてはパラジ
ウム炭素等があげられ、水素圧は1〜8気圧が好ましい
。Examples of the solvent that can be used in the above reaction include lower alcohols such as methanol and ethanol, esters such as dioxane and ethyl acetate, aromatic hydrocarbons such as toluene, water, and mixtures thereof. Examples of the catalyst include palladium on carbon, and the hydrogen pressure is preferably 1 to 8 atmospheres.
また好ましくは、脱ハロゲン化水素剤の存在下で反応を
行なうつ脱ハロゲン化水素剤としてハ、例えばアンモニ
ア、水酸化ナトリウム、炭酸ナトリウム、酢酸ナトリウ
ム等の塩基あるいはDowex 1■(ダウケミカル社
登録商標)等の塩基性イオン交換樹脂があげられる。Preferably, the reaction is carried out in the presence of a dehydrohalogenating agent, such as a base such as ammonia, sodium hydroxide, sodium carbonate, sodium acetate, etc., or Dowex 1 (registered trademark of The Dow Chemical Company). ) and other basic ion exchange resins.
反応終了後の反応液は、触媒を濾過にて除き、減圧濃縮
する。次いで、脱ハロゲン化水素剤を使用しない場合は
、炭酸ナトリウム水溶液等の無口塩基水溶液を加えた後
、有機溶媒抽出し、脱ハロゲン化水素剤を使用した場合
は、水を加えた後、有機溶媒抽出を行うつその後、減圧
濃縮等の通常の後処理を行い、必要に応じ、クロマトグ
ラフィー等の操作に付すことにより目的化合物を得るこ
とができる。After the reaction is completed, the catalyst is removed from the reaction solution by filtration, and the reaction solution is concentrated under reduced pressure. Next, when a dehydrohalogenating agent is not used, an aqueous base solution such as sodium carbonate is added, followed by extraction with an organic solvent, and when a dehydrohalogenating agent is used, water is added and then an organic solvent is extracted. After the extraction, the target compound can be obtained by performing usual post-treatments such as concentration under reduced pressure and, if necessary, subjecting it to operations such as chromatography.
また本発明化合物のうち、一般式
〔式中、R1、R2、Rs、R4、R,およびnは前記
と同じ意味を表わし、R6″は低級アルコキシ基、低級
アルケニルオキシ基または低級アルキルチオ基を表わす
。〕
で示されるピリジルピリミジン誘導体は、一般式〔厘〕
で示されるハロピリミジン誘導体と一般式
%式%[
〔式中、9−6″は前記と同じ意味を表わし、Yはアル
カリ金属原子を表わす。〕
で示されるアルカリ金属誘導体とを反応させることによ
って得られる。Furthermore, among the compounds of the present invention, compounds of the general formula [wherein R1, R2, Rs, R4, R, and n represent the same meanings as above, and R6'' represents a lower alkoxy group, a lower alkenyloxy group, or a lower alkylthio group] ] The pyridylpyrimidine derivative represented by the general formula [厘]
By reacting a halopyrimidine derivative represented by the general formula % with an alkali metal derivative represented by the general formula % [[wherein 9-6'' represents the same meaning as above and Y represents an alkali metal atom]] can get.
該アルカリ金属誘導体のアルカリ金属原子としては、例
えばナトリウム、カリウム等があげられる。Examples of the alkali metal atom of the alkali metal derivative include sodium and potassium.
上記反応において標準的には、反応温度は10〜120
”Q、反応時間は10分間〜48時間であるう
また上記反応に供される試剤の量は、通常、上記一般式
〔門〕で示されるハロパリミジン誘導体1当量に対して
、一般式〔v〕で示されるアルカリ金属誘導体が1〜1
.5当量である。In the above reaction, the reaction temperature is typically 10 to 120
"Q. The reaction time is 10 minutes to 48 hours. Also, the amount of the reagent used in the above reaction is usually one equivalent of the haloparimidine derivative represented by the general formula [v] The alkali metal derivative represented by is 1 to 1
.. It is 5 equivalents.
上記反応において、反応溶媒は必ずしも必要ではないが
、一般的には溶媒の存在下に行われるっ使用しうる溶媒
としては、一般式[”V]においてR6が低級アルコキ
シ基または低級アルケニルオキシ基であるアルカリ金属
化合物の場合は、対応するアルコール、例えば、メタノ
ール、エタノール、アリルアルコール等またはジエチル
エーテル、ジオキサン、テトラヒドロフラン等のエーテ
ル類、トルエン等の芳香族炭化水素類あるいはそれらの
混合物等があげられる。In the above reaction, a reaction solvent is not necessarily required, but it is generally carried out in the presence of a solvent. Examples of solvents that can be used include those in which R6 is a lower alkoxy group or a lower alkenyloxy group in the general formula [''V]. In the case of certain alkali metal compounds, examples include corresponding alcohols such as methanol, ethanol, allyl alcohol, ethers such as diethyl ether, dioxane, and tetrahydrofuran, aromatic hydrocarbons such as toluene, or mixtures thereof.
R6″が低級アルキルチオ基であるアルカリ金属化合物
の場合は、ジエチルエーテル、ジオキサン、テトラヒド
ロフラン等のエーテル類、アセトニトリル等のニトリル
類、トルエン等の芳香族炭化水素類、水等またはそれら
の混合物等があげられる。In the case of an alkali metal compound in which R6'' is a lower alkylthio group, examples include ethers such as diethyl ether, dioxane, and tetrahydrofuran, nitrites such as acetonitrile, aromatic hydrocarbons such as toluene, water, etc., or mixtures thereof. It will be done.
反応終了後の反応液は、減圧濃縮等の通常の後処理操作
を行ない、必要に応じクロマトグラフィー、再結晶等の
操作に付することにより目的化合物を得ることができる
。After completion of the reaction, the reaction solution is subjected to usual post-treatment operations such as concentration under reduced pressure, and optionally subjected to operations such as chromatography and recrystallization to obtain the target compound.
さらに本発明化合物のうち一般式
〔式中、R1、R2、R3、k4、λ、およびnは前記
と同じ意味を表わし、視″′は低級アルキル基を表わす
う〕
で示されるピリジルピリミジン誘導体は一般式〔辺〕で
示されるハロピリミジン誘導体と一般式R,CH(CO
OR8)2C■〕
〔式中、λ7は水素原子または低級アルキル基を表わし
、−は低級アルキル基を表わすう〕で示されるマロン酸
ジエステル誘導体とを塩基の存在下反応させた後、加水
分解し、さらに脱炭酸することにより得られる。Furthermore, among the compounds of the present invention, pyridylpyrimidine derivatives represented by the general formula [wherein R1, R2, R3, k4, λ, and n represent the same meanings as above, and the symbol "' represents a lower alkyl group]" The halopyrimidine derivative represented by the general formula [side] and the general formula R, CH(CO
OR8)2C■] [In the formula, λ7 represents a hydrogen atom or a lower alkyl group, and - represents a lower alkyl group] is reacted with a malonic acid diester derivative in the presence of a base, and then hydrolyzed. , further decarboxylated.
上記一般式〔瓜〕で示されるへロビリミジン誘導体と一
般式CVM”Jで示されるマロン酸ジエステル誘導体と
の反応において、該反応に用いられる塩基としては、例
えば、水素化ナトリウム等の水素化アルカリ金属類、n
−ブチルリチウム等のアルキルリチウム類、リチウムジ
イソプロピルアミド(LDA )等のリチウムジアルキ
ルアミド類、ナトリウムメトキシド等のアルカリ金属ア
ルコキシド類、水酸化ナトリウム等の水酸化アルカリ金
属類等があげられる。In the reaction of the herobyrimidine derivative represented by the above general formula [melon] with the malonic acid diester derivative represented by the general formula CVM''J, the base used in the reaction may include, for example, an alkali metal hydride such as sodium hydride. kind, n
Examples include alkyllithiums such as -butyllithium, lithium dialkylamides such as lithium diisopropylamide (LDA), alkali metal alkoxides such as sodium methoxide, and alkali metal hydroxides such as sodium hydroxide.
上記反応において標準的には、反応温度はO〜150°
C1反応時間は80分間〜24時間であり、該反応に供
される試剤の看は、通常、上記一般式〔I〕で示される
ハロピリミジン誘導体1当量に対して、一般式αI〕で
示されるマロン酸ジエステル誘導体および塩基は夫々1
〜2当量である。In the above reaction, the reaction temperature is typically 0 to 150°.
C1 reaction time is 80 minutes to 24 hours, and the reagents used for the reaction are usually expressed by the general formula αI] per equivalent of the halopyrimidine derivative represented by the above general formula [I]. Malonic acid diester derivative and base are each 1
~2 equivalents.
上記反応において、反応溶媒は必ずしも必要ではないが
、一般的には溶媒の存在下に行なわれる。使用しうる溶
媒としては、メタノール、エタノール等の低級アルコー
ル類、アセトニトリル等のニトリル類、ジエチルエーテ
ル、テトラヒドロフラン等のエーテル類、クロロホルム
等のハロ炭化水素類、ベンゼン、トルエン等の芳香族炭
化水素類、クロロベンゼン等の八日芳香族炭化水素類、
アセトン、メチルイソブチルケトン等のケトン類、酢酸
エチル等のエステル類、ジメチルスルホキシド、スルホ
ラン等の硫黄化合物またはそれらの混合物等があげられ
る。In the above reaction, although a reaction solvent is not necessarily required, it is generally carried out in the presence of a solvent. Usable solvents include lower alcohols such as methanol and ethanol, nitriles such as acetonitrile, ethers such as diethyl ether and tetrahydrofuran, halohydrocarbons such as chloroform, aromatic hydrocarbons such as benzene and toluene, octoday aromatic hydrocarbons such as chlorobenzene,
Examples include ketones such as acetone and methyl isobutyl ketone, esters such as ethyl acetate, sulfur compounds such as dimethyl sulfoxide and sulfolane, and mixtures thereof.
次に、上記反応の終了後、これを加水分解および脱炭酸
することにより目的化合物に導びくことができるう代表
的には上記、一般式〔厘〕で示されるハロピリミジン誘
導体1当量に対して2.1〜5当鑞の塩基例えば水酸化
ナトリウム等の水酸化アルカリ金属類、または炭酸ナト
リウム等のアルカリ金属炭酸塩等の水溶液あるいはメタ
ノール、エタノール等の低級アルコールと該塩基の水溶
液との混合溶液を加えて反応温度10〜100’C,反
応時間10分間〜24時間でアルカリ加水分解反応を行
う。次いで、反応液に上記一般式〔腸〕で示されるハロ
ピリミジン誘導体1当量に対して2.5〜6当量の酸、
例えば硫酸等の無機酸または酢酸等の有機酸を加えて、
反応温度20〜150”C!、反応時間10分間〜24
時間で脱炭酸反応を行う。Next, after the completion of the above reaction, the target compound can be obtained by hydrolysis and decarboxylation. 2.1 to 5 bases For example, an aqueous solution of an alkali metal hydroxide such as sodium hydroxide, or an alkali metal carbonate such as sodium carbonate, or a mixed solution of an aqueous solution of the base and a lower alcohol such as methanol or ethanol. is added to carry out an alkali hydrolysis reaction at a reaction temperature of 10 to 100'C and a reaction time of 10 minutes to 24 hours. Next, 2.5 to 6 equivalents of acid per equivalent of the halopyrimidine derivative represented by the above general formula [intestinal] are added to the reaction solution,
For example, by adding an inorganic acid such as sulfuric acid or an organic acid such as acetic acid,
Reaction temperature 20-150"C!, reaction time 10 minutes-24
The decarboxylation reaction takes place over a period of time.
反応終了後は、水酸化ナトリウム等の水酸化アルカリ金
属類、水酸化カルシウム等の水酸化アルカリ土類金属類
、炭酸ナトリウム等のアルカリ金属炭酸塩、重曹等のア
ルカリ金属炭酸水素塩、トリエチルアミン等の有機塩基
等で反応液を中性にした後、減圧濃縮、抽出等の通常の
後処理を行い、必要に応じて再結晶、カラムクロマトグ
ラフィー等の操作に付すことにより目的化合物を得るこ
とができる。After the reaction is complete, alkali metal hydroxides such as sodium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, alkali metal carbonates such as sodium carbonate, alkali metal hydrogen carbonates such as baking soda, triethylamine, etc. After neutralizing the reaction solution with an organic base, etc., the desired compound can be obtained by performing usual post-treatments such as concentration under reduced pressure and extraction, and if necessary, subjecting it to operations such as recrystallization and column chromatography. .
さらに本発明化合物のうち一般式
〔式中、R,、R2、”4 s R4およびnは前記と
同じ意味を表わし、R5′およびR61は水素原子を表
わす、〕
で示されるピリジルピリ芝ジン誘導体は、一般式
〔式、朗、艮2およびに3 は前記と同じ意味を表わ
す、〕
テ示すれるピコリンアミジン誘導体またはその塩と、一
般式
〔式中、ζおよびnは前記と同じ意味を表わし、へは低
級アルキル基を表わすう 〕で示されるエナミン誘導体
とを塩基存在下反応させることによって得ることができ
る。Furthermore, among the compounds of the present invention, pyridylpyridhizine derivatives represented by the general formula [wherein R,, R2, "4s R4 and n represent the same meanings as above, and R5' and R61 represent hydrogen atoms] , the general formula [where ζ and n represent the same meanings as above], a picolinamidine derivative or a salt thereof represented by the general formula [where ζ and n represent the same meanings as above, It can be obtained by reacting enamine derivatives represented by 〇 representing a lower alkyl group in the presence of a base.
上記反応において標準的には、反応温度は50〜150
°C1反応時間は1〜6時間である。In the above reaction, the reaction temperature is typically 50 to 150℃.
C1 reaction time is 1-6 hours.
また、上記反応に供される試剤の量は、通常、上記一般
式〔■〕で示されるピコリンアミジン誘導体またはその
塩1当量に対して、一般式〔X〕で示されるエナミン誘
導体は1〜1.5当量であり、塩基は触媒量から2.5
当量である。In addition, the amount of the reagent used in the above reaction is usually 1 to 1 equivalent of the enamine derivative represented by the general formula [X] per 1 equivalent of the picolinamidine derivative represented by the above general formula [■] or its salt. .5 equivalents, and the base is 2.5 equivalents from the catalytic amount.
It is equivalent.
使用しうる塩基としては、ナトリウムメトキシド等のア
ルカリ金属アルコキシドまたはトリエチルアミン等の有
機塩基があげられるう用いうる溶媒としては、メタノー
ル等の低級アルコール類、テトラヒドロフラン等の環状
エーテル類、ピリジン、N、N−ジメチルホルムアミド
等およびそれらの混合物等があげられるが、通常メタノ
ール中、ナトリウムメトキシドまたはエタノール中、ナ
トリウムエトキシドを用いて行なうのが好ましいう
反応終了後の反応液は、減圧濃縮等の通常の後処理を行
ない、必要に応じ、クロマトグラフィー等に付すること
により目的化合物を得ることができる。Examples of bases that can be used include alkali metal alkoxides such as sodium methoxide, or organic bases such as triethylamine. Examples of solvents that can be used include lower alcohols such as methanol, cyclic ethers such as tetrahydrofuran, pyridine, N, N, etc. - Dimethylformamide, etc. and mixtures thereof, etc., but it is usually preferable to use sodium ethoxide in methanol, sodium methoxide or ethanol. The target compound can be obtained by post-treatment and, if necessary, subjecting it to chromatography or the like.
尚、前記一般式〔I〕で示される本発明化合物は、これ
に、常法に従かい塩化水素、臭化水素、硫酸、硝酸等の
怖酸を作用させることにより、夫々の塩に導びくことか
できろう
これらの塩を製造する場合、例えば一般式〔■〕で示さ
れる本発明化合物を溶媒に溶解し、水冷下ないし室温に
て酸を気体あるいは水溶液にて1当量加えて10分〜1
時間放置した後、減圧濃縮等の後処理を行い、必要に応
じて再結晶等によって処理する。The compound of the present invention represented by the above general formula [I] can be converted into the respective salt by reacting it with a feared acid such as hydrogen chloride, hydrogen bromide, sulfuric acid, or nitric acid according to a conventional method. When producing these salts, for example, the compound of the present invention represented by the general formula [■] is dissolved in a solvent, and 1 equivalent of acid in gas or aqueous solution is added under water cooling or at room temperature for 10 minutes or more. 1
After standing for a period of time, post-treatment such as concentration under reduced pressure is performed, and if necessary, treatment is performed by recrystallization.
反応溶媒としてはメタノール、エタノール等の低級アル
コール、トルエン、ベンゼン等の芳香族炭化水素、エチ
ルエーテル、テトラヒドロフラン、ジオキサン等のエー
テル類、クロロホルム等のハロゲン化炭化水素類、アセ
トン等のケトン類、酢酸エチル等のエステル類、ヘキサ
ン等の炭化水素類、水またはそれらの混合物等があげら
れるう
本発明化合物を製造する場合の原料化合物である一般式
〔■〕で示されるハロピリミジン誘導体および一般式〔
■〕で示されるピコリンアミジン誘導体はたとえば以下
の合成ルートで合成することができる、
C’l]〔ff]
に1
rff〕rXIV)
0日
〔xv〕
〔式中、艮1、R2、R3、R4、R5およびnは前記
と同じ意味を表わし、K、。およびに、。Reaction solvents include lower alcohols such as methanol and ethanol, aromatic hydrocarbons such as toluene and benzene, ethers such as ethyl ether, tetrahydrofuran and dioxane, halogenated hydrocarbons such as chloroform, ketones such as acetone, and ethyl acetate. , hydrocarbons such as hexane, water or mixtures thereof, etc. Halopyrimidine derivatives represented by the general formula [■] which are raw materials for producing the compounds of the present invention, and the general formula [
The picolinamidine derivative represented by [2] can be synthesized, for example, by the following synthetic route. R4, R5 and n represent the same meanings as above, K. and to.
は低級アルキル基を表わし、Mはアルカリ金属原子を表
わす、〕
すなわち、J、Org、Chem、、 48. 18
75〜1877(198B )等に記載されている方法
で得られる一般式〔II’)で示されるシアノピリジン
誘導体と、一般式[][1で示されるアルコキシドとを
反応させることにより、一般式〔■〕で示されるイミデ
ート誘導体が得られ、該イミデート誘導体とアンモニウ
ム基とを反応させることにより、一般式〔DDで示され
るピコリンアミジン誘導体が得られる。represents a lower alkyl group, and M represents an alkali metal atom.] That is, J, Org, Chem, 48. 18
75-1877 (198B), etc., and an alkoxide represented by the general formula [][1]. An imidate derivative represented by the formula (2) is obtained, and by reacting the imidate derivative with an ammonium group, a picolinamidine derivative represented by the general formula [DD] is obtained.
次いでこのようにして得られる該ピコリンア、ミジン誘
導体またはその塩と一般式CM、で示されるβ−オキソ
カルボン酸エステルとを塩基の存在下に反応させること
により、一般式J〕で示されるヒドロキシピリミジン誘
導体が得られ、該ヒドロキシピリミジン誘導体とハロゲ
ン化剤とを反応させることにより、一般式〔1lllで
示されるハロピリミジン誘導体が得られる。Next, by reacting the thus obtained picorinia, midine derivative or salt thereof with a β-oxocarboxylic acid ester represented by the general formula CM in the presence of a base, a hydroxypyrimidine represented by the general formula J] is obtained. A derivative is obtained, and by reacting the hydroxypyrimidine derivative with a halogenating agent, a halopyrimidine derivative represented by the general formula [1lll] is obtained.
以下に、上記の製法につき詳細に説明する。The above manufacturing method will be explained in detail below.
一般式印〕で示されるシアノピリジン誘導体と、一般式
〔■〕で示されるアルコキシドとの反応に於いて、用い
られるアルコキシドのアルカリ金ga子としては例えば
、ナトリウム原子、カリウム原子等があげられる。In the reaction between the cyanopyridine derivative represented by the general formula [■] and the alkoxide represented by the general formula [■], examples of the alkali gold oxide of the alkoxide used include sodium atoms, potassium atoms, etc.
また該反応において、標準的には反応温度は10〜50
°C1反応時間は1〜48時間であり、反応に供される
試剤の量は一般式〔(〕で示されるシアノピリジン誘導
体1当量に対して一般式〔xII〕で示されるアルコキ
シドは0.1〜1当量である。In addition, in this reaction, the reaction temperature is typically 10 to 50°C.
The reaction time at °C1 is 1 to 48 hours, and the amount of reagent used for the reaction is 0.1 equivalent of the alkoxide represented by the general formula [xII] per equivalent of the cyanopyridine derivative represented by the general formula [(]). ~1 equivalent.
上記反応において、反応溶媒は必ずしも必要ではないが
、一般的には溶媒の存在下に行なわれる。In the above reaction, although a reaction solvent is not necessarily required, it is generally carried out in the presence of a solvent.
使用しうる溶媒としては、一般式〔Xl〕で示されるア
ルコキシドのRqoに対応の低級アルコール、例えハ、
メタノール、エタノール、n−プロピルアルコール、イ
ソプロピルアルコール、n−ブチルアルコール等であり
、好ましくはメタノール、エタノールがあげられろう
反応終了後の反応液は、酸により中和し、減圧濃縮した
後、有機溶媒に溶解し、不溶のアルカリ金属塩を沖去し
、を液を減圧濃縮して、必要に応じ、蒸留等の操作に付
すことにより目的の一般式l〕で示されるイミデート誘
導体を得ることができる。As solvents that can be used, lower alcohols corresponding to Rqo of the alkoxide represented by the general formula [Xl], such as
Methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, etc. are preferred, and methanol and ethanol are preferred.The reaction solution after the reaction is neutralized with an acid, concentrated under reduced pressure, and then mixed with an organic solvent. The desired imidate derivative represented by the general formula 1 can be obtained by dissolving the insoluble alkali metal salt in the solution, removing the insoluble alkali metal salt, concentrating the solution under reduced pressure, and subjecting it to operations such as distillation, if necessary. .
次に上記で得られた一般式[”X11で示されるイミデ
ート誘導体とアンモニウム塩との反応において、用いら
れるアンモニウム塩としては、例えば塩酸、臭化水素酸
、酢酸、蟻酸等のアンモニウム塩があげられる。Next, in the reaction of the imidate derivative represented by the general formula [" .
また該反応において、標準的には反応温度は30〜10
0”C,反応時間は30分〜5時間であり、反応に供さ
れる試剤の量は、一般式l〕で示されるイミデート誘導
体1当濾に対してアンモニウム塩は通常1〜1.1当量
である。In addition, in this reaction, the reaction temperature is typically 30 to 10
0''C, the reaction time is 30 minutes to 5 hours, and the amount of reagent used in the reaction is usually 1 to 1.1 equivalents of ammonium salt per 1 equivalent of the imidate derivative represented by the general formula 1]. It is.
1記反応において溶媒は必ずしも必要ではないが一般的
には溶媒の存在下に行なわれる。Although a solvent is not necessarily required in the reaction 1, it is generally carried out in the presence of a solvent.
使用しうる溶媒としては低級アルコール、好ましくはエ
タノールと水との混合溶媒があげられる。Examples of solvents that can be used include lower alcohols, preferably a mixed solvent of ethanol and water.
反応終了後の反応液は、減圧濃縮等の通常の後処理を行
い、必要に応じ、再結晶等の操作により一般式(DOで
示されるピコリンアミジン誘導体の塩酸、臭化水素酸、
酢酸、蟻酸等の塩を得ることができる。After completion of the reaction, the reaction solution is subjected to usual post-treatments such as concentration under reduced pressure, and if necessary, recrystallization and other operations are performed to prepare the picolinamidine derivative represented by the general formula (DO) with hydrochloric acid, hydrobromic acid,
Salts of acetic acid, formic acid, etc. can be obtained.
このようにして得られた塩は、これを水酸化ナトリウム
、水酸化カリウム等の無機塩基あるいはナトリウムメト
キシド、ナトリウムエトキシド等のアルカリ金属アルコ
キシドなどにて中和するなどの通常の方法にて分解する
ことにより、一般式〔■〕で示されるピコリンアミジン
誘導体に導くことができる。The salt thus obtained is decomposed by a conventional method such as neutralization with an inorganic base such as sodium hydroxide or potassium hydroxide or an alkali metal alkoxide such as sodium methoxide or sodium ethoxide. By doing so, a picolinamidine derivative represented by the general formula [■] can be obtained.
また、該塩をそのまま次工程の反応に供し、該反応系内
で塩分解を行なうこともできる。Alternatively, the salt can be directly subjected to the reaction in the next step, and the salt can be decomposed within the reaction system.
次に、と記で得られた一般式CEX〕で示されるピコリ
ンアミジン誘導体と一般式可で示されるβ−オキソカル
ボン酸エステルとの反応に於いて、標準的には反応温度
は50〜150’C。Next, in the reaction between the picolinamidine derivative represented by the general formula CEX obtained by C.
反応時間は1〜24時間であり、反応に供される試剤の
量は、一般式CTX’Jで示されるピコリンアミジン誘
導体またはその塩1当量に対して、当量であるう上記反
応において溶媒は必ずしも必要ではないが、一般的には
溶媒の存在下に行なわれる。The reaction time is 1 to 24 hours, and the amount of reagent used in the reaction is equivalent to 1 equivalent of the picolinamidine derivative or its salt represented by the general formula CTX'J.In the above reaction, the solvent is not necessarily used. Although not required, it is generally carried out in the presence of a solvent.
使用しうる溶媒としては、例えばメタノール、エタノー
ル等の低級アルコール類、ジオキサン、テトラヒドロフ
ラン等の環状エーテル類、ピリジン、N、N−ジメチル
ホルムアミド、水等またはそれらの混合物があげられ、
塩基としては例えば、水酸化ナトリウム、水酸化カリウ
ム、炭」カリウム等の無機塩基、ナトリウムメトキシド
等のアルカリ金属アルコキシド、トリエチルアミン、N
、N−ジエチルアニリン等の有機塩基等があげられる。Examples of solvents that can be used include lower alcohols such as methanol and ethanol, cyclic ethers such as dioxane and tetrahydrofuran, pyridine, N,N-dimethylformamide, water, etc., or mixtures thereof.
Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, potassium charcoal, alkali metal alkoxides such as sodium methoxide, triethylamine, N
, N-diethylaniline, and other organic bases.
反応終了後の反応液は、必要に応じ、塩を一過等で除去
し、減圧a縮等の通常の後処理を行い、必要に応じ、ク
ロマトグラフィー、再結晶導の操作により目的の一般式
r″Xv〕で示されるヒドロキシピリミジン誘導体を得
ることができる。After the completion of the reaction, the reaction solution is subjected to normal post-treatments such as removal of salt by passing through, etc., and condensation under reduced pressure, as necessary.If necessary, chromatography and recrystallization are performed to obtain the desired general formula. A hydroxypyrimidine derivative represented by r″Xv] can be obtained.
次に上記で得られた一般式c′xV〕で示されるヒドロ
キシピリミジン誘導体とハロゲン化剤との反応において
、用いられるハロゲン化剤としては、例えば、塩化チオ
ニル、ホスゲン、オキシ塩化リン、五塩化リン、オキシ
臭化リン、三臭化リン等があげられる。Next, in the reaction of the hydroxypyrimidine derivative represented by the general formula c' , phosphorus oxybromide, phosphorus tribromide, etc.
上記反応において、標準的には反応温度は50〜150
°C1反応時間は1〜10時間であり、反応に供される
試剤の量は、一般式〔■〕で示されるヒドロキシピリミ
ジン誘導体1当量に対してハロゲン化剤は通常1〜10
当量である。In the above reaction, the reaction temperature is typically 50 to 150
The reaction time at °C1 is 1 to 10 hours, and the amount of the halogenating agent used for the reaction is usually 1 to 10 hours per equivalent of the hydroxypyrimidine derivative represented by the general formula [■].
It is equivalent.
上記反応において溶媒は必ずしも必要ではないが一般的
には溶媒の存在下に行なわれる。Although a solvent is not necessarily required in the above reaction, it is generally carried out in the presence of a solvent.
使用しうる溶媒としては、ベンゼン、トルエン等の芳香
族炭化水素類、クロロベンゼン等のハロゲン化炭化水素
類等があげられる。Examples of solvents that can be used include aromatic hydrocarbons such as benzene and toluene, and halogenated hydrocarbons such as chlorobenzene.
反応終了後の反応液は、減圧濃縮後、水酸化ナトリウム
等の無機塩基等で中和後、有機溶媒抽出および濃縮等の
通常の後処理を行い、必要に応じ、クロマトグラフィー
、再結晶等の操作により目的の一般式(”l〕で示され
るハロピリミジン誘導体を得ることができる。After the reaction is completed, the reaction solution is concentrated under reduced pressure, neutralized with an inorganic base such as sodium hydroxide, and subjected to usual post-treatments such as organic solvent extraction and concentration.If necessary, chromatography, recrystallization, etc. By this operation, the desired halopyrimidine derivative represented by the general formula ("l") can be obtained.
本発明化合物を植物病害防除剤の有効成分として用いる
場合は、他の何らの成分も加えずそのまま使用してもよ
いが、通常は、固体担体、液体担体、界面活性剤その他
の製剤用補助剤と混合して、乳剤、水和剤、懸濁剤、粒
剤、粉剤液剤等に製剤して使用する。When the compound of the present invention is used as an active ingredient in a plant disease control agent, it may be used as is without adding any other ingredients, but it is usually used in combination with solid carriers, liquid carriers, surfactants, and other formulation auxiliaries. It is used by mixing it with other ingredients and preparing it into emulsions, wettable powders, suspensions, granules, powder solutions, etc.
これらの製剤には有効成分として本発明化合物を、重量
比で0.1〜99%、好ましくは0.2〜95%含有す
る。These preparations contain the compound of the present invention as an active ingredient in a weight ratio of 0.1 to 99%, preferably 0.2 to 95%.
固体担体としては、カオリンクレー、アッタバルジャイ
トクレー、ベントナイト、酸性白土、パイロフィライト
、タルク、珪藻土、方解石、トウモロコシ穂軸粉、クル
ミ殻粉、尿素、硫酸アンモニウム、合成含水酸化珪素等
の微粉末あるいは粒状物があり、液体担体には、キシレ
ン、メチルナフタレン等の芳香族炭化水素類、イソプロ
パツール、エチレングリコール、セロソルブ等のアルコ
ール類、アセトン、シクロヘキサノン、イソホロン等の
ケトン類、大豆油、綿実油等の植物油、ジメチルスルホ
キシド、アセトニトリル、水等があげられる。Examples of solid carriers include fine powders such as kaolin clay, attabulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, corn cob powder, walnut shell powder, urea, ammonium sulfate, and synthetic hydrous silicon oxide. Liquid carriers include aromatic hydrocarbons such as xylene and methylnaphthalene, alcohols such as isopropanol, ethylene glycol, and cellosolve, ketones such as acetone, cyclohexanone, and isophorone, soybean oil, cottonseed oil, etc. Examples include vegetable oil, dimethyl sulfoxide, acetonitrile, water, etc.
乳化、分散、湿層等のために用いられる界面活性剤とし
ては、アルキル硫酸エステル塩、アルキル(アリール)
スルホン酸塩、ジアルキルスルホこはく酸塩、ポリオキ
シエチレンアルキルアリールエーテルりん酸エステル塩
、ナフタレンスルホン酸ホルマリン縮合物等の陰イオン
界面活性剤、ポリオキシエチレンアルキルエーテル、ポ
リオキシエチレンポリオキシプロピレンブロックコポリ
マー、ソルビタン脂肪駿エステル、ポリオキシエチレン
ソルビタン脂肪袋エステル等の非イオン界面活性剤等が
あげられる。Surfactants used for emulsification, dispersion, wet layer, etc. include alkyl sulfate salts, alkyl (aryl)
Anionic surfactants such as sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkylaryl ether phosphate ester salts, naphthalene sulfonic acid formalin condensates, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene block copolymers, Examples include nonionic surfactants such as sorbitan fatty acid ester and polyoxyethylene sorbitan fatty acid ester.
製剤用補助剤としては、リグニンスルホン@塩、アルキ
ン[1、ポリビニルアルコール、アラビアガム、CN(
C(カルボキシメチルセルロース)、PAL’ (酸性
りん酵イソプロピル)等があげられる。As formulation auxiliaries, lignin sulfone @ salt, alkyne [1, polyvinyl alcohol, gum arabic, CN (
Examples include C (carboxymethyl cellulose) and PAL' (acidic phosphorylated isopropyl).
これらの製剤は、そのままで吏用するか、あるいは水で
希釈して、茎蘂敢市するか、土壌に散粉、散粒して混和
するかあるいは土壌施用等する。また、池の植物病害防
除剤と混合して用いることにより、防除効力の増強をも
期待できる。さらに、殺虫剤、殺ダニ剤、殺線虫剤、除
草剤、植物生長調節剤、肥料、土壌改良剤暮と混合して
用いることもできる。These preparations can be taken as they are, or diluted with water and sprinkled on a stalk, sprinkled or granulated and mixed into the soil, or applied to the soil. In addition, by mixing it with a pond plant disease control agent, it can be expected to increase the control effect. Furthermore, it can be used in combination with insecticides, acaricides, nematicides, herbicides, plant growth regulators, fertilizers, and soil conditioners.
本発明化合物を植物病害防除剤の有効成分として用いる
場合、その処理量は、気象条件、製剤形態、処理時期、
方法、場所、対象病害、対象作物等によっても異なるが
、通常1アールあたり0.2〜200g、好ましくは1
〜100gであり、乳剤、水和剤、懸濁剤、液剤等を水
で希釈して施朋する場合、その施用濃度は、0、005
〜0.5%好ましくは0.01〜0.2%であり、粒剤
、粉剤等は、なんら希釈することなくそのまま施用する
う
〈実施例〉
以下に、本発明を製造例、参考例、製剤例および試験例
によりさらに詳しく説明する。When the compound of the present invention is used as an active ingredient of a plant disease control agent, the amount to be treated depends on weather conditions, formulation form, treatment time,
Although it varies depending on the method, location, target disease, target crop, etc., it is usually 0.2 to 200 g per are, preferably 1
~100g, and when applying emulsions, wettable powders, suspensions, solutions, etc. diluted with water, the application concentration is 0.005g.
~0.5% Preferably 0.01~0.2%, and granules, powders, etc. are applied as they are without any dilution.<Example> The present invention will be described below with production examples, reference examples, This will be explained in more detail with formulation examples and test examples.
まず製造例を示す。First, a manufacturing example will be shown.
製造例1 (化合物(5))
4−クロロ−2−(6−メチル−2−ピリジル)−6−
o−1リルピリミジン1fをトルエン10−とエタノー
ル5−に溶解し、これに炭酸ナトリウムQ、 271を
水5−に溶かした溶液と5%パラジウム−炭素0.11
を加え、室温にて水素ガスと接融させた。80分後、触
媒を沖去し、水207!とトルエン8〇−を加え抽出し
た。有機層を無水硫酸マグネシウムで乾燥した後、減圧
濃縮して、2−(6−メチル−2−ピリジル”)−6−
0−)リルピリミジン0.829を得たつ
rllLp* 119.4℃
PMR(CDC4M) δ ppm二2.58(8
,8H,−CH5)
2.74 (8、8H、−CHx )
9.00(d、IH,ピリミジン−H’ 、J=4.2
H2)製造例2 (化合物(14))
4−クロロ−6−(2,4−ジメチルフェニル)−2−
(6−メチル−2−ピリジル)ピリミジン1fにメタノ
ール5−を加え、これに28%ナトリウムメトキシドメ
タノール溶液0.8gを加え80分間室温で攪拌した。Production Example 1 (Compound (5)) 4-chloro-2-(6-methyl-2-pyridyl)-6-
o-1 Lylpyrimidine 1f was dissolved in toluene 10- and ethanol 5-, and to this was added a solution of sodium carbonate Q, 271 dissolved in water 5- and 5% palladium-carbon 0.11.
was added and melted with hydrogen gas at room temperature. After 80 minutes, remove the catalyst and water 207! and 80% of toluene were added for extraction. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give 2-(6-methyl-2-pyridyl")-6-
0-) Lylpyrimidine 0.829 was obtained rlllLp* 119.4°C PMR (CDC4M) δ ppm2 2.58 (8
, 8H, -CH5) 2.74 (8, 8H, -CHx) 9.00 (d, IH, pyrimidine-H', J=4.2
H2) Production Example 2 (Compound (14)) 4-chloro-6-(2,4-dimethylphenyl)-2-
Methanol 5- was added to (6-methyl-2-pyridyl)pyrimidine 1f, and 0.8 g of 28% sodium methoxide methanol solution was added thereto, followed by stirring at room temperature for 80 minutes.
反応液に水80−、クロロホルム100fntを加え分
液し、クロロホルム層を水洗した後、無水硫酸マグネシ
ウムで乾燥した。減圧濃縮して6−(2,4−ジメチル
フェニル)−4−メトキシ−2−(6−メLルー2−ピ
リジル)ピリミジン0.9gを得た。To the reaction solution were added 80 mm of water and 100 fnt of chloroform to separate the layers, and the chloroform layer was washed with water and then dried over anhydrous magnesium sulfate. Concentration under reduced pressure yielded 0.9 g of 6-(2,4-dimethylphenyl)-4-methoxy-2-(6-mer-2-pyridyl)pyrimidine.
m、p* 97.7℃
PMR(CDC1,り δppm
1.28(S、3H,CH,)
1.42(3,8H,CHi )
L、62 (s 、 80.CH,)
4.07(S 、8H,QC)I、)
6.70(S、IH,ピリミジン−o 5 )7.52
(t 、IH,ピリジン−H’、J=7.2Hz)8.
16(d、to、ピリジン−Hs、 J=7.2Hz
)製造例8 (化合物(19) )
4−クロロ−6−o−フルオロフェニル−2−(6−メ
チルニ2−ピリジル)ピリミジン1fに、金属ナトリウ
ム0.1gとメタノール10−より調製したナトリウム
メトキシドを加え1時間室温で攪拌したつこれに水8〇
−と酢酸エチル100−を加え抽出した。m, p* 97.7℃ PMR (CDC1,ri δppm 1.28 (S, 3H, CH,) 1.42 (3,8H, CHi) L, 62 (s, 80.CH,) 4.07 ( S,8H,QC)I,) 6.70(S,IH,pyrimidine-o5)7.52
(t, IH, pyridine-H', J=7.2Hz)8.
16(d,to,pyridine-Hs, J=7.2Hz
) Production Example 8 (Compound (19)) Sodium methoxide prepared from 4-chloro-6-o-fluorophenyl-2-(6-methylni-2-pyridyl)pyrimidine 1f, 0.1 g of sodium metal and 10-methanol The mixture was stirred at room temperature for 1 hour, and 80% of water and 100% of ethyl acetate were added thereto for extraction.
有機層を無水硫酸マグネシウムで乾燥した後、m圧ss
して、4−0−フルオロフェニル−6−メドキシー2−
(6−メチル−2−ピリジル)ピリミジン0.829を
得たつ
m1Ip・ 99.5℃
PMR(CDC1s) δppm
2.65 (8、8H、−CHl )
4.08(8,8H,−QC旦−3)
7.58(t、IH,ピリジン−H’ 、J=7.2H
z)製造例4 (化合物(7))
ジエチルマロン酸1.4gと60%油性水素化ナトリウ
ムQ、 851をテトラヒドロフラン80−に加え、こ
れに4−クロロ−2−(6−メチル−2−ピリジル)−
6−o−トリルピリミジン2fを加えた。これを80分
間加熱還流した後、水酸化ナトリウム0.81を水10
−とエタノール10−に溶解した混液を加えさらに80
分間加熱還流した。After drying the organic layer with anhydrous magnesium sulfate, m pressure ss
and 4-0-fluorophenyl-6-medoxy2-
(6-Methyl-2-pyridyl)pyrimidine 0.829 m1Ip 99.5℃ PMR (CDC1s) δppm 2.65 (8,8H, -CHl) 4.08 (8,8H, -QC tan- 3) 7.58 (t, IH, pyridine-H', J=7.2H
z) Production Example 4 (Compound (7)) 1.4 g of diethylmalonic acid and 60% oily sodium hydride Q, 851 were added to tetrahydrofuran 80-, and 4-chloro-2-(6-methyl-2-pyridyl )−
6-o-tolylpyrimidine 2f was added. After heating this under reflux for 80 minutes, add 0.81 sodium hydroxide to 10 ml of water.
Add a mixture of - and ethanol 10- and add 80
The mixture was heated to reflux for a minute.
さらに反応液に濃硫酸1.51を加え、30分間加熱還
流した。反応後反応液を炭酸ナトリウム溶液で中性し減
圧濃縮した後、残渣をシリカゲルカラムクロマトグラフ
ィー(ヘキサン:アセトン=2 : 1 )で処理し、
4−メチル−2−(6−メチル−2−ピリジル)−6−
0−トリルピリミジン1.2gを得た。Furthermore, 1.51 g of concentrated sulfuric acid was added to the reaction solution, and the mixture was heated under reflux for 30 minutes. After the reaction, the reaction solution was neutralized with sodium carbonate solution and concentrated under reduced pressure, and the residue was treated with silica gel column chromatography (hexane:acetone=2:1).
4-Methyl-2-(6-methyl-2-pyridyl)-6-
1.2 g of 0-tolylpyrimidine was obtained.
mepa 88.2℃
P M R(CDCLM )δppm
2.47(s、8H,CH,)
2.69(3、6H,2XCH,)
7.68(t、IH,ピリジン−H,J=7.802)
製造例5 (化合物(84) )
ジエチルマロン!1.5fと60%油性水素化ナトリウ
ム0.41をテトラヒドロフラン8〇−に加え、これに
4−クロロ−6−〇−クロロフェニルー2−(6−メチ
ル−2−ピリジル)ピリミジン1fを加えた。添加後、
80分間加熱還流した後、水酸化ナトリウム0.81を
水10−とメタノール10−の混液に溶解した溶液を加
え、さらに20分間加熱還流した。室温まで放冷した後
、濃硫酸1.51を注意深く加え、さらに80分間加熱
還流した。mepa 88.2°C PMR (CDCLM) δppm 2.47 (s, 8H, CH,) 2.69 (3, 6H, 2XCH,) 7.68 (t, IH, pyridine-H, J=7. 802)
Production Example 5 (Compound (84)) Diethylmalon! 1.5f and 0.41 of 60% oily sodium hydride were added to 80% of tetrahydrofuran, and 4-chloro-6-0-chlorophenyl-2-(6-methyl-2-pyridyl)pyrimidine 1f was added thereto. After addition,
After heating under reflux for 80 minutes, a solution prepared by dissolving 0.81 of sodium hydroxide in a mixture of 10 parts of water and 10 parts of methanol was added, and the mixture was further heated under reflux for 20 minutes. After cooling to room temperature, 1.5 l of concentrated sulfuric acid was carefully added, and the mixture was further heated under reflux for 80 minutes.
室温まで放冷後、INの炭酸ナトリウム水溶液を加え中
性にした後減圧濃縮した。After cooling to room temperature, an aqueous IN sodium carbonate solution was added to neutralize the mixture, and the mixture was concentrated under reduced pressure.
残渣をシリカゲルカラムクロマトグラフィー(n−ヘキ
サン:アセトン=3 : 1 )で処理し、4−O−ク
ロロフェニル−6−メチル−2−(6−メチル−2−ピ
リジル)ピリミジン1.42gを得た。The residue was treated with silica gel column chromatography (n-hexane:acetone=3:1) to obtain 1.42 g of 4-O-chlorophenyl-6-methyl-2-(6-methyl-2-pyridyl)pyrimidine.
m、p、 90.8°C
P M R(CDCts ) δppm:170(s
、6H,−CHgx2)
8.31(d、IH,ピリジン−H3、J=7.8Hz
)製造例6 (化合物(1))
6−メチル−2−ピコリンアミジン塩酸塩1.51をメ
タノール50−に溶解し、これに28%ナトリウムメト
キシドメタノール溶液2.21と8−ジメチルアミノ−
1−フェニル−2−ブテン−1−オン1.7gを加え、
2時間加熱還流した。m, p, 90.8°C PMR (CDCts) δppm: 170 (s
, 6H, -CHgx2) 8.31 (d, IH, pyridine-H3, J = 7.8Hz
) Production Example 6 (Compound (1)) 1.51 of 6-methyl-2-picolinamidine hydrochloride was dissolved in 50% of methanol, and 2.21% of a 28% sodium methoxide methanol solution and 8-dimethylamino-
Add 1.7 g of 1-phenyl-2-buten-1-one,
The mixture was heated under reflux for 2 hours.
反応液を減圧濃縮した後、残渣をシリカゲルカラムクロ
マトグラフィー(n−ヘキサン:酢酸エチル=2 :
1 )で処理し、2−(6−メチル−2−ピリジル)−
4−フェニルピ1トン1.6gを得た。After concentrating the reaction solution under reduced pressure, the residue was subjected to silica gel column chromatography (n-hexane: ethyl acetate = 2:
1), 2-(6-methyl-2-pyridyl)-
One ton (1.6 g) of 4-phenylpi was obtained.
nD t、6829
P M R(CDCLg ) δppm:2.74
(8,8H,−CHり
8.48(d、IH,ピリジン−Hl 、J=7.28
Z)8.92(d、IH,ピリミジン−H’ 、J=5
.9H2)次にこの様な製造法によって製造できる本発
明化合物のいくつかについて第1表に示す。nDt, 6829 PMR(CDCLg) δppm: 2.74
(8,8H, -CH 8.48 (d, IH, pyridine-Hl, J = 7.28
Z) 8.92 (d, IH, pyrimidine-H', J=5
.. 9H2) Next, Table 1 shows some of the compounds of the present invention that can be produced by such a production method.
第 1 表 一般式 次にこれらの原料化合物の製造例を参考例として示す。Table 1 general formula Next, production examples of these raw material compounds will be shown as reference examples.
参考例1〔ピコリンアミジン誘導体〔■〕(塩酸塩)の
製造〕
2−シアノ−6−メチルピリジン80gをメタノール8
00−に溶解し、28%ナトリウムメトキシドメタノー
ル溶液14.7jlを加え室温で8時間放置した1反応
液に酢@4.61を加え、減圧濃縮し、得られた残渣に
エーテル800−および水100−を加え分液し、エー
テル層を無水硫酸マグネシウムで乾燥した後、減圧濃縮
してメチル6−メチル−2−ピコリンイミデートを得た
1次いでこれにエタノール200s+Jl111え、さ
らに塩化アンモニウム18.6jlを水50−に溶解し
た溶液を加えて80分間加熱還流した1反応液を充分に
減圧濃縮し、得られた結晶状残渣をアセトンで洗浄して
6−メチル−2−ピコリンアミジン塩酸塩87Nを得た
。Reference Example 1 [Production of picolinamidine derivative [■] (hydrochloride)] 80 g of 2-cyano-6-methylpyridine was mixed with 80 g of methanol
14.7 jl of a 28% sodium methoxide methanol solution was added to the reaction solution, which was left at room temperature for 8 hours. Vinegar @4.61 was added to the reaction mixture, and the mixture was concentrated under reduced pressure. The resulting residue was diluted with ether 800- and water. After drying the ether layer with anhydrous magnesium sulfate, it was concentrated under reduced pressure to obtain methyl 6-methyl-2-picolinimidate.Next, to this was added 200 s of ethanol + 111 liters of ethanol, and further added 18.6 liters of ammonium chloride. A solution of 50% of water was added and heated under reflux for 80 minutes.The reaction solution was thoroughly concentrated under reduced pressure, and the resulting crystalline residue was washed with acetone to obtain 87N of 6-methyl-2-picolinamidine hydrochloride. Obtained.
maps 188.0’C
次にこの様な製造法によって製造される一役式〔■〕で
示されるピコリンアミジン3導体およびその塩のいくつ
かを第2表に示す。maps 188.0'C Next, Table 2 shows some of the picolinamidine 3 conductors represented by the monochrome formula [■] and their salts produced by such a production method.
第2表
参考例2 〔ヒドロキシピリミジン誘導体(IVIの製
造〕
6−メチル−2−ピコリンアミジン塩酸塩5gをメタノ
ール50−に加え、これに28%ナトリウムメトキシド
メタノール溶液6.81および2.4−ジメチルベンゾ
イル酢酸エチル6.761を加えて1時間加熱還流した
。Table 2 Reference Example 2 [Hydroxypyrimidine derivative (manufacture of IVI)] 5 g of 6-methyl-2-picolinamidine hydrochloride was added to 50% methanol, and to this was added 28% sodium methoxide methanol solution 6.81 and 2.4%. 6.761 ml of ethyl dimethylbenzoylacetate was added, and the mixture was heated under reflux for 1 hour.
放冷後、反応液に酢酸を加え中性にし、減圧濃縮した。After cooling, acetic acid was added to the reaction solution to make it neutral, and the mixture was concentrated under reduced pressure.
得られた残渣を水で洗浄し次いでヘキサンで洗浄して6
−(2,4−ジメチルフェニル)−4−ヒドロキシ−2
−(6〜メチル−2−ピリジル)ピリミジン6.9gを
得た。The resulting residue was washed with water and then with hexane.
-(2,4-dimethylphenyl)-4-hydroxy-2
6.9 g of -(6-methyl-2-pyridyl)pyrimidine was obtained.
mop@ 145.6℃
P M R(CDCLs )δppm
2.84 (s、8H,CH,、)
2.48 (S、8)1.C1(、)
2.58 (s、8H,CHs)
6.49 (s、II(、ピ’J Z シン−H5)
7.66 (t、IH,ピリジン−〇’、J−7.2
Hz )8.19 (d、U(、ピリジン−H’ 、
J == 7.2 Hz。mop @ 145.6°C PMR (CDCLs) δppm 2.84 (s, 8H, CH,,) 2.48 (S, 8) 1. C1 (,) 2.58 (s, 8H, CHs) 6.49 (s, II (, Pi'J Z Shin-H5)
7.66 (t, IH, pyridine-〇', J-7.2
Hz)8.19 (d, U(, pyridine-H',
J = = 7.2 Hz.
次にこの様な製造法によって製造できる一般式(XV)
で示されるヒドロキシピリミジンgWKのいくつかにつ
いて第8表に示すっ
第8表
一般式
参考例8 〔ハロピリミジン誘導体〔m〕の製造〕6−
(2,4−ジメチルフェニル)−4−ヒドロキシ−2−
(6−メチル−2−ピリジル)ピリεジン5gにトルエ
ン100−およびオキシ塩化リン5gを加え、1時間加
熱還流した。放冷後、炭酸ナトリウム水溶液で中和し、
分液した。トルエン層を水洗し、無水硫酸ナトリウムで
乾燥した後、減圧濃縮して、4−クロロ−6−(2,4
−ジメチルフェニル)−2−(6−メチル−2−ピリジ
ル)ピリミジン4.81を得た。Next, the general formula (XV) that can be produced by such a production method
Some of the hydroxypyrimidine gWK shown in Table 8 are shown in Table 8. Table 8 General Formula Reference Example 8 [Production of halopyrimidine derivative [m]] 6-
(2,4-dimethylphenyl)-4-hydroxy-2-
To 5 g of (6-methyl-2-pyridyl)pyridine, 100 toluene and 5 g of phosphorus oxychloride were added, and the mixture was heated under reflux for 1 hour. After cooling, neutralize with sodium carbonate aqueous solution,
The liquid was separated. The toluene layer was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give 4-chloro-6-(2,4
-dimethylphenyl)-2-(6-methyl-2-pyridyl)pyrimidine 4.81 was obtained.
m、p、 127.2°C
PMR(CDC1s)δppm
2.85 (8,8H9CHs)
2.47 (8,8H,CHs)
2.69 (lB、af(、CHs)
7.66 (t、IH,ピリジン−H’、J=7.2
8Z)8.26 (d、IH,ピリジン−H”、J=
7.2)1z)次にこの様な製造法によって製造できる
一般式〔1〕で示されるハロピリミジン誘導体のいくつ
かについて第4表に示す。m, p, 127.2°C PMR (CDC1s) δppm 2.85 (8,8H9CHs) 2.47 (8,8H,CHs) 2.69 (lB, af(,CHs) 7.66 (t, IH , pyridine-H', J=7.2
8Z) 8.26 (d, IH, pyridine-H”, J=
7.2) 1z) Next, Table 4 shows some halopyrimidine derivatives represented by the general formula [1] that can be produced by such a production method.
第4表
一般式
次に製剤例を示す。なお本発明化合物は第1表の化合物
番号で示し、部は重量部である。Table 4 General formulas Examples of formulations are shown below. The compounds of the present invention are indicated by compound numbers in Table 1, and parts are parts by weight.
製剤例1
本発明化合物(1)〜(50)各々50部、リグニンス
ルホン酸カルシウム8部、ラウリル硫酸ナトリウム2部
および合成含水酸化珪素45部をよく粉砕混合して本発
明化合物各々の水和剤を得る。Formulation Example 1 50 parts each of the compounds (1) to (50) of the present invention, 8 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and 45 parts of synthetic hydrous silicon oxide were thoroughly ground and mixed to form a hydrating agent for each of the compounds of the present invention. get.
製剤例2
本発明化合物(1)〜(50)各々25部、ポリオキシ
エチレンソルビタンモノオレエート8部CMCg部およ
び水69部を混合し、有効成分の粒度が5ミクロン以下
になるまで湿式粉砕して本発明化合物各々の懸濁剤を得
る。Formulation Example 2 25 parts each of the compounds (1) to (50) of the present invention, 8 parts of polyoxyethylene sorbitan monooleate, 8 parts of CMC, and 69 parts of water were mixed and wet-pulverized until the particle size of the active ingredient became 5 microns or less. A suspension of each of the compounds of the present invention is obtained.
製剤例8
本発明化合物(1)〜(50)各々2部、カオリンクレ
ー88部およびタルク10部をよく粉砕混合して本発明
化合物各々の粉剤を得る。Formulation Example 8 2 parts each of the compounds (1) to (50) of the present invention, 88 parts of kaolin clay, and 10 parts of talc are thoroughly ground and mixed to obtain a powder of each of the compounds of the present invention.
製剤例4
本発明化合物(1)〜(50)各々20部、ポリオキシ
エチレンスチリルフェニルエーテル14部、ドデシルベ
ンゼンスルホン酸カルシウム6部、およびキシレン60
部をよく混合して本発明化合物各々の乳剤を得る。Formulation Example 4 20 parts each of the compounds (1) to (50) of the present invention, 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate, and 60 parts of xylene
The components are thoroughly mixed to obtain an emulsion of each compound of the present invention.
製剤例5
本発明化合物(1)〜(50)各々2部、合成含水酸化
珪素1部、リグニンスルホン酸カルシウム2部、ベント
ナイト80部およびカオリンクレー65部をよく粉砕混
合し、水を加えてよく練り合わせた後、造粒乾燥して本
発明化合物各々の粒剤を得る。Formulation Example 5 2 parts each of the compounds (1) to (50) of the present invention, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 80 parts of bentonite and 65 parts of kaolin clay are thoroughly ground and mixed, and water may be added. After kneading, the mixture is granulated and dried to obtain granules of each compound of the present invention.
次に、本発明化合物が殺菌剤として有用であることを試
験例で示す。なお、本発明化合物は第1表の化合物番号
で示し、比較対照に用いた化合物は第5表の化合物記号
で示すう
第 5 表
また防除効力は、調査時の供試植物の発病状態すなわち
葉、茎等の菌叢、6斑の程度を肉眼観察し、菌叢、病斑
が全く認められなければ「5」、10部程度認められれ
ば「4」、80部程度認められれば18」、50部程度
認められれば「2J 、 70部程度認められれば「1
」、それ以上で化合物を供試していない場合の発病状態
と差が認められなければ「0」として、6段階に評価し
、それぞれ5.4,3.2,1.0でしめす。Next, test examples will show that the compounds of the present invention are useful as fungicides. The compounds of the present invention are indicated by the compound numbers in Table 1, and the compounds used for comparison are indicated by the compound symbols in Table 5. , Visually observe the bacterial flora on the stems, etc., and the degree of 6 spots. If no bacterial flora or lesions are observed, rate it as ``5'', if around 10 parts are observed, rate it as ``4'', and if around 80 parts are observed, rate it as ``18''. If around 50 copies are approved, it will be ``2J'', and if around 70 copies are approved, it will be ``1J''.
'', and if there is no difference from the disease onset state when no compound is tested, it is evaluated as ``0'' and evaluated on a 6-level scale, with 5.4, 3.2, and 1.0, respectively.
試験例1 イネいもち病防除試験(予防効果)プラス
チックポットに砂壌土を詰め、イネ(近畿33号)を帰
国し、温室内で20日間育成した。イネの幼苗に、製剤
例2に準じて懸濁剤にした供試薬剤を水で希釈して所定
濃度にし、それを葉面に充分付着するように茎葉散布し
たう散布後、植物を風乾し、いもち病菌の胞子懸濁液を
噴霧、接種したう接種後、28°C1暗黒、多湿下で4
日装置いた後、防除効力を調査した。その結果を第6表
にじめす。Test Example 1 Rice blast control test (preventive effect) A plastic pot was filled with sandy loam, and rice (Kinki No. 33) was returned to Japan and grown in a greenhouse for 20 days. A test drug made into a suspension according to Formulation Example 2 was diluted with water to a specified concentration on young rice seedlings, and the solution was sprayed on the foliage to ensure sufficient adhesion to the leaf surface.After spraying, the plants were air-dried. , Spray and inoculate with a spore suspension of blast fungus.After inoculation, incubate at 28°C1 in darkness and humidity
After installing the equipment, we investigated its pesticidal efficacy. The results are shown in Table 6.
第6表
試験例2 イネいもち病防除試験(治療効果)プラ
スチックポットに砂壌土を詰め、イネ(近畿88号)を
播種し、温室内で20日間育成した。イネの幼苗に、い
もち病菌の胞子懸濁液を噴霧、接種した。接種後、28
℃、暗黒、多湿下で16時間装いた後、製剤例1に準じ
て水和剤にした供試薬剤を水で希釈して所定濃度にし、
それを葉面に充分付着するように茎葉散布した。散布後
、28°C1暗黒、多湿下で8日間生育し、防除効力を
調査した。Table 6 Test Example 2 Rice blast control test (therapeutic effect) A plastic pot was filled with sandy loam, and rice (Kinki No. 88) was sown and grown in a greenhouse for 20 days. Rice seedlings were sprayed and inoculated with a spore suspension of the blast fungus. After vaccination, 28
℃, dark, and humid for 16 hours, the test drug made into a wettable powder according to Formulation Example 1 was diluted with water to a predetermined concentration.
It was sprayed on the foliage so that it adhered sufficiently to the leaf surface. After spraying, the plants were grown for 8 days at 28° C. in darkness and high humidity, and their control efficacy was investigated.
その結果を第7表にしめす。The results are shown in Table 7.
試験例8 イネ紋枯病防除試験(予防効果)プラス
チックポットに砂壌土を詰め、イネ(近畿88号)を播
種し、温室内で28日間育成した。イネの幼苗に、製剤
例4に準じて乳剤にした供試薬剤を水で希釈して所定濃
度にし、それを葉面に充分付着するように茎葉散布した
う散布後、植物を風乾し紋枯病菌の食菌寒天懸濁液を噴
霧、接覆した。接涌後、28℃、暗黒、多湿下で4日装
置いた後、防除効力を調査した。その結果を第8表にし
めす。Test Example 8 Rice sheath blight control test (preventive effect) A plastic pot was filled with sandy loam, and rice (Kinki No. 88) was sown and grown in a greenhouse for 28 days. The test drug, made into an emulsion according to Formulation Example 4, was diluted with water to a specified concentration on young rice seedlings, and sprayed on the foliage so that it adhered sufficiently to the leaf surface.After spraying, the plants were air-dried and sheathed. A edible agar suspension of diseased bacteria was sprayed and covered. After being exposed to water, the plants were kept in the apparatus for 4 days at 28°C in darkness and high humidity, and then their pesticidal efficacy was investigated. The results are shown in Table 8.
第8表
試験例4 コムギ眼紋病防除試験(予防効果)プラ
スチックポットに砂壌土を詰め、コムギ(農林78号)
を播種し、温室内で10日間育成した、コムギの幼苗に
、製剤例1に準じて水和剤にした供試薬剤を水で希資し
て所定濃度にし、それを葉面に充分付着するように茎葉
散布したつ散布後、植物を風乾しMBC耐性眼紋病菌の
胞子懸濁液を噴霧、接種した。Table 8 Test Example 4 Wheat Eye Spot Disease Control Test (Preventive Effect) Fill plastic pots with sandy loam and grow wheat (Norin No. 78)
To wheat seedlings, which were sown and grown in a greenhouse for 10 days, dilute the test drug prepared as a wettable powder with water according to Formulation Example 1 to a predetermined concentration, and thoroughly adhere it to the leaf surface. After spraying on the foliage as described above, the plants were air-dried and then sprayed and inoculated with a spore suspension of MBC-resistant eyelid fungus.
接種後、15℃、暗黒、多湿下で4日間慧いた後、さら
に照明、多湿下で4日間生育し、防除効力を調査した。After inoculation, the seeds were grown for 4 days at 15° C. in the dark and humid, and then grown for another 4 days in light and humid to investigate the control efficacy.
その結果を第9表にしめす。The results are shown in Table 9.
第 9 表
試験例 ♂ コムギ葉枯肩防除試験(治療効果)プラス
チックゴツトに砂壌土を詰め、コムギ(農林78号)を
播種し、温室内で8日間育成した。コムギの幼苗に、葉
枯病菌の胞子懸濁液を噴霧、接種した。接種後、15°
C1暗黒、多湿下で8日間f!1き、さらに照明下で4
日間生育した後、製剤例4に準じて乳剤にした供試薬剤
を水で希釈して所定濃度にし、それを葉面に充分付着す
るように茎葉散布した。散布後、15°C照明下で11
日間生育させて、防除効力を調査した。その結果を第1
0表にしめす。Table 9 Test Examples ♂ Wheat leaf blight control test (therapeutic effect) Sand loam was packed into a plastic pot, and wheat (Norin No. 78) was sown and grown in a greenhouse for 8 days. Wheat seedlings were sprayed and inoculated with a spore suspension of the leaf blight fungus. After inoculation, 15°
C1 f for 8 days in darkness and high humidity! 1, then 4 under the lighting
After growing for one day, the test drug was made into an emulsion according to Formulation Example 4, diluted with water to a predetermined concentration, and sprayed on the foliage so that it would sufficiently adhere to the leaf surface. After spraying, 11 hours under 15°C lighting.
The control efficacy was investigated after growing for several days. The result is the first
Shown in table 0.
第 10 表
試験例6 リンゴ黒星病防除試験(予防効果)プラ
スチックポットに砂壌土を詰め、リンゴの種子を播種し
、温室内で20日間育成したう第4〜5本葉が展開した
リンゴの幼苗に、製剤例2に準じて懸濁剤にした供試薬
剤を水で希釈して所定濃度にし、それを葉直に充分付着
するように茎葉散布した。散布後1.リンゴ黒星病菌の
胞子懸濁液を噴震、接柵した。Table 10 Test Example 6 Apple scab control test (preventive effect) Apple seeds were sown in plastic pots filled with sandy loam soil and grown in a greenhouse for 20 days. Apple seedlings with 4th to 5th true leaves developed. Next, a test drug prepared as a suspension according to Formulation Example 2 was diluted with water to a predetermined concentration, and the solution was sprayed on the leaves so that it would adhere sufficiently to the leaves. After spraying 1. A spore suspension of apple scab fungus was sprayed and fenced.
接種後、15°C1多湿下で4日置いた後、さらに照明
下で15日間生育し、防除効力を調査した。その結果を
第11表にしめすう第 11 表
試験例7 キュウリ炭そ病防除試験(予防効果)プ
ラスチックポットに砂J土を詰め、キュウリ(相撲半白
)を播種し、温室内で14日間育成した。子葉が展開し
たキュウリの幼苗に、製剤例1に準じて水和剤にした供
試薬剤を水で希釈して所定濃度にし、それを葉面に充分
付着するように茎葉散布した1散布後、キュウリ炭そ病
菌の胞子懸濁液を噴甥、接種した。接種後、28℃、多
湿下で1日量いた後、さらに照明下で4日間生育し、防
除効力を調査した。その結果を第12表にしめす。After inoculation, the seeds were left at 15° C. under humid conditions for 4 days, and then grown under lighting for 15 days to investigate the pesticidal efficacy. The results are shown in Table 11. Table 11 Test Example 7 Cucumber anthracnose control test (preventive effect) Fill a plastic pot with sand J soil, sow cucumbers (Sumo Hanshiro), and grow them in a greenhouse for 14 days. did. After 1 spraying, the test drug, which had been made into a hydrating powder according to Formulation Example 1, was diluted with water to a predetermined concentration, and was sprayed on the foliage of cucumber seedlings with developed cotyledons so that it would sufficiently adhere to the leaf surface. A spore suspension of cucumber anthracnose was inoculated by spraying. After inoculation, the seeds were grown for 1 day at 28° C. under high humidity, and then grown for 4 days under lighting, and the pesticidal efficacy was investigated. The results are shown in Table 12.
第 12 表
試験例8 コムギうどんこ病防除試験(治療効果)
プラスチックポットに砂壌土を詰め、コムギ(農林78
号)を播種し、温室内で10日間育成した。コムギの幼
苗にうどんこ病菌を接種した。接種後28゛Cで3日間
生育した後、製剤例4に準じて乳剤にした供試薬剤を水
で希釈して所定濃度にし、それを葉面に充分付着するよ
うに茎葉散布した。散布後、28°C1温室内で7日間
生育し、防除効力を調査した。Table 12 Test Example 8 Wheat powdery mildew control test (therapeutic effect)
Fill plastic pots with sandy loam and grow wheat (Agricultural and Forestry 78)
No.) was sown and grown in a greenhouse for 10 days. Young wheat seedlings were inoculated with powdery mildew. After inoculation and growing for 3 days at 28°C, the test drug was made into an emulsion according to Formulation Example 4, diluted with water to a predetermined concentration, and sprayed on the leaves so that it would adhere sufficiently to the leaf surface. After spraying, the seeds were grown for 7 days in a greenhouse at 28°C, and the control efficacy was investigated.
その結果を第18表にしめす。The results are shown in Table 18.
第 18 表
試験例9 キュウリ灰色かび病防除試@(予防効果
)プラスチックポットに砂壌土を詰め、キュウリ(相撲
半白)を播種し、温室内で14日間育成した。子葉が腰
囲したキュウリの幼苗に製剤例1に準じて水和剤にした
供試薬剤を水で希釈して所定濃度にし、それを葉面に充
分付着するように茎葉散布した。散布後、植物を風乾し
、ベンズイミダゾール・チオノ1ネールメチル系殺菌剤
耐性キュウリ灰色かび病菌の菌糸を接種した。接種後、
15°C1暗黒、多湿下で8日間生育し、防除効力を調
査した。その結果を第14表にしめす。Table 18 Test Example 9 Cucumber gray mold control test @ (preventive effect) A plastic pot was filled with sandy loam, and cucumbers (Sumo Hanshiro) were sown and grown in a greenhouse for 14 days. A test drug prepared as a hydrating powder according to Formulation Example 1 was diluted with water to a predetermined concentration on cucumber seedlings surrounded by cotyledons, and sprayed on the foliage of the cucumber seedlings so as to sufficiently adhere to the leaf surface. After spraying, the plants were air-dried and inoculated with mycelia of cucumber botrytis fungus resistant to benzimidazole-thiononel-methyl fungicides. After vaccination,
The plants were grown for 8 days at 15°C in darkness and high humidity, and their pesticidal efficacy was investigated. The results are shown in Table 14.
第14表
試験例10 コムギ赤さび病防除試験(治療効果)
プラスチックポットに砂壌土を詰め、コムギ(農林78
号)を播種し、温室内で8日間育成した。コムギの幼苗
に、赤さび病菌の胞子を散粉、接種した。接種後、28
°C1暗黒、多湿下で1日量いた後、製剤例2に準じて
懸濁剤にした供試薬剤を水で希釈して所定濃度にし、そ
れを葉面に充分付着するように茎葉散布した。散布後、
28°C照明下で7日間生育させて、防除効力を調査し
た。その結果を第15表にしめす、
〈発明の効果〉
本発明化合物は、種々の植物病害菌による植物病害に対
して優れた効果を有することから植物病害防除剤の有効
成分として種々の用途に供しうるうTable 14 Test Example 10 Wheat rust control test (therapeutic effect)
Fill plastic pots with sandy loam and grow wheat (Agricultural and Forestry 78)
No.) was sown and grown in a greenhouse for 8 days. Young wheat seedlings were sprinkled with spores of Fusarium rust and inoculated. After vaccination, 28
After being left in the dark and humid at 1°C for 1 day, the test drug made into a suspension according to Formulation Example 2 was diluted with water to a specified concentration, and then sprayed on the foliage to ensure sufficient adhesion to the leaf surface. . After spraying,
The plants were grown under illumination at 28°C for 7 days and their control efficacy was investigated. The results are shown in Table 15. <Effects of the Invention> The compounds of the present invention have excellent effects against plant diseases caused by various plant pathogens, and therefore can be used in various applications as active ingredients of plant disease control agents. Uruuu
Claims (6)
びR_3は同一または相異なり水素原子またはメチル基
を表わし、nは0〜5の 整数を表わし、R_4は同一または相異なり、低級アル
キル基、低級アルコキシ基、低級 ハロアルキル基またはハロゲン原子を表わ し、R_5は水素原子または低級アルキル基を表わし、
R_6は水素原子、低級アルキル基、低級アルコキシ基
、低級アルケニルオキシ 基または低級アルキルチオ基を表わす。〕 で示されるピリジルピリミジン誘導体またはその塩。(1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. , R_4 is the same or different and represents a lower alkyl group, lower alkoxy group, lower haloalkyl group or halogen atom, R_5 represents a hydrogen atom or a lower alkyl group,
R_6 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower alkenyloxy group or a lower alkylthio group. ] A pyridylpyrimidine derivative or a salt thereof.
びR_3は同一または相異なり水素原子またはメチル基
を表わし、nは0〜5の整 数を表わし、R_4は同一または相異なり、低級アルキ
ル基、低級アルコキシ基、低級 ハロアルキル基またはハロゲン原子を表わ し、R_5は水素原子または低級アルキル基を表わし、
Xはハロゲン原子を表わす。〕 で示されるハロピリミジン誘導体を還元することを特徴
とする一般式 ▲数式、化学式、表等があります▼ 〔式中、R_1、R_2、R_3、R_4、R_5およ
びnは前記と同じ意味を表わし、R_6′は水素原子を
表わす。〕 で示されるピリジルピリミジン誘導体の製造法。(2) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 represents a lower alkyl group, R_2 and R_3 are the same or different and represent a hydrogen atom or a methyl group, and n is an integer from 0 to 5. , R_4 is the same or different and represents a lower alkyl group, lower alkoxy group, lower haloalkyl group or halogen atom, R_5 represents a hydrogen atom or a lower alkyl group,
X represents a halogen atom. ] General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. that are characterized by reducing the halopyrimidine derivative represented by [In the formula, R_1, R_2, R_3, R_4, R_5 and n represent the same meanings as above, R_6' represents a hydrogen atom. ] A method for producing a pyridylpyrimidine derivative.
びR_3は同一または相異なり水素原子またはメチル基
を表わし、nは0〜5の整 数を表わし、R_4は同一または相異なり、低級アルキ
ル基、低級アルコキシ基、低級 ハロアルキル基またはハロゲン原子を表わ し、R_5は水素原子または低級アルキル基を表わし、
Xはハロゲン原子を表わす。〕 で示されるハロピリミジン誘導体と一般式 R_6″Y 〔式中、R_6″は低級アルコキシ基、低級アルケニル
オキシ基または低級アルキルチオ 基を表わし、Yはアルカリ金属を表わす。〕で示される
アルカリ金属化合物とを反応させることを特徴とする一
般式 ▲数式、化学式、表等があります▼ 〔式中、R_1、R_2、R_3、R_4、R_5、R
_6″およびnは前記と同じ意味を表わす。〕 で示されるピリジルピリミジン誘導体の製造法。(3) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 represents a lower alkyl group, R_2 and R_3 are the same or different and represent a hydrogen atom or a methyl group, and n is an integer from 0 to 5. , R_4 is the same or different and represents a lower alkyl group, lower alkoxy group, lower haloalkyl group or halogen atom, R_5 represents a hydrogen atom or a lower alkyl group,
X represents a halogen atom. ] A halopyrimidine derivative represented by the general formula R_6''Y [wherein R_6'' represents a lower alkoxy group, a lower alkenyloxy group or a lower alkylthio group, and Y represents an alkali metal. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1, R_2, R_3, R_4, R_5, R
_6'' and n represent the same meanings as above.] A method for producing a pyridylpyrimidine derivative represented by the following.
びR_3は同一または相異なり水素原子またはメチル基
を表わし、nは0〜5の整数 を表わし、R_4は同一または相異なり、低級アルキル
基、低級アルコキシ基、低級ハロ アルキル基またはハロゲン原子を表わし、 R_5は水素原子または低級アルキル基を表わし、Xは
ハロゲン原子を表わす。〕 で示されるハロピリミジン誘導体と一般式 R_7CH(COOR_8)_2 〔式中、R_7は水素原子または低級アルキル基を表わ
し、R_8は低級アルキル基を表わす。〕で示されるマ
ロン酸ジエステル誘導体とを塩基の存在下反応させた後
、加水分解し、さらに脱炭酸することを特徴とする一般
式 ▲数式、化学式、表等があります▼ (式中、R_1、R_2、R_3、R_4、R_5およ
びnは前記と同じ意味を表わし、R_6″′は低級アル
キル基を表わす。〕 で示されるピリジルピリミジン誘導体の製造法。(4) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 represents a lower alkyl group, R_2 and R_3 are the same or different and represent a hydrogen atom or a methyl group, and n is an integer from 0 to 5. R_4 are the same or different and represent a lower alkyl group, a lower alkoxy group, a lower haloalkyl group or a halogen atom, R_5 represents a hydrogen atom or a lower alkyl group, and X represents a halogen atom. ] A halopyrimidine derivative represented by the general formula R_7CH(COOR_8)_2 [wherein R_7 represents a hydrogen atom or a lower alkyl group, and R_8 represents a lower alkyl group. ] The general formula is characterized by reacting a malonic acid diester derivative represented by the following in the presence of a base, followed by hydrolysis and further decarboxylation ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1, R_2, R_3, R_4, R_5 and n represent the same meanings as above, and R_6'' represents a lower alkyl group.] A method for producing a pyridylpyrimidine derivative represented by the following.
びR_3は同一または相異なり、水素原子またはメチル
基を表わす。〕 で示されるピコリンアミジン誘導体またはその塩と一般
式 ▲数式、化学式、表等があります▼ 〔式中、nは0〜5の整数を表わし、R_4は低級アル
キル基、低級アルコキシ基、低級 ハロアルキル基またはハロゲン原子を表わ し、R_9は低級アルキル基を表わす。〕 で示されるエナミン誘導体とを塩基存在下反応させるこ
とを特徴とする一般式 ▲数式、化学式、表等があります▼ 〔式中、R_1、R_2、R_3、R_4およびnは前
記と同じ意味を表わし、R′_5およびR′_6は水素
原子を表わす。〕 で示されるピリジルピリミジン誘導体の製造法。(5) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R_1 represents a lower alkyl group, and R_2 and R_3 are the same or different and represent a hydrogen atom or a methyl group. ] Picolinamidine derivatives or their salts represented by the general formula ▲ Numerical formulas, chemical formulas, tables, etc. or represents a halogen atom, and R_9 represents a lower alkyl group. ] A general formula characterized by reacting with an enamine derivative shown in the presence of a base ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1, R_2, R_3, R_4 and n represent the same meanings as above. , R'_5 and R'_6 represent hydrogen atoms. ] A method for producing a pyridylpyrimidine derivative.
びR_3は同一または相異なり水素原子またはメチル基
を表わし、nは0〜5の整数 を表わし、R_4は同一または相異なり、低級アルキル
基、低級アルコキシ基、低級ハロ アルキル基またはハロゲン原子を表わし、 R_5は水素原子または低級アルキル基を表わし、R_
6は水素原子、低級アルキル基、低級アルコキシ基、低
級アルケニルオキシ基また は低級アルキルチオ基を表わす。〕 で示されるピリジルピリミジン誘導体またはその塩を有
効成分として含有することを特徴とする植物病害防除剤
。(6) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 represents a lower alkyl group, R_2 and R_3 are the same or different and represent a hydrogen atom or a methyl group, and n is an integer from 0 to 5. R_4 is the same or different and represents a lower alkyl group, lower alkoxy group, lower haloalkyl group or halogen atom, R_5 represents a hydrogen atom or a lower alkyl group, R_
6 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower alkenyloxy group or a lower alkylthio group. ] A plant disease control agent characterized by containing a pyridylpyrimidine derivative or a salt thereof as an active ingredient.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62299044A JP2517992B2 (en) | 1986-12-03 | 1987-11-26 | Pyridylpyrimidine derivative and plant disease controlling agent containing the same |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP28835086 | 1986-12-03 | ||
JP61-288350 | 1986-12-03 | ||
JP62299044A JP2517992B2 (en) | 1986-12-03 | 1987-11-26 | Pyridylpyrimidine derivative and plant disease controlling agent containing the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS63264478A true JPS63264478A (en) | 1988-11-01 |
JP2517992B2 JP2517992B2 (en) | 1996-07-24 |
Family
ID=26557136
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP62299044A Expired - Lifetime JP2517992B2 (en) | 1986-12-03 | 1987-11-26 | Pyridylpyrimidine derivative and plant disease controlling agent containing the same |
Country Status (1)
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JP (1) | JP2517992B2 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003535109A (en) * | 2000-06-08 | 2003-11-25 | シンジエンタ パーテイスィペイシヨンズ アクチエンゲゼルシヤフト | N-phenyl- (4-pyridyl) -2-pyrimidineamine derivative |
JP2007182430A (en) * | 2005-12-07 | 2007-07-19 | Sumitomo Chemical Co Ltd | Pyridazine compound and bactericide containing the same |
JP2013028624A (en) * | 2006-03-29 | 2013-02-07 | F Hoffmann La Roche Ag | PYRIDINE AND PYRIDINE DERIVATIVE AS mGluR2 ANTAGONIST |
WO2022239808A1 (en) * | 2021-05-11 | 2022-11-17 | 国立研究開発法人理化学研究所 | Compound having antiparasitic activity |
-
1987
- 1987-11-26 JP JP62299044A patent/JP2517992B2/en not_active Expired - Lifetime
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003535109A (en) * | 2000-06-08 | 2003-11-25 | シンジエンタ パーテイスィペイシヨンズ アクチエンゲゼルシヤフト | N-phenyl- (4-pyridyl) -2-pyrimidineamine derivative |
JP2007182430A (en) * | 2005-12-07 | 2007-07-19 | Sumitomo Chemical Co Ltd | Pyridazine compound and bactericide containing the same |
JP2013028624A (en) * | 2006-03-29 | 2013-02-07 | F Hoffmann La Roche Ag | PYRIDINE AND PYRIDINE DERIVATIVE AS mGluR2 ANTAGONIST |
WO2022239808A1 (en) * | 2021-05-11 | 2022-11-17 | 国立研究開発法人理化学研究所 | Compound having antiparasitic activity |
Also Published As
Publication number | Publication date |
---|---|
JP2517992B2 (en) | 1996-07-24 |
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