CN103582417A - 用于控制农药抗性害虫的组合物和方法 - Google Patents
用于控制农药抗性害虫的组合物和方法 Download PDFInfo
- Publication number
- CN103582417A CN103582417A CN201280012842.8A CN201280012842A CN103582417A CN 103582417 A CN103582417 A CN 103582417A CN 201280012842 A CN201280012842 A CN 201280012842A CN 103582417 A CN103582417 A CN 103582417A
- Authority
- CN
- China
- Prior art keywords
- insect
- anabasine
- formula
- composition
- compound shown
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000000575 pesticide Substances 0.000 title claims abstract description 13
- 241000607479 Yersinia pestis Species 0.000 title claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 51
- 239000002917 insecticide Substances 0.000 claims abstract description 11
- 241000238631 Hexapoda Species 0.000 claims description 80
- MTXSIJUGVMTTMU-JTQLQIEISA-N (S)-anabasine Chemical compound N1CCCC[C@H]1C1=CC=CN=C1 MTXSIJUGVMTTMU-JTQLQIEISA-N 0.000 claims description 57
- 229930014345 anabasine Natural products 0.000 claims description 57
- 238000009472 formulation Methods 0.000 claims description 19
- 239000005906 Imidacloprid Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- YWTYJOPNNQFBPC-UHFFFAOYSA-N imidacloprid Chemical group [O-][N+](=O)\N=C1/NCCN1CC1=CC=C(Cl)N=C1 YWTYJOPNNQFBPC-UHFFFAOYSA-N 0.000 claims description 9
- 229940056881 imidacloprid Drugs 0.000 claims description 9
- WCXDHFDTOYPNIE-RIYZIHGNSA-N (E)-acetamiprid Chemical compound N#C/N=C(\C)N(C)CC1=CC=C(Cl)N=C1 WCXDHFDTOYPNIE-RIYZIHGNSA-N 0.000 claims description 4
- PGOOBECODWQEAB-UHFFFAOYSA-N (E)-clothianidin Chemical compound [O-][N+](=O)\N=C(/NC)NCC1=CN=C(Cl)S1 PGOOBECODWQEAB-UHFFFAOYSA-N 0.000 claims description 4
- CFRPSFYHXJZSBI-DHZHZOJOSA-N (E)-nitenpyram Chemical compound [O-][N+](=O)/C=C(\NC)N(CC)CC1=CC=C(Cl)N=C1 CFRPSFYHXJZSBI-DHZHZOJOSA-N 0.000 claims description 4
- NWWZPOKUUAIXIW-DHZHZOJOSA-N (E)-thiamethoxam Chemical compound [O-][N+](=O)/N=C/1N(C)COCN\1CC1=CN=C(Cl)S1 NWWZPOKUUAIXIW-DHZHZOJOSA-N 0.000 claims description 4
- HOKKPVIRMVDYPB-UVTDQMKNSA-N (Z)-thiacloprid Chemical compound C1=NC(Cl)=CC=C1CN1C(=N/C#N)/SCC1 HOKKPVIRMVDYPB-UVTDQMKNSA-N 0.000 claims description 4
- 239000005875 Acetamiprid Substances 0.000 claims description 4
- 239000005888 Clothianidin Substances 0.000 claims description 4
- 241000255925 Diptera Species 0.000 claims description 4
- 239000005940 Thiacloprid Substances 0.000 claims description 4
- 229940079888 nitenpyram Drugs 0.000 claims description 4
- 241000254173 Coleoptera Species 0.000 claims description 2
- 241000255777 Lepidoptera Species 0.000 claims description 2
- 230000001055 chewing effect Effects 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- 241001124076 Aphididae Species 0.000 description 12
- 239000003905 agrochemical Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 238000011953 bioanalysis Methods 0.000 description 8
- 241001147381 Helicoverpa armigera Species 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 241000272639 Brachycaudus mimeuri Species 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 241000256259 Noctuidae Species 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- FTNJQNQLEGKTGD-UHFFFAOYSA-N 1,3-benzodioxole Chemical compound C1=CC=C2OCOC2=C1 FTNJQNQLEGKTGD-UHFFFAOYSA-N 0.000 description 3
- 241000254127 Bemisia tabaci Species 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 241000258916 Leptinotarsa decemlineata Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000001784 detoxification Methods 0.000 description 3
- 231100000225 lethality Toxicity 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DAXJNUBSBFUTRP-RTQNCGMRSA-N (8r,9s,10r,13s,14s)-6-(hydroxymethyl)-10,13-dimethyl-7,8,9,11,12,14,15,16-octahydro-6h-cyclopenta[a]phenanthrene-3,17-dione Chemical compound O=C1C=C[C@]2(C)[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CC(CO)C2=C1 DAXJNUBSBFUTRP-RTQNCGMRSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 2
- 244000221633 Brassica rapa subsp chinensis Species 0.000 description 2
- 235000010149 Brassica rapa subsp chinensis Nutrition 0.000 description 2
- 235000000536 Brassica rapa subsp pekinensis Nutrition 0.000 description 2
- 241000219193 Brassicaceae Species 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 108090000371 Esterases Proteins 0.000 description 2
- 244000068988 Glycine max Species 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 241000594036 Liriomyza Species 0.000 description 2
- 241000124008 Mammalia Species 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 241001585712 Noctua Species 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 101710097943 Viral-enhancing factor Proteins 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000008485 antagonism Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- ABADUMLIAZCWJD-UHFFFAOYSA-N 1,3-dioxole Chemical compound C1OC=CO1 ABADUMLIAZCWJD-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- WEZSYTDTTOKPOF-UHFFFAOYSA-N 5-dodecyl-1,3-benzodioxole Chemical compound CCCCCCCCCCCCC1=CC=C2OCOC2=C1 WEZSYTDTTOKPOF-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 241001600408 Aphis gossypii Species 0.000 description 1
- 240000008100 Brassica rapa Species 0.000 description 1
- 235000011292 Brassica rapa Nutrition 0.000 description 1
- 241001444260 Brassicogethes aeneus Species 0.000 description 1
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 1
- 241001367803 Chrysodeixis includens Species 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- 241001124568 Helicoverpa punctigera Species 0.000 description 1
- 241000256244 Heliothis virescens Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 1
- 241000721621 Myzus persicae Species 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 241000819999 Nymphes Species 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 241000256248 Spodoptera Species 0.000 description 1
- 241001389006 Tuta absoluta Species 0.000 description 1
- 241001530229 Wiseana cervinata Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 239000003405 delayed action preparation Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 231100000673 dose–response relationship Toxicity 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 231100000636 lethal dose Toxicity 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 239000012747 synergistic agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
- A01N43/26—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings
- A01N43/28—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3
- A01N43/30—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3 with two oxygen atoms in positions 1,3, condensed with a carbocyclic ring
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
提供了组合物,所述组合物包含(i)新烟碱;和(ii)式(I)或(II)所示的化合物,优选地其中所述组合物为农药组合物,例如杀虫剂组合物。还提供了式(I)或(II)所示的化合物作为新烟碱增效剂的用途和式(I)或(II)所示的化合物与新烟碱组合的用途。还提供了用于控制害虫的方法。
Description
本发明涉及农药增效剂,特别是提高新烟碱类抗害虫的功效的增效剂,所述害虫显示对新烟碱类的抗性。
自从第一例杀虫剂抗性在1914年被科学地记录后,杀虫剂抗性已经逐渐变得更加广泛。目前超过500种昆虫和螨物种显示对农药的耐受性,并且农药抗性已成为对未来使用化学品成功地控制害虫的严重的威胁。
许多昆虫具有解毒系统,所述解毒系统最初进化以保护昆虫免受环境中的天然毒素的危害。当杀虫剂接触那些使其毒性降低或更容易被排泄或两者的解毒酶时,杀虫剂可以在其到达其靶位点之前发生代谢。这对于许多类型的杀虫剂是真实的,包括新烟碱类。
新烟碱类是一类作用于昆虫的中枢神经系统的杀虫剂,对哺乳动物具有更低的毒性。新烟碱类是全世界最广泛使用的杀虫剂,而昆虫对新烟碱类的抗性是一个日益严重的问题。
为了尝试并防止或克服害虫对农药的抗性,一种策略是在施用杀虫剂的同时或在施用杀虫剂不久后施用农药增效剂。在该策略背后的意图是为了使增效剂抑制害虫的解毒系统以使农药更加有效。虽然该策略已经在某些情况下有效地采用,但仍然需要改进的组合物和方法来提高农药的功效,尤其是对农药抗性昆虫的功效。
特别是需要用于提高新烟碱类对新烟碱抗性害虫的功效的改进的方法和组合物。
发明概述
根据本发明的一个方面,提供了包含(i)新烟碱;和(ii)式I或II所示的化合物的组合物。
优选地,所述组合物为农药组合物,优选地为杀虫剂组合物。
优选地,所述组合物包含式I或II所示的化合物的速释制剂,和新烟碱的非速释制剂。
根据本发明的另一个方面,提供了式I或II所示的化合物作为新烟碱增效剂的用途。
在这个方面,术语“新烟碱增效剂”是指式I或II所示的化合物能够使新烟碱对抗新烟碱抗性害虫有效,或能够使新烟碱对抗新烟碱抗性害虫和/或新烟碱敏感性害虫更有效。
在这个方面,术语“新烟碱敏感性害虫”是指对新烟碱的作用敏感的害虫。例如,新烟碱敏感性害虫可以是能够被新烟碱破坏能力或杀死的害虫。
有利地,式I或II所示的化合物作为新烟碱增效剂的用途是指在新烟碱敏感性害虫方面,需要更少的新烟碱来实现与单独使用新烟碱时相同的结果。
根据本发明的另一个方面,提供了式I或II所示的化合物与新烟碱组合的用途。
根据本发明的另一个方面,提供了用于控制害虫的方法,所述方法包括将害虫与(i)式I或II所示的化合物和(ii)新烟碱接触。
优选地,所述害虫在与新烟碱接触之前与式I或II所示的化合物接触。
优选地,所述害虫在与新烟碱接触之前至少约30分钟,优选地在与新烟碱接触之前至少约1小时,优选地至少约2小时,优选地至少约3小时,例如约4小时与式I或II所示的化合物接触。
优选地,害虫直接与式I或II所示的化合物和新烟碱接触。例如,式I或II所示的化合物和新烟碱可以直接喷在害虫上。可供选择地,害虫可以间接地与式I或II所示的化合物和新烟碱接触。例如,在其上发现害虫的表面(例如农作物)可以与式I或II所示的化合物和新烟碱接触。
根据本发明的另一个方面,提供了用于控制害虫的方法,所述方法包括将害虫与本发明的组合物接触。
优选地,使害虫直接与本发明的组合物接触。例如,本发明的组合物可以直接喷在害虫上。可供选择地,害虫可以间接地与本发明的组合物接触。例如,在其上发现害虫的表面(例如农作物)可以与本发明的组合物接触。
优选地,所述新烟碱选自吡虫啉、啶虫脒、噻虫胺、呋虫胺、烯啶虫胺、噻虫啉和噻虫嗪。
最优选地,所述新烟碱为吡虫啉。
优选地,所述害虫为新烟碱抗性害虫或新烟碱敏感性害虫。
优选地,所述害虫为昆虫。
优选地,所述害虫选自吸啜式或咀嚼式昆虫,例如选自半翅目、鞘翅目、双翅目和鳞翅目。
优选地,所述害虫选自棉铃虫(Helicoverpa armigera)、斑实夜蛾(Helicoverpa punctigera)、烟芽夜蛾(Heliothis virescens)、棉蚜(Aphisgossypii)、桃蚜(Myzus persicae)、大豆夜蛾(Pseudoplusia includens)、蝙蝠蛾(Wiseana cervinata)、烟粉虱(Bemisia tabaci)、油菜露尾甲(Meligethesaeneus)、马铃薯叶甲(Leptinotarsa decemlineata)、番茄斑潜蝇夜蛾属种(Tutaabsoluta Spodoptera sp.)和蚊子物种。
优选地,所述害虫为蚜虫,例如无翅蚜虫。
发明详述
本发明涉及用于控制新烟碱抗性害虫的组合物和方法。特别地,本发明涉及包含新烟碱和新烟碱增效剂的新型组合物。
本发明的详细实例列于下文。
在本说明书中,描述了实施方案,所述描述的方式使其能够写出清楚和简洁的说明书,但其目的在于,并且可以理解为,在不脱离本发明的前提下,实施方案可以进行各种组合或分离。
在本说明书中,提及式I所示的化合物是指具有以下结构的化合物:
其中,
R1为C1到C12烷基;且
R2选自H和C1到C5烷基。
在本说明书中,提及式II所示的化合物是指具有以下结构的化合物:
在本说明书中,术语“EN126”是指式II所示的化合物。
在本说明书中,术语“新烟碱抗性害虫”是指对新烟碱显示至少一些抗性的害虫,例如昆虫。所述抗性可以是部分的或完全的,并且可以理解的是,所有程度的抗性均包括在该术语的含义中,无论它们是非常低的抗性、低的抗性、高的抗性、非常高的抗性还是完全的抗性。
世界卫生组织将抗性定义为“在一个品系的昆虫中耐受毒物的剂量的能力的发展,所述毒物被证明对相同物种的正常群体中的大多数个体是致命的”。因此,对杀虫剂抗性进行类似的解释,但是本文讨论的主要的害虫是昆虫。
在本说明书中,术语“包括(comprise)”和“包括(comprising)”应解释为意思是“除了别的之外包括”。这些术语不意图解释为“仅由......组成”。
在本说明书中,术语“约”是指加或减20%,更优选地加或减10%,甚至更优选地加或减5%,最优选地加或减2%。
在本说明书中,可以理解的是对术语“控制害虫”的提及包括对杀死或使害虫失去能力的提及。优选地,该术语是指杀死或使所有或相当大的比例的与本发明的组合物接触的害虫群体失去能力。
术语“相当大的比例”可以指至少约50%、至少约60%、至少约70%、至少约80%、至少约90%、至少约95%、至少约98%或至少约99%。
如本文所述,本发明的组合物可以包含式I或II所示的化合物的速释制剂,和新烟碱的非速释制剂。合适的速释和非速释制剂详细描述于第PCT/GB03/01861号国际专利申请,于2003年11月13日公开为WO03/092378。
例如,速释制剂和非快速(持续)释放制剂可以以物理掺加物包含在组合物中。可供选择地,速释制剂和非速释制剂可以分别施用,但是可以在大约相同的时间与害虫接触,以避免再次访问害虫位点的需要,以应用两种制剂中的第二种。因此两种制剂将在数秒内与害虫彼此接触,优选地在10秒内,和更优选地,在一或两秒内,而不是在数分钟内或更长时间内与害虫彼此接触。优选地,同时施用所述制剂。
速释制剂适当地为本领域技术人员已知的或待发现的并且适用于该目的的任何标准农药制剂。这样的制剂包括,例如,可湿性粉剂、颗粒剂、可乳化的浓缩物和超低体积制剂,可向其加入水以形成乳液、悬浮液等。优选地,包含式I或II所示的化合物的速释制剂是可乳化的浓缩物的形式。
非速释制剂适当地为本领域已知的或待发现的任何非速释制剂,如适用于该目的的持续释放、控释或缓释制剂。优选地,非速释制剂是防止有效剂量的农药被释放或与害虫或其在害虫中的靶点有效接触,直到式I或II所示的化合物至少对其在害虫中的靶点开始作用的制剂。
适当地,所述速释制剂在应用组合物之后至少约30分钟,优选地至少约1小时,优选地至少约2小时,优选地至少约3小时,例如约4小时防止农药的释放或其与害虫的接触。这样的制剂包括,例如,包封在可降解的胶囊中的农药,并优选地包括微包封技术。
非速释制剂优选地包含相当于农药的标准剂量的量。
式I或II所示的化合物的量应足以防止或降低害虫(或多种害虫)对农药的抗性,并将取决于害虫大小(例如,粉虱需要的量少于棉铃虫幼虫)、抗性程度等,但是可由本领域技术人员确定。
本发明的组合物所针对的害虫(或多种害虫)可以是已知提供对新烟碱的至少一些抗性并认为有必要使其失去能力和/或杀死的任何害虫。实例包括攻击或损害或降低作用物(substrate)的商业或其它价值的那些,所述作用物包括农作物,特别是可耕种作物,如食物,和材料作物,包括棉花。
其它害虫包括其它活有机体的妨害者或敌对者的那些,所述活有机体包括哺乳动物,如人类。
在一个实例中,害虫(或多种害虫)可以包括棉铃虫、斑实夜蛾、烟芽夜蛾、棉蚜、桃蚜、大豆夜蛾、蝙蝠蛾、烟粉虱、油菜露尾甲、马铃薯叶甲、番茄斑潜蝇夜蛾属种和蚊子物种中的一种或多种。
为了向在其上可能发现害虫的表面(也称为“作用物”)施用,可以使用本领域已知的任意方法来向作用物应用农药等,并可以取决于因素,如特定作用物(例如,农作物)、农作物的靶害虫阶段等。
这样的方法的实例包括通过地面或空中应用来喷洒。为了施用于农作物,特别是广阔的区域如澳大利亚棉田,优选的是喷洒包含一种或两种制剂的水溶液的悬浮液或乳液的组合物,所述组合物任选地还包含表面活性剂或其它赋形剂,或在储槽中提供的超低体积(省略水)组合物,如适于被飞机运输的组合物,或例如在粉虱喷洒的情况下,通过地面装备(如拖拉机、坦克或吊杆喷洒)。
根据本发明的组合物的施用速率将根据已知的或已批准的(注册的)每种制剂的活性成分的速率。
本发明的化合物可以根据以下描述的方法合成。
式I所示的化合物,其中R1为C1到C12烷基,且R2选自H和C1到C5烷基,
可以通过已知的化学反应制备,例如:
A)式III所示的卤代甲基衍生物,其中R1代表C1-C12烷基,且Hal为Cl或Br,
与合适的R≡C-CH2OH所示的化合物的醇(式IV),其中R2代表H或C1-C5烷基,在合适的碱如氢氧化钠或氢氧化钾、碳酸钠或碳酸钾的存在下,在无水的或惰性的芳香族溶剂如甲苯或二甲苯中,在60℃到140℃的温度下的缩合(醚化);优选在无水的或甲苯中。
B)式III所示的卤代甲基衍生物,其中R1代表C1-C12烷基,Hal为Cl或Br,
与合适的R2≡C-CH2OMe所示的化合物的碱性醇盐(式V),其中R2代表H或C1-C5烷基,且Me为钠或钾,在合适的溶剂如N,N-二甲基甲酰胺、Ν,Ν-二甲基乙酰胺、N-甲基吡咯烷酮、四氢呋喃、2-甲基四氢呋喃或二氧六环中,在50℃到150℃的温度下的缩合(醚化)。优选50℃到80℃的温度。
C)式VI的羟甲基衍生物,其中R1代表C1-C12烷基,
与合适的R2≡C-CH2Hal所示的化合物的碱性卤化物(式VII),其中R2代表H或C1-C5烷基,且Hal为Cl、Br或I(优选Br),在合适的碱如氢化钠的存在下,和在合适的溶剂如N,N-二甲基甲酰胺、Ν,Ν-二甲基乙酰胺、N-甲基吡咯烷酮、四氢呋喃、2-甲基四氢呋喃或二氧六环中,在50℃到150℃的温度下的缩合(醚化)。优选50℃到80℃的温度。
D)如US6,320,085中所描述的,式III所示的卤代甲基衍生物,其中R1代表C1-C12烷基,且Hal为Cl或Br,
与合适的R2≡C-CH2OH所示的化合物的醇(式IV),其中R2代表H或C1-C5烷基,在合适的金属氧化物如氧化锌和合适的非极性质子性溶剂如二氯甲烷或二氯乙烷的存在下,并且在20℃到90℃的温度下的缩合(醚化)。优选20℃到40℃的温度。
E)如US6,608,232中所描述的,式VI所示的羟甲基衍生物,其中R1代表C1-C12烷基,
与合适的R2≡C-CH2OH所示的化合物的醇(式IV),其中R2代表H或C1-C5烷基,在有效量的多相催化剂如仅以酸性形式或与矿物酸组合的沸石的存在下的缩合(醚化)。该反应优选地在50℃到100℃的无水的条件下进行。
如US6,881,869所描述的,另一种可能的合成途径是通过与R2-O-SO2-O-R2(式VIII)或R2-Hal(式IX)所示的化合物的烷基化试剂,其中R2代表C1-C5烷基,Hal为Cl、Br或I,在阴离子化剂(anionisation agent)如酰胺碱(amide base)、金属醇化物或碱金属的存在下的已知的和显示的缩合反应得到式I所示的化合物,其中R2为氢。
如例如US2,878,265和US2,878,266所描述的,式III所示的化合物
可以通过熟知的式X所示的化合物与甲醛或仲甲醛,在浓缩的盐酸或氢溴酸水溶液的存在下的卤代甲基化反应由式X所示的化合物获得。
如例如US7,402,709中所描述的,式VI所示的化合物可以通过与合适的碱性醋酸盐反应并随后水解的反应,由式III所示的化合物获得。
如US6,342,613中所描述的,式X所示的化合物可以通过熟知的苯并间 二氧杂环戊烯环的酰化步骤和随后的还原获得。
5-(丁-2-炔氧基甲基)-6-丙基-苯并[1,3]间二氧杂环戊烯(EN126)的合成
在配备有搅拌器的烧瓶中,放置16g(0.41摩尔)的氢化钠(在矿物油中60%w/w)和400ml的Ν,Ν-二甲基甲酰胺。在搅拌下和氮气气氛中将混合物冷却至0℃-5℃。然后缓慢加入75g(0.38摩尔)的5-(羟甲基)-6-丙基-苯并[1,3]间二氧杂环戊烯在80ml的Ν,Ν-二甲基甲酰胺中的溶液,并在室温下再搅拌一小时。
然后将混合物冷却至0℃-5℃,并将温度保持在0℃-5℃下缓慢加入50.5g(0.38摩尔)的1-溴-2-丁炔。然后在室温下再搅拌反应两个小时。
然后将混合物冷却至5℃,加入1000ml的水并使用二异丙醚(3x200ml)萃取。收集有机相,用无水硫酸钠干燥,过滤并蒸发u.v.(30℃/21毫巴)。然后在118℃-125℃/0.3毫巴下蒸馏油状残留物,获得63.3g的油状产物(GC标题98.8%),其NMR和MS分析符合上述化合物的NMR和MS。
根据本发明的一个方面,提供了用于合成式I或II所示的化合物的方法,例如本文所例示的。
因此,本发明还提供了:
(a)根据本发明的组合物在治疗或预防农药抗性中的用途。
(b)根据本发明的组合物在治疗或预防害虫造成的作用物的损害或破坏中的用途。
(c)根据本发明的组合物在害虫控制中的用途;和
(d)用于制备根据本发明的组合物的方法,所述方法包括使式I或II所示的化合物与新烟碱成为物理掺加物。
实施例
昆虫
用于生物分析的蚜虫饲养在保持18±2℃和16h光:8h暗的光周期的小塑料箱笼(Blackman箱)中的大白菜叶(Brassica rapa L.var.Pekinensis c.vWong Bok)(十字花科)(Brassicaceae)上。每箱含有两只放置在叶子上的成年蚜虫,并静置5天以产生若虫。在第5天后,去除成虫并测定它们的酯酶水平,以确保在饲养过程中酯酶表达在不同的克隆中没有发生污染或缺失(回复)。约13-15天后,将成虫用于生物分析。
克隆5191A是于2007年从希腊的烟草中收集的,并由单一的孤雌生殖的雌性建立的。
化学品
技术级PBO(“超级”,94%)和PBO类似物(>90%)。技术级吡虫啉(分析标准99.7%)从Promochem Ltd,Welwyn Garden City,UK获得。
昆虫生物分析
将无翅蚜虫从Blackman箱(第2.1.1节)中转移到固定在塑料容器中的1%琼脂上的大白菜叶盘的背轴面(约10只成虫每叶盘)(直径4cm,A.W.Gregory&Co Limited,Kent,UK)。每个容器的上边缘涂覆有(Whitford Plastics,Cheshire,UK)以防止蚜虫从叶子表面逃脱。添加网状盖以确保无翅蚜虫不能逃脱。允许蚜虫安定30min后,使用Burkard微涂药器(Burkhard Scientific,Middx,UK)对每只给药0.25μL的溶于丙酮的1gL-1的增效剂或仅给药丙酮。选择的增效剂浓度在最初的生物分析中与丙酮对照处理相比没有赋予显著的死亡率。五小时后,使用0.25μl一系列浓度的吡虫啉的丙酮溶液,每个生物分析的每种浓度至少3次重复。使用0.25μl丙酮或1g L-1增效剂的丙酮溶液处理对照,5h后使用另外0.25μl的丙酮处理。发现该5h的预处理时间对于桃蚜和PBO是最佳的。
经处理的蚜虫保持在18±2℃和16h光:8h暗的光周期中,并在处理后72h评分。不能协调运动(如果必要,在使用油漆刷轻轻地触摸后)的蚜虫记录为死亡。所有生物分析最少进行三次。
分析
使用统计程序PC Polo Plus(LeOra,Sonware,Berkelev,USA),通过概率单位分析来分析从至少三个独立的生物分析中合并的原始数据。PoloPlus程序计算出杀死50%的群体所需的浓度(LC50)、95%置信区间(CL95%)、具有标准误差的斜率(SE)、卡方(χ2)和自由度(df)。当对照死亡率发生时,也估计了自然响应。如果在对照中未观察到死亡率,那么将自然响应估计为零。
结果
表1:在全剂量反应生物分析中使用5h预处理的胡椒基丁醚(PBO)
的类似物与吡虫啉针对桃蚜克降5191A的增效因子。
处理 | aLC50(ppm) | bCL95% | 斜率±SE | cdf | dχ2 | cSF | 昆虫数 |
吡虫啉 | 90.4 | 51.0-185 | 0.93±0.07 | 58 | 193 | -- | 667 |
+1gL-1PBO | 6.22 | 4.04-8.70 | 1.50±0.14 | 86 | 154 | 14.5 | 980 |
+1gL-1EN16-5 | 12.2 | 8.80-16.4 | 1.24±0.09 | 89 | 105 | 7.41 | 956 |
+1gL-1EN164 | 1.25 | 0.74-1.97 | 1.23±0.08 | 77 | 266 | 72.4 | 869 |
+1gL-1EN126 | 0.31 | 0.21-0.43 | 1.69±0.14 | 87 | 154 | 292 | 911 |
+1gL-1EN163 | 2.98 | 1.90-4.51 | 0.81_+0.05 | 80 | 138 | 30.3 | 954 |
+1gL-1EN25-10 | 4.88 | 1.20-11.0 | 1.13±0.15 | 33 | 84.8 | 18.5 | 389 |
+1gL-1EN129 | 28.4 | 13.6-45.8 | 1.39±0.19 | 42 | 70.0 | 3.18 | 499 |
+1gL-1EN16-17 | 7.11 | 5.12-9.53 | 1.13±0.06 | 146 | 265 | 12.7 | 1600 |
+1gL-1EN16-18 | 18.4 | 9.69-29.5 | 1.14±0.11 | 79 | 156 | 4.91 | 862 |
+1gL-1EN14-5 | 41.5 | 26.1-62.6 | 1.12±0.13 | 42 | 42.1 | 2.17 | 506 |
aLC50=杀死50%的群体的致死浓度,bCL=置信区间,cdf=自由度,dχ2=卡方,eSF=增效因子(LC50未增效的/LC50增效的)。
5-((2-(2-丁氧基乙氧基)乙氧基)甲基)-6-丙基苯并[d][1,3]间二氧杂环戊烯
(式XI)
6-((2-(2-丁氧基乙氧基)乙氧基)甲基)-5-丙基-2,3-二氢苯并呋喃
(式XII)
5-(丁-2-炔氧基)-6-丙基苯并[d][1,3]间二氧杂环戊烯
(式XIII)
5-(丁-2-炔氧基甲基)-6-丙基-苯并[1,3]间二氧杂环戊烯
(式II)
5-(丁-2-炔氧基)苯并[d][1,3]间二氧杂环戊烯
(式XIV)
(R)-4-(1-(丁-2-炔氧基)乙基)-1,2-二甲氧基苯
(式XV)
5-十二烷基苯并[d][1,3]间二氧杂环戊烯
(式XVI)
6-(丁-2-炔氧基)-5-丙基-2,3-二氢苯并呋喃
(式XVII)
5-(丁-2-炔氧基)-2,3-二氢苯并呋喃
(式XVIII)
5-((2-(2-丁氧基乙氧基)乙氧基)甲基)-6-丙基-2,3-二氢-1H-茚
(式XIX)
结论
从上述结果可以看出,由292的协同因子表示的EN126(式II)获得的结果,比测试的其它化合物所获得的结果明显更好,这是完全未预料到的。
应当理解的是,本文描述的目前优选的实施方案的各种变化和改变对本领域技术人员是显而易见的。在不脱离本发明的精神和范围,以及在不减少其伴随的优点的前提下,可以作出这样的变化和改变。因此,意在由所附权利要求覆盖这样的变化和改变。
将本文引用的所有参考文献的内容整体引入本文作为参考。
Claims (15)
3.根据权利要求1或2所述的组合物,其中所述组合物为农药组合物,优选地为杀虫剂组合物。
4.根据前述任一项权利要求所述的组合物,所述组合物包含式I或II所示的化合物的速释制剂,和新烟碱的非速释制剂。
5.根据前述任一项权利要求所述的组合物,其中所述新烟碱选自吡虫啉、啶虫脒、噻虫胺、呋虫胺、烯啶虫胺、噻虫啉和噻虫嗪。
6.式I或II所示的化合物作为新烟碱增效剂的用途。
7.式I或II所示的化合物与新烟碱组合的用途。
8.根据权利要求6或7所述的用途,其中所述新烟碱选自吡虫啉、啶虫脒、噻虫胺、呋虫胺、烯啶虫胺、噻虫啉和噻虫嗪。
9.用于控制害虫的方法,所述方法包括将害虫与(i)式I或II所示的化合物和(ii)新烟碱接触。
10.根据权利要求9所述的方法,其中所述害虫在与新烟碱接触之前与式I或II所示的化合物接触。
11.根据权利要求9或10所述的方法,其中所述新烟碱选自吡虫啉、啶虫脒、噻虫胺、呋虫胺、烯啶虫胺、噻虫啉和噻虫嗪。
12.用于控制害虫的方法,所述方法包括将所述害虫与根据权利要求1至5中任一项所述的组合物接触。
13.根据权利要求9至12中任一项所述的方法,其中所述害虫是新烟碱抗性害虫或新烟碱敏感性害虫。
14.根据权利要求9至13中任一项所述的方法,其中所述害虫是昆虫。
15.根据权利要求9至14中任一项所述的方法,其中所述害虫选自吸啜式昆虫或咀嚼式昆虫,例如选自半翅目、鞘翅目、双翅目和鳞翅目。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB1104156.3 | 2011-03-11 | ||
GBGB1104156.3A GB201104156D0 (en) | 2011-03-11 | 2011-03-11 | Compositions and methods for controlling pesticide resistant pests |
PCT/GB2012/050500 WO2012123714A1 (en) | 2011-03-11 | 2012-03-07 | Compositions and methods for controlling pesticide resistant pests |
Publications (2)
Publication Number | Publication Date |
---|---|
CN103582417A true CN103582417A (zh) | 2014-02-12 |
CN103582417B CN103582417B (zh) | 2016-08-31 |
Family
ID=43980844
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201280012842.8A Expired - Fee Related CN103582417B (zh) | 2011-03-11 | 2012-03-07 | 用于控制农药抗性害虫的组合物和方法 |
Country Status (11)
Country | Link |
---|---|
US (1) | US10104890B2 (zh) |
EP (1) | EP2683236B1 (zh) |
CN (1) | CN103582417B (zh) |
AP (1) | AP3523A (zh) |
AU (1) | AU2012228059B2 (zh) |
BR (1) | BR112013022765B1 (zh) |
ES (1) | ES2616121T3 (zh) |
GB (1) | GB201104156D0 (zh) |
PL (1) | PL2683236T3 (zh) |
WO (1) | WO2012123714A1 (zh) |
ZA (1) | ZA201307307B (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107365335A (zh) * | 2016-05-11 | 2017-11-21 | 浙江合糖科技有限公司 | 1,2,5,6-二-异亚丙基-3-O-苄基-α-D-呋喃葡萄糖苷的制备方法 |
CN108366557A (zh) * | 2015-09-09 | 2018-08-03 | 恩德拉股份公司 | 被取代的亚甲二氧基苄基化合物及其作为增效剂的用途 |
CN108471746A (zh) * | 2015-09-09 | 2018-08-31 | 恩德拉股份公司 | 被取代的二氢苯并呋喃化合物及其作为增效剂的用途 |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2512112B (en) * | 2013-03-21 | 2016-03-30 | Rothamsted Res Ltd | Compositions and methods for controlling herbicide resistant weeds |
ES2686735T3 (es) | 2015-09-09 | 2018-10-19 | Endura S.P.A. | 2,3-dihidrobenzofuranos 5,7-disustituidos y sus usos como sinergistas |
WO2019175712A1 (en) | 2018-03-14 | 2019-09-19 | Basf Corporation | New uses for catechol molecules as inhibitors to glutathione s-transferase metabolic pathways |
EP3920697A4 (en) * | 2019-02-07 | 2022-12-07 | Board Of Trustees Of Michigan State University | INHIBITION OF INSECTICIDE RESISTANCE AND HYPERSENSITIZATION OF SENSITIVE INSECTS TO PESTICIDES |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997019040A2 (en) * | 1995-11-21 | 1997-05-29 | Chinoin Gyógyszer és Vegyészeti Termékek Gyára Rt. | Pesticide compounds, compositions and process for the preparation thereof |
EP0617890B1 (en) * | 1993-03-18 | 1998-11-18 | Nihon Bayer Agrochem K.K. | Synergistic insecticidal compositions |
DE10119421A1 (de) * | 2001-03-05 | 2002-09-12 | Bayer Ag | Insektizide Mittel |
CN101163401A (zh) * | 2005-04-22 | 2008-04-16 | 恩德拉(共同)股份公司 | 新制剂 |
CN101163399A (zh) * | 2005-04-22 | 2008-04-16 | 恩德拉(共同)股份公司 | 基于环糊精超分子络合物的生物活性制剂 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2878265A (en) | 1956-09-10 | 1959-03-17 | Fmc Corp | Production of methylenedioxyphenyl derivatives |
US2878266A (en) | 1957-03-21 | 1959-03-17 | Fmc Corp | Chloromethylation process |
HU220961B1 (hu) * | 1996-11-18 | 2002-07-29 | AGRO-CHEMIE Növényvédőszer Gyártó, Értékesítő és Forgalmazó Kft. | Eljárás benzil-éterek előállítására fázistranszferrel |
HU220573B1 (hu) | 1996-11-18 | 2002-03-28 | AGRO-CHEMIE Növényvédőszer Gyártó, Értékesítő és Forgalmazó Kft. | Eljárás benzil-éterek előállítására |
IT1304513B1 (it) | 1998-12-30 | 2001-03-19 | Endura Spa | Processo per la sintesi di 5-(alfa-idrossialchil)benzo(1,3)diossoli. |
FR2788269B1 (fr) | 1999-01-08 | 2001-02-09 | Rhodia Chimie Sa | Procede de preparation d'un ether de type benzylique |
FR2798928B1 (fr) | 1999-09-29 | 2003-04-11 | Rhodia Chimie Sa | Procede de preparation d'ethers mixtes alcyniques substitues |
GB0209749D0 (en) * | 2002-04-29 | 2002-06-05 | Rothamsted Ex Res Station | Compositions and methods |
ITMI20032103A1 (it) | 2003-10-30 | 2005-04-30 | Endura Spa | Procedimento per la sintesi di eliotropina e suoi derivati. |
JP2006298767A (ja) | 2005-04-15 | 2006-11-02 | Sumitomo Chemical Co Ltd | ハエ亜目害虫防除剤 |
JP2008201710A (ja) | 2007-02-20 | 2008-09-04 | Sumitomo Chemical Co Ltd | 有害生物防除剤 |
EP2289889A1 (en) | 2009-08-18 | 2011-03-02 | Endura S.p.a. | Substituted alkynyl phenoxy compounds and their uses |
-
2011
- 2011-03-11 GB GBGB1104156.3A patent/GB201104156D0/en not_active Ceased
-
2012
- 2012-03-07 US US14/004,506 patent/US10104890B2/en active Active
- 2012-03-07 EP EP12710991.6A patent/EP2683236B1/en active Active
- 2012-03-07 WO PCT/GB2012/050500 patent/WO2012123714A1/en active Application Filing
- 2012-03-07 PL PL12710991T patent/PL2683236T3/pl unknown
- 2012-03-07 BR BR112013022765A patent/BR112013022765B1/pt not_active IP Right Cessation
- 2012-03-07 AP AP2013007218A patent/AP3523A/xx active
- 2012-03-07 ES ES12710991.6T patent/ES2616121T3/es active Active
- 2012-03-07 AU AU2012228059A patent/AU2012228059B2/en not_active Ceased
- 2012-03-07 CN CN201280012842.8A patent/CN103582417B/zh not_active Expired - Fee Related
-
2013
- 2013-09-30 ZA ZA2013/07307A patent/ZA201307307B/en unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0617890B1 (en) * | 1993-03-18 | 1998-11-18 | Nihon Bayer Agrochem K.K. | Synergistic insecticidal compositions |
WO1997019040A2 (en) * | 1995-11-21 | 1997-05-29 | Chinoin Gyógyszer és Vegyészeti Termékek Gyára Rt. | Pesticide compounds, compositions and process for the preparation thereof |
DE10119421A1 (de) * | 2001-03-05 | 2002-09-12 | Bayer Ag | Insektizide Mittel |
CN101163401A (zh) * | 2005-04-22 | 2008-04-16 | 恩德拉(共同)股份公司 | 新制剂 |
CN101163399A (zh) * | 2005-04-22 | 2008-04-16 | 恩德拉(共同)股份公司 | 基于环糊精超分子络合物的生物活性制剂 |
Non-Patent Citations (1)
Title |
---|
GEORGINA BINGHAM 等: "Temporal synergism can enhance carbamate and neonicotinoid insecticidal activity against resistant crop pests", 《PEST MANAG SCIENCE》 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108366557A (zh) * | 2015-09-09 | 2018-08-03 | 恩德拉股份公司 | 被取代的亚甲二氧基苄基化合物及其作为增效剂的用途 |
CN108471746A (zh) * | 2015-09-09 | 2018-08-31 | 恩德拉股份公司 | 被取代的二氢苯并呋喃化合物及其作为增效剂的用途 |
CN108366557B (zh) * | 2015-09-09 | 2021-05-25 | 恩德拉股份公司 | 被取代的亚甲二氧基苄基化合物及其作为增效剂的用途 |
CN107365335A (zh) * | 2016-05-11 | 2017-11-21 | 浙江合糖科技有限公司 | 1,2,5,6-二-异亚丙基-3-O-苄基-α-D-呋喃葡萄糖苷的制备方法 |
CN107365335B (zh) * | 2016-05-11 | 2020-06-19 | 浙江合糖科技有限公司 | 1,2,5,6-二-异亚丙基-3-O-苄基-α-D-呋喃葡萄糖苷的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
PL2683236T3 (pl) | 2017-07-31 |
GB201104156D0 (en) | 2011-04-27 |
BR112013022765B1 (pt) | 2019-12-03 |
EP2683236B1 (en) | 2016-11-16 |
BR112013022765A2 (pt) | 2015-09-15 |
US20140107162A1 (en) | 2014-04-17 |
AP3523A (en) | 2016-01-11 |
AU2012228059B2 (en) | 2014-05-29 |
AU2012228059A1 (en) | 2013-01-31 |
ES2616121T3 (es) | 2017-06-09 |
AP2013007218A0 (en) | 2013-10-31 |
CN103582417B (zh) | 2016-08-31 |
ZA201307307B (en) | 2015-06-24 |
EP2683236A1 (en) | 2014-01-15 |
US10104890B2 (en) | 2018-10-23 |
WO2012123714A1 (en) | 2012-09-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103582417A (zh) | 用于控制农药抗性害虫的组合物和方法 | |
Oguh et al. | Natural pesticides (biopesticides) and uses in pest management-a critical review | |
Sánchez-Bayo | Impacts of agricultural pesticides on terrestrial ecosystems | |
Reddy et al. | Laboratory and field studies on the integrated pest management of Helicoverpa armigera (Hübner) in cotton, based on pheromone trap catch threshold level | |
UA121855C2 (uk) | Склади зі стриголактоном і їх застосування | |
WO2007092184A3 (en) | Method for improving harvestability of crops | |
CN102696665A (zh) | 含有茚虫威的杀虫剂组合物 | |
KR20110099712A (ko) | 살충제 및 uv 흡수제를 포함한 농약 조성물 | |
Chen | Toxicity and efficacy of two emulsifiable concentrates of 2-tridecanone against red imported fire ants | |
AU2013101482A4 (en) | Compositions and methods for controlling pesticide resistant pests | |
Harris et al. | Toxicological studies on cutworms. IX. Laboratory and microplot field studies on effectiveness and persistence of some experimental insecticides used for control of the darksided cutworm | |
AU675957B2 (en) | Method of controlling insects | |
KR101861913B1 (ko) | 아마이드를 포함하는 살충용 조성물 | |
KR101869107B1 (ko) | 용해된 살충제 및 현탁된 살충제, 알킬 락테이트 및 알콜을 포함하는 무수 조성물 | |
Mac Intyre Allen et al. | Evaluation of application methods for the chemical control of striped cucumber beetle (Coleoptera: Chrysomelidae) attacking seedling cucurbits | |
NZ253070A (en) | Ovicidal compositions and method of combatting insect eggs | |
EP3869961B1 (en) | New abamectin soluble concentrate composition (sl) | |
CN107494580A (zh) | 一种含有戊吡虫胍的增效杀虫组合物 | |
JP2990541B2 (ja) | 複合殺菌殺虫剤 | |
CN106259532A (zh) | 一种带香气农药 | |
KR20220087615A (ko) | 2,3-디하이드록시프로필도코노에이트를 이용한 닭진드기에 대한 살충·살비제 조성물 | |
CN105104410B (zh) | 一种农用增效剂与拟除虫菊酯类杀虫剂的组合物 | |
WO2014147387A1 (en) | Compositions and methods for controlling herbicide resistant weeds | |
WO2023230092A1 (en) | Ascaroside combinations | |
WO2019030650A1 (en) | PESTICIDAL COMPOSITION AND PROCESS FOR PREPARING THE SAME |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160831 |
|
CF01 | Termination of patent right due to non-payment of annual fee |