CN1042027C - 杀菌剂1,2,4-三唑化合物 - Google Patents
杀菌剂1,2,4-三唑化合物 Download PDFInfo
- Publication number
- CN1042027C CN1042027C CN93107634A CN93107634A CN1042027C CN 1042027 C CN1042027 C CN 1042027C CN 93107634 A CN93107634 A CN 93107634A CN 93107634 A CN93107634 A CN 93107634A CN 1042027 C CN1042027 C CN 1042027C
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- China
- Prior art keywords
- alkyl
- phenyl
- group
- compound
- halogen
- 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.)
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- 230000000855 fungicidal effect Effects 0.000 title claims abstract description 13
- 150000000178 1,2,4-triazoles Chemical class 0.000 title 1
- -1 acetoxyl group Chemical group 0.000 claims description 101
- 150000001875 compounds Chemical class 0.000 claims description 61
- 238000000034 method Methods 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 38
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 34
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 34
- 239000002253 acid Substances 0.000 claims description 26
- 229910052736 halogen Inorganic materials 0.000 claims description 25
- 150000002367 halogens Chemical class 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 21
- 239000000460 chlorine Substances 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 14
- 239000011833 salt mixture Substances 0.000 claims description 11
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 125000001188 haloalkyl group Chemical group 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 125000004648 C2-C8 alkenyl group Chemical group 0.000 claims description 5
- 125000004649 C2-C8 alkynyl group Chemical group 0.000 claims description 5
- 241000233866 Fungi Species 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 125000001624 naphthyl group Chemical group 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 125000002541 furyl group Chemical group 0.000 claims description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 4
- 125000004076 pyridyl group Chemical group 0.000 claims description 4
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 4
- 230000001954 sterilising effect Effects 0.000 claims description 4
- 238000004659 sterilization and disinfection Methods 0.000 claims description 4
- 125000001544 thienyl group Chemical group 0.000 claims description 4
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 229960003328 benzoyl peroxide Drugs 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 125000001425 triazolyl group Chemical group 0.000 claims description 3
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 claims description 2
- 125000000081 (C5-C8) cycloalkenyl group Chemical group 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 229940073608 benzyl chloride Drugs 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 125000002757 morpholinyl group Chemical group 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000005544 phthalimido group Chemical group 0.000 claims description 2
- 125000005936 piperidyl group Chemical group 0.000 claims description 2
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical group ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 claims 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims 2
- 125000004429 atom Chemical group 0.000 claims 2
- 125000004953 trihalomethyl group Chemical group 0.000 claims 2
- 125000006656 (C2-C4) alkenyl group Chemical group 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 1
- 125000001231 benzoyloxy group Chemical group C(C1=CC=CC=C1)(=O)O* 0.000 claims 1
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical group CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 claims 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims 1
- QFXZANXYUCUTQH-UHFFFAOYSA-N ethynol Chemical group OC#C QFXZANXYUCUTQH-UHFFFAOYSA-N 0.000 claims 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 1
- 125000004433 nitrogen atom Chemical group N* 0.000 claims 1
- 125000004193 piperazinyl group Chemical group 0.000 claims 1
- 150000003573 thiols Chemical class 0.000 claims 1
- JDIPHBYZUMQFQV-UHFFFAOYSA-N 5-ethyl-1h-1,2,4-triazole Chemical class CCC1=NC=NN1 JDIPHBYZUMQFQV-UHFFFAOYSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 53
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 43
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 41
- 239000007787 solid Substances 0.000 description 29
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 28
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 26
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 25
- 229910052799 carbon Inorganic materials 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000000243 solution Substances 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 20
- 241000209140 Triticum Species 0.000 description 20
- 235000021307 Triticum Nutrition 0.000 description 19
- 239000002904 solvent Substances 0.000 description 19
- 241000196324 Embryophyta Species 0.000 description 18
- 238000005406 washing Methods 0.000 description 17
- 241000209094 Oryza Species 0.000 description 16
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical class N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- 235000007164 Oryza sativa Nutrition 0.000 description 14
- 201000010099 disease Diseases 0.000 description 14
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 14
- 235000009566 rice Nutrition 0.000 description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000012074 organic phase Substances 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 11
- 238000013019 agitation Methods 0.000 description 11
- 150000001408 amides Chemical group 0.000 description 11
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- 239000002585 base Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 8
- 241000221785 Erysiphales Species 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000012141 concentrate Substances 0.000 description 8
- 235000008504 concentrate Nutrition 0.000 description 8
- 229940083608 sodium hydroxide Drugs 0.000 description 8
- 235000011121 sodium hydroxide Nutrition 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 125000003342 alkenyl group Chemical group 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 238000011081 inoculation Methods 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 description 6
- DNSISZSEWVHGLH-UHFFFAOYSA-N butanamide Chemical compound CCCC(N)=O DNSISZSEWVHGLH-UHFFFAOYSA-N 0.000 description 6
- 150000001721 carbon Chemical group 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 6
- 238000003810 ethyl acetate extraction Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000012280 lithium aluminium hydride Substances 0.000 description 6
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 description 5
- JVBNBNSOSNMVRJ-UHFFFAOYSA-N 2-ethyltriazole Chemical class CCN1N=CC=N1 JVBNBNSOSNMVRJ-UHFFFAOYSA-N 0.000 description 5
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 5
- 125000000304 alkynyl group Chemical group 0.000 description 5
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical group N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 230000002070 germicidal effect Effects 0.000 description 5
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 150000002825 nitriles Chemical class 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000012312 sodium hydride Substances 0.000 description 5
- 229910000104 sodium hydride Inorganic materials 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
- 150000003852 triazoles Chemical class 0.000 description 5
- 239000004563 wettable powder Substances 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical class [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
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- 150000002148 esters Chemical class 0.000 description 4
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- 230000026030 halogenation Effects 0.000 description 4
- 238000005658 halogenation reaction Methods 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 3
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- 235000007340 Hordeum vulgare Nutrition 0.000 description 3
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- 229910019142 PO4 Inorganic materials 0.000 description 3
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
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- 125000003373 pyrazinyl group Chemical group 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
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- 239000007921 spray Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 239000000080 wetting agent Substances 0.000 description 3
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 2
- MVXMNHYVCLMLDD-UHFFFAOYSA-N 4-methoxynaphthalene-1-carbaldehyde Chemical compound C1=CC=C2C(OC)=CC=C(C=O)C2=C1 MVXMNHYVCLMLDD-UHFFFAOYSA-N 0.000 description 2
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 2
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- 239000005864 Sulphur Substances 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 235000009754 Vitis X bourquina Nutrition 0.000 description 2
- 235000012333 Vitis X labruscana Nutrition 0.000 description 2
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- 239000005870 Ziram Substances 0.000 description 2
- CRAFAURDODIIGN-UHFFFAOYSA-N [NH4+].C(C(O)C)(=O)[O-].C(O)CN.[Hg].C1=CC=CC=C1 Chemical compound [NH4+].C(C(O)C)(=O)[O-].C(O)CN.[Hg].C1=CC=CC=C1 CRAFAURDODIIGN-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- 238000005902 aminomethylation reaction Methods 0.000 description 2
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- YORCIIVHUBAYBQ-UHFFFAOYSA-N propargyl bromide Chemical compound BrCC#C YORCIIVHUBAYBQ-UHFFFAOYSA-N 0.000 description 1
- KKMLIVYBGSAJPM-UHFFFAOYSA-L propineb Chemical compound [Zn+2].[S-]C(=S)NC(C)CNC([S-])=S KKMLIVYBGSAJPM-UHFFFAOYSA-L 0.000 description 1
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- QTENRWWVYAAPBI-YCRXJPFRSA-N streptomycin sulfate Chemical compound OS(O)(=O)=O.OS(O)(=O)=O.OS(O)(=O)=O.CN[C@H]1[C@H](O)[C@@H](O)[C@H](CO)O[C@H]1O[C@@H]1[C@](C=O)(O)[C@H](C)O[C@H]1O[C@@H]1[C@@H](N=C(N)N)[C@H](O)[C@@H](N=C(N)N)[C@H](O)[C@H]1O.CN[C@H]1[C@H](O)[C@@H](O)[C@H](CO)O[C@H]1O[C@@H]1[C@](C=O)(O)[C@H](C)O[C@H]1O[C@@H]1[C@@H](N=C(N)N)[C@H](O)[C@@H](N=C(N)N)[C@H](O)[C@H]1O QTENRWWVYAAPBI-YCRXJPFRSA-N 0.000 description 1
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- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- QGHREAKMXXNCOA-UHFFFAOYSA-N thiophanate-methyl Chemical group COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC QGHREAKMXXNCOA-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- ILERPRJWJPJZDN-UHFFFAOYSA-N thioquinox Chemical compound C1=CC=C2N=C(SC(=S)S3)C3=NC2=C1 ILERPRJWJPJZDN-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 125000005389 trialkylsiloxy group Chemical group 0.000 description 1
- WCLDITPGPXSPGV-UHFFFAOYSA-N tricamba Chemical compound COC1=C(Cl)C=C(Cl)C(Cl)=C1C(O)=O WCLDITPGPXSPGV-UHFFFAOYSA-N 0.000 description 1
- DQJCHOQLCLEDLL-UHFFFAOYSA-N tricyclazole Chemical compound CC1=CC=CC2=C1N1C=NN=C1S2 DQJCHOQLCLEDLL-UHFFFAOYSA-N 0.000 description 1
- RROQIUMZODEXOR-UHFFFAOYSA-N triforine Chemical compound O=CNC(C(Cl)(Cl)Cl)N1CCN(C(NC=O)C(Cl)(Cl)Cl)CC1 RROQIUMZODEXOR-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- JARYYMUOCXVXNK-IMTORBKUSA-N validamycin Chemical compound N([C@H]1C[C@@H]([C@H]([C@H](O)[C@H]1O)O[C@H]1[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O1)O)CO)[C@H]1C=C(CO)[C@H](O)[C@H](O)[C@H]1O JARYYMUOCXVXNK-IMTORBKUSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- CHNQZRKUZPNOOH-UHFFFAOYSA-J zinc;manganese(2+);n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[Zn+2].[S-]C(=S)NCCNC([S-])=S.[S-]C(=S)NCCNC([S-])=S CHNQZRKUZPNOOH-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- C—CHEMISTRY; METALLURGY
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Abstract
2-芳基或2-杂环基-2,2-二取代乙基-1,2,4-三唑已显示出具有杀菌作用。
Description
本发明涉及(2-芳基或2-杂环基-2,2-二取代)-乙基-1,2,4-三唑、其对映体、酸加成盐、金属盐复合物、含有这些化合物的组合物以及这些化合物作为杀菌剂、尤其是抗植物病原性真菌的应用。
美国专利4,366,165公开了1-和4-芳基氰基烷基-1,2,4-三唑杀菌剂。该专利所公开的化合物仅限于氰基与三唑上烷基取代基的β-碳键合的化合物。
欧洲专利公开号61,798公开了2-乙基三唑衍生物,其乙基的β-碳原子上带有苯基取代基。该专利所公开的所有化合物也带有与β-碳原子相连的氢原子以及一个仲氨基或叔氨基。
欧洲专利公开号52,424公开了2-乙基取代的三唑化合物,其中乙基的β-碳原子带有氯、氰基或氧取代基。
英国专利申请GB2104065A公开了微生物的扁桃酸衍生物和扁桃腈。这些化合物一般为2-乙基三唑,其中乙基的β-碳原子被芳族取代基、氧取代基和羧基或氰基取代。其中所公开的所有化合物均要求乙基的β-碳原子上的取代基中至少一个为氧取代基。
美国专利US.4,672,335公开了杀菌的羟乙基吡咯基肟衍生物。其中所公开的化合物除了在不对称碳原子上的肟官能度外,所有化合物在同一碳原子还带有羟基。
美国专利US.4,598,085公开了将具有杀菌作用的1-(2-芳基-2-R-乙基)-1H-1,2,4-三唑用作杀菌剂。这里所公开的所有化合物在乙基取代的三唑的β-碳原子上均具有氢原子,并且还可具有任意取代的苯基和低级烷基、环烷基、低级链烯基、芳甲基和芳乙基取代基。
德国专利公开号3408127公开了具有杀菌作用的N-(吡咯基乙基)羧酰胺。据报道,这些化合物带有与三唑的乙基取代基上的β-碳原子相连的羧酰胺基。
美国专利4,398,942公开了具有除草活性的苯基乙腈。这些化合物为取代的乙基三唑,且在乙基取代基的β-碳原子上带有氰基或乙炔基。
美国专利4,411,687公开了具有杀菌作用的吡咯二醇衍生物,它们在2-乙基三唑的β-碳原子上带有醚键或酯键,且在α-碳原子上有二醇取代基。
德国专利公开号3221915公开了具有杀菌作用的酯,它们在2-乙基三唑的α-碳原子上带有氯取代基,且在β-碳原子上带有烷基酯。
欧洲专利公开号234,242公开了具有杀菌作用的2-乙基三唑,其乙基链的β-碳原子上带有氟烷氧基取代基。
欧洲专利公开号46,658公开了双三唑酮,其中桥连亚乙基带有低级烷基羰基取代基。
本发明涉及新的(2-芳基或2-杂环基-2,2-二取代)乙基-1,2,4-三唑,其对映体、酸加成盐、金属盐复合物,以及它们作为高效广谱内吸杀菌剂的应用。
x为任意取代的芳基或任意取代的杂环基,如吡啶基、嘧啶基、吡嗪基、噻吩基、呋喃基等;
Q为任意取代的1-(1,2,4-三唑基)或4-(1,2,4-三唑基);
Z为烷基、卤代烷基、链烯基、卤代链烯基、链炔基、环烷基、环烯基、环烷基烷基、芳基、芳烷基、杂环基或杂环烷基,条件是x和z不同时为杂环基;
W为醚、酯、胺、酰胺、磺酸酯、尿烷、二烷基磷酸酯或三烷基甲硅烷氧基,以上所有基团均可被取代;或为卤素或羟基;
R为氢原子或烷基;
n为整数1-6。
x为任意取代的芳基,如苯基、萘基等,或为任意取代的杂环基,如吡啶基、嘧啶基、吡嗪基、噻吩基或呋喃基;
Q为任意取代的1-(1,2,4-三唑基)或4-(1,24-三唑基);
Z为(C1-C12)烷基、卤代(C1-C12)烷基、(C2-C8)链烯基、卤代(C2-C8)链烯基、(C2-C8)链炔基、(C3-C8)环烷基、(C5-C8)环烯基、环烷基烷基、芳基、芳烷基、杂环基或杂环基烷基,条件是x和z不同时为杂环基;
W为-OR、-OCOR″、-OCOY、-OCOR′Y、-OCOR′OR″、-OR′OCOR″、-OR′OR、-NH2、-NHCOR、-NHCOR′Y、-NHCOY、-OCONHY、-OSO2A、-OSiA3、-OPO(OA)2或卤素;其中A为(C2-C6)烷基,
R为(C1-C12)烷基、x、y-烷基、(C3-C8)链烯基、(C3-C8)链炔基、(C3-C8)环烷基、氰基烷基或环氧烷基,以上所有基团均可被卤化;或为氢原子,条件是当Z为甲基时,R不为卤代烷基;
R′为(-CH(CH3)-)p(-CH2-)m或(-CH2-)sCH=CH(-CH2-)t;
m为整数0-6;
p为0或1,条件是m和p不能都为0;
s和t各自独立地为整数0-3;
R″为苯基、(C1-C6)烷基、(C2-C4)链烯基或(C1-C2-三烷基甲硅烷基(C1-C4)烷基,所有这些基团均可被卤化,或为氢原子;
R为氢原子或(C1-C6)烷基;
n为整数1-6;
Y为苯基、萘基、哌啶基、三唑基、吡嗪基、嘧啶基、苯二甲酰亚氨基、吗啉基、吡啶基、噻吩基、呋喃基或环烷基,所有这些基团均可被取代。
术语“芳基”意指具有6-10个碳原子的芳族环结构,较好的是苯基或萘基。该芳基可任意被高达三个、优选高达两个的取代基取代,取代基系选自羟基、卤素、乙酸基、三卤甲基、(C1-C4)烷基、(C1-C4)烷氧基、(C1-C4)烷硫基、(C1-C4)烷基亚磺酰基、(C1-C4)烷基磺酰基、(C1-C4)烷氧基(C1-C4)烷氧基、(C1-C4)烷基羧基、(C2-C8)链烯基、(C2-C4)链烯氧基、(C2-C8)炔基、(C2-C4)炔氧基、苯基、被卤素、烷基或烷氧基单取代的苯基、苯氧基、被卤素、烷基或烷氧基单取代的苯氧基。典型的芳基包括但不限于:苯基、萘基、4-氯苯基、4-氟苯基、2-甲氧基苯基、4-苯基苯基、4-(4′-氯苯基)苯基、4-苯氧基苯基、2-氯-4-(4′-氯苯氧基)苯基、2,4-二溴苯基、3,5-二氟苯基、2,4,6-三氯苯基、2,3,4-三溴苯基、3,4-二氯苯基、2-氯-4-碘苯基、3-氯-4-硝基苯基、3,4,5-三甲基苯基、2-氯萘基、2,4-二甲氧基苯基、4-(三氟甲基)苯基、3,5-二(甲硫基)苯基、2-氰基-5-甲基苯基、2,4-二(甲基亚磺酰基)苯基、2,4-二(甲基磺酰基)苯基、2,4-二碘萘基和2-碘-4-甲基苯基。
术语“杂环基”意指五元和六元环,带有高达三个的独立选自氮、氧和硫的杂原子,包括但不限于呋喃、噻吩、三唑、咪唑、吡啶、嘧啶、吡唑、噁唑、哌嗪和吗啉,它们均可被高达两个的独立选自烷基和卤素的取代基任意取代。
除非另有说明,术语“烷基”包括具有1-12个碳原子的直链和支链烷基。典型的烷基有甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、新戊基、异戊基、己基、庚基、异辛基、壬基、癸基、异癸基、十一烷基、十二烷基等。烷基可被卤化。
术语“亚烷基”指二价烷基,其中两个游离键可存在于相同或不同碳原子上。
术语“芳烷基”指其中烷基链为有1-4个碳原子直链或支链基团且其中芳基部分定义同前的基团。典型的芳烷基包括但不限于2,4-二氯苄基、2,4-二溴苄基、2,4,6-三氯苄基、3,5-二甲氧基苯乙基、2,5-二(甲基磺酰基)苯乙基、3,4,5-三甲基苯丁基、2,4-二氰基萘甲基、2,4-二溴萘丁基、4-氯苯乙基、4-氟苯乙基、4-(三氟甲基)苯乙基等。
术语“链烯基”和“链炔基”包括具有至少一个不饱和键的直链和支链C2-C8烃。这些取代基可被卤化。
术语“亚烯基”指在不同碳原子上存在两个游离键的二价链烯基。
在Q的定义中,术语“任意取代的1-(1,2,4-三唑基)或4-(1,2,4-三唑基)”包括未取代的1-和4-(1,2,4-三唑基)和被不超过两个选自卤素、(C1-C4)烷基、硝基、氰基、巯基和(C1-C5)烷基巯基取代的1-和4-(1,2,4-三唑基)。
本说明书及所附权利要求书中所用的符号“OCOR”指其中羰基的碳原子与R键合的基团;符号“COOR”指其中非羰基氧与R键合的基团。
可用于制备“本发明酸加成盐的酸包括盐酸、氢溴酸、硝酸、硫酸、磷酸、氢碘酸、氢氟酸、高氯酸、对一甲苯磺酸、甲磺酸、乙酸、柠檬酸、酒石酸、苹果酸、草酸、富马酸、邻苯二甲酸等。
本发明的另一实施方案是式(II)的金属盐复合物:其中X、Z、Q、R和W的定义同式(I),M为选自元素周期表IIA、IVA、IB、IIB、VIB、VIIB和VIII族的阳离子,Y为选择用于中和阳离子M的电荷的阴离子抗衡离子。
本发明典型的阳离子包括镁、锰、铜、镍、锌、铁、钴、钙、锡、镉、汞、铬、钡等。
本发明典型的阴离子为氯、溴、碘、氟、硫酸根、硫酸氢根、高氯酸根、硝酸根、亚硝酸根、磷酸根、碳酸根、碳酸氢根、革酸根、酒石酸根、苹果酸根、马来酸根、富马酸根、对一甲苯磺酸根、甲磺酸根、一或二(C1-C4)烷基二硫代氨基甲酸根、(C1-C4)亚烷基双二硫代氨基甲酸根等。
本发明优选的是如下的式(I)和(II)化合物、其对映体、盐和复合物,其中X为可被高达三个、优选高达二个的取代基任意取代的苯基,该取代基选自卤素(优选氯)、三卤甲基(优选三氟甲基)、(C1-C4)烷基、(C1-C4)烷氧基、(C1-C4)烷硫基、苯氧基、单卤苯氧基和苯基;Z为(C1-C8)烷基、卤代(C1-C12)烷基、(C5-C7)环烷基、(C3-C7)环烷基(C1-C5)烷基、(C2-C5)链烯基、卤代(C2-C5)链烯基、(C5-C6)环链烯基、(C2-C4)链炔基、苯基、苄基和苯乙基,该芳香环被高达两个卤素取代基或三卤甲基取代,R为H,且n为1,条件是当Z为甲基时R不为卤代烷基,Q为1-(1,2,4-三唑基)。
本发明更优选的是如下的式(I)和式(II)化合物、其对映体、盐和复合物,其中X为苯基,其4-位被氯、溴、氟、羟基、乙酸基、甲氧基、乙氧基或三氟甲基任意取代;Z为(C1-C6)烷基、(C5-C6)环烷基(优选乙基或正丁基)、苯基、苄基、苯乙基或-氯苯基、苄基或苯乙基,如4-氯苯基、2-氯苄基、4-氯苯乙基;R为(C1-C4)烷基、(C1-C4)卤代烷基、(C3-C4)链烯基、(C3-C4)链炔基、或任意被卤素取代的苯基、苄基或苯乙基,且R″为(C1-C4)烷基或苯基,条件是当X为苯基时R不为卤代烷基,Q为1-(1,2,4-三唑基)。
说明书及权利要求书中所述的化合物均由Miller的美国专利US.4,366,165中的芳基氰基烷基-1,2,4-三唑合成,该文献中所公开的内容并入这里以作参考。其一般步骤为:
A.水解腈为酸;
B.水解腈为酰胺;
C.水解酰胺为酸;
D.还原酸为羟甲基化合物;
E.还原腈为氨甲基化合物;
F.酰化羟甲基化合物为酰基甲基化合物;
G.形成磺酸酯;
H.酰化氨甲基化合物为酰氨基甲基化合物;
I.醚化羟甲基化合物为烷氧基甲基化合物;
J.Grignard加成腈,形成羰基,然后还原。
将以上步骤施用于其中芳基被取代或未被取代的(2-芳基)乙基-1,2,4-三唑。所使用的方法是人们熟知的,并可在合成化学领域的任何普通论文中发现,如March,AdvoncedOrganic Checristry Reactions,Mechanismand Structure,3rd.Edition,John Wiley &Sons,1985(以下简称为“March”),其中所公开的内容并入这里以作参考。下面的反应流程概述了其串连。在该流程中,X、Q、Z、R和A的定义同式I中,且G可为式I中所定义的R或R′。流程1
步骤A:水解腈为酸(March,第788页)
腈衍生物(1)水解为羧酸(2)是在强酸性条件下用浓盐酸、50-96%硫酸、48%氢溴酸及浓硝酸等酸完成;优选的是在约100-140℃的温度下用48%氢溴酸或浓盐酸水解最多至四天。
步骤B;水解腈为酰胺(March,第788页)
利用强酸(如步骤A中所用的酸)或强碱可很方便地将腈(1)水解为酰胺(3)。当使用酸时,优选在约80-130℃更优选在约90-110℃的温度下用95%硫酸水解最多至7天。
强碱条件可通过选择浓氢氧化钠、氢氧化钾或氢氧化锂等碱获得。除水外,水解也可在另一种溶剂,如二甲基亚砜等偶极非质子传递溶剂存在下进行。优选用浓氢氧化钠水解约1-3小时,其温度一般为约80-130℃,更优选约90-110℃。
步骤C:水解酰胺为酸(March,第388页)
可直接用如步骤A的强酸将酰胺(3)水解为相应的羧酸(2),或用如步骤B的强碱水解为羧酸盐。强酸最好为45-95%硫酸或约48%的氢溴酸。酰胺与合适的酸或碱在约80-160℃,更优选约80-130℃的温度下反应,该方法优选适用于邻位取代的苯基衍生物。
步骤D:还原酸为羟甲基化合物(March,第1099页)
于0℃至室温(优选5-20℃)在无水四氢呋喃(THF)或乙醚等醚类溶剂中用金属氢化物(优选氢化铝锂)还原羧酸(2)或酯高达约24小时可很容易地制备出羟甲基(伯醇)衍生物(5)。
步骤E:还原腈为氨甲基化合物(March,第815页)
于0℃至室温条件下在无水THF或乙醚等醚类溶剂中用金属氢化物(优选氢化铝锂)还原腈(1)至最高达约24小时(一般为1-6小时)可很容易地制备出氨甲基(伯胺)衍生物(4)。
步骤F:酰化羟甲基化合物为酰甲基化合物(March,第346-348页)
通过醇解酰基卤或酐或用羟甲基衍生物(5)酯化酸可制备出酰甲基衍生物(7)。可在碱(如三乙胺或吡啶)存在下于合适的溶剂(如THF)中将酰基氯加到羟甲基化合物中。反应温度为室温至60℃,反应时间最高达约24小时。
步骤G:形成磺酸酯(March,第358页)
由羟甲基化合物(5)和烷基氯或芳基磺酰氯(如一氯甲烷、一氯乙烷、氯苯或甲苯磺酰氯)反应可制备磺酸酯。存在于二氯甲烷或甲苯等溶剂中的羟甲基化合物是在碱(如三乙胺或吡啶存在下与磺酰氯反应)。反应温度为0-50℃,优选约10-30℃,反应时间最高达约24小时。
步骤H:酰化氨甲基化合物为酰氨基甲基化合物(March,第370页)
通过用酰基卤、酸酐或羧酸酯酰化氨甲基化合物(4)可合成酰氨基甲基化合物(N-取代的酰胺)。优选于0-50℃(尤其是10-35℃)在非极性溶剂(如二氯甲烷或甲苯)存在下将酰基氯与氨基甲基化合物反应最高达24小时。或者,于0-50℃(优选约15-35℃)在碱(如吡啶)存在下将酸酐(如乙酸酐)与氨基甲基化合物反应最高达约12小时。
步骤I:醚化羟甲基化合物为烷氧基甲基化合物(March,第342页)
通过首先于0-50℃(优选10-30℃)在偶极非质子传递溶剂(如DMF或四氢呋喃)中利用强碱(如碱金属氢化物,优选氢化钠)产生羟甲基(醇)化合物(5)的碱金属盐可制备出烷氧基甲基化合物(醚)(8)。加入烷基卤、芳烷基卤、链烯基烷基卤或链炔基烷基卤,于0-50℃(优选10-30℃)反应最高达24小时。
或者,于0-50℃在合适的溶剂(如THF)中将磺酸酯(9)或卤素衍生物(W=卤素)与醇盐或酚盐(由醇或酚和碱(如氢化钠)在THF中反应得到)反应最高达24小时得到。
步骤J:Grignard加成腈并还原(March,第828和1093页)
当式I中R不为H时,通过将腈(1)与有机金属试剂如烷基锂,或更优选的是Grignard试剂(RMgX)于回流温度下在THF或乙醚中反应可很方便地制备出羟甲基衍生物(仲醇)。所产生的酮(10)可被还原(步骤D),产生仲醇,它可自步骤F、G和I衍生。
当式I中n为2时,该衍生物可通过于80-130℃(优选90-120℃)在DMF(更优选的是DMSO)中将碱金属氰化物(如氰化钾或氰化钠)与化合物(9)反应最高达约24小时制得。然后可按流程1将(1)的氰基甲基类似物进行反应。可重复该转化,产生其中n大于2的同系物。
本发明1,2,4-三唑的酸加成盐可利用本领域熟知的常规技术制备。例如,可将式(I)的1,2,4-三唑溶解在合适的溶剂(如乙醚、四氢呋喃、乙醇、甲醇及其类似物或其混合物)中,并用等量或过量的无机或有机酸处理,该无机或有机酸可溶于或不溶于合适溶剂。然后冷却或蒸发该混合物,所产生的盐可直接使用或用合适溶剂或其混合物重结晶。
通过在搅拌下滴加溶于合适溶剂或其混合物中的化学计算量的金属盐可制备出上述1,2,4-三唑的金属盐复合物。稍稍搅拌反应混合物并减压除去溶剂后,得到式(II)的1,2,4-三唑的金属盐复合物。
也可在刚要喷洒植物之前将化学计算量或过量的金属盐和式(I)三唑在含有合适助剂的所需量溶剂中混合来制备金属盐复合物。可包括在该原位制备法中的助剂可以是除垢剂、乳化剂、湿润剂、铺展剂、分散剂、粘着剂、吸附剂、以及可应用于农业的其它试剂。
可用于这些方法中的溶剂包括任何极性溶剂,如水、甲醇、乙醇、异丙醇或乙二醇;和任何非质子传递偶极溶剂,如二甲基亚砜、乙腈、二甲基甲酰胺、硝基甲烷或丙酮。
可用于这些方法中的金属盐阳离子可选自钙、镁、锰、铜、镍锌、铁、钴、锡、镉、汞、铬、铝、钡等。
可用作金属盐的抗衡离子的阴离子有氯化物、溴化物、碘化物硫酸根、硫酸氢根、磷酸根、硝酸根、高氯酸根、碳酸根、碳酸氢根、氢硫根、氢氧根、乙酸根、草酸根、苹果酸根、柠檬酸根等。
当代替金属盐使用时含金属杀菌剂也可用作安全剂。可用于这些方法中的典型含金属杀菌剂有:(1)二硫代氨基甲酸酯及其衍生物,如福美铁、福美锌、代森锰、mancozeb和代森锌;(b)含铜杀菌剂,如氧化亚铜、氯氧化铜、环烷酸铜和Bordeaux混合物以及(c)杂杀菌剂,如乙酸苯汞、N-乙基汞-1,2,3,6-四氢-3,6-桥亚甲基-3,4,5,6,7,7-六氯邻苯二甲酰亚胺、苯汞单乙醇乳酸铵、含镍化合物和氰氨化钙。
本发明化合物具有不对称碳原子,因此存在外消旋混合物。该外消旋混合物中的d和l对映体可利用常规技术分离,如用d-酒石酸、l-酒石酸、l-奎尼酸分级结晶,接着碱化并萃取d或l对映体游离碱。
实施例A(方法A)2-(4-氯苯基)-2-〔(1,2,4-三唑-1-基)甲基〕己酸
向500ml烧瓶中加入60.0g(0.208mole)α-正丁基-α-(4-氯苯基)-1H-1,2,4-三唑-1-丙腈,接着加入200ml 48%氢溴酸。将混合物在回流温度下搅拌96小时,此后气液色谱(GLC)显示起始物的消失。用乙醚稀释反应物,并用水萃取至pH中性。用足量的10%氢氧化钠萃取醚至pH14,用35%盐酸分离,形成白色固体沉淀。过滤收集该固体,并用水洗涤至水洗液中性。真空干燥产物,得到49.0g(产率76.5%)白色固体,熔点169-171℃。实施例B-1(方法B)2-(2,4-二氯苯基)-2-〔(1,2,4-三唑-1-基)甲基〕己酰胺
向250ml烧瓶中加入38.16g(0.119mole)α-正丁基-α-(2,4-二氯苯基)-1H-1,2,4-三唑-1-丙腈,再加入100ml(0.63mole)48%氢溴酸。回流搅拌混合物48小时后,通过GLC测得起始物已消失。将反应物冷却至室温并用浓氢氧化铵(100ml)中和至pH8,然后用浓盐酸中和至中性,形成的胶质油用100ml水洗(3X)。干燥并浓缩有机相后得到的褐色固体用乙醚重结晶。过滤产物,得到22.78g(56.3%)固体,熔点为170-172℃。实施例B-2(方法B)2-(4-氯苯基)-2-〔(1,2,4-三唑-1-基)甲基〕己酰胺
向500ml烧瓶中加入75.0g(0.24mole)α-正丁基-α-(4-氯苯基)-1H-1,2,4-三唑-1-丙腈,以及300ml 95%硫酸。混合物于90℃搅拌7天后冷却至室温,用冰稀释并用氢氧化铵中和至碱性(pH8)。产物经二氯乙烷萃取及水洗涤后于硫酸镁上干燥。浓缩溶剂后得到45g(56.5%)固体,熔点197-199℃。实施例B-3(方法B)2-(4-氯苯基)-2-〔(1,2,4-三唑-1-基)甲基〕丁酰胺
向500ml烧瓶中加入100.0g(0.38mole)α-(4-氯苯基)-α-乙基-1H-1,2,4-三唑-1-丙腈和100ml二甲基亚砜。再向该搅拌溶液中加入100g(1.25mole)50%氢氧化钠。反应混合物于100℃加热1小时后通过GLC测得起始物被消耗。反应产物倒入水中,用乙酸乙酯萃取。盐水洗涤后的有机相于硫酸镁上干燥,并在不加热情况下真空浓缩。除去溶剂后得到多泡透明固体,经己烷研制和过滤后,得到97g(91%)白色固体,熔点139-140℃。实施例B-4(方法B)2-(2,4-二氯苯基)-2-〔(1,2,4-三唑-1-基)甲基〕丁酰胺
向1l烧瓶中加入206.5g(0.7mole)α-(24-二氯苯基)-α-乙基-1H-1,2,4-三唑-1-丙腈、500ml二甲基亚砜和200ml水。再向该搅拌溶液中加入67.2g(0.84mole)50%氢氧化钠。于91℃(蒸汽浴)加热反应混合物3小时后,通过GLC测得起始物已被消耗、冷却至30℃后倒入水中并用乙酸乙酯萃取,干燥后用活性炭处理乙酸乙酯,并用Celile过滤。除去溶剂后得到泡沫状油,经搅拌和用乙酸乙酯稀释后,用己烷处理至混浊,1小时内形成固体,将其冷却至0℃。过滤产物并用乙醚和己烷混合物洗涤,干燥后得到172g(79%)白色固体,熔点164-165℃。实施例B-5(方法B)4-(4-氯苯基)-2-苯基-2-〔(1,2,4-三唑-1基)甲基〕丁酰胺
向2l烧瓶中装入320.0g(0.95mole)α-(2,4-氯苯基)-乙基)-α-苯基-1H-1,2,4-三唑-1-丙腈、685ml二甲基亚砜和275ml水。再向该搅拌溶液中加入91.3g(1.14mole)50%氢氧化钠。反应混合物于95℃加热3小时后,通过GLC测得起始物已被消耗。冷却至20℃后将混合物转移到5升的分液漏斗中,并加入1000ml乙酸乙酯和3000ml水。分离出固体并除去水相。再加入1000ml乙酸乙酯并将混合物加热至55℃以溶解固体,分离水相并用500ml乙酸乙酯萃取。合并有机相并用1升热水和500ml盐水洗涤。于硫酸镁上干燥并除去溶剂后得到372g固体,它含有10%乙酸乙酯。除去残余溶剂后得到固体,熔点169-171℃。实施例C-1(方法C)2-(4-氯苯基)-2-〔(1,2,4-三唑-1-基)甲基〕丁酸
向500ml烧瓶中加入95g(0.34mole)2-(4-氯苯基-2-〔(1,2,4-三唑-1-基)甲基〕丁酰胺、95g(0.97mole)95%硫酸和95g冰。反应混合物回流搅拌55小时后冷却至10℃,并在乙酸乙酯和水之间分配。用200g 10%氢氧化钠处理混合物,产生pH10的水相。有机相用200g水、200g 10%氧氧化钠及200ml水依次萃取。合并水相,用乙醚洗涤,然后酸化至形成固体的pH5。过滤固体,水洗,干燥后得到73g(77%)白色固体,熔点182-184℃。实施例C-2(方法C)2-(2,4-二氯苯基)-2-〔(1,2,4-三唑-1-基)甲基〕丁酸
向1升烧瓶中加入170g(0.54mole)2-(2,4-二氯苯基-2-〔(1,2,4-三唑-1-基)甲基〕丁酰胺、170g(1.73mole)95%硫酸和170g冰。于113℃(回流)搅拌14天后将反应混合物冷却至10℃,并在乙酸乙酯和水之间分配。用915ml 14%氢氧化钠处理混合物,产生pH为10的水相。搅拌混合物10分钟,除去水层,并用乙酸乙酯萃取。合并乙酸乙酯,水洗干燥及浓缩后得到固体,用己烷研制,95g(55.8%)起始酰胺被回收。
酸化水相至pH2,加入1000ml乙酸乙酯,并加热至50℃。过滤所形成的不溶性固体,得到28.5g酸。分离两相,有机相经盐水洗涤、干燥及浓缩后产生另一固体,经用己烷研制和过滤后得到36.2g酸。产物总产率为38%,熔点206-208℃。实施例C-3(方法C)4-(4-氯苯基)-2-苯基-2-〔(1,2,4-三唑-1-基)甲基〕丁酸
向2l烧瓶中加入220g(0.62mole)2-(4-氯苯基)-2-苯基-2-〔(1,2,4-三唑-1-基)甲基〕丁酰胺、1000ml(6.3mole)48%氢溴酸。反应混合物于80-85℃加热6天后冷却至室温,并倒入4升冰水。用2×1000ml水和饱和氯化钠溶液(盐水)萃取溶液。于硫酸镁上干燥后用活性炭处理,Celite过滤并浓缩。固体残余物在乙醚中淤浆化,再经过滤和干燥后得到139g(63%)产物,熔点188-190℃。实施例2(方法D)2-(4-氯苯基)-2-〔(1,2,4-三唑-1-基)甲基〕己-1-醇
于氮气环境及搅拌条件下向装有机械搅拌器的3升烧瓶中加入10.2g(0.325mole)氢化铝锂的400ml无水四氢呋喃溶液。45分钟内向该淤浆中加入100g(0.325mole)2-(4-氯苯基)-2-〔(1,2,4-三唑-1-基)甲基〕己酸的1600ml无水四氢呋喃溶液。加完之后,析出氢气并将淤浆搅拌2小时。过夜放置混合物,通过加入浓硫酸钠溶液终止反应,过滤,浓缩并再次水洗。溶剂经干燥、过滤、浓缩后得到63g(66.3%)浅黄色半固体,经用乙醚研制使其固化,熔点113-115℃。实施例77(方法D)2-(2,4-二氯苯基)-2-〔(1,2,4-三唑-1-基)甲基〕丁-1-醇
于氮气环境及搅拌条件下向装有机械搅拌器的2升烧瓶中加入14.5g(0.38mole)氢化铝锂的300ml无水四氢呋喃溶液中。于45分钟内向该淤浆中加入60g(0.19mole)2-(2,4-二氯苯基)-2-〔(1,2,4-三唑-1-基)甲基〕丁酸的900ml无水四氢呋喃,同时将温度维持在10℃。搅拌16小时后用饱和硫酸钠终止反应。过滤并用乙酸乙酯洗涤。浓缩有机相,所得残余物悬浮于500ml乙酸乙酯中,用500ml水、300ml饱和碳酸氢钠和3000ml盐水洗涤。干燥并除去溶剂后得到一粘性固体,再经用乙醚研制后得到15g固体。用乙醚研制母液后得到2.9g产物。重复两次后总共得到22.1g(38.7%)产物,熔点160-163℃实施例52(方法D)4-(4-氯苯基)-2-〔(1,2,4-三唑-1-基)甲基〕丁-1-醇
于氮气环境及搅拌条件下向装有机械搅拌器的5升烧瓶中加入16g(0.42mole)氢化铝锂的1000ml无水四氢呋喃溶液。将该淤浆冷却至5℃,并在将温度维持在5-10℃的情况下于4小时内滴加142g(0.40mole)2-(4-氯苯基)-2-〔(1,2,4-三唑-1-基)甲基〕丁酸。于室温下搅拌混合物16小时,于5℃加入500ml饱和硫酸钠终止反应,并真空除去溶剂。用甲苯过滤凝胶状固体,并用2×1000ml水和1000ml盐水洗涤。干燥溶剂,用Celite过滤,浓缩,得到99g(72.6%)缓慢结晶的粘性黄色玻璃,熔点40-45℃。实施例64(方法E)2-苯基-2-〔(1,2,4-三唑-1-基)甲基〕-1-己胺
于氮气环境及搅拌条件下向装有机械搅拌器的5升烧瓶中加入21g(0.55mole)氢化铝锂。在2.5小时内向氢化铝锂中加入127g(0.50mole)α-丁基-α-苯基-1H-1,2,4-三唑-1-丙腈于2500ml无水乙醚的溶液。继续搅拌5小时后,通过GLC测得反应已完全。用硫酸钠终止反应,过滤并分离有机相。水相用1000ml乙醚萃取,合并有机相,用3×1.5l冰水洗涤,干燥,过滤并在不另外加热情况下浓缩,得到88g(69.2%)浅绿色油状物。实施例76(方法E)4-(4-氯苯基)-2-〔(1,2,4-三唑-1-基)甲基〕-1-丁胺
于氮气环境及搅拌条件下向装有机械搅拌器的5升烧瓶中加入18g(0.45mole)氢化铝锂的1000ml无水四氢呋喃溶液,然后冷却至5℃。在3小时内向该淤浆中加入152g(0.45mole)α-(2-(4-氯苯基)乙基)-α-苯基-1H-1,2,4-三唑-1-丙腈的2000ml无水四氢呋喃。在加料过程中温度维持在5-10℃,然后加热至室温并搅拌过夜。于冰浴中冷却反应并通过缓慢加入硫酸钠终止反应。除去溶剂,残余物用乙酸乙酯萃取并用1000ml水和1000ml盐水洗涤。干燥后除去溶剂,产生137g(89.5%)极粘性油状物。实施例11(方法F)2-(4-氯苯基)-2-〔(1,2,4-三唑-1-基)甲基〕丙烯酸己酯
于氮气环境及搅拌条件下向100ml烧瓶中加入2.88g(0.0098mole)2-(4-氯苯基)-2-〔(1,2,4-三唑-1-基)甲基〕己-1-醇的25ml四氢呋喃溶液。向该混合物中加入2.5ml吡啶,接着加入1.0g(0.011mole)丙烯酰氯,形成沉淀。通过GLC监测反应,1小时后完成60%。再加入1.0g丙烯酰氯和20ml二甲基甲酰胺。于60℃搅拌反应,直至沉淀溶解,然后于室温下搅拌过夜。用20ml水终止反应,并用10ml乙酸乙酯萃取,用2×10ml水和2×20ml饱和碳酸氢钠洗涤。干燥溶剂并浓缩。残余物在50g硅胶上进行色谱。用1∶1的己烷和乙酸乙酯混合物洗脱产物,得到1.72g(50.4%)油。实施例29(方法F)2-(4-氯苯基)-2-〔(1,2,4-三唑-1-基)甲基〕己基4-氯苯基尿烷
向100ml烧瓶中加入3.0g 2-(4-氯苯基)-2-〔(1,2,4-三唑-1-基〕甲基〕己-1-醇(0.010mole,1.0eq.)的60ml氯仿溶液及0.5g三乙胺。于室温下搅拌混合物15分钟后滴加1.5g对-氯苯基异氰酸酯(0.010mole,1.0eq.)。回流搅拌反应24小时用水和二氯甲烷终止反应。浓缩溶剂后得到5.0g粗产物,经色谱(4∶1的乙酸乙酯和己烷混合物)后得到3.0g(66%)浅黄色透明固体,熔点70-75℃。实施例66(方法H)N-{2-苯基-2-〔(1,2,4-三唑-1-基)甲基〕己基}乙酰胺
于氮气环境及搅拌条件下向1000ml烧瓶中加入2.58g(0.010mole)2-苯基-2-〔(1,2,-三唑-1-基)甲基〕-1-己胺和15ml乙酸酐。再向该混合物中加入1.5ml吡啶,并于室温下搅拌3小时。经GLC测得反应完全后,用20ml水和100ml乙醚终止反应,并真空除去酸酐和吡啶。残余物溶于乙醚并用2×50ml水和2×50ml饱和碳酸氢钠洗涤。干燥有机相,浓缩后得到2.68g(89.3%)固体,熔点112-115℃。实施例21(方法I)1-〔2-(4-氯苯基)-2-(甲氧基甲基)己基〕-1,2,4-三唑
于氮气环境及搅拌条件下向100ml三颈烧瓶中加入0.40g(0.010mole)60%氢化钠(已用己烷预洗)的30ml二甲基甲酰胺溶液。淤浆冷却至10℃,并在15分钟内加入2.12g(0.00723mole)2-(4-氯苯基)-2-〔(1,2,4-三唑-1-基)甲基〕己-1-醇的15ml二甲基甲酰胺。加热至室温后直接加入1.17g(0.00812mole)甲基碘,并于室温下搅拌过夜。用10ml水和100ml乙醚终止反应。用2×25ml水洗涤有机相,浓缩后得到1.53g(69%)油状产物。实施例62(方法I)1-〔4-(4-氯苯基)-2-苯基-2-(炔丙氧基甲基)丁基〕-1,2,4-三唑
于氮气及搅拌条件下向250ml三颈烧瓶中加入1.1g(0.022mole)60%氢化钠(已用己烷预洗)的40ml二甲基甲酰胺溶液。于室温下搅拌淤浆,并在5分钟内加入5.12g(0.015mole)4-(4-氯苯基)-2-苯基-〔(1,2,4-三唑-1-基)甲基〕丁-1-醇的30ml二甲基甲酰胺溶液。淤浆搅拌45分钟后加入2.45g(0.0165mole)炔丙基溴。4小时后通过GLC测得起始醇被消耗。用20ml水和75ml乙醚终止反应。分离有机相,用2×50ml水洗涤,用活性炭脱色,用Celite过滤,浓缩,得到4.19g(70.7%)油状产物。实施例39(方法I)2-〔2-(4-氯苯基)-2-〔(1,2,4-三唑-1-基)甲基〕己氧基〕嘧啶
将烧瓶中加入0.15g(0.0034mole)60%氢化钠(已用2×30ml己烷洗涤)的20ml四氢呋喃溶液。于室温搅拌条件下加入1.0g(0.0034mole)2-(4-氯苯基)-2-〔(1,2,4-三唑-1-基)甲基〕己-1-醇。于室温下搅拌淤浆,并加入0.39g 2-氯嘧啶(0.0034mole)。过夜搅拌反应混合物后,利用乙酸乙酯进行TLC测得反应已完全。终止反应并水洗后从乙醚中分离出产物。干燥并除去溶剂后得到1.30g(100%)油状物。实施例9(方法G)2-(4-氯苯基)-2-〔(1,2,4-三唑-1-基)甲基〕己基甲磺酸酯
于氮气环境及搅拌条件下向200ml三颈烧瓶中加入8.76g(0.030mole)2-(4-氯苯基)-2-〔(12,4-三唑-1-基)甲基〕-己-1-醇的40ml二氯甲烷溶液。将该溶液冷却至10℃,加入6.3ml(0.045mole)三乙胺及2.5ml(0.033mole)甲磺酰氯。1小时后,另加入3.1ml三乙胺和1.75ml甲磺酰氯。6小时反应完成70%,用15ml水使其终止并用150ml二氯甲烷萃取。经2×50ml水和50ml 10%盐酸洗涤后,干燥有机相并浓缩。产物在100g硅胶上色谱,并用1∶1的乙醚和乙酸乙酯混合物洗脱,得到6.5g(57.2%稠油状产物。
表1列出了本发明的部分化合物及其熔点,对于其熔点不能得到的化合物,在表2中给出了元素分析结果,或在表3中给出了NMR移动。
本领域普通技术人员可明显看出,通过取代反应流程1中所示反应中的合适起始物可制备出表1化合物以及本发明的其它化合物。
表1
实施例号 | 方法 | T | Z | W | 熔点(℃) |
123456789101112131415 | DDDFFGFFGFFIIFF | H4Cl2OHHHH2OCOCH34Cl4ClH4ClH4ClH4Cl | n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9 | OHOHOHClOCOCH3OSO2CH3OCOCH3OCOCH3OSO2CH3OCOCH=CH2OCOCH=CH2OSi(CH3)2(t-C4H9)OSi(CH3)2(t-C4H9)OCOCH2ClCOCCH2Cl | 84-85113-11562-65油油油油油油油油油油79-8093-94 |
表1(续)
实施例号 | 方法 | T | Z | W | 熔点(℃) |
1617181920212223242526272829303132333435363738 | FFFFFIIIIIIIIFFIFFFFFFF | H4Cl4Cl4Cl4Cl4Cl4Cl4Cl4Cl4ClHH4Cl4Cl4Cl4Cl4Cl4Cl4Cl4Cl4Cl4Cl4Cl | n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9 | OCOC(CH3)3OCOC6H5OCOC6H3(2,4Cl)OCOC6H3(3,5Cl)OCOCH2C6H5OCH3OCH2C6H3(2,4Cl)OCH2CH=CH2OCH2OCOC(CH3)3OCH2C≡CHOCH2(2PYRIDYL)OCH2(4PYRIDYL)OCH2CH2OC2H5OCONHC6H4(4Cl)OCO-c-C3-H5OCH2CH3OCOCH2OC6H4(4Cl)OCOCH2C6H4(4Cl)OCO(2-FURYL)OCOCCl3OCH2(3PYRIDYL)OCOCH=CHC6H5OCOC6H4(4OCH3) | 油油85-87129-130油油油油油油油油油70-75油油油油油油油油油 |
表1(续)
实施例号 | 方法 | T | Z | W | 熔点(℃) |
3940414243444546474849505152535455565758596061 | IIIIFFFFFFFFFDFFFIFIIID | 4Cl4Cl4Cl4Cl4Cl4Cl4Cl4Cl4Cl4Cl4Cl4Cl4ClHHHHHHH2,4Cl2,4Cl2,4Cl | n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9CH2CH2C6H4(4Cl)CH2CH2C6H4(4Cl)CH2CH2C6H4(4Cl)CH2CH2C6H4(4Cl)CH2CH2C6H4(4Cl)CH2CH2C6H4(4Cl)CH2CH2C6H4(4Cl)n-C4H9n-C4H9n-C4H9 | O(2PYRIMIDINYL)O(2PYRIDYL)OCH2(1H-1,2,4-triazolyl)O(PYRAZINYL)OCOCH2C6H4(4F)OCOCH2C6H4(4CF3)OCOCH2C6H3(2,4Cl)OCOCH2C6H4(4Br)OCOCF3OPO(OET)2OPO(OC2H5)2OCOCH2(2-THIENYL)OCOCF2CF2CF3OHOCOCH2C6H5OCOCH3OCO(2-FURYL)OCH3OCOC6H5OCH2CH=CH2OCH2CH2OC2H5O(i-C3H7)OH | 油油油油油油油油玻璃油油油油40-45油油油油油油油树脂220-221 |
表1(续)
实施例号 | 方法 | T | Z | W | 熔点(℃) |
6263646566676869707172737475767778 | IDEEHHHHHHHHHEEDE | H4ClH4ClH4Cl4Cl4Cl4Cl4Cl4Cl4Cl4Cl4ClH2,4Cl2,4Cl | CH2CH2C6H4(4Cl)C2H5n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9n-C4H9CH2CH2C6H4(4Cl)C2H5C2H5 | OCH2C≡CHOHNH2NH2NHCOCH3NHCOCH3NHCOCH2C6H5NHCOC6H5NHCO(2-FURYL)NHCO-c-C3H5NHCOCH2ClNHCOCCl3NHCOCH=CH2NH2NH2OHNH2 | 油125-126油油112-115玻璃玻璃破璃玻璃油油油油油油160-163油 |
表2
对C、H、N、O、Cl和其它元素的元素分析
实施例号 | 分析 | C | H | N | O | Cl |
4567810111213 | 理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值 | 64.8369.2767.7367.3156.9355.6363.4763.0360.5961.2768.9667.4262.1361.6167.4467.1061.7962.24 | 7.267.377.707.386.877.377.017.326.896.737.407.646.386.509.457.878.408.22 | 15.1315.9313.9513.9512.4511.7611.6912.0912.4812.2613.4213.6512.0912.0111.2512.4010.3010.74 | 10.6211.5614.2313.4317.8117.559.519.4311.5610.229.209.304.2810.963.920.76 | 10.5310.4210.2010.118.698.70 |
表2(续)
实施例号 | 分析 | C | H | N | O | Cl |
1721222324252627283032 | 理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值 | 66.3866.6462.4162.6864.7464.6958.3357.0961.8061.3865.1264.3171.9569.9871.9568.3762.8661.8963.0462.0658.6558.64 | 6.086.057.297.257.257.255.355.237.427.386.696.747.487.327.487.316.957.316.696.745.605.51 | 10.578.4413.6613.1412.5011.839.288.3310.3010.2212.6712.1615.9916.2215.9915.3711.5811.1211.6211.529.338.77 | 8.0511.205.705.694.805.433.534.2711.7711.754.825.928.8210.108.859.9710.6610.94 | 8.917.6611.5211.5810.6810.4723.5025.088.709.0210.7010.639.779.729.809.8115.7515.96 |
表2(续)
实施例号 | 分析 | C | H | N | O | Cl |
3334353637384344454647 | 理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值 | 61.8661.3560.6961.3546.4746.4465.5164.9567.9868.0264.5363.8764.2364.0260.6459.9157.4357.3556.2656.4652.1552.15 | 5.655.605.905.764.364.426.556.556.196.316.136.125.875.755.255.215.034.985.145.264.915.39 | 9.429.0711.1810.879.539.1714.5614.319.929.369.839.209.789.528.768.448.747.918.578.1910.7910.86 | 7.177.9112.7712.847.187.874.165.047.558.7611.2213.277.458.446.677.546.667.976.527.588.218.32 | 15.8915.889.449.2232.3032.049.229.238.377.758.297.708.257.947.397.0922.1321.457.226.289.099.49 |
表2(续)
实施例号 | 分析 | C | H | N | O | Cl |
4849505153545556575862 | 理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值 | 53.0654.2259.4558.3560.3260.3346.5646.8970.4870.0965.6865.5666.1164.8267.4866.4469.8570.1569.3568.4969.5369.76 | 6.806.845.495.585.795.773.924.075.705.915.786.135.095.176.236.515.645.746.096.375.846.02 | 9.7810.6410.418.7910.069.598.588.979.149.1910.9510.419.648.5911.8111.799.419.2311.0410.7411.0610.59 | 14.8912.307.9310.987.669.306.547.246.967.608.347.0311.0114.574.495.677.168.804.205.044.215.22 | 8.259.068.787.228.497.487.717.479.248.838.136.739.979.827.945.909.319.229.348.94 |
表2(续)
实施例号 | 分析 | C | H | N | O | Cl |
6465676869707172737475 | 理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值 | 69.7168.7661.5162.5960.9661.5967.2067.1366.5566.2762.0762.0863.2163.0255.2753.3046.5847.3562.3161.7655.0355.10 | 8.598.867.237.486.926.916.626.616.356.255.996.296.997.066.016.554.604.726.646.936.165.88 | 21.6920.5419.1417.4316.3415.3913.6412.9714.7213.3614.4913.4215.5314.6115.1813.3512.1912.1516.1614.9217.1214.40 | 4.795.513.894.934.635.348.288.854.446.274.349.993.654.774.616.35 | 12.1112.0310.5910.278.638.618.948.609.178.679.839.1432.3731.0010.229.8921.6720.87 |
表2(续)
实施例号 | 分析 | C | H | N | O | Cl |
7678 | 理论值实测值理论值实测值 | 66.9367.7852.1653.93 | 6.216.245.395.49 | 16.4414.2218.7315.06 | 10.4010.1823.7123.95 |
表2(续)
实施例号 | 分析 | Si | F | Br | S | P |
121343444648495051 | 理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值理论值实测值 | 7.517.026.885.68 | 4.424.4511.8812.2827.1625.36 | 16.2916.23 | 7.949.927.688.16 | 7.215.34 |
表3
本发明化合物的NMR移动
实施例9NMR:60MHz(CDCl3)1.0-2.0(m,9H),3.3(s,3H),4.4-4.8(ABq,4H),7.0-7.6(ABq,4H),7.8(s,1H),and 8.0(s,1H).实施例16NMR:90MHz(CDCl3)0.9-1.9(m,9H),1.2(br s,9H),4.2-4.6(ABq,2H),4.5(brs,2H),7.1-7.5(m,6H),and 7.9(s,1H).实施例20NMR:90MHz(CDCl3)0.8-1.8(m,9H),3.7(s,2H),4.0-4.5(m,4H),7.9-8.4(m,10H),and 7.9(s,1H).实施例31NMR:90MHz(CDCl3)0.8-1.8(m,12H),3.3-3.8(m,4H),4.5(br s,2H),7.0-7.3(ABq,2H),7.8(s,1H),and 7.9(s,1H).实施例39NMR:90MHz(CDCl3)0.8-2.0(m,9H),4.2-4.8(ABq,2H),4.6(s,2H),6.9-7.0(t,1H),7.2-7.4(ABq,4H),7.8(s,1H),7.9(s,1H),8.5(s,1H),and 8.6(s,1H).实施例40NMR:90MHz(CDCl3)0.8-2.0(m,9H),4.2-4.8(ABq,2H),4.8(s,2H),6.9-7.0(t,1H),7.4(s,1H),7.6(m,1H),7.7(s,1H)7.8(s,1H),and 8.0-8.2(m,1H). |
表3(续)
实施例41NMR:90MHz(CDCl3)0.8-2.0(m,9H),3.6-4.0(ABq,2H),4.2-4.6(ABq,2H),5.6(s,2H),6.8-7.4(ABq,4H),7.4(s,1H),7.8(s,1H),8.0(s,1H),and 8.3(s,1H).实施例42NMR:90MHz(CDCl3)0.8-2.0(m,9H),4.4-4.8(ABq,2H),4.6(s,2H),7.0-7.4(ABq,2H),7.6(s,1H),7.8(s,1H),8.0-8.2(m,2H),and 8.4(s,1H).实施例59NMR:60MHz(CDCl3)1.0-1.3(t,3H),1.0-2.2(m,9H),3.3-3.8(twooverlapping ABq,4H),4.3-4.5(m,2H),4.9-5.0(ABq,2H),6.9-7.5(m,3H),7.3(s,1H),and 7.8(s,1H).实施例60NMR:60MHz(CDCl3)0.8-2.2(m,9H),1.2(s,3H),1.3(s,3H),4.7-5.2(ABq,2H),5.1-5.3(t,1H),6.8-7.2(d,1H),7.2-7.4(dd,1H),7.6(d,1H),7.4(o,1H),and8.0(s,1H).实施例61NMR:60MHz(CDCl3)0.9-2.0(m,9H),2.0-2.2(br 5,2H),5.0-5.2(br 5,2H),7.1-7.5(m,2H),7.9-8.0(m,2H). |
本发明1,2,4-三唑、其对映体、酸加成盐和金属盐复合物可用作农业杀菌剂,并可施用于各种场所,如种子、土壤或树叶当作为除草剂使用时,该化合物既可施用于植物本身也可施用于需要控制的植物所生长的位置。为此,可将这些化合物直接使用或组成溶液或配方后使用。通常是将化合物吸附在载体上或制成配方,以便于以后的施洒。例如,可将这些化学剂配制成可湿性粉剂、乳油、粉剂、颗粒配方、烟雾剂或可流动乳油。在这些配方中,这些化合物是与液体或固体载体一起播撒,并根据需要加入合适的表面活性剂。
根据农业实际性情况通常需要在配方中包括助剂,如湿润剂、铺展剂、分散剂、粘着剂、吸附剂,对于叶面喷洒配方尤其如此。本领域所常用的这类助剂可从John W.McCutcheon,Ine.Publication“Detergents andEmulsifiers,Aunual”中查到。
一般来说,可将本发明化合物溶解在某些溶剂(如丙酮、甲醇、乙醇、二甲基甲酰胺、吡啶或二甲基亚砜)中,并可用水稀释该溶液。溶液的浓度范围为约1%-90%,优选的范围为约5%-50%。
为了制备乳油,可将化合物与乳化剂一起溶解在合适有机溶剂或溶剂混合物中,增强化合物在水中的分散。乳油中活性成分的浓度通常为100%-90%,在可流动乳油中这一浓度可高达75%。
将化合物与细分固体(如粘土、无机硅酸盐和碳酸盐)和硅石混合并向该混合物中加入湿润剂、粘着剂和/或分散剂。可制备出适于喷洒的可湿性粉剂。该配方中活性成分的浓度通常为20%--98%,优选40%-75%。一典型可湿性粉剂是通过混合50份1,2,4-三唑、45份人工沉淀的水化二氧化硅(如商标为Hi.SilR的产品)和5份木素磺酸钠而制得。在另一制剂中是用高岭型(Barden)粘土代替上述可湿性粉剂中的Hi.Sil,在又一制剂中是用合成的硅铝酸钠(市售商标为Zeolex7)代替25%的Hi-Sil。
粉剂是通过将1,2,4-三唑、其对映体、盐或复合物与有机或无机性质的细分惰性固体混合制得。可用于此处的材料包括植物粉、硅石、硅酸盐、碳酸盐和粘土。一种制备粉剂的简便方法是用细分载体稀释可湿性粉剂。通常是制成含有20%-80%活性成分的粉剂浓缩物,然后稀释至1%-10%的使用浓度。
可利用常规方法,如常规的高加仑量水力喷洒、低加仑量水力喷洒、鼓风喷洒、航空喷洒和撒粉等方法施用作为杀菌剂的1,24-三唑、其对映体、盐和复合物。稀释倍数和施用量取决于所用设备的类型、施用方法、所要处理的植物以及所要控制的疾病。一般可按每英亩0.05磅-50磅活性成分的量施用本发明化合物。
当用作种子保护剂时,施涂在种子上的药物的剂量一般为每百磅种子0.05-20盎司,优选0.05-4盎司,更优选0.1-1盎司。作为土壤杀菌剂使用时,可按每英亩0.02-20磅、优选0.05-10磅、更优选0.1-5磅的量将该化学制剂加到土壤中或施用于土壤表面。作为叶面杀菌剂使用时,施用于生长植物的药量一般为每英亩0.01-10磅、优选0.02-5磅,更优选0.25-1磅。
可与本发明化合物结合使用的杀菌剂包括:
(a)二硫代氨基甲酸盐及其衍生物,如:福美铁、福美锌、代森锰、代森锰锌、代森锌、甲基代森锌、威百亩、福美双、代森锌与聚乙烯二硫化四烷基秋兰姆的复合物、棉隆、以及它们与铜盐的混合物;
(b)硝基酚衍生物,如:敌螨普、乐杀螨、和2-叔丁基-4,6-二硝基苯基碳酸异丙酯;
(c)杂环结构化合物,如:克菌丹、灭菌丹、果绿宝、敌菌灵、ditalimfos、4-丁基-1,2,4-三唑、5-氨基-1-〔双(二甲基氨基)氧膦基〕-3-苯基-1,2,4-三唑、etradiazde、二噻农、克杀螨、苯菌灵、涕必灵、4-(2-氯苯基亚肼基)-3-甲基-5-异噁唑酮、vinclozollin、iprodione、procymidone、tribdimenol、triadimefon、bitertanol、prochloraz、fenarimol、双-(对-氯苯基)-3-吡啶甲醇、双-(对-氯苯基)-5-嘧啶甲醇、嘧菌醇、flutriafol、flasila-zole、propcconazole、ectaconazole、myclobutanil、α-〔2-(4-氯苯基)乙基〕-α-苯基-1H-1,2,4-三唑-1-丙腈、hexaconazole、cyproconazole、tebuconazole、diniconazole、flaoroimide、吡啶-2-硫醇-1-氧化物、8-羟基喹啉硫酸酯及其金属盐、2,3-二氢5-羧酰苯胺基-6-甲基-1,4-氧硫杂环己二烯-4,4-二氧化物、2,3-二氢-5-羧酰苯胺基-6-甲基-1,4-氧硫杂环己二烯、顺-N-〔(1,1,2,2-四氯乙基)硫醇〕-4-环己烯-1,2-二羧酰亚胺、环己酰亚胺、脱氢乙酸、敌菌丹、乙菌定、灭菌锰、D,L-甲基-N-(2,6-二甲基苯基)-N-(2′-甲氧乙酰基)丙氨酸甲基酯、D,L-甲基-N-(2,6-二甲基苯基)-N-氯乙酰基-D,L-2-氨基丁内酯、D,L-N-(2,6-二甲基苯基)-N-(苯基乙酰基)丙氨酸甲酯、5-甲基-5-乙烯基-3-(3,5-二氯苯基)-2,4-二氧-1,3-噁唑烷、3-(3,5-二氯苯基)-5-甲基-5-(甲氧基甲基)-1,3-噁唑烷-2,4-二酮。3-(3,5-二氯苯基)-1-异丙基氨基甲酰基海因、2-氰基-〔N-(乙氨基羰基)-2-甲氧亚氨基〕乙酰胺、fenpropimorphfenpropidine、2,6-二甲基-N-十三烷基吗啉、吗菌灵和嗪氨灵;
(d)杂卤代杀菌剂,如四氯对醌、二氯萘醌、地茂散、杀草畏、TCPN、氯硝胺、2-氯-1-硝基丙烷、多氯代硝基苯如五氯硝基苯(PCNB)、四氟二氯丙酮;
(e)杀菌抗生素,如:灰黄霉素、春雷霉素、多氧霉素、有效霉素和链霉素;
(f)含铜杀菌剂,如:氢氧化铜、氧化亚铜、碱性氯化铜、碱性碳酸铜、对苯二酸酮、邻苯二酸铜和Bordeaux混合物;和
(g)杂杀菌剂,如:多果定、乙酸苯汞、N-乙基汞-1,2,3,6-四氢-3,6-桥亚甲基-3,4,5,6,7,7-六氯苯邻二甲酰亚胺、苯汞单乙醇乳酸铵、对-二甲基氨基苯磺酸钠、异硫氰酸甲酯、1-硫氰基-2,4-二硝基苯、1-苯基氨基硫脲、含镍化合物、氰氨化钙、石硫合剂、甲基托布津、flutolanil、edinophos、富士一号、propenazole和tricyclazole。
1,2,4-三唑、其对映体、酸加成盐和金属盐复合物可按各种方式使用。由于这些化合物具有广谱杀菌活性,它们可用于谷物的储存,还可用作小麦、大麦、黑麦、水稻、花生、大豆、葡萄草皮、水果、坚果、植物园以及高尔夫球场的杀菌剂。
可用本发明化合物控制的病害的例子有:玉米和大麦菌核病、小麦和大麦白粉病、小麦叶和柄锈病、番茄早疫病、番茄晚疫病、花生早黑斑病、葡萄白粉病、葡萄黑腐病、苹果黑病、苹果白粉病、黄瓜白粉病、水果黑腐病、僵腐病、大豆白粉病、黄瓜炭疽病、wheat septria nodoram、水稻酸枯病和稻瘟病。
本发明各种化合物对小麦白粉病(WPW)、小麦柄锈病(WSR)、稻瘟病(RB)、水稻纹枯病(RSB)和小麦叶锈病(WLR)的杀菌活性已进行过体内试验。在对各类(用于试验稻瘟病的水稻植物除外)的试验中,于施用本发明杀菌化合物前24小时修剪植株以提供同样高度的植株并有助于化合物的均匀施用,并且接种真菌。化合物溶于水、丙酮和甲醇的2∶1∶1混合物中,喷洒至植株上,干燥(4-6小时),然后用真菌接种。每次试验所使用的对照植株上所喷洒的是水、丙酮和甲醇的混合物并接种了真菌。每一试验的其余部分在下面给出。且其结果总结于表4中,以病虫害控制百分数(被本发明化合物处理而缺失病害迹象或病状的植株与未处理的对照植株的百分比)表示。
小麦白粉病(WPM)
在温度控制为65°-70°F条件下于小麦苗上培养禾白粉菌。从培养植株上去掉自粉孢子,并接种到已预先喷洒过杀菌化合物的麦苗上。将接种过的麦苗保持在65°-75°F的控制温度下,并用地下的水灌溉。接种后8-10天评估病害控制百分数。
小麦柄锈病(WSR)
于室温中将禾柄锈菌(f.sp.tritici Race15B-2)在Wanzer小麦苗上培养14天,制备出感染植株孢子的水悬浮液,并将孢子浓度调至每ml去离子水2×105孢子。利用Devilbirs喷雾器按每平方英寸5磅气压用柄锈菌孢子悬浮接种已预先用杀菌化合物处理过的Wanzer小麦植株。接种后,将植株置于约75°F的湿环境中,在经过连续12小时的暗处放置后紧接至少3-4小时强度为500尺烛光的光照。室中温度不超过85°F。光照期结束后,植物放置在温室中生长2周,测定病害控制百分数。
稻瘟病(RB)
通过用喷枪喷洒叶和杆将Nato水稻植株接种稻瘟病菌(每ml约20,000个分生孢子),直至在叶面上观察到一均匀接种物层。接种植物于湿环境(75°-85°F)培养24小时,然后放置于温室环境下(70°-75°F)。接种后7-8天测定病害控制百分数。
水稻纹枯病(RSB)
于500ml锥形瓶中的高压灭菌的碎稻种和稻种的马铃薯葡萄糖培养液混合物(每30ml马铃薯葡萄糖培养液中含100g稻种)上接种丝核薄膜革菌。10天后,将培养物在混合器中混合以产生均匀接种物。将约1茶匙接种物播种在每盆(直径3英寸)土壤表面的Lebonnet稻苗上。接种后的稻苗于湿度室(85°-90°F)中培养5天。在从该室中取出稻苗后立即测定疾病控制百分数。
小麦叶锈病(WLR)
将小麦叶锈病菌(f.sp.tritici Races PKB和PLD)于温室中7天龄的小麦(Cultichr Fielder)上培养14天。利用气旋真空或铝箔从叶上收集孢子,用250μm筛清扫孢子,并保存或直接使用。保存所使用的是超低温冷冻机上的密封袋。被保存过的孢子在使用前必须热振荡2分钟。通过向每ml Soltrol油中加入20mg(9.5百万孢子)可从夏孢子制备孢子悬液。将该悬液分散至明胶胶囊(0.7ml容量)中。它与油喷雾器相连。对20个平方英寸盆苗床中的每一个上的7天龄Fielder小麦使用一个胶囊。待油从小麦叶上蒸发至少15分钟后,将植物移至暗室(18-20℃,100%相对湿度)放置24小时。然后在温室中放置潜伏期,并在10天后评估病害水平。对于保护和治疗试验,在用杀菌化合物喷洒植物前将植株分别接种1天和2天。
表4本发明化合物的杀菌效力
实施例号 | 等级 | RB | RSB | WLR | WPM | WSR |
12345678910111213141516171819 | bcccccccccccccccccc | 700931001000085020009080958590100 | —20350045455000000050000— | ——————————————————— | —10010094100459710085501009010010095751009090 | —100999935909010010090100609575958010000 |
表4(续)
实施例号 | 等级 | RB | RSB | WLR | WPM | WSR |
20212223242526272829303132333435363738394041 | cbbbbbbbbbbbbbbbbbbbbb | 1000000600070010050008000000500 | 008500400—0005000000005000 | —————————————————————— | 1001001009010010090801009090901001001006050100100959595 | 851001001001001008010010070609070100100010010010095—50 |
表4(续)
实施例号 | 等级 | RB | RSB | WLR | WPM | WSR |
4243444546474849505152535455565758 | bbbbbbaaaaaaaaaaa | 050000809050908080080909010080 | 095000000000000000 | —9595——7550500005050507500 | 9510095955010095957599508595951009999 | 99—509995———————————— |
表4(续)
实施例号 | 等级 | RB | RSB | WLR | WPM | WSR |
596061626364656667686970717273747576 | aaaaaccccaaaaaaaab | 0500—00003005000050000 | 000000000000000000 | 0950850————50500000508580 | 9999859510098999090858585959599857575 | —————808500————————— |
1试验等级:a=100ppm;b=200ppm;c=300ppm;d=600ppm;
2稻瘟病(稻瘟病菌)
3水稻纹枯病(丝核薄膜革菌f.sp.Sasiki)
4小麦叶锈病(小麦叶锈病菌(f.sp.triticiRaces PKB和PLD))
5小麦白粉病(禾白粉菌f.sp.tritici)
6小麦柄锈病(禾柄锈菌f.sp.tritici)
7表示未测试
Claims (9)
其中
X为C6-C10芳基或被1-3个下列取代基取代的C6-C10芳基:羟基、卤素、乙酰氧基、三卤代甲基、C1-C4烷基、C1-C4烷氧基、C1-C4烷硫基、C1-C4烷基亚磺酰基、C1-C4烷基磺酰基、C1-C4烷氧基-C1-C4烷氧基、C1-C4烷基羰基、C2-C8链烯基、C2-C4链烯氧基、C2-C8链炔基、C2-C4链炔氧基;苯基或被下列基团单取代的苯基:卤素、C1-C4烷基或C1-C4烷氧基;苯氧基或被下列基团单取代的苯氧基:卤素、C1-C4烷基或C1-C4烷氧基;
或为具有独立选自氮原子、原子和硫原子的1-3个杂原子的六元杂环,该环上所有原子均未被取代或可被独立选自C1-C12烷基和卤素的1-2个取代基取代;
Q为1-(1,2,4-三唑基)或4-(1,2,4-三唑基),或可被1-2个取代基取代的上述三唑基,该取代基选自:卤素、C1-C4烷基、硝基、氰基、巯基和C1-C5烷基巯基;
Z为C1-C12烷基,卤代-C1-C12烷基,C2-C8链烯基,卤代-C2-C8链烯基,C2-C8链炔基,C5-C8环烯基,C1-C12烷芳基,C6-C10芳基或被1-3个取代基取代的C6-C10芳基,该取代基选自:羟基、卤素、乙酰氧基、三卤代甲基、C1-C4烷基、C1-C4烷氧基、C1-C4烷硫基、C1-C4烷基亚磺酰基、C1-C4烷基磺酰基、C1-C4烷氧基-C1-C4烷氧基、C1-C4烷基羰基、C2-C8链烯基、C2-C4链烯氧基、C2-C8炔基或C2-C4炔氧基,苯基或被卤素、C1-C4烷基或C1-C4烷氧基单取代的苯基,苯氧基或被卤素、C1-C4烷基或C1-C4烷氧基单取代的苯氧基,C6-C10芳基-C1-C12烷基;
W为-OR、-OCOR″、-OCOY、-OCOR′Y、
-OCOR′OR″、-OR′OCOR″、-OR′OR、
-NH2、-NHCOR、-NHCOR′Y、-NHCOY、
-OCONHY、-OSO2A、-OSiA3、-OPO(OA)2
或卤素,其中A为C1-C6烷基;
R为C1-C12烷基、X、Y-烷基、C3-C8链烯基、C3-C8炔基、C3-C8环烷基、氰基烷基或环氧烷基,它们均可被卤代;或为氢;条件是当Z为甲基时,R不为卤代烷基;
R′为(-CH(CH3)-)p(-CH2-)m或(-CH2-)sCH=CH(-CH2-)t;
m为整数0-6;
p为0或1,条件是m和p不能同时为0;
s和t各自独立地为整数0-3;
R″为苯基、C1-C6烷基、C2-C4链烯基或C1-C2三烷基甲硅烷基C1-C4烷基,它们均可被卤代;或为氢;
R为氢或C1-C6烷基;
n为整数1-6;和
Y为苯基、萘基、哌啶基、三唑基、哌嗪基、嘧啶基、苯二甲酰亚氨基、吗啉基、吡啶基、噻吩基、呋喃基或环烷基,它们未被取代或被前面X定义中所述的取代基所取代。
2.根据权利要求1的化合物,其中Z选自C1-C8烷基、C5-C7环烷基、苯基、苄基或苯乙基、或芳环被高达两个卤素取代基取代的苯基、芳基或苯乙基;R为H,n为1,条件是当Z为甲基时,R不为卤代烷基,且Z为1-(1,2,4-三唑基)。
3.根据权利要求2的化合物,其中X为苯基,它可被氯、羟基、乙羧基、甲氧基取代;Z为C1-C6烷基、C5-C6环烷基、苯基、芳基或苯乙基、或单取代的苯基、苄基或苯乙基,条件是当X为苯基时,R不为卤代烷基且Z为1-(1,2,4-三唑基)。
4.根据权利要求3的化合物,其中X为苯基,它可被氯、羟基、乙酸基、甲氧基或乙氧基取代,且Z为乙基、正丁基、苄基、2-氯苄基或4-氯苯乙基。
5.根据权利要求4的化合物,其中R为C1-C4烷基、C1-C4卤代烷基、C3-C4链烯基、C3-C4炔基,或可被卤素取代的苯基、苄基或苯乙基,且R″为C1-C4烷基或苯基。
6.根据权利要求5的化合物,其中X为苯基、4-氯苯基、2-羟苯基、2-乙酸基苯基或2,4-二氯苯基;且W为苯甲酰氧基、苯乙基羰氧基、2-呋喃氧基、4-氟苯乙基羰氧基或氯代乙酸基。
7.根据权利要求5的化合物,其中X为苯基、4-氯苯基、2-羟基苯基、2-乙酸基苯基或2,4-二氯苯基;Z为乙基、正丁基或4-氯苯乙基;且W为卤素。
8.一种杀菌组合物,它包括农学上可接受的载体以及杀菌有效量的权利要求1化合物。
9.一种控制真菌的方法,它包括施用杀真菌有效量的权利要求1化合物于所要控制的地方。
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US07/904,230 | 1992-06-25 | ||
US07/904,230 US5358939A (en) | 1992-06-25 | 1992-06-25 | Fungicidal 2-aryl-2,2-disubstituted ethyl-1,2,4-triazoles |
Publications (2)
Publication Number | Publication Date |
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CN1081674A CN1081674A (zh) | 1994-02-09 |
CN1042027C true CN1042027C (zh) | 1999-02-10 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CN93107634A Expired - Fee Related CN1042027C (zh) | 1992-06-25 | 1993-06-25 | 杀菌剂1,2,4-三唑化合物 |
Country Status (18)
Country | Link |
---|---|
US (3) | US5358939A (zh) |
EP (1) | EP0576201B1 (zh) |
JP (1) | JPH0680517A (zh) |
KR (1) | KR940005593A (zh) |
CN (1) | CN1042027C (zh) |
AT (1) | ATE204261T1 (zh) |
AU (1) | AU656861B2 (zh) |
BR (1) | BR9302445A (zh) |
CA (1) | CA2098466A1 (zh) |
DE (1) | DE69330584T2 (zh) |
ES (1) | ES2164068T3 (zh) |
HU (1) | HUT65125A (zh) |
IL (1) | IL106024A0 (zh) |
MX (1) | MX9303750A (zh) |
NZ (1) | NZ247903A (zh) |
TR (1) | TR26839A (zh) |
TW (1) | TW242106B (zh) |
ZA (1) | ZA934500B (zh) |
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US5358939A (en) * | 1992-06-25 | 1994-10-25 | Rohm And Haas Company | Fungicidal 2-aryl-2,2-disubstituted ethyl-1,2,4-triazoles |
GB9602080D0 (en) | 1996-02-02 | 1996-04-03 | Pfizer Ltd | Pharmaceutical compounds |
JP2000053657A (ja) * | 1998-08-12 | 2000-02-22 | Rikagaku Kenkyusho | ブラシノステロイド生合成阻害剤 |
CA2479618A1 (en) * | 2002-03-26 | 2003-10-09 | William K. Hagmann | Spirocyclic amides as cannabinoid receptor modulators |
RU2329009C2 (ru) * | 2002-12-17 | 2008-07-20 | Колгейт-Палмолив Компани | Зубная щетка с приводом и с уникальной рукояткой |
US8637089B2 (en) | 2003-04-09 | 2014-01-28 | Osmose, Inc. | Micronized wood preservative formulations |
SG163438A1 (en) * | 2003-04-09 | 2010-08-30 | Osmose Inc | Micronized wood preservative formulations |
US8747908B2 (en) | 2003-04-09 | 2014-06-10 | Osmose, Inc. | Micronized wood preservative formulations |
CA2530044C (en) | 2003-06-17 | 2012-09-25 | Phibro-Tech, Inc. | Particulate wood preservative and method for producing same |
US20050252408A1 (en) * | 2004-05-17 | 2005-11-17 | Richardson H W | Particulate wood preservative and method for producing same |
US20060075923A1 (en) * | 2004-10-12 | 2006-04-13 | Richardson H W | Method of manufacture and treatment of wood with injectable particulate iron oxide |
US20060062926A1 (en) * | 2004-05-17 | 2006-03-23 | Richardson H W | Use of sub-micron copper salt particles in wood preservation |
US7316738B2 (en) * | 2004-10-08 | 2008-01-08 | Phibro-Tech, Inc. | Milled submicron chlorothalonil with narrow particle size distribution, and uses thereof |
US20050255251A1 (en) * | 2004-05-17 | 2005-11-17 | Hodge Robert L | Composition, method of making, and treatment of wood with an injectable wood preservative slurry having biocidal particles |
PL2431430T3 (pl) * | 2004-10-14 | 2017-07-31 | Koppers Performance Chemicals Inc. | Zastosowanie mikronizowanych kompozycji konserwujących drewno w nośnikach organicznych |
US20070259016A1 (en) * | 2006-05-05 | 2007-11-08 | Hodge Robert L | Method of treating crops with submicron chlorothalonil |
IN2014DN06792A (zh) | 2012-01-20 | 2015-05-22 | Viamet Pharmaceuticals Inc | |
JP2015505538A (ja) * | 2012-01-20 | 2015-02-23 | ヴィアメット ファーマスーティカルズ,インコーポレイテッド | 金属酵素阻害剤化合物 |
CN104725447A (zh) * | 2015-04-02 | 2015-06-24 | 天津理工大学 | 一种3-S-四羟基-β-D-葡萄糖苷-1,2,4-三唑类化合物 |
CN105111261A (zh) * | 2015-09-08 | 2015-12-02 | 天津理工大学 | 一种3-S-四羟基-β-D-葡萄糖苷-1,2,4-三唑类化合物及其制备方法和应用 |
CN105669575B (zh) * | 2016-03-08 | 2018-06-15 | 华中师范大学 | 3-(1,2,3-三唑-4-基)-2-(1,2,4-三唑-1-基)丙醇类化合物及其制备方法与用途 |
WO2018214754A1 (zh) * | 2017-05-24 | 2018-11-29 | 东莞东阳光科研发有限公司 | 三唑衍生物及其在农业中的应用 |
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-
1992
- 1992-06-25 US US07/904,230 patent/US5358939A/en not_active Expired - Lifetime
-
1993
- 1993-06-15 CA CA002098466A patent/CA2098466A1/en not_active Abandoned
- 1993-06-15 IL IL106024A patent/IL106024A0/xx unknown
- 1993-06-16 EP EP93304697A patent/EP0576201B1/en not_active Expired - Lifetime
- 1993-06-16 ES ES93304697T patent/ES2164068T3/es not_active Expired - Lifetime
- 1993-06-16 NZ NZ247903A patent/NZ247903A/en not_active IP Right Cessation
- 1993-06-16 DE DE69330584T patent/DE69330584T2/de not_active Expired - Fee Related
- 1993-06-16 AT AT93304697T patent/ATE204261T1/de not_active IP Right Cessation
- 1993-06-17 AU AU41304/93A patent/AU656861B2/en not_active Ceased
- 1993-06-22 MX MX9303750A patent/MX9303750A/es not_active IP Right Cessation
- 1993-06-23 ZA ZA934500A patent/ZA934500B/xx unknown
- 1993-06-23 BR BR9302445A patent/BR9302445A/pt not_active Application Discontinuation
- 1993-06-23 KR KR1019930011494A patent/KR940005593A/ko not_active Application Discontinuation
- 1993-06-24 JP JP5153920A patent/JPH0680517A/ja not_active Withdrawn
- 1993-06-25 TR TR00496/93A patent/TR26839A/xx unknown
- 1993-06-25 HU HU9301873A patent/HUT65125A/hu unknown
- 1993-06-25 CN CN93107634A patent/CN1042027C/zh not_active Expired - Fee Related
- 1993-07-02 TW TW082105269A patent/TW242106B/zh active
-
1994
- 1994-06-30 US US08/269,874 patent/US5462931A/en not_active Expired - Lifetime
-
1995
- 1995-06-12 US US08/489,416 patent/US5624916A/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JPH0680517A (ja) | 1994-03-22 |
EP0576201A2 (en) | 1993-12-29 |
TR26839A (tr) | 1994-08-19 |
ZA934500B (en) | 1993-12-27 |
CA2098466A1 (en) | 1993-12-26 |
TW242106B (zh) | 1995-03-01 |
US5462931A (en) | 1995-10-31 |
MX9303750A (es) | 1994-05-31 |
CN1081674A (zh) | 1994-02-09 |
US5624916A (en) | 1997-04-29 |
ES2164068T3 (es) | 2002-02-16 |
BR9302445A (pt) | 1994-01-11 |
EP0576201A3 (en) | 1994-06-01 |
IL106024A0 (en) | 1993-10-20 |
HUT65125A (en) | 1994-04-28 |
DE69330584D1 (de) | 2001-09-20 |
AU4130493A (en) | 1994-01-06 |
EP0576201B1 (en) | 2001-08-16 |
US5358939A (en) | 1994-10-25 |
DE69330584T2 (de) | 2002-06-27 |
HU9301873D0 (en) | 1993-09-28 |
NZ247903A (en) | 1996-02-27 |
KR940005593A (ko) | 1994-03-21 |
ATE204261T1 (de) | 2001-09-15 |
AU656861B2 (en) | 1995-02-16 |
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