JPH044310B2 - - Google Patents
Info
- Publication number
- JPH044310B2 JPH044310B2 JP8007082A JP8007082A JPH044310B2 JP H044310 B2 JPH044310 B2 JP H044310B2 JP 8007082 A JP8007082 A JP 8007082A JP 8007082 A JP8007082 A JP 8007082A JP H044310 B2 JPH044310 B2 JP H044310B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- formula
- general formula
- morpholino
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 150000001875 compounds Chemical class 0.000 claims description 38
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 12
- -1 ethyleneimino group Chemical group 0.000 claims description 12
- 239000004480 active ingredient Substances 0.000 claims description 11
- 239000000417 fungicide Substances 0.000 claims description 10
- 125000003277 amino group Chemical group 0.000 claims description 7
- 230000000855 fungicidal effect Effects 0.000 claims description 7
- DDWBEROMBZXLNB-UHFFFAOYSA-N 2,4,6-trichloro-5-methylsulfanylpyrimidine Chemical compound CSC1=C(Cl)N=C(Cl)N=C1Cl DDWBEROMBZXLNB-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- SEYKEMHUCORTTB-UHFFFAOYSA-N 4-chloro-2,6-dimethoxy-5-methylsulfanylpyrimidine Chemical compound COC1=NC(Cl)=C(SC)C(OC)=N1 SEYKEMHUCORTTB-UHFFFAOYSA-N 0.000 claims description 5
- IBMKUYMVNFUNOW-UHFFFAOYSA-N 5-methylsulfanylpyrimidine Chemical class CSC1=CN=CN=C1 IBMKUYMVNFUNOW-UHFFFAOYSA-N 0.000 claims description 5
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims 2
- 125000005078 alkoxycarbonylalkyl group Chemical group 0.000 claims 2
- 125000000217 alkyl group Chemical group 0.000 claims 2
- 125000004103 aminoalkyl group Chemical group 0.000 claims 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 125000004181 carboxyalkyl group Chemical group 0.000 claims 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 239000002904 solvent Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 230000003902 lesion Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- 241000233866 Fungi Species 0.000 description 4
- 244000141359 Malus pumila Species 0.000 description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- MXZJUUJULRVWJC-UHFFFAOYSA-N 2,6-dimethoxy-n-methyl-5-methylsulfanylpyrimidin-4-amine Chemical compound CNC1=NC(OC)=NC(OC)=C1SC MXZJUUJULRVWJC-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000005909 Kieselgur Substances 0.000 description 3
- 244000061456 Solanum tuberosum Species 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 201000010099 disease Diseases 0.000 description 3
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- XGXNTJHZPBRBHJ-UHFFFAOYSA-N n-phenylpyrimidin-2-amine Chemical compound N=1C=CC=NC=1NC1=CC=CC=C1 XGXNTJHZPBRBHJ-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000004563 wettable powder Substances 0.000 description 3
- AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- GWSKXEUCQCCJPS-UHFFFAOYSA-N 2,6-dimethoxy-5-methylsulfanyl-n-phenylpyrimidin-4-amine Chemical compound COC1=NC(OC)=NC(NC=2C=CC=CC=2)=C1SC GWSKXEUCQCCJPS-UHFFFAOYSA-N 0.000 description 2
- FOEMIZSFFWGXHX-UHFFFAOYSA-N 2-methylsulfanylpyrimidine Chemical compound CSC1=NC=CC=N1 FOEMIZSFFWGXHX-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229940126657 Compound 17 Drugs 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 241000233622 Phytophthora infestans Species 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 235000002595 Solanum tuberosum Nutrition 0.000 description 2
- WREOTYWODABZMH-DTZQCDIJSA-N [[(2r,3s,4r,5r)-3,4-dihydroxy-5-[2-oxo-4-(2-phenylethoxyamino)pyrimidin-1-yl]oxolan-2-yl]methoxy-hydroxyphosphoryl] phosphono hydrogen phosphate Chemical compound O[C@@H]1[C@H](O)[C@@H](COP(O)(=O)OP(O)(=O)OP(O)(O)=O)O[C@H]1N(C=C\1)C(=O)NC/1=N\OCCC1=CC=CC=C1 WREOTYWODABZMH-DTZQCDIJSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 229940125758 compound 15 Drugs 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000010410 dusting Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 238000003958 fumigation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000001766 physiological effect Effects 0.000 description 2
- 244000000003 plant pathogen Species 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- GIKMWFAAEIACRF-UHFFFAOYSA-N 2,4,5-trichloropyrimidine Chemical compound ClC1=NC=C(Cl)C(Cl)=N1 GIKMWFAAEIACRF-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical group CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 241000235349 Ascomycota Species 0.000 description 1
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- 241000282472 Canis lupus familiaris Species 0.000 description 1
- 235000008534 Capsicum annuum var annuum Nutrition 0.000 description 1
- 240000008384 Capsicum annuum var. annuum Species 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 241000221785 Erysiphales Species 0.000 description 1
- 241000287828 Gallus gallus Species 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 241000692870 Inachis io Species 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000699670 Mus sp. Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 241000233614 Phytophthora Species 0.000 description 1
- 241001600434 Plectroglyphidodon lacrymatus Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 241000700159 Rattus Species 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-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
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001298 alcohols 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
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 239000003443 antiviral agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000005667 attractant Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000009739 binding Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 235000013330 chicken meat Nutrition 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 230000035613 defoliation Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 244000013123 dwarf bean Species 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000005645 nematicide Substances 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000012053 oil suspension Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 235000012015 potatoes Nutrition 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229940083082 pyrimidine derivative acting on arteriolar smooth muscle Drugs 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 235000015192 vegetable juice Nutrition 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Description
本発明は一般式
〔式中、Xは−NR1R2(R1、R2は水素原子、炭
素数1〜3のアルキル基、アルケニル基、フエニ
ル基、アルコキシカルボニルアルキル基、カルボ
キシアルキル基、アミノアルキル基、またはアミ
ノ基をそれぞれ表わす。)エチレンイミノ基、モ
ルホリノ基、または2,6−ジメチル−4−モル
ホリノ基を表わす。〕で示される5−メチルチオ
ピリミジン誘導体とその製造法、およびそれらの
化合物を有効成分として含有する農園芸用殺菌剤
に関するものである。
従来からピリミジン誘導体に関しては、非常に
数多くの研究がなされており、膨大な数の化合物
が合成され、農医薬の分野で特徴ある生理活性を
示す化合物が多数見い出されてきた。しかしなが
ら、その多くは製造が容易なピリミジン骨格の
2,4および6位の置換基を交換したものであ
り、5位は反応性が低く、直接置換基を導入する
にはニトロ化やハロゲン化等を限定された条件下
で行なう方法が少数例知られているだけである。
5位の置換基のなかでも、特にメチルチオ基を
有し、かつピリミジン骨格の2,4または6位に
アミノ基を有する化合物の合成例は少ない。ケミ
カルアブストラクト(Chemical Abstracts)に
記載されている関連化合物として以下に示すもの
があるだけである。
The present invention is based on the general formula [ In the formula , Each represents an amino group.) An ethyleneimino group, a morpholino group, or a 2,6-dimethyl-4-morpholino group. The present invention relates to 5-methylthiopyrimidine derivatives represented by the following formulas, methods for producing the same, and agricultural and horticultural fungicides containing these compounds as active ingredients. A large number of studies have been conducted on pyrimidine derivatives, a huge number of compounds have been synthesized, and many compounds have been discovered that exhibit characteristic physiological activities in the field of agricultural medicine. However, in many cases, substituents at the 2, 4, and 6 positions of the pyrimidine skeleton, which are easy to manufacture, are exchanged, and the 5-position has low reactivity, so direct introduction of substituents requires nitration, halogenation, etc. There are only a few known methods for performing this under limited conditions. Among the substituents at the 5-position, there are few synthesis examples of compounds having a methylthio group and an amino group at the 2-, 4-, or 6-position of the pyrimidine skeleton. The only related compounds listed in Chemical Abstracts are listed below.
【表】【table】
【表】
本発明者らは、5位にメチルチオ基を有し、か
つ2,4位にメトキシ基、6位にアミノ基をもつ
化合物については現在まで全く合成されたことが
ないことに着目して、種々の誘導体を合成し、そ
の生理活性について試験した結果、これらの本発
明化合物が多くの植物病原菌に対して、公知化合
物からは予想もできない非常にすぐれた防除効果
を有することを見い出し、本発明を完成させた。
本発明化合物は植物病原菌に対して優れた殺菌
力および増殖阻止力を有し、広範囲に亘る様々の
菌類による植物病害の防除のために適用できる。
例えば本発明化合物は散布剤または土壌処理剤と
して、藻菌類によるジヤガイモ疫病、トマト疫
病、ピーマン疫病、キユウリベと病等、または不
完全菌類による灰色かび病、リンゴ斑点落葉病、
子のう菌類による各種作物のうどんこ病等に卓効
を示す。
また本発明化合物は栽培植物に対しては実用上
全く薬害を示さない。温血動物、例えばマウス、
ラツト、イヌ、ニワトリなどに対する毒性は極め
て微弱であり、魚毒性も全く示さず、農業用殺菌
剤として極めて優れた性質を有する。
本発明の化合物は次の反応式の経路(a)また
は(b)に従つて製造することができる。
(一般式()〜()のXは前出と同じ)
出発物質である5−メチルチオ−2,4,6−
トリクロロピリミジンはケミカルアブストラクト
(Chemical Abstracts)72,3499sに記載された
方法に従つて製造することができる。以下に本発
明の製造法を前記反応式にもとづいて工程毎に詳
しく、説明する。
経路(a)
工程(i):溶媒としてテトラヒドロフラン、ジオ
キサン、N,N−ジメチルホルムアミド、ジメチ
ルスルホキシド、ヘキサメチルホスホルアミド、
ベンゼン、トルエンまたはエーテル等の金属ナト
リウムに不活性なものかまたはメタノールそのも
のを用いることができる。反応は最初2当量かや
や過剰のメタノールを溶媒に希釈し(メタノール
を溶媒とする場合は必要な容量を使用する。)、2
当量かやや過剰の金属ナトリウム、または水素化
ナトリウムを加えてよく撹拌し、ナトリウムメチ
ラートを調整する。ナトリウムメチラートが生成
した後、5−メチルチオ−2,4,6−トリクロ
ロピリミジンを固体のままか、または溶媒に溶解
して少量ずつ加える。この場合、反応温度は−10
℃から溶媒の沸点までであるが、室温以下で加え
ると選択性よく6−クロロ−2,4−ジメトキシ
−5−メチルチオピリミジンを生成する。生成物
は容易に単離することができるが、単離しないで
そのまま次の工程(ii)へ続けることもできる。
工程(ii):溶媒としては工程(i)と同様のものを使
用することができ、更に沸点の低いアミン類に対
しては水を使用することもできる。脱酸剤とし
て、炭酸ナトリウム、炭酸水素ナトリウム、炭酸
カリウム、炭酸水素カリウム、トリエチルアミン
等の第三級アミンまたは一般式()で示される
XHそのものを用いることができる。上記脱酸剤
の存在下、6−クロロ−2,4−ジメトキシ−5
−メチルチオピリミジンの溶液に前記XH()
を1当量かやや過剰量加える。反応温度は0℃か
ら溶媒の沸点まで可能であるが、加熱した場合、
反応が2〜4時間で完結するものが多い。沸点の
低いアミン類の場合にはオートクレーブを用いて
もよい。生成した一般式()で示される目的化
合物を精製するには再結晶またはカラムクロマト
グラフイーによる。
経路(b)
工程(iii):工程(ii)と同様である。脱酸剤の存在
下、5−メチルチオ−2,4,6−トリクロロピ
リミジンの溶液に1当量かやや過剰の一般式
()で示されるXHを加える。反応温度は0℃
から溶媒の沸点まで可能であるが、なるべく室温
以下で行なう方が、多置換体等の副反応を防ぐこ
とができる。反応は2〜5時間で完結するものが
多い。一般式()で示される化合物は再結晶ま
たはカラムクロマトグラフイーで容易に単離でき
るが、単離しないでそのまま次工程(iv)へ続けるこ
ともできる。
工程(iv):工程(ii)と同様である。2当量かやや過
剰のナトリウムメチラートの溶液に一般式()
の化合物を加えるか、または一般式()の化合
物の溶液にあらかじめ調整したナトリウムメチラ
ートの溶液を加えてもよい。反応温度は室温から
溶媒の沸点まで可能であるが、加熱した方が順調
に進行し、反応は2〜5時間で完結するものが多
い。目的化合物の精製法は工程(ii)の場合と同様で
ある。
以下に合成例を挙げて本発明化合物の製造法を
具体的に説明する。
合成例 1
2,4−ジメトキシ−6−(N−メチルアミノ)
−5−メチルチオピリミジン(化合物番号1)
の合成……経路(a)
6−クロロ−2,4−ジメトキシ−5−メチ
ルチオピリミジンの合成
塩化カルシウム管付還流冷却器、温度計および
撹拌機を付した50ml四ツ口フラスコに無水メタノ
ール30mlを装入した後、金属ナトリウム0.37gを
小片にして加えた。金属ナトリウムが溶解した
後、0℃で5−メチルチオ−2,4,6−トリク
ロロピリミジン1.84gを少量ずつ加えた。0℃で
15分、室温で15分撹拌した後、反応液を氷水中に
あけた。析出した固体を取し、イソプロピルア
ルコールから再結晶して6−クロロ−2,4−ジ
メトキシ−5−メチルチオピリミジン(mp58.5
〜59.5℃)を得た。収量1.40g(収率79.1%)
NMR(CCl4)δ2.30(3H,s,)、3.97(3H,s)
4.04(3H,s)
なお、NMRのδ値3.97と4.04に現れるシング
レツトピークは、それぞれ3個の水素に相当し、
2個のメトキシ基に起因する。しかもこのシング
レツトピークが不等価であることから、得られた
化合物を、6−クロロ−2,4−ジメトキシ−5
−メチルチオピリミジンと同定した。
2,4−ジメトキシ−6−(N−メチルアミ
ノ)−5−メチルチオピリミジンの合成
オートクレーブ中で、6−クロロ−2,4−ジ
メトキシ−5−メチルチオピリミジン1.76gと40
%メチルアミン水溶液1.49gとジメチルスルホキ
シド25mlとを2時間110℃で加熱した。反応液を
水にあけ酢酸エチルで抽出した。水洗、脱水後、
溶媒を除去して得た粗生成物をイソプロピルエー
テルから再結晶して、2,4−ジメトキシ−6−
(N−メチルアミノ)−5−メチルチオピリミジン
(mp57.5〜59℃)を得た。収量1.37g(収率80
%)。
NMR(CCl4)δ2.08(3H,s)、4.99(3H,d,
J=4.8Hz)、3.86(3H,s)、3.92(3H,s)、5.94
(1H,broad)
合成例 2
2,4−ジメトキシ−5−メチルチオ−6−
(N−フエニルアミノ)ピリミジン(化合物番
号2)の合成……経路(b)
2,4−ジクロロ−5−メチルチオ−6−
(N−フエニルアミノ)ピリミジンの合成
還流冷却器、温度計および撹拌機を付した100
ml四ツ口フラスコに5−メチルチオ−2,4,6
−トリクロロピリミジン2.30g、炭酸カリウム
2.76g、とジメチルスルホキシド30mlとを装入し
懸濁させた。アニリン1.12gを加え、室温で3時
間撹拌した。反応液を希塩酸中にあけ、酢酸エチ
ルで抽出した。水洗、脱水後、溶媒を除去して得
た粗生成物をイソプロピルエーテルから再結晶し
て2,4−ジクロロ−5−メチルチオ−6−(N
−フエニルアミノ)ピリミジン(mp130〜131℃)
を得た。収量1.63g(収率57%)。
NMR(CDCl3)δ2.39(3H,s)、7.1−7.7(5H,
m)、8.44(1H,broad)
2,4−ジメトキシ−5−メチルチオ−6−
(N−フエニルアミノ)ピリミジンの合成
塩化カルシウム管付還流冷却器、温度計および
撹拌機を付した100ml四ツ口フラスコに無水メタ
ノール30mlを装入した。次に金属ナトリウム0.55
gを小片にして加え、完全に溶解した後、2,4
−ジクロロ−5−メチルチオ−6−(N−フエニ
ルアミノ)ピリミジン1.14gを室温で加えた。2
時間加熱還流した後、反応液を希塩酸にあけ、酢
酸エチルで抽出した。水洗、脱水後、溶媒を除去
して得た粗生成物をn−ヘキサンから再結晶して
2,4−ジメトキシ−5−メチルチオ−6−(N
−フエニルアミノ)ピリミジン(mp−65〜68℃)
を得た。収量0.73g(収率66%)。
NMR(CCl4)δ2.20(3H,s)、3.92(3H,s)、
3.99(3H,s)、6.99(1H,d,J=8.0Hz)、7.24
(2H,dd,J=8.0、8.0Hz)、7.62(2H,d,J=
8.0Hz)、8.08(1H,broad)
なお、NMRのδ値3.92と3.97に現れるシング
レツトピークは、それぞれ3個の水素に相当し、
2個のメトキシ基に起因する。しかもこのシング
レツトピークが不等価であることから、得られた
化合物、2,4−ジメトキシ−5−メチルチオ−
6−(N−フエニルアミノ)ピリミジン同定した。
前記一般式()で示される本発明化合物はい
ずれも以上の合成例に準拠して合成できる。
上記の方法で製造した本発明化合物とその物性
値を次の第1表に示す。[Table] The present inventors focused on the fact that no compound having a methylthio group at the 5th position, a methoxy group at the 2nd and 4th positions, and an amino group at the 6th position has been synthesized to date. As a result of synthesizing various derivatives and testing their physiological activities, we found that these compounds of the present invention have extremely excellent control effects against many plant pathogens, which could not be expected from known compounds. The present invention has been completed. The compounds of the present invention have excellent bactericidal and growth-inhibiting properties against plant pathogens, and can be applied to control plant diseases caused by a wide variety of fungi.
For example, the compound of the present invention can be used as a spray agent or soil treatment agent to treat potato late blight, tomato late blight, green pepper late blight, yellowtail mildew, etc. caused by algal fungi, or botrytis blight, apple spot leaf blight caused by Deuteromycetes, and the like.
It is highly effective against powdery mildew of various crops caused by ascomycetes. Furthermore, the compounds of the present invention do not show any practical damage to cultivated plants. warm-blooded animals, such as mice,
It has extremely low toxicity to rats, dogs, chickens, etc., and shows no toxicity to fish, and has extremely excellent properties as an agricultural fungicide. The compound of the present invention can be produced according to route (a) or (b) of the following reaction formula. (X in general formulas () to () is the same as above) Starting material 5-methylthio-2,4,6-
Trichloropyrimidine can be produced according to the method described in Chemical Abstracts 72, 3499s. Below, the manufacturing method of the present invention will be explained in detail for each step based on the above reaction formula. Route (a) Step (i): Tetrahydrofuran, dioxane, N,N-dimethylformamide, dimethyl sulfoxide, hexamethylphosphoramide,
Something inert to the sodium metal, such as benzene, toluene or ether, or methanol itself can be used. For the reaction, first dilute 2 equivalents or a slight excess of methanol into the solvent (if methanol is used as the solvent, use the required volume),
Add an equivalent amount or a slight excess of sodium metal or sodium hydride and stir well to adjust the sodium methylate. After the sodium methylate is formed, 5-methylthio-2,4,6-trichloropyrimidine is added in portions, either as a solid or dissolved in a solvent. In this case, the reaction temperature is −10
℃ to the boiling point of the solvent, but when added below room temperature, 6-chloro-2,4-dimethoxy-5-methylthiopyrimidine is produced with good selectivity. The product can be easily isolated, but it can also be carried on to the next step (ii) without isolation. Step (ii): As the solvent, the same solvent as in step (i) can be used, and water can also be used for amines with a low boiling point. As a deoxidizing agent, tertiary amines such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, triethylamine, etc. or those represented by the general formula ()
XH itself can be used. In the presence of the above deoxidizing agent, 6-chloro-2,4-dimethoxy-5
-XH() in a solution of methylthiopyrimidine
Add 1 equivalent or a slight excess of. The reaction temperature can range from 0°C to the boiling point of the solvent, but when heated,
In many cases, the reaction is completed in 2 to 4 hours. In the case of amines with a low boiling point, an autoclave may be used. The produced target compound represented by the general formula () is purified by recrystallization or column chromatography. Route (b) Step (iii): Same as step (ii). In the presence of a deoxidizing agent, 1 equivalent or a slight excess of XH represented by the general formula () is added to a solution of 5-methylthio-2,4,6-trichloropyrimidine. Reaction temperature is 0℃
to the boiling point of the solvent, but side reactions such as polysubstituted products can be prevented by performing the reaction at temperatures as low as room temperature or below. The reaction is often completed in 2 to 5 hours. The compound represented by the general formula () can be easily isolated by recrystallization or column chromatography, but it can also be directly carried on to the next step (iv) without being isolated. Step (iv): Same as step (ii). In a solution of 2 equivalents or a slight excess of sodium methylate, the general formula ()
or a previously prepared solution of sodium methylate may be added to the solution of the compound of general formula (). The reaction temperature can range from room temperature to the boiling point of the solvent, but heating progresses more smoothly, and the reaction is often completed in 2 to 5 hours. The method for purifying the target compound is the same as in step (ii). The method for producing the compound of the present invention will be specifically explained below by giving synthesis examples. Synthesis example 1 2,4-dimethoxy-6-(N-methylamino)
-5-methylthiopyrimidine (compound number 1)
Synthesis...route (a) Synthesis of 6-chloro-2,4-dimethoxy-5-methylthiopyrimidine Add 30 ml of anhydrous methanol to a 50 ml four-necked flask equipped with a reflux condenser with a calcium chloride tube, a thermometer, and a stirrer. After charging, 0.37 g of sodium metal was added in small pieces. After the metallic sodium was dissolved, 1.84 g of 5-methylthio-2,4,6-trichloropyrimidine was added little by little at 0°C. at 0℃
After stirring for 15 minutes at room temperature, the reaction solution was poured into ice water. The precipitated solid was collected and recrystallized from isopropyl alcohol to give 6-chloro-2,4-dimethoxy-5-methylthiopyrimidine (mp58.5
~59.5°C) was obtained. Yield 1.40g (yield 79.1%)
NMR (CCl 4 ) δ2.30 (3H, s,), 3.97 (3H, s)
4.04 (3H, s) The singlet peaks that appear at NMR δ values of 3.97 and 4.04 each correspond to three hydrogen atoms,
Due to two methoxy groups. Moreover, since the singlet peaks are unequal, the obtained compound is 6-chloro-2,4-dimethoxy-5
-Identified as methylthiopyrimidine. Synthesis of 2,4-dimethoxy-6-(N-methylamino)-5-methylthiopyrimidine In an autoclave, 1.76 g of 6-chloro-2,4-dimethoxy-5-methylthiopyrimidine and 40
% methylamine aqueous solution and 25 ml of dimethyl sulfoxide were heated at 110° C. for 2 hours. The reaction solution was poured into water and extracted with ethyl acetate. After washing and dehydrating,
The crude product obtained by removing the solvent was recrystallized from isopropyl ether to give 2,4-dimethoxy-6-
(N-methylamino)-5-methylthiopyrimidine (mp 57.5-59°C) was obtained. Yield 1.37g (yield 80
%). NMR (CCl 4 ) δ2.08 (3H, s), 4.99 (3H, d,
J=4.8Hz), 3.86 (3H, s), 3.92 (3H, s), 5.94
(1H, broad) Synthesis example 2 2,4-dimethoxy-5-methylthio-6-
Synthesis of (N-phenylamino)pyrimidine (compound number 2)...Route (b) 2,4-dichloro-5-methylthio-6-
Synthesis of (N-phenylamino)pyrimidine
5-methylthio-2,4,6 in a 4-necked flask
- 2.30 g of trichloropyrimidine, potassium carbonate
2.76 g and 30 ml of dimethyl sulfoxide were charged and suspended. 1.12 g of aniline was added and stirred at room temperature for 3 hours. The reaction solution was poured into dilute hydrochloric acid and extracted with ethyl acetate. After washing with water and dehydration, the crude product obtained by removing the solvent was recrystallized from isopropyl ether and 2,4-dichloro-5-methylthio-6-(N
-phenylamino)pyrimidine (mp130~131℃)
I got it. Yield: 1.63g (yield 57%). NMR (CDCl 3 ) δ2.39 (3H, s), 7.1−7.7 (5H,
m), 8.44 (1H, broad) 2,4-dimethoxy-5-methylthio-6-
Synthesis of (N-phenylamino)pyrimidine A 100 ml four-necked flask equipped with a reflux condenser with a calcium chloride tube, a thermometer and a stirrer was charged with 30 ml of anhydrous methanol. Next, metallic sodium 0.55
Add 2,4 g in small pieces and after completely dissolving
1.14 g of -dichloro-5-methylthio-6-(N-phenylamino)pyrimidine was added at room temperature. 2
After heating under reflux for an hour, the reaction solution was poured into dilute hydrochloric acid and extracted with ethyl acetate. After washing with water and dehydration, the crude product obtained by removing the solvent was recrystallized from n-hexane and 2,4-dimethoxy-5-methylthio-6-(N
-phenylamino)pyrimidine (mp -65~68℃)
I got it. Yield: 0.73g (66% yield). NMR (CCl 4 ) δ2.20 (3H, s), 3.92 (3H, s),
3.99 (3H, s), 6.99 (1H, d, J=8.0Hz), 7.24
(2H, dd, J=8.0, 8.0Hz), 7.62 (2H, d, J=
8.0Hz), 8.08 (1H, broad) The singlet peaks that appear at NMR δ values of 3.92 and 3.97 correspond to three hydrogen atoms, respectively.
Due to two methoxy groups. Moreover, since these singlet peaks are unequal, the obtained compound, 2,4-dimethoxy-5-methylthio-
6-(N-phenylamino)pyrimidine was identified. Any of the compounds of the present invention represented by the general formula () can be synthesized according to the above synthesis examples. The compounds of the present invention produced by the above method and their physical properties are shown in Table 1 below.
【表】【table】
【表】
本発明化合物はそのまま農園芸用殺菌剤として
使用できるが、実際には担体および必要に応じて
他の補助剤と混合して、農園芸用殺菌剤として通
常用いられる製剤形態、たとえば粉剤、粗粉剤、
微粒剤、粒剤、水和剤、乳剤、水溶液剤、水溶
剤、油懸濁剤等に調製されて使用される。
ここでいう担体とは、処理すべき部位へ有効成
分の到達を助け、また有効成分化合物の貯蔵、輸
送、取扱いを容易にするために、農園芸用殺菌剤
中に配合される合成または天然の無機または有機
物質を意味する。
適当な固体担体としてはモンモリロナイト、カ
オリナイトなどの粘土類、ケイソウ土、白土、タ
ルク、バーミキユライト、石こう、炭酸カルシウ
ム、シリカゲル、硫安等の無機物質、大豆粉、オ
ガクズ、小麦粉等の植物性有機物質および尿素等
があげられる。
適当な液体担体としてはベンゼン、トルエン、
キシレン、クメン等の芳香族系炭化水素、ケロシ
ン、鉱油等のパラフイン系炭化水素、四塩化炭
素、クロロホルム、ジクロルエタン等のハロゲン
化炭化水素、アセトン、メチルエチルケトン等の
ケトン類、ジオキサン、テトラヒドロフラン等の
エーテル類、メタノール、プロパノール、エチレ
ングリコール等のアルコール類、ジメチルホルム
アミド、ジメチルスルホキシド、水等があげられ
る。
さらに本発明の化合物の効力を増強するため
に、製剤の剤型、適用場面等を考慮して目的に応
じ、それぞれ単独に、または組合わせて以下のよ
うな補助剤を使用することもできる。
乳化、分散、拡展、湿潤、結合、安定化等の目
的ではリグニンスルホン酸塩等の水溶性塩基、ア
ルキルベンゼンスルホン酸塩、アルキル硫酸エス
テル等のアニオン界面活性剤、ポリオキシエチレ
ンアリルエーテル等の非イオン性界面活性剤、ス
テアリン酸カルシウム、ワツクス等の滑剤、イソ
プロピルヒドロジエンホスフエート等の安定剤、
その他メチルセルロース、カルボキシメチルセル
ロース、カゼイン、アラビアゴム等が挙げられ
る。しかしこれらの成分は以上のものに限定され
るものではない。
また本発明化合物が殺菌剤として適用されると
きに同時に使用される他の農薬、例えば殺虫剤、
殺菌剤、殺ダニ剤、殺線虫剤、抗ウイルス剤、除
草剤、植物生長調節剤、誘引剤、例えば有機リン
酸エステル系化合物、カーバメート系化合物、ジ
チオカーバメート系化合物、チオールカーバメー
ト系化合物、有機塩素系化合物、ジニトロ系化合
物、抗生物質、尿素系化合物、トリアジン系化合
物、および肥料等と併用して、または混合剤とし
て使用することもできる。
本発明の前記活性成分を含有する種々の製剤ま
たは散布用調製物は農薬製造分野にて通常一般に
行われている施用方法、すなわち、散布、(例え
ば液剤散布、ミステイング、アトマイジング、散
粉、散粒、水面施用)、燻蒸、土壌施用(例えば
混入、燻蒸、潅注)、表面施用(例えば塗布、粉
衣、被覆)浸漬等により行うことができる。
次に本発明の農園芸用殺菌剤の製剤法を実施例
によつて説明する。
有効成分化合物は前記合成例および前記第1表
の化合物番号で示す。「部」は「重量部」を表わ
す。
実施例 1
水和剤
化合物3:300部、ケイソウ土:440部、白土:
200部、リグニンスルホン酸ナトリウム:25部、
アルキルベンゼンスルホン酸ナトリウム:15部、
およびポリオキシエチレンノニルフエニルエーテ
ル:20部を、均一に粉砕混合して、有効成分とし
て化合物3を30%含む水和剤を得た。
実施例 2
乳剤
化合物15:400部、シクロヘキサノン:100部、
キシレン:300部、およびソルポール(東邦化学
製界面活性剤)200部を均一に溶解混合し、有効
成分として化合物15を40%含む乳剤を得た。
実施例 3
粒剤
化合物2:10部、ベントナイト:62部、タル
ク:20部、ドデシルベンゼンスルホン酸ナトリウ
ム:2部、およびリグニンスルホン酸ナトリウ
ム:1部を混合し、適量の水を加えて混練した
後、押し出し造粒機を用いて通常の方法により造
粒し、有効成分として化合物2を10%含む粒剤を
得た。
実施例 4
粉剤
化合物8:20部、ステアリン酸カルシウム:5
部、粉状シリカゲル:5部、ケイソウ土:200部、
白土:300部、およびタルク:470部を均一に粉砕
混合して、有効成分として化合物8を2%含む粉
剤を得た。
実施例 5
油剤
化合物17:10部、およびエチルセロソルブ:90
部を混合溶解して、有効成分として化合物17を10
%含む油剤を得た。
次に本発明化合物の殺菌剤としての効果を試験
例によつて詳しく説明する。供試化合物は前記合
成例および前記第1表の化合物番号で示す。
試験例 1
リンゴ斑点落葉病試験
3号素焼鉢に植えた新展開葉が約8葉のリンゴ
幼苗(品種、スターキング、2年生苗)に所定濃
度の薬剤(供試化合物を前記実施例1の方法にて
水和剤となし、これを水で所定濃度に希釈したも
の)をスプレーガン(1.0Kg/cm2)を使用して3
鉢当り100mlを散布した。風乾後、あらかじめ培
養したリンゴ斑点落葉病菌(V−8野菜ジユース
培地で7日間培養)の分生胞子懸濁液を噴霧接種
し、温度23〜25℃、湿度95%以上に3日間保つ
た。各鉢の8葉について各々病斑数を調査し、1
葉当りの平均病斑数を求め、次式により防除価を
算出した。
防除価(%)=(1−散布区の平均病斑数/無散布区
の平均病斑数)×
100
結果を下記第2表に示す。[Table] The compound of the present invention can be used as it is as an agricultural and horticultural fungicide, but in reality, it is mixed with a carrier and other auxiliary agents as necessary to form a formulation commonly used as an agricultural and horticultural fungicide, such as a powder. , coarse powder,
It is prepared and used as fine granules, granules, wettable powders, emulsions, aqueous solutions, aqueous solutions, oil suspensions, etc. The carrier here refers to a synthetic or natural carrier that is added to agricultural and horticultural fungicides to help the active ingredient reach the area to be treated and to facilitate the storage, transportation, and handling of the active ingredient compound. means an inorganic or organic substance. Suitable solid carriers include clays such as montmorillonite and kaolinite, inorganic materials such as diatomaceous earth, clay, talc, vermiculite, gypsum, calcium carbonate, silica gel, and ammonium sulfate, and vegetable organic materials such as soybean flour, sawdust, and wheat flour. substances, urea, etc. Suitable liquid carriers include benzene, toluene,
Aromatic hydrocarbons such as xylene and cumene, paraffinic hydrocarbons such as kerosene and mineral oil, halogenated hydrocarbons such as carbon tetrachloride, chloroform and dichloroethane, ketones such as acetone and methyl ethyl ketone, ethers such as dioxane and tetrahydrofuran. , alcohols such as methanol, propanol, and ethylene glycol, dimethylformamide, dimethyl sulfoxide, and water. Furthermore, in order to enhance the efficacy of the compound of the present invention, the following adjuvants may be used alone or in combination depending on the purpose, taking into consideration the dosage form of the preparation, the application situation, etc. For purposes of emulsification, dispersion, spreading, wetting, binding, stabilization, etc., water-soluble bases such as lignin sulfonates, anionic surfactants such as alkylbenzene sulfonates and alkyl sulfate esters, and non-containing surfactants such as polyoxyethylene allyl ether are used. Ionic surfactants, calcium stearate, lubricants such as wax, stabilizers such as isopropylhydrodiene phosphate,
Other examples include methylcellulose, carboxymethylcellulose, casein, and gum arabic. However, these components are not limited to the above. Also, when the compound of the present invention is applied as a fungicide, other agricultural chemicals, such as insecticides,
Fungicides, acaricides, nematicides, antiviral agents, herbicides, plant growth regulators, attractants, such as organic phosphate compounds, carbamate compounds, dithiocarbamate compounds, thiol carbamate compounds, organic It can also be used in combination with chlorine compounds, dinitro compounds, antibiotics, urea compounds, triazine compounds, fertilizers, etc., or as a mixture. The various formulations or spray preparations containing the active ingredients of the present invention can be applied by application methods customary in the field of agrochemical manufacturing, namely spraying, spraying, misting, atomizing, dusting, granulating, etc. , water surface application), fumigation, soil application (e.g. incorporation, fumigation, irrigation), surface application (e.g. spreading, dusting, covering), immersion, etc. Next, the formulation method of the agricultural and horticultural fungicide of the present invention will be explained with reference to Examples. The active ingredient compounds are shown in the synthesis examples and compound numbers in Table 1 above. "Part" represents "part by weight." Example 1 Wettable powder Compound 3: 300 parts, diatomaceous earth: 440 parts, white clay:
200 parts, sodium ligninsulfonate: 25 parts,
Sodium alkylbenzenesulfonate: 15 parts,
and polyoxyethylene nonyl phenyl ether: 20 parts were uniformly ground and mixed to obtain a wettable powder containing 30% of Compound 3 as an active ingredient. Example 2 Emulsion Compound 15: 400 parts, cyclohexanone: 100 parts,
300 parts of xylene and 200 parts of Solpol (a surfactant manufactured by Toho Chemical) were uniformly dissolved and mixed to obtain an emulsion containing 40% of Compound 15 as an active ingredient. Example 3 Granule Compound 2: 10 parts, bentonite: 62 parts, talc: 20 parts, sodium dodecylbenzenesulfonate: 2 parts, and sodium ligninsulfonate: 1 part were mixed, and an appropriate amount of water was added and kneaded. Thereafter, the mixture was granulated in a conventional manner using an extrusion granulator to obtain granules containing 10% of Compound 2 as an active ingredient. Example 4 Powder Compound 8: 20 parts, calcium stearate: 5
part, powdered silica gel: 5 parts, diatomaceous earth: 200 parts,
300 parts of white clay and 470 parts of talc were uniformly ground and mixed to obtain a powder containing 2% of Compound 8 as an active ingredient. Example 5 Oil Compound 17: 10 parts and ethyl cellosolve: 90
Mix and dissolve 10 parts of Compound 17 as the active ingredient.
An oil solution containing % was obtained. Next, the effect of the compound of the present invention as a fungicide will be explained in detail using test examples. The test compounds are shown by the compound numbers in the Synthesis Example and Table 1 above. Test Example 1 Apple Spot Leaf Disease Test Apple seedlings (variety: Starking, 2-year-old seedlings) with approximately 8 newly developed leaves planted in a No. 3 clay pot were treated with a prescribed concentration of the drug (test compound of Example 1). Using a spray gun (1.0Kg/cm 2 ), use
100ml was sprayed per pot. After air-drying, a conidial suspension of a pre-cultured apple spot defoliation fungus (cultivated for 7 days in V-8 vegetable juice medium) was spray inoculated and maintained at a temperature of 23 to 25°C and a humidity of 95% or higher for 3 days. The number of lesions was investigated on each of the 8 leaves in each pot, and 1
The average number of lesions per leaf was determined, and the control value was calculated using the following formula. Control value (%) = (1 - average number of lesions in sprayed area/average number of lesions in non-sprayed area) x 100 The results are shown in Table 2 below.
【表】【table】
【表】
試験例 2
灰色かび病防除試験
展開したインゲン子葉(品種:トツプクロツ
プ)を所定濃度の薬剤液(供試化合物を前記実施
例1の方法にて水和剤となし、これを水で所定濃
度に希釈したもの)に1分間浸漬した。風乾後、
あらかじめ培養した灰色かび病菌(Botrytis
cinenea、PSA培地にて5日間培養)の菌糸片
(直径6mm)をインゲン葉上におき、温度20℃、
湿度95%以上に4日間保つた。各葉の病斑直径を
調査し、次式により防除価を算出した。
防除価(%)=(1−処理区の平均病斑直径/無処理
区の平均病斑直径)
×100
結果を下記第3表に示す。[Table] Test Example 2 Botrytis blight control test Expanded green bean cotyledons (variety: Topcrop) were mixed with a chemical solution of a specified concentration (the test compound was made into a wettable powder by the method of Example 1 above, and this was mixed with water to the specified concentration). (diluted to a certain concentration) for 1 minute. After air drying,
Pre-cultured gray mold fungus (Botrytis)
cinenea (cultivated for 5 days in PSA medium) mycelial pieces (diameter 6 mm) were placed on kidney bean leaves and incubated at a temperature of 20°C.
The humidity was maintained at over 95% for 4 days. The diameter of the lesion on each leaf was investigated, and the control value was calculated using the following formula. Control value (%) = (1 - average lesion diameter of treated area/average lesion diameter of untreated area) x 100 The results are shown in Table 3 below.
【表】
試験例 4
ジヤガイモ疫病防除試験
温室内でポツトに育生したジヤガイモ(品種、
男シヤク、草丈25cm程度)に所定濃度の薬剤(供
試化合物を前記実施例1の方法にて水和剤とな
し、これを水で所定濃度に希釈したもの)をスプ
レーガンを使用して3鉢当り50ml散布し、風乾し
た。予めジヤガイモ切片上にて7日間培養したジ
ヤガイモ疫病菌より遊走子のう浮遊液を調製し、
更にこの浮遊液を7℃で3時間保ち、遊走子浮遊
液を調製した。この浮遊液を薬剤散布したジヤガ
イモ植物体上に噴霧接種し、被検植物を温度17〜
19℃、湿度95%以上で5時間保つた後、病斑の形
成程度を調査した。
評価基準は次のとうりである。
罹病度 0:病斑面積割合 0%
1: 1〜5%
2: 6〜25%
3: 26〜50%
4: 51%以上
結果を第4表に示した。[Table] Test example 4 Potato late blight control test Potatoes grown in pots in a greenhouse (varieties,
A predetermined concentration of the drug (the test compound was made into a hydrating agent using the method of Example 1 and diluted with water to a predetermined concentration) was applied to a 3-year-old man's peacock, plant height approximately 25 cm, using a spray gun. Spread 50ml per pot and air dry. A zoospore suspension was prepared from Phytophthora bacillus which had been cultured in advance on potato sections for 7 days,
This suspension was further maintained at 7°C for 3 hours to prepare a zoospore suspension. This suspension was spray-inoculated onto the drug-sprayed potato plants, and the test plants were grown at a temperature of 17 to
After being kept at 19°C and humidity of 95% or higher for 5 hours, the degree of lesion formation was investigated. The evaluation criteria are as follows. Disease severity 0: Lesion area ratio 0% 1: 1-5% 2: 6-25% 3: 26-50% 4: 51% or more The results are shown in Table 4.
Claims (1)
素数1〜3のアルキル基、アルケニル基、フエニ
ル基、アルコキシカルボニルアルキル基、カルボ
キシアルキル基、アミノアルキル基、またはアミ
ノ基をそれぞれ表わす。)、エチレンイミノ基、モ
ルホリノ基、または2,6−ジメチル−4−モル
ホリノ基を表わす。〕で示される5−メチルチオ
ピリミジン誘導体。 2 5−メチルチオ−2,4,6−トリクロロピ
リミジンとナトリウムメチラートとを反応させ
て、6−クロロ−2,4−ジメトキシ−5−メチ
ルチオピリミジンを製造し、次にこれを一般式
XH〔式中、Xは−NR1R2(R1、R2は水素原子、
炭素数1〜3のアルキル基、アルケニル基、フエ
ニル基、アルコキシカルボニルアルキル基、カル
ボキシアルキル基、アミノアルキル基、またはア
ミノ基をそれぞれ表わす。)、エチレンイミノ基、
モルホリノ基、または2,6−ジメチル−4−モ
ルホリノ基を表わす。〕で示されるアミン類と反
応させることを特徴とする一般式() (式中、Xは前出と同じ)で示される5−メチ
ルチオピリミジン誘導体の製造法。 3 5−メチルチオ−2,4,6−トリクロロピ
リミジンと一般式XH〔式中、Xは−NR1R2(R1、
R2は水素原子、炭素数1〜3のアルキル基、ア
ルケニル基、フエニル基、アルコキシカルボニル
アルキル基、カルボキシアルキル基、アミノアル
キル基、またはアミノ基をそれぞれ表わす。)、エ
チレンイミノ基、モルホリノ基、または2,6−
ジメチル−4−モルホリノ基を表わす。〕で示さ
れるアミン類とを反応させて、一般式() (式中、Xは前出と同じ。)で示される化合物
を製造し、次にこれをナトリウムメチラートと反
応させることを特徴とする一般式() (式中、Xは前出と同じ。)で示される5−メ
チルチオピリミジン誘導体の製造法。 4 一般式() 〔式中、Xは−NR1R2(R1、R2は水素原子、炭
素数1〜3のアルキル基、アルケニル基、フエニ
ル基、アルコキシカルボニルアルキル基、カルボ
キシアルキル基、アミノアルキル基、またはアミ
ノ基をそれぞれ表わす。)、エチレンイミノ基、モ
ルホリノ基、または2,6−ジメチル−4−モル
ホリノ基を表わす。〕で示される5−メチルチオ
ピリミジン誘導体を有効成分として含有すること
を特徴とする農園芸用殺菌剤。[Claims] 1 General formula () [ In the formula , each represents an amino group), an ethyleneimino group, a morpholino group, or a 2,6-dimethyl-4-morpholino group. ] A 5-methylthiopyrimidine derivative represented by: 2 5-Methylthio-2,4,6-trichloropyrimidine and sodium methylate are reacted to produce 6-chloro-2,4-dimethoxy-5-methylthiopyrimidine, which is then expressed by the general formula
XH [wherein, X is -NR 1 R 2 (R 1 and R 2 are hydrogen atoms,
Each represents an alkyl group, alkenyl group, phenyl group, alkoxycarbonylalkyl group, carboxyalkyl group, aminoalkyl group, or amino group having 1 to 3 carbon atoms. ), ethyleneimino group,
Represents a morpholino group or a 2,6-dimethyl-4-morpholino group. ] General formula () characterized by reacting with amines represented by A method for producing a 5-methylthiopyrimidine derivative represented by the formula (wherein, X is the same as above). 3 5-methylthio-2,4,6-trichloropyrimidine and general formula XH [wherein, X is -NR 1 R 2 (R 1 ,
R2 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkenyl group, a phenyl group, an alkoxycarbonylalkyl group, a carboxyalkyl group, an aminoalkyl group, or an amino group, respectively. ), ethyleneimino group, morpholino group, or 2,6-
Represents dimethyl-4-morpholino group. ] by reacting with amines represented by the general formula () (In the formula, X is the same as above.) A general formula () characterized by producing a compound represented by the formula (wherein, X is the same as above) and then reacting this with sodium methylate. (In the formula, X is the same as above.) A method for producing a 5-methylthiopyrimidine derivative. 4 General formula () [ In the formula , each represents an amino group), an ethyleneimino group, a morpholino group, or a 2,6-dimethyl-4-morpholino group. ] An agricultural and horticultural fungicide characterized by containing a 5-methylthiopyrimidine derivative represented by the following as an active ingredient.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8007082A JPS58198472A (en) | 1982-05-14 | 1982-05-14 | 2,4-dimethoxy-5-methylthiopyrimidine derivative, its preparation, and agricultural and gardening fungicide |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8007082A JPS58198472A (en) | 1982-05-14 | 1982-05-14 | 2,4-dimethoxy-5-methylthiopyrimidine derivative, its preparation, and agricultural and gardening fungicide |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS58198472A JPS58198472A (en) | 1983-11-18 |
JPH044310B2 true JPH044310B2 (en) | 1992-01-27 |
Family
ID=13707958
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP8007082A Granted JPS58198472A (en) | 1982-05-14 | 1982-05-14 | 2,4-dimethoxy-5-methylthiopyrimidine derivative, its preparation, and agricultural and gardening fungicide |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS58198472A (en) |
-
1982
- 1982-05-14 JP JP8007082A patent/JPS58198472A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS58198472A (en) | 1983-11-18 |
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