CN115872901A - 一种亚胺类化合物及其应用 - Google Patents
一种亚胺类化合物及其应用 Download PDFInfo
- Publication number
- CN115872901A CN115872901A CN202211123363.5A CN202211123363A CN115872901A CN 115872901 A CN115872901 A CN 115872901A CN 202211123363 A CN202211123363 A CN 202211123363A CN 115872901 A CN115872901 A CN 115872901A
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- Prior art keywords
- radical
- group
- haloalkyl
- halogen
- alkyl
- Prior art date
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- 150000002466 imines Chemical class 0.000 title claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 94
- 241000607479 Yersinia pestis Species 0.000 claims abstract description 19
- 230000000895 acaricidal effect Effects 0.000 claims abstract description 13
- 241000238876 Acari Species 0.000 claims abstract description 9
- 239000000642 acaricide Substances 0.000 claims abstract description 7
- 239000002917 insecticide Substances 0.000 claims abstract description 7
- -1 C 2 -C 6 Alkenyl radical Chemical class 0.000 claims description 111
- 229910052736 halogen Inorganic materials 0.000 claims description 32
- 150000002367 halogens Chemical class 0.000 claims description 32
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 15
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 14
- 125000000171 (C1-C6) haloalkyl group Chemical group 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 9
- 125000004995 haloalkylthio group Chemical group 0.000 claims description 8
- 125000004737 (C1-C6) haloalkoxy group Chemical group 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 229910052740 iodine Inorganic materials 0.000 claims description 7
- 125000006677 (C1-C3) haloalkoxy group Chemical group 0.000 claims description 6
- 125000006643 (C2-C6) haloalkenyl group Chemical group 0.000 claims description 6
- 125000004194 piperazin-1-yl group Chemical group [H]N1C([H])([H])C([H])([H])N(*)C([H])([H])C1([H])[H] 0.000 claims description 6
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 6
- 125000004471 alkyl aminosulfonyl group Chemical group 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 5
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 claims description 5
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 5
- 125000004455 (C1-C3) alkylthio group Chemical group 0.000 claims description 4
- 125000004916 (C1-C6) alkylcarbonyl group Chemical group 0.000 claims description 4
- 125000006771 (C1-C6) haloalkylthio group Chemical group 0.000 claims description 4
- 125000006650 (C2-C4) alkynyl group Chemical group 0.000 claims description 4
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 claims description 4
- 125000004786 difluoromethoxy group Chemical group [H]C(F)(F)O* 0.000 claims description 4
- 125000000232 haloalkynyl group Chemical group 0.000 claims description 4
- 125000005034 trifluormethylthio group Chemical group FC(S*)(F)F 0.000 claims description 4
- 125000006619 (C1-C6) dialkylamino group Chemical group 0.000 claims description 3
- 125000006798 (C1-C6) haloalkylamino group Chemical group 0.000 claims description 3
- 125000006766 (C2-C6) alkynyloxy group Chemical group 0.000 claims description 3
- 125000006765 (C2-C6) haloalkenyloxy group Chemical group 0.000 claims description 3
- 125000006767 (C2-C6) haloalkynyloxy group Chemical group 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000004438 haloalkoxy group Chemical group 0.000 claims description 3
- 125000006698 (C1-C3) dialkylamino group Chemical group 0.000 claims description 2
- 125000004454 (C1-C6) alkoxycarbonyl group Chemical group 0.000 claims description 2
- 125000006700 (C1-C6) alkylthio group Chemical group 0.000 claims description 2
- 125000004741 (C1-C6) haloalkylsulfonyl group Chemical group 0.000 claims description 2
- 125000004195 4-methylpiperazin-1-yl group Chemical group [H]C([H])([H])N1C([H])([H])C([H])([H])N(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 230000000749 insecticidal effect Effects 0.000 abstract description 7
- 125000001424 substituent group Chemical group 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 65
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 45
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 239000000243 solution Substances 0.000 description 28
- 239000012074 organic phase Substances 0.000 description 24
- 238000002360 preparation method Methods 0.000 description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- 239000007787 solid Substances 0.000 description 20
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 16
- 238000004440 column chromatography Methods 0.000 description 16
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000003960 organic solvent Substances 0.000 description 12
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 150000001263 acyl chlorides Chemical class 0.000 description 8
- 125000004122 cyclic group Chemical group 0.000 description 8
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- 235000017557 sodium bicarbonate Nutrition 0.000 description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 239000005457 ice water Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 241000238631 Hexapoda Species 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 125000003342 alkenyl group Chemical group 0.000 description 6
- 125000000304 alkynyl group Chemical group 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 241001477931 Mythimna unipuncta Species 0.000 description 5
- 241000500437 Plutella xylostella Species 0.000 description 5
- 241001414989 Thysanoptera Species 0.000 description 5
- 238000003556 assay Methods 0.000 description 5
- 125000006165 cyclic alkyl group Chemical group 0.000 description 5
- 241000721621 Myzus persicae Species 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 3
- 241001124076 Aphididae Species 0.000 description 3
- 240000007124 Brassica oleracea Species 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 241000257303 Hymenoptera Species 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 241000344246 Tetranychus cinnabarinus Species 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 150000001448 anilines Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012312 sodium hydride Substances 0.000 description 3
- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- 230000004083 survival effect Effects 0.000 description 3
- HQYNSFAFYFMRLG-UHFFFAOYSA-N tribromo phosphite Chemical compound BrOP(OBr)OBr HQYNSFAFYFMRLG-UHFFFAOYSA-N 0.000 description 3
- WLGUSLGYTNJJFV-UHFFFAOYSA-N 2-fluoro-3-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC([N+]([O-])=O)=C1F WLGUSLGYTNJJFV-UHFFFAOYSA-N 0.000 description 2
- KUUCCWUWJBJSGJ-UHFFFAOYSA-N 2-fluoro-3-nitrobenzoyl chloride Chemical compound [O-][N+](=O)C1=CC=CC(C(Cl)=O)=C1F KUUCCWUWJBJSGJ-UHFFFAOYSA-N 0.000 description 2
- KFCHYDKJTWTUOP-UHFFFAOYSA-N 3-[(2,2-difluoro-1,3-benzodioxole-5-carbonyl)-methylamino]-2-fluorobenzoic acid Chemical compound N(C1=C(F)C(C(=O)O)=CC=C1)(C(=O)C1=CC=2OC(OC=2C=C1)(F)F)C KFCHYDKJTWTUOP-UHFFFAOYSA-N 0.000 description 2
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 2
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 2
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 2
- 241000255925 Diptera Species 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 241000258937 Hemiptera Species 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 125000005108 alkenylthio group Chemical group 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- 125000005109 alkynylthio group Chemical group 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 230000026030 halogenation Effects 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000000361 pesticidal effect Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 2
- 229920000053 polysorbate 80 Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 description 2
- 125000006656 (C2-C4) alkenyl group Chemical group 0.000 description 1
- FKTXDTWDCPTPHK-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoropropane Chemical group FC(F)(F)[C](F)C(F)(F)F FKTXDTWDCPTPHK-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- WGCYRFWNGRMRJA-UHFFFAOYSA-N 1-ethylpiperazine Chemical compound CCN1CCNCC1 WGCYRFWNGRMRJA-UHFFFAOYSA-N 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- 125000000530 1-propynyl group Chemical group [H]C([H])([H])C#C* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241001093951 Ailanthus altissima Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241001498622 Cixius wagneri Species 0.000 description 1
- 241000254173 Coleoptera Species 0.000 description 1
- 241001427543 Elateridae Species 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 241000578422 Graphosoma lineatum Species 0.000 description 1
- 240000004658 Medicago sativa Species 0.000 description 1
- 235000010624 Medicago sativa Nutrition 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000488581 Panonychus citri Species 0.000 description 1
- 241000488583 Panonychus ulmi Species 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 241000256247 Spodoptera exigua Species 0.000 description 1
- 241001454295 Tetranychidae Species 0.000 description 1
- 241001454293 Tetranychus urticae Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000004457 alkyl amino carbonyl group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 1
- 125000004644 alkyl sulfinyl group Chemical group 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000006309 butyl amino group Chemical group 0.000 description 1
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 125000004772 dichloromethyl group Chemical group [H]C(Cl)(Cl)* 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 150000002333 glycines Chemical class 0.000 description 1
- 235000021384 green leafy vegetables Nutrition 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000005980 hexynyl group Chemical group 0.000 description 1
- 238000003898 horticulture Methods 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- NQMRYBIKMRVZLB-UHFFFAOYSA-N methylamine hydrochloride Chemical compound [Cl-].[NH3+]C NQMRYBIKMRVZLB-UHFFFAOYSA-N 0.000 description 1
- 125000006216 methylsulfinyl group Chemical group [H]C([H])([H])S(*)=O 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical group CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000005981 pentynyl group Chemical group 0.000 description 1
- UXCDUFKZSUBXGM-UHFFFAOYSA-N phosphoric tribromide Chemical compound BrP(Br)(Br)=O UXCDUFKZSUBXGM-UHFFFAOYSA-N 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- RMBAVIFYHOYIFM-UHFFFAOYSA-M sodium methanethiolate Chemical compound [Na+].[S-]C RMBAVIFYHOYIFM-UHFFFAOYSA-M 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
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Abstract
本发明属于杀虫剂和杀螨剂领域,具体涉及一种亚胺类化合物及其应用。结构如通式I所示,式中各取代基定义见说明书。通式I化合物具有优异的杀虫和杀螨活性,可用于防治各种害虫或害螨。
Description
技术领域
本发明属于杀虫剂和杀螨剂领域,具体涉及一种亚胺类化合物及其应用。
背景技术
在农业和园艺等的作物生产中,由于害虫和害螨等引起的侵害依然显著以及害虫和害螨对现有杀虫剂和杀螨剂产生抗性,因此需要不断研发新型杀虫剂和杀螨剂,及其组合物。
WO2005073165A1和WO2010018714A1公开了具有杀虫活性的双酰胺结构类型化合物。
为发现新型杀虫剂或杀螨剂,发明人经潜心研究发现本发明的亚胺结构类型化合物,如通式I所示,其结构新颖,并具有优异的杀虫和杀螨活性。本发明所示的亚胺类化合物及其杀虫和杀螨活性未见报道。
发明内容
本发明的目的在于提供一种亚胺类化合物及其作为杀虫剂或杀螨剂的应用。
为实现上述目的,本发明的技术方案如下:
一种亚胺类化合物:亚胺类化合物结构如通式I所示:
式中:
X1选自卤素、硝基、氰基、CONH2、CHO、C1-C6烷基、C1-C6卤代烷基、C2-C6烯基、C2-C6卤代烯基、C2-C6炔基、C2-C6卤代炔基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6卤代烷硫基、C1-C6烷基氨基、C1-C6二烷基氨基、C1-C6烷氧基羰基、C1-C6烷基羰基、C1-C6卤代烷基羰基、C1-C6烷基磺酰基、C1-C6卤代烷基磺酰基、C1-C6烷基亚磺酰基、C1-C6卤代烷基亚磺酰基、C1-C6烷基氨基羰基或C1-C6烷基氨基磺酰基;
m选自0、1、2、3、4或5;
X2和X3可相同或不同的分别选自H、卤素、硝基、氰基、C1-C6烷基、C1-C6卤代烷基、C2-C6烯基、C2-C6卤代烯基、C2-C6炔基、C2-C6卤代炔基;
R1选自H、C1-C6烷基、C1-C6卤代烷基或氰基亚甲基;
R2选自H、卤素、C1-C6烷基、C1-C6卤代烷基、C2-C6烯基、C2-C6卤代烯基、C1-C6烷基胺基、C1-C6卤代烷基胺基、C1-C6二烷基胺基、C1-C6卤代二烷基胺基、C1-C6烷氧基、C1-C6卤代烷氧基、C2-C6烯基氧基、C2-C6卤代烯基氧基、C2-C6炔基氧基、C2-C6卤代炔基氧基、C1-C6烷硫基、C1-C6卤代烷硫基、C2-C6烯基硫基、C2-C6卤代烯基硫基、C2-C6炔基硫基、C2-C6卤代炔基硫基、C1-C6烷氧基亚甲基、C1-C6卤代烷氧基亚甲基、C1-C6烷硫基亚甲基、C1-C6卤代烷硫基亚甲基、C1-C6烷胺基亚甲基、C1-C6卤代烷胺基亚甲基、C1-C6二烷胺基亚甲基、C1-C6卤代二烷胺基亚甲基、苯基、氨基、肼基、氰基、氰基亚甲基、1-吡咯烷基、1-哌啶基、4-吗啉基、1-1H-吡唑基、1-1H-咪唑基、1-1H-1,2,4-三氮唑基或2-2H-1,2,3-三氮唑基或4位被下述基团取代的哌嗪-1-基,其中下述基团为:C1-C6烷基、C1-C6烷基羰基或苯基;
Y1和Y2可相同或不同的选自卤素、C1-C6烷基、C1-C6卤代烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基或C1-C6卤代烷硫基。
优选,所述通式I中:
X1选自卤素、硝基、氰基、CONH2、CHO、C1-C3烷基、C1-C3卤代烷基、C2-C4烯基、C2-C4卤代烯基、C2-C4炔基、C2-C4卤代炔基、C1-C3烷氧基、C1-C3卤代烷氧基、C1-C3烷硫基、C1-C3卤代烷硫基、C1-C3烷基氨基、C1-C3二烷基氨基、C1-C3烷氧基羰基、C1-C3烷基羰基、C1-C3卤代烷基羰基、C1-C3烷基磺酰基、C1-C3卤代烷基磺酰基、C1-C3烷基亚磺酰基、C1-C3卤代烷基亚磺酰基、C1-C3烷基氨基羰基或C1-C3烷基氨基磺酰基;
m选自0、1、2、3、4或5;
X2和X3可相同或不同的分别选自H、卤素、硝基、氰基、C1-C3烷基、C1-C3卤代烷基、C2-C4烯基、C2-C4卤代烯基、C2-C4炔基或C2-C4卤代炔基;
R1选自H、C1-C3烷基、C1-C3卤代烷基或氰基亚甲基;
R2选自H、卤素、C1-C3烷基、C1-C3卤代烷基、C2-C4烯基、卤代C2-C4烯基、C1-C3烷基胺基、C1-C3卤代烷基胺基、C1-C3二烷基胺基、C1-C3卤代二烷基胺基、C1-C3烷氧基、C1-C3卤代烷基氧基、C2-C4烯基氧基、C2-C4卤代烯基氧基、C2-C4炔基氧基、C2-C4卤代炔基氧基、C1-C3烷硫基、C1-C3卤代烷基硫基、C2-C4烯基硫基、C2-C4卤代烯基硫基、C2-C4炔基硫基、C2-C4卤代炔基硫基、C1-C3烷氧基亚甲基、C1-C3卤代烷氧基亚甲基、C1-C3烷硫基亚甲基、C1-C3卤代烷硫基亚甲基、C1-C3烷胺基亚甲基、C1-C3卤代烷胺基亚甲基、C1-C3二烷胺基亚甲基、C1-C3卤代二烷胺基亚甲基、苯基、氨基、肼基、氰基、氰基亚甲基、1-吡咯烷基、1-哌啶基、4-吗啉基、1-1H-吡唑基、1-1H-咪唑基、1-1H-1,2,4-三氮唑基或2-2H-1,2,3-三氮唑基或4位被下述基团取代的哌嗪-1-基,其中下述基团为:C1-C3烷基、C1-C3烷基羰基或苯基;
Y1和Y2可相同或不同的选自卤素、C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、C1-C3烷硫基或C1-C3卤代烷硫基。
进一步优选,所述通式I中:
X1选自卤素、硝基、氰基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基或C1-C3卤代烷硫基;
m选自0、1、2或3;
X2和X3可相同或不同的分别选自H或卤素;
R1选自H或C1-C3烷基;
R2选自卤素、C1-C3烷基胺基、C1-C3烷氧基、C1-C3烷硫基、1-1H-1,2,4-三氮唑基或4位被下述基团取代的哌嗪-1-基,其中下述基团为:C1-C3烷基、C1-C3烷基羰基或苯基;
Y1和Y2可相同或不同的选自卤素、C1-C3卤代烷基或C1-C3卤代烷氧基。
再进一步优选,所述通式I中:
X1选自F、Cl、Br、I、硝基、氰基、三氟甲基、甲氧基、二氟甲氧基、三氟甲氧基或三氟甲硫基;
m选自0、1或2;
X2和X3均选自F;
R1选自H或甲基;
R2选自F、Cl、Br、I、甲胺基、乙胺基、丙胺基、环丙烷基胺基、甲氧基、乙氧基、丙氧基、甲硫基、乙硫基、丙硫基、1-1H-1,2,4-三氮唑基或4-甲基哌嗪-1-基、4-乙基哌嗪-1-基、4-乙酰基哌嗪-1-基、4-苯基哌嗪-1-基;
Y1和Y2可相同或不同的选自F、Cl、Br、I、三氟甲基、三氟甲氧基或二氟甲氧基。
更进一步优选,所述通式I中:
X1选自F、Cl、硝基、氰基、三氟甲基、甲氧基、二氟甲氧基、三氟甲氧基或三氟甲硫基;
m选自0、1或2;
X2和X3均选自F;
R1选自甲基;
R2选自Cl、Br、甲胺基、乙氧基、甲硫基、乙硫基、1-1H-1,2,4-三氮唑基或4-乙基哌嗪-1-基;
Y1和Y2可相同或不同的选自Br、三氟甲基或二氟甲氧基。
本发明的通式I化合物可按照以下方法制备,除另有注明外,式中各基团的定义同前。
方法一(R2为H、C1-C6烷基、C1-C6卤代烷基、C2-C6烯基、C2-C6卤代烯基、C1-C6烷氧基亚甲基、C1-C6卤代烷氧基亚甲基、C1-C6烷硫基亚甲基、C1-C6卤代烷硫基亚甲基、C1-C6烷胺基亚甲基、C1-C6卤代烷胺基亚甲基、C1-C6二烷胺基亚甲基、C1-C6卤代二烷胺基亚甲基、苯基或氰基亚甲基)
具体合成方法如下,通式IV化合物与酰氯化试剂(如草酰氯和氯化亚砜等)反应制备酰氯III,酰氯III与通式V-a化合物反应制备通式II化合物,通式II化合物与取代苯胺V脱水反应制备亚胺,即通式I化合物。
方法二(R2为卤素)
具体合成方法如下,通式VIII化合物与酰氯化试剂(如草酰氯和氯化亚砜等)反应制备酰氯VII,酰氯VII与取代苯胺V反应制备通式VI化合物,通式VI化合物与卤化试剂(如三氯氧磷和三溴氧磷等)脱水反应制备亚胺,即通式I化合物。
方法三(R2为卤素)
具体合成方法如下,2-氟-3-硝基苯甲酸与酰氯化试剂(如草酰氯和氯化亚砜等)反应制备2-氟-3-硝基苯甲酰氯,2-氟-3-硝基苯甲酰氯与取代苯胺V反应制备通式XI化合物,通式XI化合物硝基还原反应制备通式X化合物,通式X化合物烷基化反应制备通式IX化合物,通式IX化合物与酰氯III反应制备通式VI化合物,通式VI化合物与卤化试剂(如三氯氧磷和三溴氧磷等)脱水反应制备亚胺,即通式I化合物。
方法四(R2为C1-C6烷基胺基、C1-C6卤代烷基胺基、C1-C6二烷基胺基、C1-C6卤代二烷基胺基、C1-C6烷氧基、C1-C6卤代烷氧基、C2-C6烯基氧基、C2-C6卤代烯基氧基、C2-C6炔基氧基、C2-C6卤代炔基氧基、C1-C6烷硫基、C1-C6卤代烷硫基、C2-C6烯基硫基、C2-C6卤代烯基硫基、C2-C6炔基硫基、C2-C6卤代炔基硫基、氨基、肼基、氰基、1-吡咯烷基、1-哌啶基、4-取代哌嗪-1-基、4-吗啉基、1-1H-吡唑基、1-1H-咪唑基、1-1H-1,2,4-三氮唑基或2-2H-1,2,3-三氮唑基)
具体合成方法如下,通式VI化合物与三溴氧磷反应制备通式I-a化合物,通式I-a化合物进一步取代反应制备通式I化合物。
上述制备方法中所涉及的原料及中间体来源如下:
中间体V、中间体V-1和中间体X可以按US8853440B2方法制备。
酰卤化试剂、其它常规原料和试剂通常有市售,也可按照常规方法自制。
上面给出的通式化合物的定义中,汇集所用术语一般代表如下取代基:
卤素:指氟、氯、溴或碘。
烷基:直链、支链或环状烷基,例如甲基、乙基、正丙基、异丙基或环丙基等。
卤代烷基:直链、支链或环状烷基,在这些烷基上的氢原子可部分或全部被卤素所取代,例如氯甲基、二氯甲基、三氯甲基、氟甲基、二氟甲基、三氟甲基、五氟乙基或七氟异丙基等。
烯基:直链、支链或环状烯基,例如乙烯基、1-丙烯基、2-丙烯基和不同的丁烯基、戊烯基和己烯基异构体;烯基还包括多烯类如1,2-丙二烯基和2,4-己二烯基等。
卤代烯基:可被卤原子取代至少一个或多个氢原子的烯基。
炔基:包括直链或支链炔基,如乙炔基、1-丙炔基和不同的丁炔基、戊炔基和己炔基异构体;炔基还包括由多个三键组成的基团,例如2,5-己二炔基。
卤代炔基:可被卤原子取代至少一个或多个氢原子的炔基。
烷氧基:直链、支链或环状烷氧基,例如甲氧基、乙氧基、正丙氧基、异丙氧基、环丙基氧基或正丁氧基等。
卤代烷氧基:直链、支链或环状烷氧基,在这些烷氧基上的氢原子可部分或全部被卤素所取代,例如氯甲氧基、二氯甲氧基、三氯甲氧基、氟甲氧基、二氟甲氧基、三氟甲氧基、氯氟甲氧基、三氟乙氧基、七氟异丙基氧基等。
烷硫基:直链、支链或环状烷基,经硫原子键连接到结构上,例如甲硫基、乙硫基等。
卤代烷硫基:直链、支链或环状烷硫基,在这些烷硫基上的氢原子可部分或全部被卤素所取代,例如二氟甲硫基、三氟乙硫基等。
烯基硫基:直链、支链或环状烯基,经硫原子键连接到结构上,例如1-丙烯基-3-硫基、2-丁烯基-4-硫基等。
卤代烯基硫基:直链、支链或环状烯基硫基,在这些烯基硫基上的氢原子可部分或全部被卤素所取代。
炔基硫基:直链、支链或环状炔基,经硫原子键连接到结构上,例如1-丙炔基-3-硫基、2-丁炔基-4-硫基等。
卤代炔基硫基:直链、支链或环状炔基硫基,在这些炔基硫基上的氢原子可部分或全部被卤素所取代。
烷基氨基:直链、支链或环状烷基,经氮原子键连接到结构上,例如甲基氨基、乙基氨基、正丙基氨基、异丙基氨基或同分异构的丁基胺基。
二烷基氨基:两个相同或不同的直链、支链或环状烷基,经氮原子键连接到结构上,例如二甲基氨基、甲基乙基氨基、二环丙基氨基等。
烷氧基羰基:烷基-O-CO-,例如CH3OCO-。
烷基羰基:烷基-CO-,例如CH3CO-
烷基磺酰基:烷基-S(O)2-,例如甲基磺酰基。
烷基亚磺酰基:烷基-S(O)-,例如甲基亚磺酰基。
烷基氨基羰基:烷基-NH-CO-,例如CH3NHCO-。
烷基氨基磺酰基:烷基-NH-S(O)2-,例如CH3NH S(O)2-。
在本发明的化合物中,由于X2和X3的不同,通式I化合物是手性(chirality)结构化合物,此时,化合物可以以单一手性异构体或两种手性异构体混合形式存在;通式I化合物亚胺结构的存在几何异构,化合物可以以单一几何异构体或两种几何异构体混合形式存在,本发明所要保护的通式I所示化合物并不受上述异构体结构存在形式限定。
表1中列出的具体化合物可以用来说明本发明,但并不限定本发明。
表1
部分化合物的1H NMR(600MHz,CDCl3,ppm)及物化性质如下:
在有机分子中,由于取代基的电负性、体积大小或空间构型的不同,整个分子在昆虫和植物等生物体内的输导性能或与受体结合差异性会很大,表现出的生物活性差异也会有很大,而分子的输导性能和与受体结合的合适性是不可预测的,需要大量的创造性劳动才能获知。
本发明的新型亚胺类衍生物(通式I化合物)具有优异的杀虫和杀螨活性,可以防治如下害虫:鳞翅目害虫,如粘虫、甜菜夜蛾和小菜蛾等;同翅目害虫,如桃蚜、叶婵和飞虱等;半翅目害虫,如玉米长蝽、番茄盲蝽和稻臭椿等;缨翅目害虫,如棉蓟马、苜蓿蓟马和黄豆蓟马、西花蓟马等;鞘翅目害虫,如马铃薯甲虫和叩甲等;双翅目害虫,如蝇和蚊等;膜翅目害虫,如蜂和蚁等。可以防治如下害螨:叶螨科(二斑叶螨、朱砂叶螨、苹果全爪螨、柑橘全爪螨等)、瘿螨科、跗线螨科等。因此,本发明还包括通式I化合物用于农业、林业及卫生领域中控制虫害和螨害的用途。
本发明的技术方案还包括防治害虫的方法:将本发明的杀虫化合物施于所述的害虫或其生长介质上。通常选择的较为适宜有效量为每公顷10克到1000克,优选有效量为每公顷20克到500克。
本发明的技术方案还包括防治害螨的方法:将本发明的杀虫化合物施于所述的害螨或其生长介质上。通常选择的较为适宜有效量为每公顷10克到1000克,优选有效量为每公顷20克到500克。
应该明确的是,在本发明的权利要求所限定的范围内,可以进行各种变换和改动。本发明所具有的优点:
本发明化合物结构新颖,兼具杀虫和杀螨,用途广泛。
具体实施方式
以下具体实施例用来进一步说明本发明,但本发明绝非限于这些例子。
合成实施例
实施例1:化合物I-38的制备
1)N-(2-溴-4-七氟异丙基-6-三氟甲基苯基)-2-氟-3-硝基苯甲酰胺的制备
向反应瓶中加入2-氟-3-硝基苯甲酸(8.23g,44.00mmol)、氯化亚砜(34.08g)和DMF(0.35g),升温至80℃反应8小时,减压蒸出氯化亚砜,得到酰氯。向酰氯中加入1,3-二甲基-2-咪唑啉酮(130mL)、2-溴-6-三氟甲基-4-七氟异丙基苯胺(16.48g,40.00mmol)和碘化钾(1.68g,10.00mmol),升温至100℃反应48小时。将反应液降至室温,过滤除去不溶物,加入乙酸乙酯(100mL)溶解,依次用饱和碳酸氢钠水溶液和饱和食盐水洗涤,分出有机相,将有机相用无水硫酸镁干燥,过滤后减压蒸出有机溶剂,残余物经柱色谱分离纯化得标题物,白色固体1.86g,收率为8%(以2-溴-4-七氟异丙基-6-三氟甲基苯胺计)。
1H NMR(600MHz,CDCl3,ppm):8.47-8.42(m,1H),8.32-8.26(m,1H),8.21(d,1H),8.17(s,1H),7.94(s,1H),7.55-7.49(m,1H).
2)N-(2-溴-4-七氟异丙基-6-三氟甲基苯基)-2-氟-3-氨基苯甲酰胺的制备
向反应瓶中加入N-(2-溴-4-七氟异丙基-6-三氟甲基苯基)-2-氟-3-硝基苯甲酰胺(1.74g,3.00mmol)、二氧六环(10mL)和氯化亚锡二水合物(2.73g,12.00mmol),缓慢滴入36%浓盐酸(3mL)。升温至65℃保温反应,TLC监测至反应完全。将反应体系冷却至室温,将反应液倾入冰水(15mL)中,加入乙酸乙酯(30mL),缓慢加入5%氢氧化钠水溶液中和至pH=8-9。将析出的沉淀经硅藻土过滤后,用乙酸乙酯(10mL)洗涤滤饼,将滤液分层。将有机相用无水硫酸镁干燥,过滤后减压蒸出有机溶剂,残余物经柱色谱分离纯化得标题物,黄色固体1.46g,收率为88%(以N-(2-溴-4-七氟异丙基-6-三氟甲基苯基)-2-氟-3-硝基苯甲酰胺计)。
1H NMR(60MHz,CDCl3,ppm):8.29(d,1H),8.13(s,1H),7.91(s,1H),7.50-7.44(m,1H),7.12-7.07(m,1H),7.04-6.94(m,1H),3.93(s,br,2H).
3)N-(2-溴-4-七氟异丙基-6-三氟甲基苯基)-2-氟-3-甲胺基苯甲酰胺的制备
向反应瓶中加入98%浓硫酸(6mL)和N-(2-溴-4-七氟异丙基-6-三氟甲基苯基)-2-氟-3-氨基苯甲酰胺(1.10g,2.00mmol),充分搅拌溶解。在30-35℃之间缓慢滴入含量37-40%甲醛水溶液(5mL),滴毕,升温至40℃继续保温反应,TLC监测至反应完全。将反应体系冷却至室温,将反应液缓慢倾入冰水(20mL)中,充分搅拌,析出固体,过滤,滤饼经柱色谱分离纯化得标题物,白色固体1.02g,收率为90%(N-(2-溴-4-七氟异丙基-6-三氟甲基苯基)-2-氟-3-氨基苯甲酰胺)。
1H NMR(600MHz,CDCl3,ppm):8.28(d,1H),8.13(s,1H),7.90(s,1H),7.40-7.36(m,1H),7.19-7.14(m,1H),6.93-6.88(m,1H),4.13(s,br,1H),2.94(s,3H).
4)N-(2-溴-4-七氟异丙基-6-三氟甲基苯基)-2-氟-3-(N-甲基-苯甲酰胺基)苯甲酰胺的制备
向反应瓶中加入甲苯(20mL)、苯甲酰氯(0.16g,1.11mmol)、N-(2-溴-4-七氟异丙基-6-三氟甲基苯基)-2-氟-3-甲胺基苯甲酰胺(0.56g,1.00mmol)升温至110℃反应,TLC监测至反应完全。将反应体系降温至室温,充分搅拌,逐渐析出固体,过滤,滤饼经柱色谱分离纯化得标题物,白色固体0.57g,收率为85%(以N-(2-溴-4-七氟异丙基-6-三氟甲基苯基)-2-氟-3-甲胺基苯甲酰胺计)。
1H NMR(600MHz,CDCl3,ppm):8.12(s,1H),8.07-7.97(m,2H),7.90(s,1H),7.47-7.42(m,1H),7.33-7.19(m,6H),3.50(s,3H).
5)N-(2-溴-4-七氟异丙基-6-三氟甲基苯基)-2-氟-3-(N-甲基-苯甲酰胺基)苯甲亚胺酰氯(化合物I-38)的制备
向反应瓶中加入甲苯(5mL)、N-(2-溴-4-七氟异丙基-6-三氟甲基苯基)-2-氟-3-(N-甲基-苯甲酰胺基)苯甲酰胺(0.53g,0.79mmol)、三氯氧磷(5ml)、DMF(0.10g)升温至130℃反应,TLC监测至反应完全。将反应体系降温至室温,将反应液缓慢倾入大量冰水中,充分搅拌,用乙酸乙酯(30mL)溶解、萃取、分层,有机相依次用饱和碳酸氢钠水溶液和饱和食盐水洗涤,分出有机相,将有机相用无水硫酸镁干燥,过滤后减压蒸出有机溶剂,残余物经柱色谱分离纯化得标题物,白色固体0.35g,收率为64%(以N-(2-溴-4-七氟异丙基-6-三氟甲基苯基)-2-氟-3-(N-甲基-苯甲酰胺基)苯甲酰胺计)。
1H NMR(600MHz,CDCl3,ppm):8.05(s,1H),7.86(s,1H),7.72(t,1H),7.33(br,2H),7.27(br,2H),7.21(br,2H),7.14(t,1H),3.47(s,3H).
实施例2:化合物I-46的制备
向反应瓶中加入甲苯(15mL)、N-(2-溴-4-七氟异丙基-6-三氟甲基苯基)-2-氟-3-(N-甲基-苯甲酰胺基)苯甲酰胺(0.53g,0.79mmol)、三溴氧磷(5.60g,19.14mmol)升温至100℃反应,TLC监测至反应完全。将反应体系降温至室温,将反应液缓慢倾入大量冰水中,充分搅拌,用乙酸乙酯(30mL)溶解、萃取、分层,有机相依次用饱和碳酸氢钠水溶液和饱和食盐水洗涤,分出有机相,将有机相用无水硫酸镁干燥,过滤后减压蒸出有机溶剂,残余物经柱色谱分离纯化得标题物(化合物I-46),白色固体0.38g,收率为65%(以N-(2-溴-4-七氟异丙基-6-三氟甲基苯基)-2-氟-3-(N-甲基-苯甲酰胺基)苯甲酰胺计)。
1H NMR(600MHz,CDCl3,ppm):8.06(s,1H),7.87(s,1H),7.65(t,1H),7.32(br,2H),7.26(br,2H),7.20(br,2H),7.14(t,1H),3.46(s,3H).
实施例3:化合物I-122的制备
1)N-(2,6-二溴-4-七氟异丙基苯基)-2-氟-3-(N-甲基-2,2-二氟-1,3-苯并二噁茂-5-甲酰胺基)苯甲酰胺的制备
向反应瓶中加入3-(N-甲基-2,2-二氟-1,3-苯并二噁茂-5-甲酰胺基)-2-氟苯甲酸(1.07g,3.0mmol)、氯化亚砜(1.80g)、甲苯(10mL)和DMF(1滴),升温至100℃反应4小时,减压蒸出氯化亚砜和甲苯,得到酰氯,白色固体,加入乙腈(15mL)、2,6-二溴-4-七氟异丙基苯胺(1.26g,2.90mmol)和碘化钾(0.09g,0.50mmol),升温回流反应8小时。将反应体系冷却至室温,加入乙酸乙酯(30mL),依次用饱和碳酸氢钠水溶液和饱和食盐水洗涤,用无水硫酸镁干燥,过滤,减压蒸出溶剂,残余物经柱色谱分离纯化得标题物,白色固体1.73g,收率为78%(以2,6-二溴-4-七氟异丙基苯胺计)。
1H NMR(600MHz,CDCl3,ppm):8.09-8.04(m,2H),7.87(s,2H),7.47-7.43(m,1H),7.34-7.29(m,1H),7.20(s,1H),7.05(d,1H),6.89(d,1H),3.50(s,3H).
2)N-(2,6-二溴-4-七氟异丙基苯基)-3-(N-甲基-2,2-二氟-1,3-苯并二噁茂-5-甲酰胺基)-2-氟苯甲亚胺酰溴(化合物I-122)的制备
向反应瓶中加入甲苯(5mL)、N-(2,6-二溴-4-七氟异丙基苯基)-2-氟-3-(N-甲基-2,2-二氟-1,3-苯并二噁茂-5-甲酰胺基)苯甲酰胺(0.76g,1.00mmol)、三溴氧磷(6.07g,20.70mmol)升温至100℃反应,TLC监测至反应完全。将反应体系降温至室温,将反应液缓慢倾入大量冰水中,充分搅拌,用乙酸乙酯(30mL)溶解、萃取、分层,有机相依次用饱和碳酸氢钠水溶液和饱和食盐水洗涤,分出有机相,将有机相用无水硫酸镁干燥,过滤后减压蒸出有机溶剂,残余物经柱色谱分离纯化得标题物,白色固体0.58g,收率为70%(以N-(2,6-二溴-4-七氟异丙基苯基)-2-氟-3-(N-甲基-2,2-二氟-1,3-苯并二噁茂-5-甲酰胺基)苯甲酰胺计)
1H NMR(600MHz,CDCl3,ppm):7.82(s,2H),7.75(t,1H),7.31(t,1H),7.21(t,1H),7.16(s,1H),7.04(d,1H),6.87(d,1H),3.46(s,3H).
实施例4:化合物I-128的制备
1)N-(2-溴-6-二氟甲氧基-4-七氟异丙基苯基)-2-氟-3-(N-甲基-2,2-二氟-1,3-苯并二噁茂-5-甲酰胺基)苯甲酰胺的制备
向反应瓶中加入3-(N-甲基-2,2-二氟-1,3-苯并二噁茂-5-甲酰胺基)-2-氟苯甲酸(1.07g,3.0mmol)、氯化亚砜(1.80g)、甲苯(10mL)和DMF(1滴),升温至100℃反应4小时,减压蒸出氯化亚砜和甲苯,得到酰氯,白色固体,加入乙腈(15mL)、2-溴-6-二氟甲氧基-4-七氟异丙基苯胺(1.19g,2.90mmol)和碘化钾(0.09g,0.50mmol),升温回流反应8小时。将反应体系冷却至室温,加入乙酸乙酯(30mL),依次用饱和碳酸氢钠水溶液和饱和食盐水洗涤,用无水硫酸镁干燥,过滤,减压蒸出溶剂,残余物经柱色谱分离纯化得标题物,白色固体1.76g,收率为81%(以2-溴-6-二氟甲氧基-4-七氟异丙基苯胺计)。
1H NMR(600MHz,CDCl3,ppm):8.03(t,1H),7.96(d,1H),7.80(d,1H),7.50(s,1H),7.43(t,1H),7.31(t,1H),7.20(s,1H),7.05(br,1H),6.89(br,1H),6.55(t,1H),3.48(s,3H).
2)N-(2-溴-6-二氟甲氧基-4-七氟异丙基苯基)-3-(N-甲基-2,2-二氟-1,3-苯并二噁茂-5-甲酰胺基-2-氟苯甲亚胺酰溴(化合物I-128)的制备
向反应瓶中加入甲苯(5mL)、N-(2-溴-6-二氟甲氧基-4-七氟异丙基苯基)-2-氟-3-(N-甲基-2,2-二氟-1,3-苯并二噁茂-5-甲酰胺基)苯甲酰胺(0.76g,1.00mmol)、三溴氧磷(6.07g,20.70mmol)升温至100℃反应,TLC监测至反应完全。将反应体系降温至室温,将反应液缓慢倾入大量冰水中,充分搅拌,用乙酸乙酯(30mL)溶解、萃取、分层,有机相依次用饱和碳酸氢钠水溶液和饱和食盐水洗涤,分出有机相,将有机相用无水硫酸镁干燥,过滤后减压蒸出有机溶剂,残余物经柱色谱分离纯化得标题物,白色固体0.57g,收率为70%(以N-(2-溴-4-七氟异丙基-6-三氟甲基苯基)-2-氟-3-(N-甲基-苯甲酰胺基)苯甲酰胺计)。
1H NMR(600MHz,CDCl3,ppm):7.76(s,1H),7.72(t,1H),7.45(s,1H),7.31(t,1H),7.21(t,1H),7.15(s,1H),7.04(d,1H),6.87(d,1H),6.45(t,1H),3.46(s,3H).
实施例5:化合物I-130的制备
向反应瓶中加入甲苯(5mL)、N-(2,6-二溴-4-七氟异丙基苯基)-2-氟-3-(N-甲基-2,2-二氟-1,3-苯并二噁茂-5-甲酰胺基)苯甲酰胺(0.76g,1.00mmol)、三氯氧磷(5ml)、DMF(0.10g)升温至130℃反应,TLC监测至反应完全。将反应体系降温至室温,将反应液缓慢倾入大量冰水中,充分搅拌,用乙酸乙酯(30mL)溶解、萃取、分层,有机相依次用饱和碳酸氢钠水溶液和饱和食盐水洗涤,分出有机相,将有机相用无水硫酸镁干燥,过滤后减压蒸出有机溶剂,残余物经柱色谱分离纯化得标题物,白色固体0.54g,收率为69%(以N-(2-溴-4-七氟异丙基-6-三氟甲基苯基)-2-氟-3-(N-甲基-苯甲酰胺基)苯甲酰胺计)。
1H NMR(600MHz,CDCl3,ppm):7.83(t,1H),7.81(s,2H),7.33(t,1H),7.22(t,1H),7.17(s,1H),7.05(d,1H),6.88(d,1H),3.46(s,3H).
实施例6:化合物I-176的制备
向反应瓶中加入四氢呋喃(5mL)、N-(2-溴-6-二氟甲氧基-4-七氟异丙基苯基)-3-(N-甲基-2,2-二氟-1,3-苯并二噁茂-5-甲酰胺基-2-氟苯甲亚胺酰溴(化合物I-128,150.0mg,0.19mmol)和甲硫醇钠(39.2mg,0.56mmol),升温至50℃反应5小时。TLC监测至反应完全。将反应体系降温至室温,将反应液倾入大量水中,用乙酸乙酯萃取、分层,有机相依次用水和饱和食盐水洗涤,分出有机相,将有机相用无水硫酸镁干燥,过滤后减压蒸出有机溶剂,残余物经柱色谱分离纯化得标题物,白色固体102.0mg,收率为70%。
1H NMR(600MHz,CDCl3,ppm):7.64(s,1H),7.22(br,2H),7.03-6.94(m,4H),6.77(br,1H),6.34(t,1H),3.26(s,br,3H),2.57(s,br,3H).
实施例7:化合物I-618的制备
向反应瓶中加入四氢呋喃(3mL)、乙硫醇(11.6mg,0.37mmol)、氢化钠(60%,22.4mg,0.56mmol),室温搅拌反应10分钟,将N-(2-溴-6-二氟甲氧基-4-七氟异丙基苯基)-3-(N-甲基-2,2-二氟-1,3-苯并二噁茂-5-甲酰胺基-2-氟苯甲亚胺酰溴(化合物I-128,150.0mg,0.19mmol)溶于四氢呋喃(2mL),并将该溶液于室温加入到上述反应体系中搅拌反应2小时,TLC检测至反应完全。用1N盐酸将体系淬灭,加水稀释,用乙酸乙酯萃取、分层,有机相依次用水和饱和食盐水洗涤,分出有机相,将有机相用无水硫酸镁干燥,过滤后减压蒸出有机溶剂,残余物经柱色谱分离纯化得标题物,白色固体88.6mg,收率为59%。
1H NMR(600MHz,CDCl3,ppm):7.64(s,1H),7.21(br,2H),7.07(br,4H),6.77(br,1H),6.34(t,1H),3.26(br,5H),1.43(s,br,3H).
实施例8:化合物I-620的制备
向反应瓶中加入四氢呋喃(3mL)、1-1H-1,2,4-三氮唑(25.8mg,0.37mmol)、氢化钠(60%,22.4mg,0.56mmol),室温搅拌反应10分钟,将N-(2-溴-6-二氟甲氧基-4-七氟异丙基苯基)-3-(N-甲基-2,2-二氟-1,3-苯并二噁茂-5-甲酰胺基-2-氟苯甲亚胺酰溴(化合物I-128,150.0mg,0.19mmol)溶于四氢呋喃(2mL),并将该溶液于室温加入到上述反应体系中,升温至50℃,搅拌反应5小时,TLC监测至反应完全。将体系降至室温,用1N盐酸淬灭,加水稀释,用乙酸乙酯萃取、分层,有机相依次用水和饱和食盐水洗涤,分出有机相,将有机相用无水硫酸镁干燥,过滤后减压蒸出有机溶剂,残余物经柱色谱分离纯化得标题物,白色固体95.5mg,收率为63%。
1H NMR(600MHz,CDCl3,ppm):9.13(s,1H),7.99(s,1H),7.67(s,1H),7.25(br,1H),7.17(br,1H),7.08-7.05(m,3H),7.00-6.97(m,1H),6.83(br,1H),6.34(t,1H),3.36(s,3H).
实施例9:化合物I-626的制备
向反应瓶中加入四氢呋喃(5mL)、N-(2-溴-6-二氟甲氧基-4-七氟异丙基苯基)-3-(N-甲基-2,2-二氟-1,3-苯并二噁茂-5-甲酰胺基-2-氟苯甲亚胺酰溴(化合物I-128,150.0mg,0.19mmol)和乙醇钠(81.0mg,0.37mmol),升温至50℃反应5小时。TLC监测至反应完全。将反应体系降温至室温,将反应液倾入大量水中,用乙酸乙酯萃取、分层,有机相依次用水和饱和食盐水洗涤,分出有机相,将有机相用无水硫酸镁干燥,过滤后减压蒸出有机溶剂,残余物经柱色谱分离纯化得标题物,白色固体71.0mg,收率为48%。
1H NMR(600MHz,CDCl3,ppm):7.61(br,1H),7.19(br,1H),7.05-7.02(m,2H),7.00-6.98(m,1H),6.94-6.92(m,1H),6.91-6.88(m,1H),6.76-6.75(m,1H),6.28(t,1H),4.51(br,2H),3.27(s,3H),1.47(t,3H).
实施例10:化合物I-628的制备
向反应瓶中加入四氢呋喃(5mL)、N-(2-溴-6-二氟甲氧基-4-七氟异丙基苯基)-3-(N-甲基-2,2-二氟-1,3-苯并二噁茂-5-甲酰胺基-2-氟苯甲亚胺酰溴(化合物I-128,150.0mg,0.19mmol)、甲胺盐酸盐(25.2mg,0.37mmol)和三乙胺(56.6mg,0.56mmol)。升温至50℃反应5小时。TLC检测至反应完毕。反应体系降至室温,倾入大量清水中,用乙酸乙酯萃取、分层,有机相依次用水和饱和食盐水洗涤,分出有机相,将有机相用无水硫酸镁干燥,过滤后减压蒸出有机溶剂,残余物经柱色谱分离纯化得标题物,白色固体122.3mg,收率为85%。
1H NMR(600MHz,CDCl3,ppm):7.57(br,1H),7.09-7.02(m,4H),6.92(br,2H),6.75(br,1H),6.31(t,1H),5.05(s,br,1H),3.27(s,3H),3.11(s,3H).
实施例11:化合物I-630的制备
向反应瓶中加入四氢呋喃(5mL)、N-(2-溴-6-二氟甲氧基-4-七氟异丙基苯基)-3-(N-甲基-2,2-二氟-1,3-苯并二噁茂-5-甲酰胺基-2-氟苯甲亚胺酰溴(化合物I-128,150.0mg,0.19mmol)和4-乙基哌嗪(63.9mg,0.56mmol),升温至50℃反应5小时。TLC监测至反应完全。将反应体系降温至室温,将反应液倾入大量水中,用乙酸乙酯萃取、分层,有机相依次用水和饱和食盐水洗涤,分出有机相,将有机相用无水硫酸镁干燥,过滤后减压蒸出有机溶剂,残余物经柱色谱分离纯化得标题物,白色固体120.7mg,收率为76%。
1H NMR(600MHz,CDCl3,ppm):7.51(br,1H),7.06-6.83(m,7H),6.31(t,1H),3.90(br,2H),3.33(br,4H),2.66-2.44(m,6H),2.17(br,1H),1.10(t,3H).
实施例12:化合物I-632的制备
向反应瓶中加入四氢呋喃(3mL)、叔丁基硫醇(33.6mg,0.37mmol)、氢化钠(60%,22.4mg,0.56mmol),室温搅拌反应10分钟,将N-(2-溴-6-二氟甲氧基-4-七氟异丙基苯基)-3-(N-甲基-2,2-二氟-1,3-苯并二噁茂-5-甲酰胺基-2-氟苯甲亚胺酰溴(化合物I-128,150.0mg,0.19mmol)溶于四氢呋喃(2mL),并将该溶液于室温加入到上述反应体系中搅拌反应2小时,TLC检测至反应完全。用1N盐酸将体系淬灭,加水稀释,用乙酸乙酯萃取、分层,有机相依次用水和饱和食盐水洗涤,分出有机相,将有机相用无水硫酸镁干燥,过滤后减压蒸出有机溶剂,残余物经柱色谱分离纯化得标题物,白色固体136.8mg,收率为88%。
1H NMR(600MHz,CDCl3,ppm):7.61(br,1H),7.12(br,2H),7.03(br,1H),6.90(br,3H),6.73(br,1H),6.25(t,1H),3.21(s,br,3H),1.66(s,9H).
同时按照上述记载的方式还能够制备获得通式I所示的其它化合物。
生物活性测定
实施例13杀虫活性测定
根据待测化合物的溶解性,用丙酮或二甲基亚砜溶解,然后用0.1%的吐温80溶液配制成所需浓度的待测液50毫升,丙酮或二甲基亚砜在总溶液中的含量不超过10%,待用。
实施例13.1对粘虫活性的测定
选新鲜玉米中部叶片剪成3厘米小段,放入至上述配制好的药液中浸渍10秒,阴干后置于放有滤纸的直径为9厘米的培养皿中,接入整齐的健康试虫(3龄),每处理14头,试验设4次重复,设清水处理为空白对照。处理后放入24℃、相对湿度60%-70%、自然光照的室内培养,72小时后调查存活虫数,计算死亡率。
部分供试的化合物中,化合物I-38、I-46、I-96、I-122、I-128、I-130、I-138、I-154、I-176、I-202、I-226、I-250、I-274、I-298、I-304、I-322、I-346、I-352、I-370、I-394、I-400、I-424、I-442、I-466、I-490、I-522、I-538、I-600、I-602、I-610、I-618、I-620、I-626、I-628、I-630、I-632、I-634、I-668、I-682和I-688在浓度为600mg/L时对粘虫的防效较好,死亡率均为100%。
化合物I-38、I-46、I-96、I-122、I-128、I-130、I-138、I-154、I-176、I-202、I-226、I-250、I-274、I-298、I-304、I-322、I-346、I-352、I-370、I-394、I-400、I-424、I-442、I-466、I-490、I-522、I-538、I-600、I-602、I-610、I-618、I-620、I-626、I-628、I-630、I-632、I-634、I-668、I-682和I-688在浓度为100mg/L时对粘虫的防效较好,死亡率均为100%。
化合物I-38、I-46、I-96、I-122、I-128、I-130、I-138、I-154、I-176、I-202、I-226、I-250、I-274、I-298、I-304、I-322、I-346、I-352、I-370、I-394、I-400、I-424、I-442、I-466、I-490、I-522、I-538、I-600、I-602、I-610、I-618、I-620、I-626、I-628、I-630、I-632、I-634、I-668、I-682和I-688在浓度为10mg/L时对粘虫的防效较好,死亡率均为100%。
实施例13.2对小菜蛾活性的测定
选室温培养的甘蓝叶片,除去表面蜡质层,用打孔器打成直径为2厘米的圆形叶碟,放入至配制好的药液中浸渍10秒,阴干后置于放有滤纸的直径为9厘米的培养皿中,接入整齐的健康试虫(2龄),每处理10头,试验设4次重复,设清水处理为空白对照。处理后放入24℃、相对湿度60%-70%、自然光照的室内培养,72小时后调查存活虫数,计算死亡率。
部分供试的化合物中,化合物I-38、I-46、I-96、I-122、I-128、I-130、I-138、I-154、I-176、I-202、I-226、I-250、I-274、I-298、I-304、I-322、I-346、I-352、I-370、I-394、I-400、I-424、I-442、I-466、I-490、I-522、I-538、I-600、I-602、I-610、I-618、I-620、I-626、I-628、I-630、I-632、I-634、I-668、I-682和I-688在浓度为600mg/L时对小菜蛾的防效较好,死亡率均为100%。
化合物I-38、I-46、I-96、I-122、I-128、I-130、I-138、I-154、I-176、I-202、I-226、I-250、I-274、I-298、I-304、I-322、I-346、I-352、I-370、I-394、I-400、I-424、I-442、I-466、I-490、I-522、I-538、I-600、I-602、I-610、I-618、I-620、I-626、I-628、I-630、I-632、I-634、I-668、I-682和I-688在浓度为100mg/L时对小菜蛾的防效较好,死亡率均为100%。
化合物I-38、I-46、I-96、I-122、I-128、I-130、I-138、I-154、I-202、I-226、I-250、I-274、I-298、I-304、I-322、I-346、I-352、I-370、I-394、I-400、I-424、I-442、I-466、I-490、I-522、I-538、I-600、I-602、I-610、I-626、I-668、I-682和I-688在浓度为10mg/L时对小菜蛾的防效较好,死亡率均为100%。
实施例13.3对桃蚜活性的测定
取直径6厘米培养皿,皿底覆一层滤纸,并滴加适量自来水保湿。从培养桃蚜的甘蓝植株上剪取大小适宜(直径约3厘米)且长有15-30头蚜虫的甘蓝叶片,去除有翅蚜和叶片正面的蚜虫,调查结束后,叶背向置于培养皿内,用手持式Airbrush喷雾器进行喷雾处理,压力为10psi(约0.7kg/cm2),喷液量为0.5毫升,试验设3次重复,处理后置于标准观察室内,48小时后调查存活数,计算死亡率。
部分供试的化合物中,化合物I-38、I-46、I-96、I-122、I-128、I-130、I-138、I-154、I-202、I-226、I-250、I-298、I-304、I-322、I-346、I-352、I-370、I-400、I-424、I-442、I-466、I-490、I-610、I-626、I-628、I-634、I-668、I-682和I-688在浓度为600mg/L时对桃蚜的防效较好,死亡率均为100%。
实施例14杀螨活性测定
根据待测化合物的溶解性,用丙酮或二甲基亚砜溶解,然后用0.1%的吐温80溶液配制成所需浓度的待测液50毫升,丙酮或二甲基亚砜在总溶液中的含量不超过10%。
取两片真叶菜豆苗,接种朱砂叶螨成螨并调查基数后,用手持式Airbrush喷雾器进行整株喷雾处理,试验设3次重复,处理后置于标准观察室,72小时后调查存活螨数,计算死亡率。
部分供试的化合物中,化合物I-122、I-128、I-154、I-202、I-298、I-322、I-346、I-352、I-370、I-610、I-618、I-682和I-688在浓度为600mg/L时对朱砂叶螨成螨的防效较好,死亡率均为100%。
通过本发明上述记载的制备过程获得的通式I所示的其它化合物也具有上述相应的特性,达到意想不到的效果。
Claims (7)
1.一种亚胺类化合物,其特征在于:亚胺类化合物结构如通式I所示:
式中:
X1选自卤素、硝基、氰基、CONH2、CHO、C1-C6烷基、C1-C6卤代烷基、C2-C6烯基、C2-C6卤代烯基、C2-C6炔基、C2-C6卤代炔基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6卤代烷硫基、C1-C6烷基氨基、C1-C6二烷基氨基、C1-C6烷氧基羰基、C1-C6烷基羰基、C1-C6卤代烷基羰基、C1-C6烷基磺酰基、C1-C6卤代烷基磺酰基、C1-C6烷基亚磺酰基、C1-C6卤代烷基亚磺酰基、C1-C6烷基氨基羰基或C1-C6烷基氨基磺酰基;
m选自0、1、2、3、4或5;
X2和X3可相同或不同的分别选自H、卤素、硝基、氰基、C1-C6烷基、C1-C6卤代烷基、C2-C6烯基、C2-C6卤代烯基、C2-C6炔基、C2-C6卤代炔基;
R1选自H、C1-C6烷基、C1-C6卤代烷基或氰基亚甲基;
R2选自H、卤素、C1-C6烷基、C1-C6卤代烷基、C2-C6烯基、C2-C6卤代烯基、C1-C6烷基胺基、C1-C6卤代烷基胺基、C1-C6二烷基胺基、C1-C6卤代二烷基胺基、C1-C6烷氧基、C1-C6卤代烷氧基、C2-C6烯基氧基、C2-C6卤代烯基氧基、C2-C6炔基氧基、C2-C6卤代炔基氧基、C1-C6烷硫基、C1-C6卤代烷硫基、C2-C6烯基硫基、C2-C6卤代烯基硫基、C2-C6炔基硫基、C2-C6卤代炔基硫基、C1-C6烷氧基亚甲基、C1-C6卤代烷氧基亚甲基、C1-C6烷硫基亚甲基、C1-C6卤代烷硫基亚甲基、C1-C6烷胺基亚甲基、C1-C6卤代烷胺基亚甲基、C1-C6二烷胺基亚甲基、C1-C6卤代二烷胺基亚甲基、苯基、氨基、肼基、氰基、氰基亚甲基、1-吡咯烷基、1-哌啶基、4-吗啉基、1-1H-吡唑基、1-1H-咪唑基、1-1H-1,2,4-三氮唑基、2-2H-1,2,3-三氮唑基或4位被下述基团取代的哌嗪-1-基,其中下述基团为:C1-C6烷基、C1-C6烷基羰基或苯基;
Y1和Y2可相同或不同的选自卤素、C1-C6烷基、C1-C6卤代烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基或C1-C6卤代烷硫基。
2.按权利要求1所述的亚胺类化合物,其特征在于:所述通式I中:
X1选自卤素、硝基、氰基、CONH2、CHO、C1-C3烷基、C1-C3卤代烷基、C2-C4烯基、C2-C4卤代烯基、C2-C4炔基、C2-C4卤代炔基、C1-C3烷氧基、C1-C3卤代烷氧基、C1-C3烷硫基、C1-C3卤代烷硫基、C1-C3烷基氨基、C1-C3二烷基氨基、C1-C3烷氧基羰基、C1-C3烷基羰基、C1-C3卤代烷基羰基、C1-C3烷基磺酰基、C1-C3卤代烷基磺酰基、C1-C3烷基亚磺酰基、C1-C3卤代烷基亚磺酰基、C1-C3烷基氨基羰基或C1-C3烷基氨基磺酰基;
m选自0、1、2、3、4或5;
X2和X3可相同或不同的分别选自H、卤素、硝基、氰基、C1-C3烷基、C1-C3卤代烷基、C2-C4烯基、C2-C4卤代烯基、C2-C4炔基或C2-C4卤代炔基;
R1选自H、C1-C3烷基、C1-C3卤代烷基或氰基亚甲基;
R2选自H、卤素、C1-C3烷基、C1-C3卤代烷基、C2-C4烯基、C2-C4卤代烯基、C1-C3烷基胺基、C1-C3卤代烷基胺基、C1-C3二烷基胺基、C1-C3卤代二烷基胺基、C1-C3烷氧基、C1-C3卤代烷基氧基、C2-C4烯基氧基、C2-C4卤代烯基氧基、C2-C4炔基氧基、C2-C4卤代炔基氧基、C1-C3烷硫基、C1-C3卤代烷硫基、C2-C4烯基硫基、C2-C4卤代烯基硫基、C2-C4炔基硫基、C2-C4卤代炔基硫基、C1-C3烷氧基亚甲基、C1-C3卤代烷氧基亚甲基、C1-C3烷硫基亚甲基、C1-C3卤代烷硫基亚甲基、C1-C3烷胺基亚甲基、C1-C3卤代烷胺基亚甲基、C1-C3二烷胺基亚甲基、C1-C3卤代二烷胺基亚甲基、苯基、氨基、肼基、氰基、氰基亚甲基、1-吡咯烷基、1-哌啶基、4-吗啉基、1-1H-吡唑基、1-1H-咪唑基、1-1H-1,2,4-三氮唑基或2-2H-1,2,3-三氮唑基或4位被下述基团取代的哌嗪-1-基,其中下述基团为:C1-C3烷基、C1-C3烷基羰基或苯基;
Y1和Y2可相同或不同的选自卤素、C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、C1-C3烷硫基或C1-C3卤代烷硫基。
6.一种按照权利要求1-5任意一项所述的亚胺类化合物的应用,其特征在于:所述通式I所示化合物在农业、林业或卫生领域用作杀虫剂、杀螨剂的用途。
7.一种控制害虫或害螨的方法,其特征在于:将权利要求1所述的化合物以每公顷10克到1000克的有效剂量施于需要控制的害虫或害螨上,或其生长的介质上。
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