CN100451007C - 含芳醚双三氮唑类化合物及其用途 - Google Patents
含芳醚双三氮唑类化合物及其用途 Download PDFInfo
- Publication number
- CN100451007C CN100451007C CNB2006101408367A CN200610140836A CN100451007C CN 100451007 C CN100451007 C CN 100451007C CN B2006101408367 A CNB2006101408367 A CN B2006101408367A CN 200610140836 A CN200610140836 A CN 200610140836A CN 100451007 C CN100451007 C CN 100451007C
- Authority
- CN
- China
- Prior art keywords
- acid
- triazole
- triazol
- chloro
- phenyl
- 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.)
- Active
Links
- 150000001875 compounds Chemical class 0.000 title abstract description 14
- 150000008378 aryl ethers Chemical class 0.000 title abstract 2
- -1 C1-4 Chemical group 0.000 claims abstract description 38
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 241000233866 Fungi Species 0.000 abstract description 7
- 229910052794 bromium Inorganic materials 0.000 abstract description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 abstract description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract description 4
- 229910052736 halogen Chemical group 0.000 abstract description 4
- 150000002367 halogens Chemical group 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 229910052740 iodine Inorganic materials 0.000 abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 abstract description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 230000002401 inhibitory effect Effects 0.000 abstract description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract 1
- 125000004429 atom Chemical group 0.000 abstract 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- 239000003112 inhibitor Substances 0.000 abstract 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 abstract 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 abstract 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 abstract 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 description 24
- 208000031888 Mycoses Diseases 0.000 description 14
- 239000002253 acid Substances 0.000 description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 150000003852 triazoles Chemical class 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000005760 Difenoconazole Substances 0.000 description 7
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 7
- 239000003899 bactericide agent Substances 0.000 description 7
- BQYJATMQXGBDHF-UHFFFAOYSA-N difenoconazole Chemical compound O1C(C)COC1(C=1C(=CC(OC=2C=CC(Cl)=CC=2)=CC=1)Cl)CN1N=CN=C1 BQYJATMQXGBDHF-UHFFFAOYSA-N 0.000 description 7
- 239000011833 salt mixture Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 201000010099 disease Diseases 0.000 description 6
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000000855 fungicidal effect Effects 0.000 description 5
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- FDPIMTJIUBPUKL-UHFFFAOYSA-N dimethylacetone Natural products CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- PXMNMQRDXWABCY-UHFFFAOYSA-N 1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl)pentan-3-ol Chemical compound C1=NC=NN1CC(O)(C(C)(C)C)CCC1=CC=C(Cl)C=C1 PXMNMQRDXWABCY-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 241000235349 Ascomycota Species 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 3
- 241000221198 Basidiomycota Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000005839 Tebuconazole Substances 0.000 description 3
- 241000082085 Verticillium <Phyllachorales> Species 0.000 description 3
- 230000004071 biological effect Effects 0.000 description 3
- 239000000645 desinfectant Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 230000000452 restraining effect Effects 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 229940095064 tartrate Drugs 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 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
- KVKFSLYUIUDSOI-UHFFFAOYSA-N 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1,3-bis(1,2,4-triazol-1-yl)propan-2-ol Chemical compound C1=NC=NN1CC(C=1C(=CC(OC=2C=CC(Cl)=CC=2)=CC=1)Cl)(O)CN1C=NC=N1 KVKFSLYUIUDSOI-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000220223 Fragaria Species 0.000 description 2
- 235000016623 Fragaria vesca Nutrition 0.000 description 2
- 235000011363 Fragaria x ananassa Nutrition 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000003385 bacteriostatic effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 244000000004 fungal plant pathogen Species 0.000 description 2
- 230000001408 fungistatic effect Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 229940071870 hydroiodic acid Drugs 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 235000010603 pastilles Nutrition 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MPDDTAJMJCESGV-CTUHWIOQSA-M (3r,5r)-7-[2-(4-fluorophenyl)-5-[methyl-[(1r)-1-phenylethyl]carbamoyl]-4-propan-2-ylpyrazol-3-yl]-3,5-dihydroxyheptanoate Chemical compound C1([C@@H](C)N(C)C(=O)C2=NN(C(CC[C@@H](O)C[C@@H](O)CC([O-])=O)=C2C(C)C)C=2C=CC(F)=CC=2)=CC=CC=C1 MPDDTAJMJCESGV-CTUHWIOQSA-M 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 1
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- BQXUPNKLZNSUMC-YUQWMIPFSA-N CCN(CCCCCOCC(=O)N[C@H](C(=O)N1C[C@H](O)C[C@H]1C(=O)N[C@@H](C)c1ccc(cc1)-c1scnc1C)C(C)(C)C)CCOc1ccc(cc1)C(=O)c1c(sc2cc(O)ccc12)-c1ccc(O)cc1 Chemical compound CCN(CCCCCOCC(=O)N[C@H](C(=O)N1C[C@H](O)C[C@H]1C(=O)N[C@@H](C)c1ccc(cc1)-c1scnc1C)C(C)(C)C)CCOc1ccc(cc1)C(=O)c1c(sc2cc(O)ccc12)-c1ccc(O)cc1 BQXUPNKLZNSUMC-YUQWMIPFSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229940126639 Compound 33 Drugs 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000221785 Erysiphales Species 0.000 description 1
- NZFGOIAABVIWFM-UHFFFAOYSA-N FC1=C(C=CC(=C1)OC1=CC=C(C=C1)F)C(CN1N=CN=C1)(O)CN1N=CN=C1 Chemical compound FC1=C(C=CC(=C1)OC1=CC=C(C=C1)F)C(CN1N=CN=C1)(O)CN1N=CN=C1 NZFGOIAABVIWFM-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- PNUZDKCDAWUEGK-CYZMBNFOSA-N Sitafloxacin Chemical compound C([C@H]1N)N(C=2C(=C3C(C(C(C(O)=O)=CN3[C@H]3[C@H](C3)F)=O)=CC=2F)Cl)CC11CC1 PNUZDKCDAWUEGK-CYZMBNFOSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- OQTFFGSVBUKNQJ-UHFFFAOYSA-N [S].[O].C[NH+](C)C.I(=O)(=O)[O-] Chemical compound [S].[O].C[NH+](C)C.I(=O)(=O)[O-] OQTFFGSVBUKNQJ-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 125000005013 aryl ether group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229940049920 malate Drugs 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229940031815 mycocide Drugs 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000009711 regulatory function Effects 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- FFSJPOPLSWBGQY-UHFFFAOYSA-N triazol-4-one Chemical compound O=C1C=NN=N1 FFSJPOPLSWBGQY-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Abstract
本发明公开了一种含芳醚双三氮唑类化合物及其用途，化合物具有如下结构式(I)或所述结构式(I)在农林药物学上可接受的对映体，其中，R1、R2、R3、R4、R5、R6为氢、C1～4烷基、三氟甲基、甲氧基、硝基或卤素；所述C1～4烷基为甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基或叔丁基；所述卤素原子为氟、氯、溴或碘。所述化合物显示出很强的抑制真菌活性，可用于制备农林用杀真菌剂等用途。
Description
技术领域
本发明涉及农林用杀菌剂领域，特别涉及一种含芳醚双三氮唑类化合物及其酸加成盐、金属盐复合物，以及制备方法及其作为农林用杀菌剂在防治农林业真菌病害上的用途。
背景技术
危害动植物而使动植物致病的有害生物主要是真菌、细菌和病毒。对植物而言，植物的主要病害是真菌病害。已商品化的杀菌防病药剂绝大多数为杀真菌剂，杀细菌剂则屈指可数，防病毒剂为数甚少。因素之一就是真菌病害具有普发性，造成的危害和损失也最大。在众多的真菌病害防治剂中，三唑类杀菌剂是典型的杀真菌类型。近30年来，三唑类杀菌剂以其高效、低毒、广谱而备受青睐，不仅如此，多数三唑类杀菌剂同时具有植物生物调节功能。但另一方面三唑类杀菌剂是内吸治疗型杀菌剂，作用机制和作用位点单一，长期频繁的使用，病害已产生了较严重的抗药性，不少品种由于抗性问题已失去原有的高效性。如三唑酮防治草莓白粉病，用量少防效低，用量大则易产生药害，抑制草莓生长。因而开发新型的三唑类杀菌剂便成为当务之急。
英国专利GB2078719A公开了具有杀菌活性的双三氮唑类化合物，但该专利所公开的化合物其取代基不包括芳醚基。本发明提供了新的含芳醚双三氮唑类杀菌剂，部分化合物抑菌活性与商品化三唑类杀菌剂戊唑醇、噁醚唑相当，具有很好的商品化前景。
发明内容
本发明所要解决的技术问题在于提供一种具有高生物活性的作为农林用杀菌剂的含芳醚双三氮唑类化合物及其酸加成盐、金属盐复合物。
本发明所要解决的另一个技术问题在于提供一种上述含芳醚双三氮唑类化合物及其酸加成盐、金属盐复合物在防治农林业真菌病害上的应用，这些病害大多是由隶属于子囊菌门、担子菌门、半知菌门的多个属的真菌引起的，如葡萄孢属、交链孢属、黑星孢属、轮枝孢属、镰刀属、球壳孢属等。为解决上述技术问题，本发明提供了一种含芳醚双三氮唑类化合物，具有如下结构式(I)或所述结构式(I)在农林药物学上可接受的对映体：
其中，R1、R2、R3、R4、R5、R6为氢、C1～4烷基、三氟甲基、甲氧基、硝基或卤素；
所述C1～4烷基为甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基或叔丁基；
所述卤素原子为氟、氯、溴或碘。
所述R1、R2、R3、R4、R5、R6取代基可以相同也可以不同。
所述酸加成盐的酸可以为盐酸、氢溴酸、硝酸、硫酸、磷酸、氢碘酸、氢氟酸、高氯酸、对甲苯磺酸、甲磺酸、乙酸、柠檬酸、酒石酸、苹果酸、草酸、富马酸或邻苯二酸中的一种或几种。
所述芳醚双三氮唑类化合物的金属盐复合物，其特征在于，具有如下结构式(II)：
其中，R1、R2、R3、R4、R5、R6为氢、C1～4烷基、三氟甲基、甲氧基、硝基或卤素；
所述C1～4烷基为甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基或叔丁基；
所述卤素原子为氟、氯、溴或碘；
所述M为元素周期表IIA、IVA、IB、IIB、VIB、VIIB或VIII族的阳离子；
所述Y为中和阳离子M电荷的阴离子。
所述的含芳醚双三氮唑类化合物作为农林用杀菌剂在防治农林业真菌病害上的应用。
所述的含芳醚双三氮唑类化合物作为农林用杀菌剂在防治农林业真菌病害上的应用，所述农林业真菌病害是由隶属于子囊菌门、担子菌门、半知菌门的一个或多个属的真菌引起的。
所述的含芳醚双三氮唑类化合物作为农林用杀菌剂在防治农林业真菌病害上的应用，所述农林业真菌病害是由葡萄孢属、交链孢属、黑星孢属、轮枝孢属、镰刀属或球壳孢属的一种或多种真菌引起的。
所述的含芳醚双三氮唑类化合物的酸加成盐作为农林用杀菌剂在防治农林业真菌病害上的应用。
所述的芳醚双三氮唑类化合物的金属盐复合物作为农林用杀菌剂在防治农林业真菌病害上的应用。
本发明提供的化合物不但具有较高的生物活性，而且与类似产品比较生产成本低，是一个非常有应用前景的农用杀菌剂新品种。
具体实施方式
本发明含芳醚双三氮唑类杀菌剂化合物(I)及其农业上可接受的酸加成盐和金属盐复合物，通式为：
其中，R1、R2、R3、R4、R5、R6为H、C1～4烷基、三氟甲基、甲氧基、硝基或卤素，R1、R2、R3、R4、R5、R6可以相同或不同；
上述C1～4烷基为甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基；上述卤素原子为氟、氯、溴、碘。
表1本发明三唑类化合物中的
基团的化学结构举例
| 例号 | R<sup>1</sup> | R<sup>2</sup> | R<sup>3</sup> | R<sup>4</sup> | R<sup>5</sup> | R<sup>6</sup> |
| 1 | H | H | H | H | H | H |
| 2 | H | H | Cl | H | H | 6-Cl |
| 3 | Cl | H | Cl | H | H | H |
| 4 | H | H | Cl | H | H | H |
| 5 | H | Cl | H | 5-Cl | H | H |
| 6 | H | Cl | H | 6-Cl | H | H |
| 7 | H | Cl | H | H | H | H |
| 8 | H | Br | H | H | H | H |
| 9 | H | H | CH<sub>3</sub> | H | H | H |
| 10 | CH<sub>3</sub> | H | CH<sub>3</sub> | H | H | H |
| 11 | F | H | H | H | H | H |
| 12 | H | F | H | H | H | H |
| 13 | H | H | F | H | H | H |
| 14 | Br | H | H | H | H | H |
| 15 | H | H | Br | H | H | H |
| 16 | C<sub>2</sub>H<sub>5</sub> | H | H | H | H | H |
| 17 | H | H | C<sub>4</sub>H<sub>9</sub>-t | H | H | H |
| 18 | OCH<sub>3</sub> | H | H | H | H | H |
| 19 | H | H | NO<sub>2</sub> | H | H | H |
| 20 | CF<sub>3</sub> | H | H | H | H | H |
| 21 | H | H | CF<sub>3</sub> | H | H | H |
| 22 | Br | H | Br | H | H | H |
| 23 | Br | H | Cl | H | H | H |
| 24 | Cl | H | Br | H | H | H |
| 25 | H | Cl | Cl | 6-Cl | H | H |
| 26 | CH<sub>3</sub> | H | Cl | H | H | H |
| 27 | NO<sub>2</sub> | H | CF<sub>3</sub> | H | H | H |
| 28 | NO<sub>2</sub> | H | NO<sub>2</sub> | 6-CF<sub>3</sub> | H | H |
| 29 | Cl | Cl | H | H | H | H |
| 30 | CH<sub>3</sub> | H | H | H | 2-CH<sub>3</sub> | H |
| 31 | H | H | Cl | H | 2-CH<sub>3</sub> | H |
| 32 | Cl | H | CF<sub>3</sub> | H | H | H |
| 33 | Cl | H | CF<sub>3</sub> | H | H | 6-Cl |
| 34 | H | H | Cl | H | 2-CH<sub>3</sub> | H |
| 35 | H | F | H | H | 2-CH<sub>3</sub> | H |
| 36 | CH<sub>3</sub> | H | H | H | 2-CH<sub>3</sub> | H |
| 37 | H | H | OCH<sub>3</sub> | H | 2-CH<sub>3</sub> | H |
| 38 | H | H | F | H | 2-CH<sub>3</sub> | H |
| 39 | OCH<sub>3</sub> | H | H | H | 2-Cl | H |
| 40 | H | H | F | H | 2-OCH<sub>3</sub> | H |
| 41 | H | H | Cl | H | 3-Cl | H |
| 42 | H | H | Cl | H | 2-C<sub>2</sub>H<sub>5</sub> | H |
| 43 | H | H | H | H | 2-CH<sub>3</sub> | H |
| 44 | H | H | H | H | 2-Cl | H |
| 45 | H | H | H | H | 3-CH<sub>3</sub> | H |
| 46 | H | H | H | H | 2-CH<sub>3</sub> | 5-CH<sub>3</sub> |
| 47 | H | H | H | H | 2-C<sub>2</sub>H<sub>5</sub> | H |
| 48 | H | H | CF<sub>3</sub> | H | 3-Cl | H |
| 49 | H | H | F | H | H | 6-Cl |
| 50 | H | H | F | H | H | 6-F |
标题化合物(I)可直接用制备农用杀菌剂，也可以农业上可以接受的酸加成盐的形式来制备农用杀菌剂，酸包括盐酸、氢溴酸、硝酸、硫酸、磷酸、氢碘酸、氢氟酸、高氯酸、对甲苯磺酸、甲磺酸、乙酸、柠檬酸、酒石酸、苹果酸、草酸、富马酸和邻苯二酸。
本发明的另一实施方案为式(I)的金属盐复合物(II)：
其中R1、R2、R3、R4、R5和R6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。
本发明典型的阳离子是镁、铜、镍、锌、铁、钴、钙、锡、铬、汞、钡等。
本发明典型的阴离子为氯、溴、碘、氟、硫氰酸根、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、草酸根、酒石酸根、苹果酸根、马莱酸根、富马酸根、对甲苯磺酸根、甲磺酸根等。
本发明中有较高活性的有：
化合物2α-(2-氯-4-(4-氯苯氧基)苯基)-α-(1H-1，2，4-三唑-1-基甲基)-1H-1，2，4-三唑-1-基乙醇
化合物33α-(2-氯-4-(2-氯-4-三氟甲基苯氧基)苯基)-α-(1H-1，2，4-三唑-1-基甲基)-1H-1，2，4-三唑-1-基乙醇
化合物32α-(4-(2-氯-4-三氟甲基苯氧基)苯基)-α-(1H-1，2，4-三唑-1-基甲基)-1H-1，2，4-三唑-1-基乙醇
化合物50α-(2-氟-4-(4-氟苯氧基)苯基)-α-(1H-1，2，4-三唑-1-基甲基)-1H-1，2，4-三唑-1-基乙醇
本发明的具有结构式(I)的化合物可以按下述方法制造：
式中R1、R2、R3、R4、R5和R6含义同上所述。
反应由醚酮为原料经溴代、氮烷基化、环氧化最后与三氮唑反应开环得目标化合物。具体反应条件如下：
实施例I：α-(2-氯-4-(4-氯苯氧基)苯基)-α-(1H-1，2，4-三唑-1-基甲基)-1H-1，2，4-三唑-1-基乙醇的制备
2-溴-1-(2-氯-4-(4-氯苯氧基)苯基)乙酮
在500mL四颈瓶中加入280g(1.0mol)2-氯-4-(4-氯苯氧基)苯乙酮、200mL环己烷，室温搅拌，滴加192g(1.2mol)溴，先加入2～3滴，溶液呈红色，等红色褪去后，再将剩余的溴滴加进去，控制滴加速度，约3h滴完。维持反应温度继续搅拌2h至颜色褪去，停止反应。将反应液倒入500mL分液漏斗中，用水洗涤，分去水层，反复水洗至有机相呈中性，分出有机相，用无水硫酸镁干燥过夜。滤去硫酸镁，减压蒸除环己烷，得淡黄色固体，重结晶得白色晶体335.2g，收率93.1％。熔点：50～51℃。
2-(1H-1，2，4-三唑-1-基)-1-(2-氯-4-(4-氯苯氧基)苯基)乙酮的制备
在500mL四颈瓶中分别加入180g(0.5mol)2-溴-1-(2-氯-4-(4-氯苯氧基)苯基)乙酮、51.8g(0.75mol)三氮唑、103.5g(0.75mol)碳酸钾粉末和200mL乙酸乙酯，加热回流反应6h，过滤，滤液减蒸，得浅黄色固体，重结晶得白色固体117.2g，收率67.3％，熔点：151～154℃。
1-[2-(2-氯-4-(4-氯苯氧基)苯基)-2，3-环氧丙基]-1H-1，2，4-三唑甲磺酸盐制备
取2-(1H-1，2，4-三唑-1-基)-1-(2-氯-4-(4-氯苯氧基)苯基)乙酮34.8g(0.1mol)，碘化三甲基氧硫26.4g(0.12mol)，三甲基十六烷基溴化铵0.3g和甲苯100mL放入250mL三颈瓶中，升温至60℃，搅拌下滴加20％的氢氧化钠溶液80mL，2h滴完，保温60℃继续搅拌3小时，分离出甲苯层，浓缩至25mL。残留液加15mL乙酸乙酯稀释，0℃下滴加溶有9.6g甲磺酸的乙酸乙酯溶液5mL、再加乙酸乙酯稀释，0℃下搅拌一小时，得淡黄色沉淀1-[2-(2-氯-4-(4-氯苯氧基)苯基)-2，3-环氧丙基]-1H-1，2，4-三唑甲磺酸盐，将粗品重结晶得淡黄色固体32.2g，收率70.2％，熔点：130～134℃。
α-(2-氯-4-(4-氯苯氧基)苯基)-α-(1H-1，2，4-三唑-1-基甲基)-1H-1，2，4-三唑-1-基乙醇的制备
在50mL单口烧瓶中加入1-[2-(2-氯-4-(4-氯苯氧基)苯基)-2，3-环氧丙基]-1H-1，2，4-三唑甲磺酸盐4.6g(0.01mol)，三氮唑0.8g(0.012mol)，碳酸钾粉末1.4g(0.01mol)和N，N-二甲基甲酰胺20mL，回流反应6h，将反应液倒入水中，有白色固体析出，抽滤得α-(2-氯-4-(4-氯苯氧基)苯基)-α-(1H-1，2，4-三唑-1-基甲基)-1H-1，2，4-三唑-1-基乙醇粗品，重结晶得白色晶体1.8g，收率41.5％，熔点141～143℃。
1H NMR：8.12(2H，s，2triazole C5-H)，7.89(2H，s，2triazoleC3-H)，6.74-7.57(7H，m，Ar-H)，5.50(1H，s，OH)，5.08-5.10(2H，d，CH2)，4.59-4.61(2H，d，CH2).
其余目标化合物以不同的取代芳醚酮为合成原料，如表1所列，重复实施例I中的步骤，便能合成所需含芳醚双三氮唑类化合物。
本发明合成的含芳醚双三氮唑类化合物具有抑制真菌作用，下面阐述其生测实验结果。
实验方法：采用离体平皿法
材料与方法
(1)试验菌株
本实验选用表2中农业常见植物真菌病害，这些病害是由隶属于子囊菌门、担子菌门、半知菌门的多个属的真菌引起的，例如葡萄孢属、交链孢属、黑星孢属、轮枝孢属、镰刀属、球壳孢属等等，代表了自然界形形色色的植物病原真菌。
(2)试验方法
将供试药剂按有效成分分别稀释至所需浓度，在无菌条件下各吸取1mL药液注入培养皿内，再分别加入9mL培养基，摇匀后制成5μg/mL含药平板，以添加1mL灭菌水的平板做空白对照。用直径4mm的打孔器沿菌丝外缘切取菌盘，移至含药平板上，每处理重复三次。将培养皿放在24±1℃恒温培养箱内培养。72h后调查各处理菌盘扩展直径，求平均值，与空白对照比较计算相对抑菌率。
实验结果
部分化合物抑菌实验结果见表2、表3：
表2：杀菌活性(5μg/mL)，％
表3：杀菌活性(1μg/mL)，％
表2、表3中生物活性用杀死或抑制百分率表示
活性分级：+++≥90％；++≥70％-89％；+≥50％-69％；-＜50％。
对26种植物病原真菌菌体生长速率抑制作用发现本发明化合物具有较好的抑制农业真菌病害活性，在5.0ug/mL浓度下对供试的真菌菌体生长有很好的抑制作用，抑制率绝大多数在80％以上，甚至达到100.0％，与当今抑菌效果最好的噁醚唑(difenoconazole)，戊唑醇(difenoconazole)相当；在1.0ug/mL浓度下对供试的真菌菌体生长也有很好的抑制作用，抑制率绝大多数在80％以上，其效果略逊于5.0ug/mL浓度，但其浓度低，残留量小，基本达到抑制效果，也可以与当今抑菌效果最好的噁醚唑(difenoconazole)，戊唑醇(difenoconazole)相当。
Claims (1)
1、一种含芳醚双三氮唑类化合物，其特征在于：其结构式为
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101408367A CN100451007C (zh) | 2006-10-12 | 2006-10-12 | 含芳醚双三氮唑类化合物及其用途 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101408367A CN100451007C (zh) | 2006-10-12 | 2006-10-12 | 含芳醚双三氮唑类化合物及其用途 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1923819A CN1923819A (zh) | 2007-03-07 |
| CN100451007C true CN100451007C (zh) | 2009-01-14 |
Family
ID=37816660
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006101408367A Active CN100451007C (zh) | 2006-10-12 | 2006-10-12 | 含芳醚双三氮唑类化合物及其用途 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100451007C (zh) |
Families Citing this family (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102657184B (zh) * | 2012-04-19 | 2014-01-22 | 杭州宇龙化工有限公司 | 一种含有苯醚双唑与噻呋酰胺的杀菌组合物 |
| CN102657179B (zh) * | 2012-04-26 | 2014-04-23 | 杭州宇龙化工有限公司 | 一种含有苯醚双唑与肟菌酯的杀菌组合物 |
| CN102657199B (zh) * | 2012-05-08 | 2013-08-07 | 杭州宇龙化工有限公司 | 一种含有苯醚双唑和吡唑醚菌酯的杀菌组合物 |
| CN102696621B (zh) * | 2012-05-30 | 2013-06-12 | 杭州宇龙化工有限公司 | 一种含有苯醚双唑与丙硫菌唑的杀菌组合物 |
| CN102696623B (zh) * | 2012-06-21 | 2013-07-03 | 杭州宇龙化工有限公司 | 一种含有苯醚双唑与丙环唑的杀菌组合物 |
| CN102715168B (zh) * | 2012-06-28 | 2013-09-04 | 杭州宇龙化工有限公司 | 一种含有苯醚双唑与嘧菌酯的杀菌组合物及其用途 |
| CN102696625B (zh) * | 2012-06-28 | 2013-06-12 | 杭州宇龙化工有限公司 | 一种含有苯醚双唑与啶氧菌酯的杀菌组合物及其用途 |
| CN102715173B (zh) * | 2012-06-28 | 2013-11-13 | 杭州宇龙化工有限公司 | 一种含有苯醚双唑与氟嘧菌酯的杀菌组合物及其用途 |
| CN102696628B (zh) * | 2012-07-10 | 2014-01-22 | 杭州宇龙化工有限公司 | 一种含有苯醚双唑与嘧菌环胺的杀菌组合物 |
| CN102696627B (zh) * | 2012-07-10 | 2013-11-13 | 杭州宇龙化工有限公司 | 一种含有苯醚双唑与四氟醚唑的杀菌组合物 |
| CN102696626B (zh) * | 2012-07-10 | 2013-07-03 | 杭州宇龙化工有限公司 | 一种含有苯醚双唑与咯菌腈的杀菌组合物 |
| CN102754649B (zh) * | 2012-08-01 | 2013-08-21 | 杭州宇龙化工有限公司 | 一种含有苯醚双唑与氟环唑的杀菌组合物 |
| EP2928873A1 (en) | 2012-11-27 | 2015-10-14 | Basf Se | Substituted 2-[phenoxy-phenyl]-1-[1,2,4]triazol-1-yl-ethanol compounds and their use as fungicides |
| WO2014082871A1 (en) | 2012-11-27 | 2014-06-05 | Basf Se | Substituted 2-[phenoxy-phenyl]-1-[1,2,4]triazol-1-yl-ethanol compounds and their use as fungicides |
| WO2014124850A1 (en) | 2013-02-14 | 2014-08-21 | Basf Se | Substituted [1,2,4]triazole and imidazole compounds |
| EP2783569A1 (en) | 2013-03-28 | 2014-10-01 | Basf Se | Compositions comprising a triazole compound |
| WO2014184309A1 (en) * | 2013-05-17 | 2014-11-20 | Basf Se | Substituted [1,2,4]triazole and imidazole compounds |
| WO2014198557A1 (en) * | 2013-06-12 | 2014-12-18 | Basf Se | Substituted [1,2,4]triazole and imidazole compounds |
| EP2813499A1 (en) | 2013-06-12 | 2014-12-17 | Basf Se | Substituted [1,2,4]triazole and imidazole compounds |
| WO2014198553A1 (en) * | 2013-06-12 | 2014-12-18 | Basf Se | Substituted [1,2,4]triazole and imidazole compounds |
| CN104604888B (zh) * | 2015-02-16 | 2016-07-06 | 杭州宇龙化工有限公司 | 一种含有苯醚双唑与恶唑菌酮的杀菌组合物 |
| CN104686527A (zh) * | 2015-02-16 | 2015-06-10 | 杭州宇龙化工有限公司 | 一种含有苯醚双唑与苯酰菌胺的杀菌组合物 |
| CN104604904B (zh) * | 2015-02-16 | 2016-08-24 | 杭州宇龙化工有限公司 | 一种含有苯醚双唑和代森锰锌的杀菌组合物 |
| CN104663685A (zh) * | 2015-02-16 | 2015-06-03 | 杭州宇龙化工有限公司 | 一种含有苯醚双唑和苯噻菌胺的杀菌组合物 |
| CN104604886A (zh) * | 2015-02-16 | 2015-05-13 | 杭州宇龙化工有限公司 | 一种含有苯醚双唑与乙嘧酚磺酸酯的杀菌组合物 |
| CN104829546B (zh) * | 2015-04-13 | 2017-03-15 | 天津师范大学 | 双三唑取代的乙氧基苯化合物及其制备方法与应用 |
| CN105254577B (zh) * | 2015-08-07 | 2017-08-01 | 常州大学 | 一种双三氮唑取代苯二甲酸酯类化合物、制备方法和用途 |
| 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 |
| CN105994384A (zh) * | 2016-05-21 | 2016-10-12 | 张素香 | 一种杀菌组合物 |
| CN114365744A (zh) * | 2018-08-10 | 2022-04-19 | 江苏龙灯化学有限公司 | 一种包含噻霉酮和苯醚双唑的杀菌组合物 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0111658A2 (en) * | 1980-06-02 | 1984-06-27 | Imperial Chemical Industries Plc | 1,3-Dihalopropan-2-ols |
| US4466974A (en) * | 1982-11-16 | 1984-08-21 | Pfizer Inc. | Bistriazole antifungal agents |
| US4992458A (en) * | 1987-01-21 | 1991-02-12 | Ciba-Geigy Corporation | 1-phenoxyphenyl-1-triazolylmethyl-carbinol compound as microbicides |
| CN1259867A (zh) * | 1995-06-07 | 2000-07-12 | 普罗克特和甘保尔公司 | 双－1,2,4－三唑在制备癌症治疗药物中的用途 |
-
2006
- 2006-10-12 CN CNB2006101408367A patent/CN100451007C/zh active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0111658A2 (en) * | 1980-06-02 | 1984-06-27 | Imperial Chemical Industries Plc | 1,3-Dihalopropan-2-ols |
| US4466974A (en) * | 1982-11-16 | 1984-08-21 | Pfizer Inc. | Bistriazole antifungal agents |
| US4992458A (en) * | 1987-01-21 | 1991-02-12 | Ciba-Geigy Corporation | 1-phenoxyphenyl-1-triazolylmethyl-carbinol compound as microbicides |
| CN1259867A (zh) * | 1995-06-07 | 2000-07-12 | 普罗克特和甘保尔公司 | 双－1,2,4－三唑在制备癌症治疗药物中的用途 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1923819A (zh) | 2007-03-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100451007C (zh) | 含芳醚双三氮唑类化合物及其用途 | |
| CN101225074A (zh) | 一类含芳醚三氮唑化合物的合成及杀菌活性 | |
| JPS63141971A (ja) | ピリミジン誘導体および農園芸用殺菌剤 | |
| CN103781357A (zh) | 吡唑酰胺类化合物作为农用杀菌剂的用途 | |
| JPS6128668B2 (zh) | ||
| CN102827145A (zh) | 一种新型氘代邻氨基苯甲酰胺化合物及其制备方法和应用 | |
| JPS59112904A (ja) | 殺菌剤 | |
| CN103179857B (zh) | 包括腙衍生物和铜的协同杀藻组合物 | |
| JPH0242801B2 (zh) | ||
| CN109776410A (zh) | 一类含七氟异丙基喹啉醚类化合物、其制备方法及应用 | |
| CN103554026B (zh) | 一组3-三氟甲基-4-甲酰吡唑化合物 | |
| CN109666004B (zh) | 含有三氟甲基的吡嗪酰胺类化合物及其制备方法和应用以及杀菌剂 | |
| JPS61271276A (ja) | ジクロロシクロプロピルアルキル−ヒドロキシアルキル−アゾ−ル誘導体 | |
| CN101747290A (zh) | 一种n取代基噻唑酮衍生物及其制备方法和应用 | |
| US4481211A (en) | Microbiocidal substituted benzylimidazolium salts | |
| CN103333113A (zh) | 氟唑菌酰胺类似衍生物的制备及应用研究 | |
| CN111763231B (zh) | 含三苯基鏻阳离子的杀菌杀螨化合物的合成方法与应用 | |
| JPS6055499B2 (ja) | アルキレングリコ−ルジベンゾエ−ト | |
| CS236480B2 (en) | Agent with fungicide and bactericide effect | |
| CN110122495A (zh) | 含有1-(3-氯-2-吡啶基)-1氢-吡唑活性片段的化合物在制备杀菌剂中的应用 | |
| JPS6243967B2 (zh) | ||
| CN106749205B (zh) | 一种吡啶乙氧基香豆素类植物生长调节剂 | |
| US3859444A (en) | Methods of killing bacteria using alkylthiosemicarbazides | |
| JP3343437B2 (ja) | 含ケイ素アゾール系化合物を含有する殺菌組成物 | |
| JPS6157562A (ja) | 新規なアルキルスルホニルプロペン、それらの製造方法およびそれらの植物処理剤としての用途 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: HANGZHOU YULONG CHEMICAL ENGINEERING CO., LTD. Free format text: FORMER OWNER: QINGDAO UNIVERSITY OF SCIENCE AND TECHNOLOGY Effective date: 20080711 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20080711 Address after: Industrial Development Zone, Tangqi Town, Yuhang District, Zhejiang, Hangzhou Province, China: 311106 Applicant after: Hangzhou Udragon Chemical Co.,Ltd. Address before: 53, Zhengzhou Road, Shandong, Qingdao Province, China: 266071 Applicant before: QINGDAO University OF SCIENCE AND TECHNOLOGY |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 311106 No. 172, Zhangjiadun Road, Tangqi Town, Linping District, Hangzhou, Zhejiang Patentee after: Zhejiang Yulong Pharmaceutical Co.,Ltd. Address before: 311106 Industrial Development Zone, Tangqi Town, Yuhang District, Zhejiang, Hangzhou Patentee before: Hangzhou Udragon Chemical Co.,Ltd. |