CN107846884A - 具有含硫取代基的杀有害生物活性杂环衍生物 - Google Patents
具有含硫取代基的杀有害生物活性杂环衍生物 Download PDFInfo
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- CN107846884A CN107846884A CN201680043428.1A CN201680043428A CN107846884A CN 107846884 A CN107846884 A CN 107846884A CN 201680043428 A CN201680043428 A CN 201680043428A CN 107846884 A CN107846884 A CN 107846884A
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- alkyl
- haloalkyl
- compound
- bases
- Prior art date
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- 125000001424 substituent group Chemical group 0.000 title claims description 57
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims description 20
- 125000000623 heterocyclic group Chemical group 0.000 title claims description 11
- 239000011593 sulfur Substances 0.000 title description 5
- 229910052717 sulfur Inorganic materials 0.000 title description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 240
- 150000003839 salts Chemical class 0.000 claims abstract description 63
- 239000003905 agrochemical Substances 0.000 claims abstract description 9
- -1 hydroxyl Chemical group 0.000 claims description 171
- 239000000203 mixture Substances 0.000 claims description 126
- 229910052736 halogen Inorganic materials 0.000 claims description 86
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 claims description 80
- 150000002367 halogens Chemical class 0.000 claims description 76
- 238000000034 method Methods 0.000 claims description 65
- 239000001257 hydrogen Substances 0.000 claims description 46
- 229910052739 hydrogen Inorganic materials 0.000 claims description 46
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 41
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 37
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 36
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 36
- 229910052794 bromium Inorganic materials 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 36
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 34
- 229910052799 carbon Inorganic materials 0.000 claims description 31
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 29
- 239000000460 chlorine Substances 0.000 claims description 28
- 229910052801 chlorine Inorganic materials 0.000 claims description 28
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 239000011737 fluorine Substances 0.000 claims description 25
- 229910052731 fluorine Inorganic materials 0.000 claims description 25
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 25
- 229910052740 iodine Inorganic materials 0.000 claims description 25
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 24
- 239000011630 iodine Substances 0.000 claims description 24
- 125000003545 alkoxy group Chemical group 0.000 claims description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- 125000004770 (C1-C4) haloalkylsulfanyl group Chemical group 0.000 claims description 22
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 21
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 20
- 125000004768 (C1-C4) alkylsulfinyl group Chemical group 0.000 claims description 17
- 238000006467 substitution reaction Methods 0.000 claims description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 16
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 16
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 14
- 239000005864 Sulphur Substances 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 241000607479 Yersinia pestis Species 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 241001465754 Metazoa Species 0.000 claims description 10
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 10
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 10
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 9
- 125000004414 alkyl thio group Chemical group 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- 125000002541 furyl group Chemical group 0.000 claims description 8
- 150000002431 hydrogen Chemical group 0.000 claims description 8
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 7
- BBVIDBNAYOIXOE-UHFFFAOYSA-N 1,2,4-oxadiazole Chemical compound C=1N=CON=1 BBVIDBNAYOIXOE-UHFFFAOYSA-N 0.000 claims description 6
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Chemical compound C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 claims description 6
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims description 6
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- FYADHXFMURLYQI-UHFFFAOYSA-N 1,2,4-triazine Chemical compound C1=CN=NC=N1 FYADHXFMURLYQI-UHFFFAOYSA-N 0.000 claims description 5
- 125000005842 heteroatom Chemical group 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims description 4
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 4
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 4
- 230000004927 fusion Effects 0.000 claims description 4
- 125000002883 imidazolyl group Chemical group 0.000 claims description 4
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 4
- YGTAZGSLCXNBQL-UHFFFAOYSA-N 1,2,4-thiadiazole Chemical class C=1N=CSN=1 YGTAZGSLCXNBQL-UHFFFAOYSA-N 0.000 claims description 3
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 3
- 150000003851 azoles Chemical class 0.000 claims description 3
- 125000000335 thiazolyl group Chemical group 0.000 claims description 3
- 125000001425 triazolyl group Chemical group 0.000 claims description 3
- HCMJWOGOISXSDL-UHFFFAOYSA-N (2-isothiocyanato-1-phenylethyl)benzene Chemical compound C=1C=CC=CC=1C(CN=C=S)C1=CC=CC=C1 HCMJWOGOISXSDL-UHFFFAOYSA-N 0.000 claims description 2
- 125000004738 (C1-C6) alkyl sulfinyl group Chemical group 0.000 claims description 2
- 125000004740 (C1-C6) haloalkylsulfanyl group Chemical group 0.000 claims description 2
- 125000006643 (C2-C6) haloalkenyl group Chemical group 0.000 claims description 2
- UGUHFDPGDQDVGX-UHFFFAOYSA-N 1,2,3-thiadiazole Chemical class C1=CSN=N1 UGUHFDPGDQDVGX-UHFFFAOYSA-N 0.000 claims description 2
- 150000004869 1,3,4-thiadiazoles Chemical class 0.000 claims description 2
- 150000000182 1,3,5-triazines Chemical class 0.000 claims description 2
- AWBOSXFRPFZLOP-UHFFFAOYSA-N 2,1,3-benzoxadiazole Chemical compound C1=CC=CC2=NON=C21 AWBOSXFRPFZLOP-UHFFFAOYSA-N 0.000 claims description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 claims description 2
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 claims description 2
- 125000002619 bicyclic group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000000259 cinnolinyl group Chemical class N1=NC(=CC2=CC=CC=C12)* 0.000 claims description 2
- JKFAIQOWCVVSKC-UHFFFAOYSA-N furazan Chemical compound C=1C=NON=1 JKFAIQOWCVVSKC-UHFFFAOYSA-N 0.000 claims description 2
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 claims description 2
- SUBGVCPDXXJALB-UHFFFAOYSA-N indolizine Chemical compound C1=C=C[CH]N2C=CC=C21 SUBGVCPDXXJALB-UHFFFAOYSA-N 0.000 claims description 2
- 125000005956 isoquinolyl group Chemical group 0.000 claims description 2
- 125000000842 isoxazolyl group Chemical group 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 150000005054 naphthyridines Chemical class 0.000 claims description 2
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000001715 oxadiazolyl group Chemical group 0.000 claims description 2
- 125000002971 oxazolyl group Chemical group 0.000 claims description 2
- 150000003214 pyranose derivatives Chemical class 0.000 claims description 2
- 125000003373 pyrazinyl group Chemical group 0.000 claims description 2
- 125000003226 pyrazolyl group Chemical group 0.000 claims description 2
- YEYHFKBVNARCNE-UHFFFAOYSA-N pyrido[2,3-b]pyrazine Chemical compound N1=CC=NC2=CC=CN=C21 YEYHFKBVNARCNE-UHFFFAOYSA-N 0.000 claims description 2
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 claims description 2
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims description 2
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 claims description 2
- 125000001113 thiadiazolyl group Chemical group 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims 2
- 230000001902 propagating effect Effects 0.000 claims 2
- 125000000355 1,3-benzoxazolyl group Chemical class O1C(=NC2=C1C=CC=C2)* 0.000 claims 1
- JGLMVXWAHNTPRF-CMDGGOBGSA-N CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O Chemical compound CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O JGLMVXWAHNTPRF-CMDGGOBGSA-N 0.000 claims 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims 1
- 239000012752 auxiliary agent Substances 0.000 claims 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims 1
- 238000002405 diagnostic procedure Methods 0.000 claims 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims 1
- 125000002098 pyridazinyl group Chemical group 0.000 claims 1
- 238000003419 tautomerization reaction Methods 0.000 claims 1
- 238000002560 therapeutic procedure Methods 0.000 claims 1
- 239000002917 insecticide Substances 0.000 abstract description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 181
- YJXNJQHBVKTWCC-UHFFFAOYSA-N (3-cyclopent-2-en-1-yl-2-methyl-4-oxocyclopent-2-en-1-yl) 2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate Chemical compound CC1(C)C(C=C(C)C)C1C(=O)OC1C(C)=C(C2C=CCC2)C(=O)C1 YJXNJQHBVKTWCC-UHFFFAOYSA-N 0.000 description 128
- 239000002585 base Substances 0.000 description 114
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 77
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 64
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 45
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 45
- 241000196324 Embryophyta Species 0.000 description 43
- 150000002148 esters Chemical class 0.000 description 41
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 39
- 238000002360 preparation method Methods 0.000 description 39
- 239000003053 toxin Substances 0.000 description 38
- 231100000765 toxin Toxicity 0.000 description 38
- 238000006243 chemical reaction Methods 0.000 description 37
- 239000002904 solvent Substances 0.000 description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 36
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 32
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
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- 241000244206 Nematoda Species 0.000 description 29
- 241000238631 Hexapoda Species 0.000 description 27
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 27
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 26
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 26
- 239000003513 alkali Substances 0.000 description 26
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 21
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 21
- 235000005822 corn Nutrition 0.000 description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 20
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 20
- 239000003153 chemical reaction reagent Substances 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 19
- 239000000126 substance Substances 0.000 description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
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- 239000002671 adjuvant Substances 0.000 description 17
- 229910000027 potassium carbonate Inorganic materials 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 241000196508 Turbatrix Species 0.000 description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 15
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- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 11
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 11
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- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 10
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
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Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- 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
- A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
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- 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
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
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- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
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- A61P33/14—Ectoparasiticides, e.g. scabicides
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
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- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
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- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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Abstract
具有式(I)的化合物
Description
本发明涉及含硫取代基的杀有害生物活性(尤其是杀虫活性)杂环衍生物,涉及用于它们的制备的方法,涉及包含那些化合物的组合物,并且涉及它们用于控制动物有害生物(包括节肢动物并且尤其是昆虫或蜱螨目的代表)的用途。
具有杀有害生物作用的杂环化合物是已知的并描述于例如WO 2010/125985、WO2013/018928、WO 2016/024587和WO 2015/163478。现在已经发现具有含硫的苯基-和吡啶基取代基的杀有害生物活性杂环咪唑衍生物。
本发明因此涉及具有式I的化合物,
其中
G1是氮或CR2;
G2是氮或CR3;
G3是氮或CR4;
G4是氮或CR5;
G5是氮或CR6,其前提是不多于2个氮作为G可连续出现;
R2、R3、R4、R5或R6彼此独立地是氢、卤素、C1-C4卤代烷基、
被一个或两个羟基取代的C1-C4卤代烷基、被一个或两个甲氧基取代的C1-C4卤代烷基;
被一个或两个氰基取代的C1-C4卤代烷基;或
R2、R3、R4、R5或R6彼此独立地是C1-C4卤代烷基硫烷基、C1-C4卤代烷基亚磺酰基、
C1-C4卤代烷基磺酰基、C1-C4卤代烷氧基、SF5、苯基羰基硫基、氰基、巯基、C1-C4烷氧基羰基、C1-C4烷基羰基或-C(O)C1-C4卤代烷基;或
R2、R3、R4、R5或R6彼此独立地是可以被选自下组的取代基单或多取代的C3-C6环烷基,该组由以下各项组成:卤素、氰基和C1-C4烷基;或两个相邻的Ri,其中Ri选自R2、R3、R4、R5以及R6,可以一起形成片段-OCH2O-或-OCF2O-;
R8是氢、C1-C4烷基或C1-C4卤代烷基;
R9是氢、C1-C4烷基、C1-C4卤代烷基、氰基或卤素;
R7是选自下组的基团,该组由以下各项组成:式Q1和Q2
其中箭头表示连接至咪唑环的点;
并且其中A表示CH或N;
Q是可以被选自下组的取代基单取代或多取代的苯基,该组由以下各项组成:卤素、氰基、C1-C4烷基、C1-C4卤代烷基、C1-C4卤代烷氧基、C1-C4烷氧基、C1-C4卤代烷基硫烷基、C1-C4卤代烷基亚磺酰基、C1-C4卤代烷基磺酰基和-C(O)C1-C4卤代烷基;或者
Q是五-元至十元单环的或稠合的双环的环系统,该环系统经由碳原子连接至包含基团A的环,所述环系统可以是芳香族的、部分饱和的或完全饱和的并且包含1至4个选自下组的杂原子,该组由以下各项组成:氮、氧和硫,对于每个环系统不可能包含多于2个氧原子和多于2个硫原子,所述五元至十元环系统可以被独立地选自下组的取代基单取代至多取代,该组由以下各项组成:卤素、氰基、C1-C4烷基、C1-C4卤代烷基、C1-C4卤代烷氧基、C1-C4烷氧基、C1-C4烷基硫烷基、C1-C4烷基亚磺酰基、C1-C4烷基磺酰基、-C(O)C1-C4烷基、C1-C4卤代烷基硫烷基、C1-C4卤代烷基亚磺酰基、C1-C4卤代烷基磺酰基和-C(O)C1-C4卤代烷基;或者
Q是部分饱和的或完全饱和的五元至六元芳香族环系统,该环系统经由氮原子连接至包含基团A的环,所述环系统可以被选自下组的取代基单取代或多取代,该组由以下各项组成:卤素、氰基、C1-C4烷基、C1-C4卤代烷基、C1-C4卤代烷氧基、C1-C4烷氧基、C1-C4烷基硫烷基、C1-C4烷基亚磺酰基、C1-C4烷基磺酰基、-C(O)C1-C4烷基、C1-C4卤代烷基硫烷基、C1-C4卤代烷基亚磺酰基、C1-C4卤代烷基磺酰基和-C(O)C1-C4卤代烷基;并且所述环系统包含选自下组的1个、2个或3个杂原子,该组由以下各项组成:氮、氧和硫,其中所述环系统可以不包含多于一个氧原子和不多于一个硫原子;或者
Q是C3-C6环烷基,或被选自下组的取代基单取代或多取代的C3-C6环烷基,该组由以下各项组成:卤素、氰基、C1-C4烷基、C1-C4卤代烷基、C3-C6环烷基和苯基,其中所述苯基可以被选自下组的取代基单取代或多取代,该组由以下各项组成:卤素、氰基、C1-C4烷基、C1-C4卤代烷基、C1-C4卤代烷氧基、C1-C4烷氧基、C1-C4卤代烷基硫烷基、C1-C4卤代烷基亚磺酰基、C1-C4卤代烷基磺酰基和-C(O)C1-C4卤代烷基;或者
Q是C2-C6烯基,或被选自下组的取代基单取代或多取代的C2-C6烯基,该组由以下各项组成:卤素、氰基、C1-C4烷基、C1-C4卤代烷基、C3-C6环烷基和苯基,其中所述苯基可以被选自下组的取代基单取代或多取代,该组由以下各项组成:卤素、氰基、C1-C4烷基、C1-C4卤代烷基、C1-C4卤代烷氧基、C1-C4烷氧基、C1-C4卤代烷基硫烷基、C1-C4卤代烷基亚磺酰基、C1-C4卤代烷基磺酰基和-C(O)C1-C4卤代烷基;或者
Q是C2-C6炔基,或被选自下组的取代基单取代或多取代的C2-C6炔基,该组由以下各项组成:卤素、氰基、C1-C4烷基、C1-C4卤代烷基、C3-C6环烷基、三(C1-C4烷基)甲硅烷基和苯基,其中所述苯基可以被选自下组的取代基单取代或多取代,该组由以下各项组成:卤素、氰基、C1-C4烷基、C1-C4卤代烷基、C1-C4卤代烷氧基、C1-C4烷氧基、C1-C4卤代-烷基硫烷基、C1-C4卤代烷基亚磺酰基、C1-C4卤代烷基磺酰基和-C(O)C1-C4卤代烷基;或者
Q是C1-C6卤代烷基硫烷基、C1-C6卤代烷基亚磺酰基、C1-C6卤代烷基磺酰基、C1-C6卤代烷氧基、-C(O)C1-C4卤代烷基、C1-C6烷基硫烷基、C1-C6烷基亚磺酰基、或C1-C6烷基磺酰基;
X是S、SO或SO2;并且
R1是C1-C4烷基、C1-C4卤代烷基、C3-C6环烷基、C3-C6环烷基-C1-C4烷基;或者
R1是被选自下组的取代基单取代或多取代的C3-C6环烷基,该组由以下各项组成:卤素、氰基和C1-C4烷基;或者
R1是被选自下组的取代基单取代或多取代的C3-C6环烷基-C1-C4烷基,该组由以下各项组成:卤素、氰基和C1-C4烷基;或者
R1是C2-C6烯基、C2-C6卤代烯基或C2-C6炔基;
以及具有式I的化合物的农用化学上可接受的盐、立体异构体、对映异构体、互变异构体和N-氧化物。
具有至少一个碱性中心的具有式I的化合物可以与以下酸形成例如酸加成盐,这些酸为:例如强无机酸(例如矿物酸,例如高氯酸、硫酸、硝酸、亚硝酸、磷酸或氢卤酸),强有机羧酸(例如未经取代的或像被卤素取代的C1-C4烷羧酸,例如乙酸(像饱和或不饱和的二羧酸),例如草酸、丙二酸、琥珀酸、马来酸、富马酸或邻苯二甲酸(像羟基羧酸),例如抗坏血酸、乳酸、苹果酸、酒石酸或柠檬酸,或像苯甲酸),或有机磺酸(例如未经取代的或像被卤素取代的C1-C4烷-或芳基磺酸,例如甲烷-或对甲苯磺酸)。具有至少一个酸性基团的具有式I的化合物可以例如与碱形成盐,例如矿物盐,例如碱金属或碱土金属盐,例如钠盐、钾盐或镁盐;或与氨或有机胺形成盐,例如吗啉、哌啶、吡咯烷、单、二或三低碳数烷基胺,例如乙胺、二乙胺、三乙胺或二甲基丙基胺,或单、二或三羟基低碳数烷基胺,例如单乙醇胺、二乙醇胺或三乙醇胺。
在取代基定义中出现的烷基基团可以是直链的或支链的,并且是例如甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、戊基、己基、壬基、癸基以及它们的支链异构体。烷基硫烷基、烷基亚磺酰基、烷基磺酰基、烷氧基、烯基和炔基基团衍生自所提及的烷基基团。烯基和炔基基团可以是单不饱和的或多不饱和的。
卤素通常是氟、氯、溴或碘。相应地,这也适用于与其他含义结合的卤素,例如卤代烷基或卤代苯基。
卤代烷基基团优选地具有从1至6个碳原子的链长。卤代烷基是例如氟甲基、二氟甲基、三氟甲基、氯甲基、二氯甲基、三氯甲基、2,2,2-三氟乙基、2-氟乙基、2-氯乙基、五氟乙基、1,1-二氟-2,2,2-三氯乙基、2,2,3,3-四氟乙基以及2,2,2-三氯乙基;优选是三氯甲基、二氟氯甲基、二氟甲基、三氟甲基和二氯氟甲基。
烷氧基基团优选地具有优选的从1至6个碳原子的链长。烷氧基是例如甲氧基、乙氧基、丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁氧基和叔丁氧基并且还是同分异构的戊氧基以及己氧基基团;优选是甲氧基和乙氧基。
烷氧基烷基基团优选地具有1至6个碳原子的链长。
烷氧基烷基是例如甲氧基甲基、甲氧基乙基、乙氧基甲基、乙氧基乙基、正丙氧基甲基、正丙氧基乙基、异丙氧基甲基或异丙氧基乙基。
烷基硫烷基是例如甲基硫烷基、乙基硫烷基、丙基硫烷基、异丙基硫烷基、丁基硫烷基、戊基硫烷基、以及己基硫烷基。
烷基亚磺酰基是例如甲基亚磺酰基、乙基亚磺酰基、丙基亚磺酰基、异丙基亚磺酰基、丁基亚磺酰基、戊基亚磺酰基、以及己基亚磺酰基。
烷基磺酰基是例如甲基磺酰基、乙基磺酰基、丙基磺酰基、异丙基磺酰基、丁基磺酰基、戊基磺酰基、以及己基磺酰基。
环烷基基团优选地具有从3至6个环碳原子,例如环丙基、环丁基、环戊基和环己基。
卤代烷氧基基团优选地具有从1至4个碳原子的链长。卤代烷氧基是例如二氟甲氧基、三氟甲氧基或2,2,2-三氟乙氧基。
卤代烷基硫烷基基团优选地具有从1至4个碳原子的链长。卤代烷基硫烷基是例如二氟甲基硫烷基、三氟甲基硫烷基或2,2,2-三氟乙基硫烷基。类似的考虑适用于基团C1-C4卤代烷基亚磺酰基和C1-C4卤代烷基磺酰基,它们可以是例如三氟甲基亚磺酰基、三氟甲基磺酰基或2,2,2-三氟乙基磺酰基。
根据本发明,当两个相邻的Ri(其中Ri选自R2、R3、R4、R5以及R6)一起形成片段-OCH2O-或-OCF2O-时,那么形成另外的五元二氧戊环或二氟-二氧戊环。例如具有式I的化合物(其中G2是CR3,G3是CR4,并且其中R3和R4一起形成片段-OCF2O-),具有以下结构:
在本发明的上下文中,经由氮原子连接至包含基团A的环的部分饱和的或完全饱和的五元至六元芳香族环系统的实例选自吡唑、吡咯、吡咯烷、吡咯烷-2-酮、哌啶、吗啉、咪唑、三唑和吡啶-2-酮。
在本发明的上下文中,取代基定义中的“单取代至多取代的”典型地是指,取决于取代基的化学结构,单取代至七次取代的,优选地是单取代至五次取代的,更优选地是单、二或三取代的。
自由基表示甲基基团。
根据本发明所述的具有式I的化合物还包括在盐形成期间可以形成的水合物。
根据本发明,Q作为五元至十元单环的或稠合的二环的环系统,该环系统经由碳原子连接至包含基团A的环,所述环系统可以是芳香族的、部分饱和的或完全饱和的并且包含1至4个选自下组的杂原子,该组由以下各项组成:氮、氧和硫,对于每个环系统不可能包含多于2个氧原子和多于2个硫原子,
或者Q作为三元至十元、单环的或稠合的二环的环系统,该环系统可以是芳香族的、部分饱和的或完全饱和的;
取决于环成员的个数,优选地选自下组,该组由以下杂环基团组成:
吡咯基;吡唑基;异噁唑基;呋喃基(furanyl);噻吩基;咪唑基;噁唑基;噻唑基;异噻唑基;三唑基;噁二唑基;噻二唑基;四唑基;呋喃基(furyl);吡啶基;嘧啶基;吡嗪基;哒嗪基;三嗪基,吡喃基;喹唑啉基;异喹啉基;吲嗪基;异苯并呋喃基萘啶基;喹喔啉基;噌啉基;酞嗪基;苯并噻唑基;苯并噁唑基;苯并三唑基;吲唑基;吲哚基;(1H-吡咯-1-基)-;(1H-吡咯-2-基)-;(1H-吡咯-3-基)-;(1H-吡唑-1-基)-;(1H-吡唑-3-基)-;(3H-吡唑-3-基)-;(1H-吡唑-4-基)-;(3-异噁唑基)-;(5-异噁唑基)-;(2-呋喃基)-;(3-呋喃基)-;(2-噻吩基)-;(3-噻吩基)-;(1H-咪唑-2-基)-;(1H-咪唑-4-基)-;(1H-咪唑-5-基)-;(2-噁唑-2-基)-;(噁唑-4-基)-;(噁唑-5-基)-;(噻唑-2-基)-;(噻唑-4-基)-;(噻唑-5-基)-;(异噻唑-3-基)-;(异噻唑-5-基)-;(1H-1,2,3-三唑-1-基)-;(1H-1,2,4-三唑-3-基)-;(4H-1,2,4-三唑-4-基)-;(1H-1,2,4-三唑-1-基)-;(1,2,3-噁二唑-2-基)-;(1,2,4-噁二唑-3-基)-;(1,2,4-噁二唑-4-基)-;(1,2,4-噁二唑-5-基)-;(1,2,3-噻二唑-2-基)-;(1,2,4-噻二唑-3-基)-;(1,2,4-噻二唑-4-基)-;(1,3,4-噻二唑-5-基)-;(1H-四唑-1-基)-;(1H-四唑-5-基)-;(2H-四唑-5-基)-;(2-吡啶基)-;(3-吡啶基)-;(4-吡啶基)-;(2-嘧啶基)-;(4-嘧啶基)-;(5-嘧啶基)-;(2-吡嗪基)-;(3-哒嗪基)-;(4-哒嗪基)-;(1,3,5-三嗪-2-基)-;(1,2,4-三嗪-5-基)-;(1,2,4-三嗪-6-基)-;(1,2,4-三嗪-3-基)-;(呋咱-3-基)-;(2-喹啉基)-;(3-喹啉基)-;(4-喹啉基)-;(5-喹啉基)-;(6-喹啉基)-;(3-异喹啉基)-;(4-异喹啉基)-;(2-喹唑啉基)-;(2-喹喔啉基)-;(5-喹喔啉基)-;(吡啶并[2,3-b]吡嗪-7-基)-;(苯并噁唑-5-基)-;(苯并噻唑-5-基)-;(苯并[b]噻吩-2-基)-和(苯并[1,2,5]噁二唑-5-基)-;二氢吲哚基以及四氢喹啉基。
在优选的具有式I的化合物中,Q选自下组,该组由J-0至J-48组成(其中箭头表示基团J到包含基团A的环的附着点):
具体地选自J-1至J-47;
其中每个基团J-0至J-48被Rx单取代、二取代或三取代,其中
每个Rx独立地选自:氢、卤素、氰基、C1-C4烷基、C1-C4卤代烷基、C1-C4卤代烷氧基、C1-C4烷氧基、C1-C4烷基硫烷基、C1-C4烷基亚磺酰基、C1-C4烷基磺酰基、-C(O)C1-C4烷基、C1-C4卤代烷基硫烷基、C1-C4卤代烷基亚磺酰基、C1-C4卤代烷基磺酰基和-C(O)C1-C4卤代烷基。
具有式I的化合物的优选的组由具有式I-1的化合物表示
其中A、Q、G1、G2、G3、G4、以及G5如以上在式I下所定义;并且其中X1是S、SO或SO2;并且R11是甲基、乙基、正丙基、异丙基或环丙基甲基;R8是如以上在式I下所定义的(优选地是甲基),R9是如以上在式I下所定义的(优选地是氢),以及那些化合物的农用化学上可接受的盐、立体异构体、对映异构体、互变异构体和N-氧化物。
还优选的是具有式I-1的化合物,其G3被定义为C(卤素)、C(C1-C4卤代烷基)、C(C1-C4卤代烷基硫烷基)或C(C1-C4卤代烷基磺酰基),并且其G1、G2、G4和G5被定义为CH。
然而其他优选的具有式I-1的化合物具有G2被定义为C(C1-C4卤代烷基硫烷基),并且具有G1、G3、G4和G5被定义为CH。
进一步优选的具有式I-1的化合物具有G2被定义为N,具有G3被定义为C(C1-C4卤代烷基),和G1、G4和G5被定义为CH。
其他优选的具有式I-1的化合物具有G2被定义为N,具有G4被定义为C(C1-C4卤代烷基)、和G1、G3和G5被定义为CH。
然而进一步优选的具有式I-1的化合物具有G2和G4被定义为N,具有G3被定义为C(C1-C4卤代烷基)、和G1和G5被定义为CH。
在尤其优选的一组具有式I-1的化合物中,G3被定义为C(F)、C(CF3)、C(SCF3)或C(SO2CF3),并且具有G1、G2、G4和G5被定义为CH。
在尤其优选的一组具有式I-1的化合物中,G2被定义为C(SCF3),并且G1、G3、G4和G5被定义为CH。
在尤其优选的一组具有式I-1的化合物中,G2被定义为N,G3被定义为C(CF3),并且G1、G4和G5被定义为CH。
在尤其优选的一组具有式I-1的化合物中,G2被定义为N,G4被定义为C(CF3),并且G1、G3和G5被定义为CH。
在尤其优选的一组具有式I-1的化合物中,G2和G4被定义为N,G3被定义为C(CF3),并且G1和G5被定义为CH。
在具有式I-1的化合物的所述的特别优选的组中,R8优选地是甲基并且R9优选地是氢。所述优选的一组具有式I-1的化合物的组的进一步优选的实施例包含以下化合物,其中A优选地是N,X1优选地是SO2并且R11优选地是乙基。
在具有式I-1的化合物和上文提及的具有式I-1的化合物的所有优选的实施例中,Q优选的选自下组,该组由以下各项组成:
其中每个基团J是被Rx单取代、二取代或三取代的,其中
每个Rx独立地选自:氢、卤素、氰基、C1-C4烷基、C1-C4卤代烷基、C1-C4卤代烷氧基、C1-C4烷氧基、C1-C4烷基硫烷基、C1-C4烷基亚磺酰基、C1-C4烷基磺酰基、-C(O)C1-C4烷基、C1-C4卤代烷基硫烷基、C1-C4卤代烷基亚磺酰基、C1-C4卤代烷基磺酰基和-C(O)C1-C4卤代烷基,具体地独立地选自氢、卤素和C1-C4卤代烷基。
具有式I的化合物的另一个优选的组由具有式I-2的化合物表示
其中A、G1、G2、G3、G4、以及G5如以上在式I下所定义;并且其中X2是S、SO或SO2;并且R12是甲基、乙基、正丙基、异丙基或环丙基甲基;R8是如上在式I下所定义的,R9是如上在式I下所定义的,优选地是氢,并且其中Qa1选自下组,该组由以下各项组成:
其中每个基团J是被Rx单取代、二取代或三取代的,其中
每个Rx独立地选自:氢、卤素、氰基、C1-C4烷基、C1-C4卤代烷基、C1-C4卤代烷氧基、C1-C4烷氧基、C1-C4烷基硫烷基、C1-C4烷基亚磺酰基、C1-C4烷基磺酰基、-C(O)C1-C4烷基、C1-C4卤代烷基硫烷基、C1-C4卤代烷基亚磺酰基、C1-C4卤代烷基磺酰基和-C(O)C1-C4卤代烷基,以及那些化合物的农用化学上可接受的盐、立体异构体、对映异构体、互变异构体和N-氧化物。
还优选地是具有式I-2的化合物,其中每个Rx独立地选自氢、卤素和C1-C4卤代烷基。
更优选的具有式I-2的化合物是其中每个Rx彼此独立地选自氢、氟、氯和三氟甲基的那些。
在尤其优选的一组具有式I-2的化合物中,Qa1选自下组,该组由以下各项组成:
具体地选自J-0a和J-5a;
其中每个Rx独立地选自氢、卤素和C1-C4卤代烷基,优选地选自氢、氟、氯和三氟甲基。
在具有式I-2的化合物的所述的特别优选的组中,R8优选地是甲基并且R9优选地是氢。所述优选的一组具有式I-2的化合物的组的进一步优选的实施例包含化合物,其中A优选地是N,X2优选地是SO2并且R12优选地是乙基。
本发明的另一个优选的实施例包括具有式I的化合物,该具有式I的化合物由以下表示:具有式I-3的化合物
其中
A是N或CH;
R10是被独立地选自下组的取代基单取代或多取代的苯基,,该组由以下各项组成:卤素、C1-C4卤代烷基、C1-C4卤代烷基硫烷基和C1-C4卤代烷基磺酰基,具体地是氟、三氟甲基、三氟甲基硫烷基和三氟甲基磺酰基;或者
R10是被独立地选自下组的取代基单取代或多取代的吡啶基,该组由以下各项组成:卤素和C1-C4卤代烷基,具体地是氟和三氟甲基;或者
R10是被独立地选自下组的取代基单取代或多取代的嘧啶基,该组由以下各项组成:卤素和C1-C4卤代烷基,具体地是氟和三氟甲基;
X3是S、SO或SO2,具体地是S或SO2,优选地SO2;
Qa2选自下组,该组由以下各项组成:
其中每个基团J被Rx单取代,二取代或三取代,其中每个Rx独立地选自氢、卤素和C1-C4卤代烷基;
R13是C1-C4烷基,具体地是甲基或乙基;
R8是C1-C4烷基,具体地是甲基或乙基;
R9是氢;
以及具有式I-3的化合物的农用化学上可接受的盐、立体异构体、对映异构体、互变异构体和N-氧化物。
在包含具有式I-3的化合物的所述的优选的实施例中,R10优选地是被独立地选自下组的取代基单取代的苯基,该组由以下各项组成:卤素、C1-C4卤代烷基、C1-C4卤代烷基硫烷基和C1-C4卤代烷基磺酰基,或者R10是被独立地选自下组的取代基单取代的吡啶基,该组由以下各项组成:卤素和C1-C4卤代烷基,或者R10是被独立地选自下组的取代基单取代的嘧啶基,该组由以下各项组成:卤素和C1-C4卤代烷基;具体地,R10优选地是被独立地选自下组的取代基单取代的苯基,该组由以下各项组成:卤素、C1-C4卤代烷基、C1-C4卤代烷基硫烷基和C1-C4卤代烷基磺酰基,或者R10是被独立地选自下组的取代基单取代的吡啶基,该组由以下各项组成:卤素和C1-C4卤代烷基。
环R10上尤其优选的取代基是选自氟、三氟甲基、三氟甲基硫烷基和三氟甲基磺酰基。
在包含具有式I-3的化合物的所述优选的实施例中,Qa2优选地选自下组,该组由以下各项组成:
具体地选自J-0a和J-5a;
其中每个Rx独立地选自氢、卤素和C1-C4卤代烷基,优选地选自氢、氟、氯和三氟甲基。
本发明的尤其优选的实施例包括具有式I的化合物,该具有式I的化合物由具有式I-4的化合物表示:
其中
R10’是被独立地选自下组的取代基单取代的苯基,该组由以下各项组成:卤素、C1-C4卤代烷基、C1-C4卤代烷基硫烷基和C1-C4卤代烷基磺酰基,或者R10’是被独立地选自下组的取代基单取代的吡啶基,该组由以下各项组成:卤素和C1-C4卤代烷基,或者R10’是被独立地选自下组的取代基单取代的嘧啶基,该组由以下各项组成:卤素和C1-C4卤代烷基;并且
Qa4选自下组,该组由以下各项组成:
具体地选自J-0a和J-5a;
其中每个Rx独立地选自氢、卤素和C1-C4卤代烷基;
以及具有式I-4的化合物的农用化学上可接受的盐、立体异构体、对映异构体、互变异构体和N-氧化物。
在包含具有式I-4的化合物的所述尤其优选的实施例中在环R10’上的优选的取代基选自氟、三氟甲基、三氟甲基硫烷基和三氟甲基磺酰基;并且
每个Rx独立地,优选地选自氢、氟、氯和三氟甲基。
本发明的一个甚至进一步尤其优选的实施例包括具有式I的化合物,该具有式I的化合物由以下表示:具有式I-5的化合物
其中
R10#是基团G-10至G-12,其独立地选自下组,该组由以下各项组成:
其中
箭头表示连接至咪唑环的点;并且
每个Ry独立地选自卤素、C1-C4卤代烷基、C1-C4卤代烷基硫烷基和
C1-C4卤代烷基磺酰基;并且
Qa5选自下组,该组由以下各项组成:
其中每个Rx独立地选自氢、卤素和C1-C4卤代烷基;
以及具有式I-5的化合物的农用化学上可接受的盐、立体异构体、对映异构体、互变异构体和N-氧化物。
在包含具有式I-5的化合物的所述进一步尤其优选的实施例中,每个Ry独立地,优选地选自氟、三氟甲基、三氟甲基硫烷基和三氟甲基磺酰基;并且
每个Rx独立地,优选地选自氢、氟、氯和三氟甲基。
根据本发明的用于制备具有式I的化合物的方法原则上通过本领域普通技术人员已知的方法来进行。更具体地,具有式I的化合物(其中X是SO(亚砜)和/或SO2(砜))的亚组,可以通过对应的具有式I的硫化物化合物(其中X是S)的氧化反应的方法来获得,涉及除其他氧化剂之外的试剂如,例如间氯过氧苯甲酸(mCPBA)、过氧化氢、过硫酸氢钾、高碘酸钠、次氯酸钠或次氯酸叔丁酯。该氧化反应通常是在溶剂的存在下进行的。待用于该反应的溶剂的实例包括脂族卤代烃,如二氯甲烷和氯仿;醇类,如甲醇和乙醇;乙酸;水;及其混合物。用于该反应的氧化剂的量通常是1至3摩尔(优选地是1至1.2摩尔),相对于1摩尔的硫化物化合物I,以产生亚砜化合物I,并且优选地是2至2.2摩尔的氧化剂,相对于1摩尔的硫化物化合物I,以产生砜化合物I。此类氧化反应披露于例如WO 2013/018928中。
具有式I的化合物(其中R8、R9、G1、G2、G3、G4、G5和R7是如上所定义的)
可以通过使具有式II的化合物(其中G1、G2、G3、G4和G5是如上所定义的并且其中R”是例如氢(在这种情况下,具有式II的化合物是硼酸)或C1-C4烷基(硼酸酯))与具有式III的化合物(其中R8、R9和R7是如上所定义的并且其中LG是卤素(优选地是溴或碘或假卤素,例如C1-4卤代烷基磺酸酯,尤其是三氟甲磺酸酯)通过过渡金属-催化的反应的反应来制备。实际上,具有式II的硼酸、或其适合的盐或酯,将与具有式III的化合物在钯-或镍-催化的条件(如例如铃木-宫浦反应(Suzuki-Miyaura)条件)下进行反应。在碱(如碳酸钠、碳酸钾或碳酸铯)存在下,在惰性溶剂(如四氢呋喃、N,N-二甲基甲酰胺、二噁烷或1,2-二甲氧基乙烷,或如1,2-二甲氧基乙烷-水混合物)中,在25-200℃之间的温度(优选地是50-150℃)下,任选地在微波辐射下进行此类交叉偶联反应。多种金属、催化剂和配体可以用于此反应类型中,如例如[1,1-双(二苯基-膦)二茂铁]二氯钯(II)(PdCl2(dppf))、四(三苯基膦)钯(0)(Pd(PPh3)4)或双(三苯基膦)钯(II)二氯化物(PdCl2(PPh3)2)。这种转化的反应条件以及催化系统已经描述于例如WO 08/071405中。可替代的式类型II的基于硼的试剂可以包括衍生自2,3-二甲基-2,3-丁二醇(IIa)、2,2-二甲基-1,3-丙二醇(IIb)、以及1,3-丙二醇(IIc)的硼酸酯(boronic esters)(也称作boronate esters)和II的盐类似物,如有机三氟硼酸盐,例如三氟硼酸钾盐(IId)。
可替代地,具有式I的化合物(其中R8、R9、G1、G2、G3、G4、G5和R7是如上所定义的)
可以通过具有式III的化合物(其中R8、R9和R7是如上所定义的并且其中LG是卤素,优选地是溴或碘或假卤素,例如C1-4卤代烷基磺酸酯,尤其是三氟甲磺酸酯)和具有式IIe的化合物(其中G1、G2、G3、G4和G5是如上所定义的,并且其中R”’是C1-C4烷基)之间的施蒂勒(Stille)反应来制备。三烷基锡官能团-Sn(R”’)3优选地是三-正-丁基锡或三-甲基-锡。此类施蒂勒反应通常是在钯催化剂(例如四(三苯基膦)钯(0)或双(三苯基膦)二氯钯(II))的存在下,在惰性溶剂(如N,N-二甲基甲酰胺、乙腈、甲苯或二噁烷)中,任选地在添加剂(如氟化铯或氯化锂)的存在下,并任选地在另外的催化剂(例如碘化亚铜(I))的存在下进行。这样的施蒂勒偶联也是本领域技术人员熟知的,并且已经描述于例如J.Org.Chem.[有机化学杂志],2005,70,8601-8604,J.Org.Chem.[有机化学杂志],2009,74,5599-5602,以及Angew.Chem.Int.Ed.[应用化学国际版本],2004,43,1132-1136中。
具有式IIIa的化合物
(其中R8和R7是如以上在式I下所定义的,并且其中LG是卤素(优选地是溴或碘),并且其中R9优选地是氢)是新颖的并且被特别研发用于本发明的具有式I的化合物的制备。因此具有式IIIa的化合物构成了本发明的另一个目的。对于具有式I的化合物的优选的取代基定义也适用于具有式IIIa的化合物。
具有式III的化合物(其中R8、R9和R7是如上所定义的并且其中LG是卤素,优选地是溴或碘)
可以通过使具有式IV的化合物(其中R8、R9和R7是如上所定义的)与试剂例如N-氯代琥珀酰亚胺(NCS)、N-溴代琥珀酰亚胺(NBS)或N-碘代琥珀酰亚胺(NIS)、或可替代地,氯、溴或碘反应来制备。如例如K.G.Holden等人,J.Org.Chem.[有机化学杂志]2002,67,5913-5918中所描述的,在惰性溶剂(如氯仿、四氯化碳、1,2-二氯乙烷、乙酸、醚类、乙腈或N,N-二甲基甲酰胺)中,在25-200℃之间的温度(优选地是25-100℃)下进行此类卤化反应。
具有式IVa的化合物
(其中R8和R7是如以上在式I下所定义的,并且其中R9优选地是氢),是新颖的并且被特别研发用于本发明的具有式I的化合物的制备。因此具有式IVa的化合物构成了本发明的另一个目的。对于具有式I的化合物的优选的取代基定义也适用于具有式IVa的化合物。
具有式III和IV的化合物(其中R8、R9、R7和LG是如以上所定义的并且其中X是SO(亚砜)和/或SO2(砜))的亚组,可以通过具有式III或IV的化合物对应的硫化物(其中X是S(硫化物))的氧化反应的方法来获得,涉及使用在其他氧化剂中的试剂如,例如间氯过氧苯甲酸(mCPBA)、过氧化氢、过硫酸氢钾、高碘酸钠、次氯酸钠或次氯酸叔丁酯。该氧化反应通常是在溶剂的存在下进行的。待用于该反应的溶剂的实例包括脂族卤代烃,如二氯甲烷和氯仿;醇类,如甲醇和乙醇;乙酸;水;及其混合物。用于该反应的氧化剂的量通常是1至3摩尔(优选地是1至1.2摩尔),相对于1摩尔的化合物III或IV的硫化物,以产生亚砜化合物III或IV,并且优选地是2至2.2摩尔的氧化剂,相对于1摩尔的化合物III或IV的硫化物,以产生砜化合物III或IV。此类氧化反应例如披露于WO 2013/018928中。
具有式IV的化合物(其中R8、R9和R7是如以上所定义的并且其中X是S(硫化物)),可以通过将具有式V的化合物
(其中R8和R9是如式I中所定义的并且其中R7a是选自由式Q1a至Q2a组成的组的基团:
其中A和Q是如上所定义的,并且其中X10是卤素(优选地氟、氯或溴))与具有式VI的化合物
R1-SH (VI),
或其盐(其中R1是如式I中所定义的),任选地在适合的碱(如碱金属碳酸盐例如碳酸钠和碳酸钾,或碱金属氢化物如氢化钠,或碱金属氢氧化物如氢氧化钠和氢氧化钾)存在下,在惰性溶剂中,在优选地是25-120℃之间的温度下进行反应来制备。待使用的溶剂的实例包括醚,如THF、乙二醇二甲醚、叔丁基甲基醚和1,4-二噁烷;芳香烃,如甲苯和二甲苯;腈,如乙腈;或极性非质子溶剂,如N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基-2-吡咯烷酮或二甲亚砜。具有式VI的化合物的盐的实例包括具有式VIa的化合物
R1-S-M (VIa),
其中R1是如以上定义的并且其中M例如是钠或钾。
具有式V的化合物(其中R8、R9和R7a是如以上定义的),可以通过将具有式VII的化合物
或其盐和/或互变异构体(其中R9和R7a是如以上所描述的),
与具有式VIII的烷基化试剂,
R8-LG2 (VIII)
(其中R8是如以上定义的,并且其中LG2是卤素(尤其是溴或碘),或离去基团OSO2R38(其中R38是任选地被硝基或C1-C3烷基取代的C1-C6烷基、C1-C6卤代烷基、或苯基)(尤其是磺酸酯如甲磺酸酯,三氟甲磺酸酯或甲苯磺酸酯)或硫酸酯(在R8是甲基的具体情况下形成烷基化试剂VIII硫酸二甲酯))进行反应来制备,优选地是在适合的碱(如氢化钠或碳酸钠、碳酸钾或碳酸铯)存在下,在惰性溶剂(如四氢呋喃、二噁烷、乙腈、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基-2-吡咯烷酮或二甲基亚砜)中,在20-150℃之间的温度下。
具有式VII的化合物,或其盐和/或互变异构体(其中R9和R7a是如以上定义的),可以通过以下制备:将具有式IX的腈化合物
R7a-CN (IX),
(其中R7a是如以上所描述的),
顺序地
i)与催化的量(优选地是0.01至0.5当量)的碱如醇盐(优选地是甲醇钠NaOMe或乙醇钠NaOEt),在醇的溶剂(如甲醇或乙醇)中,在0-100℃之间的温度下进行反应,以产生式INT1的酰亚胺中间体(或其盐和/或互变异构体);随后
ii)用例如乙酸或类似的酸对该反应混合物进行酸化,并用式XI的氨基乙缩醛试剂
或其盐(其中RIV是C1-C6烷基并且R9是如以上定义的),在0-150℃之间的温度下进行处理,以产生式INT2的脒乙缩醛中间体(或其盐和/或互变异构体);随后
iii)用例如水性盐酸或类似的酸进行乙缩醛的脱保护,并伴随在0-150℃之间的温度下环化,以形成具有式VII的化合物、或其盐和/或互变异构体。所描述的从具有式IX的化合物制备具有式VII的化合物的过程可以包括中间体INT1和INT2(它们可以作为游离碱或作为盐(例如氢卤化物盐,更具体地是盐酸盐或氢溴酸盐,或任何其他等效的盐)被分离)的分离和纯化,然而该过程作为如例如在M.E.Voss等人,Tetrahedron[四面体]2008,64,645-651中所描述的一锅制备有利地进行。对于R9是氢的具体情况,在方案1中概括了该过程:
方案1
在本领域技术人员已知的条件和Pinner反应变量下,具有式INT1的化合物可以,在醇试剂(如甲醇或乙醇)存在下,优选地在惰性溶剂(如二乙醚,四氢呋喃或二噁烷)中,在-40和50℃之间的温度(优选地是-20和20℃之间)下典型地通过用氢卤化酸(优选地是盐酸)处理具有式IX的化合物替代地制备。
具有式IX的化合物(其中R7a是如以上所描述的)和具有式XI的试剂(其中R9和RIV是如以上所描述的)是已知的化合物或可以通过文献中所述的已知的方法进行制备。
可替代地,具有式I的化合物可以从具有式V的化合物进行制备,包括使用以上所描述的相同的化学过程,但改变这些步骤的顺序。在方案2中概括了该替代的途径。
方案2
具有式IV的化合物的亚组(其中R8和R9是如上所定义的并且其中R7被定义为Q1,其中A、Q、X和R1是如上所定义的)可以被定义为具有式IV-Q1的化合物。可替代地,具有式IV-Q1的化合物(其中X是SO或SO2)
方案3
可以通过铃木反应来制备(方案3),其涉及例如使具有式XII的化合物(其中A、R1、R8和R9是如上所定义的,并且其中X是SO或SO2,并且其中Xa是离去基团,向例如氯、溴或碘(优选溴)、或芳基-或烷基磺酸酯,例如三氟甲磺酸酯)与具有式X的化合物(其中Q是如上所定义的,并且其中Yb1可以是硼衍生的官能团,例如像B(OH)2或B(ORb1)2,其中Rb1可以是C1-C4烷基基团或两个基团ORb1可以与硼原子一起形成五元环,例如像频哪醇硼酸酯)反应。该反应可以被钯基催化剂(例如四(三苯基膦)-钯(0)、(1,1’双(二苯基膦基)二茂铁)二氯-钯-二氯甲烷(1∶1复合物)或氯(2-二环己基膦基-2′,4′,6′-三异丙基-1,1′-二苯基)[2-(2′-氨基-1,1′-二苯基)]钯(II)(XPhos钯环))催化,在碱(像碳酸钠、磷酸三钾或氟化铯)的存在下,在溶剂或溶剂混合物(像例如二噁烷、乙腈、N,N-二甲基甲酰胺、1,2-二甲氧基-乙烷和水的混合物或二噁烷/水的混合物、或甲苯/水的混合物)中,优选地在惰性气氛下进行催化。该反应温度可以优先地在从室温至反应混合物的沸点的范围内,或者该反应可以在微波辐射下进行。这样的铃木反应是本领域普通技术人员熟知的,并且已经综述于例如在J.Orgmet.Chem.[有机金属化学杂志]576,1999,147-168中。
可替代地,具有式IV-Q1的化合物(其中X是SO或SO2)可以通过具有式Xa的化合物(其中Q是如上所定义的,并且其中Yb2是三烷基锡衍生物,优选地是三-正-丁基锡或三-甲基-锡)和具有式XII的化合物(其中A、R1、R8和R9是如上所定义的,并且其中X是SO或SO2,并且其中Xa是离去基团,例如氯、溴或碘(优选溴)或芳基-或烷基磺酸酯,例如三氟甲磺酸酯)之间的施蒂勒反应来制备。此类施蒂勒反应通常是在钯催化剂(例如四(三苯基膦)钯(0)或双(三苯基膦)二氯钯(II))的存在下,在惰性溶剂(如N,N-二甲基甲酰胺、乙腈、甲苯或二噁烷)中,任选地在添加剂(如氟化铯或氯化锂)的存在下,并任选地在另外的催化剂(例如碘化亚铜(I))的存在下进行。这样的施蒂勒偶联也是本领域技术人员熟知的,并且已经描述于例如J.Org.Chem.[有机化学杂志],2005,70,8601-8604,J.Org.Chem.[有机化学杂志],2009,74,5599-5602,以及Angew.Chem.Int.Ed.[应用化学国际版本],2004,43,1132-1136中。
当Q是部分饱和的或完全饱和的五至六元的芳香族环系统(经氮原子连接至含有基团A的环上)时,则具有式IV-Q1的化合物(其中X是SO或SO2)可以从具有式XII的化合物(其中A、R1、R8和R9是如上所定义的,并且其中X是SO或SO2,并且其中Xa是离去基团,像例如氯、溴或碘(优选溴)或芳基-或烷基磺酸酯例如三氟甲磺酸酯)通过与杂环Q-H(其含有适宜的NH官能团)Xaa(其中Q是如上所定义的)在碱(例如碳酸钾K2CO3或碳酸铯Cs2CO3)的存在下,任选地在铜催化剂(例如,碘化亚铜(I))的存在下,在具有或不具有添加剂例如L-脯氨酸、N,N′-二甲基环己烷-1,2-二胺或N,N’-二甲基乙烯-二胺,在惰性溶剂例如N-甲基吡咯烷酮NMP或N,N-二甲基甲酰胺DMF中,在30-150℃的温度下,任选地在微波辐射下反应来制备。下文中,针对杂环Q-H J-30,展示了此类的反应(C-N键形成)(其中J30是如上所定义的)
以给出具有式XII-(J-30)的化合物,其是具有式XII的化合物的特定的亚组,其中A、R1、R8和R9是如在前所定义的。
具有式XII的化合物(其中A、R1、R8和R9是如上所定义的,并且其中X是S(硫化物),并且其中Xa是离去基团,像例如氯、溴或碘(优选溴)或芳基或烷基磺酸酯例如三氟甲磺酸酯)用合适的氧化剂氧化成具有式XII的化合物(其中X是SO或SO2)可以在上面已经描述的条件下实现。
大量的具有式X、Xa和Xaa的化合物是可商购的或可以由本领域技术人员制备。
可替代地,具有式IV-Q1的化合物(其中X是SO或SO2)可以从具有式XII的化合物(其中X是S(硫化物))通过涉及上述的相同化学过程,但是通过改变步骤的顺序(例如通过铃木、施蒂勒或C-N键形成进行XII(X是S)到IV-Q1(X是S)的顺序,随后进行氧化步骤以形成IV-Q1(X是SO或So2))来制备。
在方案3的特定的情况下,当Q是通过氮原子连接至含有基团A的环上的任选地取代的三唑时,则具有式IV-Q1的化合物(其中X是S、SO或So2)可以从具有式XII的化合物(其中A、R1、R8和R9是如上所定义的,并且其中X是S、SO或So2,并且其中Xa是离去基团,像例如氯、溴或碘(优选溴)或芳基-或烷基磺酸酯例如三氟甲磺酸酯)通过与任选地取代的三唑Q-H(其含有适宜的NH官能度)Xaa(其中Q是N-连接的三唑基)在溶剂例如醇(例如,甲醇、乙醇、异丙醇或高沸点的直链或直链醇)、吡啶或乙酸中,任选地在额外的碱(例如,碳酸钾K2CO3或碳酸铯Cs2CO3)的存在下,任选地在铜催化剂(例如碘化亚铜(I))的存在下,在30-180℃的温度下,任选地在微波辐射下反应来制备。
具有式XII的化合物(其中A、R1、R8和R9是如上所定义的,并且其中X是S(硫化物),并且其中Xa是离去基团,例如氯、溴或碘(优选溴)、或芳基或烷基磺酸酯例如三氟甲磺酸酯)可以通过具有式XIII的化合物
或其盐或互变异构体(其中Xa、A、R1和R9是如上所定义的并且其中X是S(硫化物))与具有式VIII的烷基化试剂
R8-LG2 (VIII),
(其中R8是如以上定义的,并且其中LG2是卤素(尤其是溴或碘),或离去基团OSO2R38(其中R38是任选地被硝基或C1-C3烷基取代的C1-C6烷基、C1-C6卤代烷基、或苯基)(尤其是磺酸酯如甲磺酸酯,三氟甲磺酸酯或甲苯磺酸酯)或硫酸酯(在R8是甲基的具体情况下形成烷基化试剂VIII硫酸二甲酯))进行反应来制备,优选地是在适合的碱(如氢化钠或碳酸钠、碳酸钾或碳酸铯)存在下,在惰性溶剂(如四氢呋喃、二噁烷、乙腈、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基-2-吡咯烷酮或二甲基亚砜)中,在20-150℃之间的温度下。
具有式XIII的化合物、或其盐和/或互变异构体(其中Xa、A、R1和R9是如上所定义的,并且其中X是S(硫化物))可以通过以下过程制备:使具有式XIV的腈化合物
(其中Xa、A和R1是如上所定义的,并且其中X是S(硫化物)),
顺序地
i)与催化的量(优选地是0.01至0.5当量)的碱如醇盐(优选地是甲醇钠NaOMe或乙醇钠NaOEt),在醇的溶剂(如甲醇或乙醇)中,在0-100℃之间的温度下进行反应,以产生式INT3的酰亚胺中间体(或其盐和/或互变异构体);随后
ii)用例如乙酸或类似的酸对该反应混合物进行酸化,并用式XI的氨基乙缩醛试剂
或其盐(其中RIV是C1-C6烷基并且R9是如以上定义的),在0-150℃之间的温度下进行处理,以产生式INT4的脒乙缩醛中间体(或其盐和/或互变异构体);随后
iii)用例如水性盐酸或类似的酸进行乙缩醛的脱保护,并伴随在0-150℃之间的温度下环化,以形成具有式XIII的化合物、或其盐和/或互变异构体。所描述的从具有式XIV的化合物制备具有式XIII的化合物的过程可以包括中间体INT3和INT4(它们可以作为游离碱或作为盐(例如氢卤化物盐,更具体地是盐酸盐或氢溴酸盐,或任何其他等效的盐)被分离)的分离和纯化,然而该过程作为如例如在M.E.Voss等人,Tetrahedron[四面体]2008,64,645-651中所描述的一锅制备有利地进行。对于R9是氢的具体情况,在方案4中概括了该过程:
方案4
在本领域技术人员已知的条件和Pinner反应变量下,具有式INT3的化合物可以典型地通过,在醇试剂(如甲醇或乙醇)存在下,优选地在惰性溶剂(如二乙醚,四氢呋喃或二噁烷)中,在-40℃和50℃之间的温度(优选地是-20℃和20℃之间)下用氢卤酸(优选地是盐酸)处理具有式XIV的化合物替代地制备。
具有式XIV的化合物(其中X是S(硫化物),并且其中A、R1和Xa是如上文所定义的)
可以通过使具有式XV的化合物(其中A和Xa是如上所定义的,并且Xb是离去基团,例如像卤素(优选氟、氯或溴)或硝基)与具有式VI的化合物或其盐VIa(其中R1是如在式I中所定义的)任选地在合适的碱(例如,碱性金属碳酸盐,例如碳酸钠和碳酸钾,或碱性金属氢化物,例如氢化钠,或碱性金属氢氧化物,例如氢氧化钠和氢氧化钾)的存在下,任选地在催化剂量的添加剂例如铵盐(例如四丁基溴化铵TBAB)的存在下,在惰性溶剂中,在优选25-120℃的温度下反应来制备。使用的溶剂的实例包括醚,如THF、乙二醇二甲醚、叔丁基甲基醚和1,4-二噁烷;芳香烃,如甲苯和二甲苯;腈,如乙腈;极性非质子溶剂,如N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基-2-吡咯烷酮或二甲亚砜;或水。具有式VI的化合物的盐的实例包括具有式VIa的化合物
R1-S-M (VIa),
其中R1是如以上定义的并且其中M例如是钠或钾。
具有式IV-Q1的化合物(其中X是S、SO或SO2,并且其中A、Q、R8、R9和R1是如上所定义的)
可以通过铃木反应来替代地制备,该反应涉及例如,使具有式XV的化合物(或类似的硼酸或酯)(其中A、R1、R8和R9是如上所定义的,并且其中X是S、SO或SO2)与具有式XVI的化合物(其中Q是如上所定义的并且其中Xc是离去基团,像例如氯、溴或碘(优选溴)、或芳基-或烷基磺酸酯例如三氟甲磺酸酯)反应。该反应可以被钯基催化剂(例如四(三苯基膦)-钯(0)、(1,1’双(二苯基膦基)二茂铁)二氯-钯-二氯甲烷(1∶1复合物)或氯(2-二环己基膦基-2′,4′,6′-三异丙基-1,1′-二苯基)[2-(2′-氨基-1,1′-二苯基)]钯(II)(XPhos钯环))催化,在碱(像碳酸钠、碳酸钾、磷酸三钾或氟化铯)的存在下,在溶剂或溶剂混合物(像例如二噁烷、乙腈、N,N-二甲基甲酰胺、二甲亚砜、1,2-二甲氧基-乙烷和水的混合物或二噁烷/水的混合物、或甲苯/水、或二甲亚砜/水的混合物)中,优选地在惰性气氛下进行催化。该反应温度可以优先地在从室温至反应混合物的沸点的范围内,或者该反应可以在微波辐射下进行。这样的铃木反应是本领域普通技术人员熟知的,并且已经综述于例如在J.Orgmet.Chem.[有机金属化学杂志]576,1999,147-168中。
当Q是半饱和或全部饱和的五至六元芳香族环系统(经氮原子连接至含有基团A的环)时,则具有式IV-Q1的化合物(其中X是S、SO或SO2)可以从具有式XV的化合物(其中A、R1、R8和R9是如上所定义的,并且其中X是S、SO或SO2)通过与杂环Q-H(其含有适宜的NH官能团)Xaa(其中Q是如上所定义的)反应来制备。该反应(又称为Chan-Lam偶联(P.Y.S.Lam,C.G.Clark,S.Saubem,J.Adams,M.P.Winters,D.M.T.Chan,A.Combs,Tetrahedron Lett.[四面体快报]1998,39,2941)通常在一至两当量的铜衍生物(例如乙酸铜(II))的存在下并且在含氧气氛下,用一至两当量的碱(如吡啶或三乙胺)进行。该反应可以在惰性溶剂(如二氯甲烷、二噁烷或二甲基甲酰胺)中,通常在室温或约室温下进行。
具有式XV的化合物(其中A、R1、R8和R9是如上所定义的,并且其中X是S、SO或SO2)可以通过使具有式XII的化合物(其中A、R1、R8和R9是如上所定义的,并且X是S、SO或SO2,并且其中Xa是离去基团,像例如氯、溴或碘(优选溴)、或芳基或烷基磺酸酯例如三氟甲磺酸酯)与双频哪醇乙硼烷(Bpin)2在钯催化下反应来制备。此类频哪醇硼酸酯官能团的引入可以在非质子溶剂(如二噁烷或二甲亚砜)中,在碱(优选地弱碱如乙酸钾KOAc)的存在下进行。[1,1′-双(二苯基膦基)二茂铁]二氯化钯(II)(也称为二氯化钯dppf或Pd(dppf)Cl2)是用于这类反应的常见催化剂。该反应温度优选地在0℃与反应混合物的沸点之间进行,或者该反应可以在微波辐射下进行。
所述2-步骤法从具有式XII的化合物制备具有式IV-Q1的化合物可以包括分离和任选的纯化具有式XV的中间体,然而该方法也作为一锅制备(例如,作为一锅二步骤法)有利地进行。
具有式I的化合物的亚组(其中R8、R9、G1、G2、G3、G4和G5是如上所定义的并且其中R7被定义为Q1,其中A、Q、X和R1是如上所定义的)可以被定义为具有式I-Q1的化合物。相似地,具有式III的化合物的亚组(其中R8、R9和LG是如上所定义的并且其中R7被定义为Q1,其中A、Q、X和R1是如上所定义的)可以被定义为具有式III-Q1的化合物。在又一制备方法中,具有式I-Q1的化合物(其中X是SO或SO2)
(a)铃木反应:Pd催化(例如,Pd(PPh3)4)或Pd(dppf)Cl2),碱(例如,Na2CO3),溶剂(例如,1,2-二甲氧基乙烷/水),25-180℃。
(b)施蒂勒反应:Pd催化(例如,Pd(PPh3)4)或Pd(PPh3)Cl2),溶剂(例如,甲苯),25-180℃。
(c)C-N键形成:碱(例如,K2CO3或Cs2CO3),任选的存在铜,任选的添加剂(例如N,N’-二甲基乙烯-二胺),溶剂(例如,N,N-二甲基甲酰胺DMF或N-甲基吡咯烷酮NMP),25-180℃。
可以从具有式XII的化合物(其中A、R1、R8和R9是如上所定义的,并且X是SO或SO2,并且其中Xa是离去基团,例如像氯、溴或碘(优选溴)、或芳基或烷基磺酸酯例如三氟甲磺酸酯)通过中间体化合物XVII和化合物III-Q1来制备,涉及如上所述的相同的化学过程和相同的试剂,但是改变步骤的顺序。具有式XII、III-Q1、II或IIe、X、Xa或Xaa、和I-Q1的化合物的任一个的取代基定义如上所述。具有式XVII的化合物(其中X是SO或SO2)具有R8、R9以及A、Xa和R1与在具有式XII的化合物中相同地定义并且LG被定义为卤素,优选地是溴或碘。
所述2-步骤法从具有式I-Q1的化合物制备具有式XVII的化合物可以包括分离和任选的纯化具有式III-Q1的中间体,然而该方法也作为一锅制备(例如,作为一锅二步骤法)有利地进行。
具有式XVIII的化合物
其中
R8、A、X和R1是如上文在式I下定义的;
FG是氢或卤素;优选地是氢、溴或碘;
R9优选地是氢;并且
Xa是氯、溴或碘;优选地是溴或碘,
是新颖的,并且是为了制备根据本发明的具有式I的化合物而特别研发的。因此具有式XVIII的化合物构成了本发明的另一个目的。对于具有式I的化合物的优选的取代基定义也适用于具有式XVIII的化合物。
这些反应物可以在碱的存在下进行反应。适合的碱的实例是碱金属或碱土金属氢氧化物、碱金属或碱土金属氢化物、碱金属或碱土金属酰胺、碱金属或碱土金属醇盐、碱金属或碱土金属乙酸盐、碱金属或碱土金属碳酸盐、碱金属或碱土金属二烷基酰胺或碱金属或碱土金属烷基甲硅烷基酰胺、烷基胺、亚烷基二胺、游离的或N-烷基化的饱和或不饱和的环烷基胺、碱性杂环、氢氧化铵以及碳环胺。可以提及的实例是氢氧化钠、氢化钠、氨基钠、甲醇钠、乙酸钠、碳酸钠、叔丁醇钾、氢氧化钾、碳酸钾、氢化钾、二异丙氨基锂、双(三甲基硅烷基)酰胺钾、氢化钙、三乙胺、二异丙基乙胺、三亚乙基二胺、环己胺、N-环己基-N,N-二甲胺、N,N-二乙苯胺、吡啶、4-(N,N-二甲氨基)吡啶、奎宁环、N-甲基吗啉、苄基三甲基铵氢氧化物以及1,8-二氮杂二环[5.4.0]十一-7-烯(DBU)。
这些反应物可以按照原样彼此进行反应,即:不用加入溶剂或稀释剂。然而,在大多数情况下,添加惰性溶剂或稀释剂或这些的混合物是有利的。如果该反应在碱的存在下进行,那么这些过量使用的碱(如三乙胺、吡啶、N-甲基吗啉或N,N-二乙苯胺)还可以充当溶剂或稀释剂。
该反应有利地是在从约-80℃到约+140℃,优选从约-30℃到约+100℃,在许多情况下在介于环境温度与约+80℃之间的温度下进行。
具有式I的化合物能以本身已知的方法转化为另一种具有式I的化合物,这是通过以常规方式将该起始的具有式I的化合物的一个或多个取代基用根据本发明的另一个或其他的一个或多个取代基的替代来实现的。
取决于所选的适合各自情况的反应条件以及起始材料,有可能例如,在一个反应步骤中仅将一个取代基用根据本发明的另一个取代基替代,或者在同一个反应步骤中可以将多个取代基用多个根据本发明的其他取代基来替代。
具有式I的化合物的盐能以本身已知的方式进行制备。因此,例如,具有式I的化合物的酸加成盐是通过用适合的酸或合适的离子交换试剂进行处理来获得的,并且与碱的盐是通过用适合的碱或用合适的离子交换试剂进行处理来获得的。
具有式I的化合物的盐能以常规方式转化为游离的化合物I、酸加成盐(例如通过用合适的碱性化合物或用合适的离子交换试剂进行处理)以及碱盐(例如通过用合适的酸或用合适的离子交换试剂进行处理)。
具有式I的化合物的盐能以本身已知的方式转化为具有式I的化合物的其他盐、酸加成盐,例如转变成为其他酸加成盐,例如通过在合适的溶剂中用酸的合适的金属盐(比如钠、钡或银盐,例如用乙酸银)来处理无机酸的盐(比如盐酸盐),在该溶剂中,所形成的无机盐(例如氯化银)是不溶的并且因此从该反应混合物中沉淀出。
取决于程序或反应条件,具有成盐特性的这些具有式I的化合物能以游离形式或盐的形式获得。
根据分子中存在的不对称碳原子的数目、绝对和相对构型和/或根据分子中存在的非芳香族双键的构型,在每种情况下为游离形式或为盐形式的具有式I的化合物和适当时其互变异构体可以可能的异构体之一的形式或作为其混合物存在,例如以纯异构体的形式,如对映体和/或非对映体,或作为异构体混合物,如对映异构体混合物,例如外消旋体、非对映体混合物或外消旋体混合物存在;本发明涉及纯异构体以及所有可能的异构体混合物,并且在上文和下文中都应如此理解,即使立体化学细节未在所有情况下明确提及。
处于游离形式或处于盐形式的具有式I的化合物的非对映异构体混合物或外消旋体混合物(它们的获得可以取决于已选定的起始材料和程序)能够在这些组分的物理化学差异的基础上,例如通过分步结晶、蒸馏和/或层析法以已知的方式分离成纯的非对映异构体或外消旋体。
能够以类似方式获得的对映异构体混合物(例如外消旋体)可以通过已知方法拆分成光学对映体,例如通过从光学活性溶剂再结晶;通过在手性吸附剂上的层析法,例如在乙酰纤维素上的高效液相层析法(HPLC);借助于合适的微生物,通过用特异性固定化酶裂解;通过形成包含化合物,例如使用手性冠醚,其中仅一个对映异构体被络合;或通过转化成非对映异构盐,例如通过使碱性最终产物外消旋体与光学活性酸(例如羧酸,例如樟脑酸、酒石酸或苹果酸或磺酸,例如樟脑磺酸)反应,并且分离能够以此方式获得的非对映异构体混合物,例如基于其不同溶解度通过分步结晶,从而获得非对映异构体,从这些非对映异构体可以通过合适的试剂(例如碱性试剂)的作用使所希望的对映异构体变成游离。
纯的非对映异构体或对映异构体能根据本发明来获得,不仅是通过分离合适的异构体混合物,还可以是通过普遍已知的非对映立体选择性或对映选择性合成的方法,例如通过根据本发明利用合适的立体化学的起始材料进行该方法。
可以通过使具有式I的化合物与适合的氧化剂(例如H2O2/尿素加合物)在酸酐(例如三氟乙酸酐)的存在下进行反应来制备N-氧化物。这样的氧化例如从以下文献中已知:J.Med.Chem.,32(12),2561-73,1989[药物化学杂志,32(12),2561-73,1989]或WO 00/15615。
有利的是在每一情况中分离或合成生物学地更有效的异构体,例如对映异构体或非对映异构体或异构体混合物,例如对映异构体混合物或非对映异构体混合物,如果个别组分具有不同的生物活性。
具有式I的化合物和适当时其互变异构体(在每种情况下处于游离形式或处于盐形式)如果适当的话还能以水合物的形式获得和/或包括其他溶剂,例如可以用于使以固体形式存在的化合物结晶的那些。
根据以下表1到6所述的化合物可以根据上述方法来制备。随后的这些实例旨在说明本发明并且展示优选的具有式I的化合物。
表1:该表披露了具有式I-1a的36种化合物1.001至1.036:
其中X1是S,并且QRx、R11、G1、G2、G3、G4和G5是如以下定义的:
表1:
以及表1的化合物的N-氧化物。
表2:该表披露了具有式I-1a的36种化合物2.001至2.036,其中X1是SO,并且QRx、R11、G1、G2、G3、G4和G5是如表1中所定义的。
表3:该表披露了具有式I-1a的36种化合物3.001至3.036,其中X1是SO2,并且QRx、R11、G1、G2、G3、G4和G5是如表1中所定义的。
表4:该表披露了具有式I-2a的4种化合物4.001至4.004:
其中X2是S,并且QRx、R12、G1、G2、G3、G4和G5是如以下定义的:
表4:
以及表4的化合物的N-氧化物。
表5:该表披露了具有式I-2a的4种化合物5.001至5.004,其中X1是SO,并且QRx、R12、G1、G2、G3、G4和G5是如表4中所定义的。
表6:该表披露了具有式I-2a的4种化合物6.001至6.004,其中X1是SO2,并且QRx、R12、G1、G2、G3、G4和G5是如表4中所定义的。
根据本发明的具有式I的化合物在有害生物控制领域中是有预防和/或治疗价值的活性成分,即使是在低的施用量下,它们具有非常有利的杀生物谱并且是温血物种、鱼以及植物良好耐受的。根据本发明的这些活性成分作用于正常敏感的以及还有抗药的动物有害生物(如昆虫或蜱螨目的代表)的所有的或个别的发育阶段。根据本发明的活性成分的杀昆虫或杀螨活性可以本身直接显示,亦即或者立即或者仅在过去一些时间之后(例如在蜕皮期间)发生破坏害虫;或间接显示,例如降低产卵和/或孵化率,对应于至少50%到60%的破坏率(死亡率)的良好活性。
上述动物有害生物的实例是:
来自蜱螨目,例如
下毛瘿螨属(Acalitus spp.)、针刺瘿螨属(Aculus spp)、窄瘿螨属(Acaricalusspp.)、瘤瘿螨属(Aceria spp.)、粗脚粉螨(Acarus siro)、钝眼蜱属(Amblyomma spp.)、锐缘蜱属(Argas spp.)、牛蜱属(Boophilus spp.)、短须螨属(Brevipalpus spp.)、苔螨属(Bryobia spp)、上三节瘿螨属(Calipitrimerus spp.)、皮螨属(Chorioptes spp.)、鸡皮刺螨(Dermanyssus gallinae)、表皮螨属(Dermatophagoides spp)、始叶螨属(Eotetranychus spp)、瘿螨属(Eriophyes spp.)、半跗线螨属(Hemitarsonemus spp)、璃眼蜱属(Hyalomma spp.)、硬蜱属(Ixodes spp.)、小爪螨属(Olygonychus spp)、钝缘蜱属(Ornithodoros spp.)、侧多食跗线螨(Polyphagotarsone latus)、全爪螨属(Panonychusspp.)、桔芸锈螨(Phyllocoptruta oleivora)、植食螨(Phytonemus spp.)、跗线螨属(Polyphagotarsonemus spp)、痒螨属(Psoroptes spp.)、扇头蜱属(Rhipicephalusspp.)、根嗜螨属(Rhizoglyphus spp.)、疥螨属(Sarcoptes spp.)、狭跗线螨属(Steneotarsonemus spp)、跗线属(Tarsonemus spp.)以及叶螨属(Tetranychus spp.);
来自虱目,例如
血虱属、长颚虱属、人虱、天疱疮属和木虱;
来自鞘翅目,例如
缺隆叩甲属(Agriotes spp.)、欧洲鳃角金龟(Amphimallon majale)、东方异丽金龟(Anomala orientalis)、花象属(Anthonomus spp.)、蜉金龟属(Aphodius spp)、玉米拟花萤(Astylus atromaculatus)、Ataenius属、甜菜隐食甲(Atomaria linearis)、甜菜胫跳甲(Chaetocnema tibialis)、萤叶甲属(Cerotoma spp)、单叶叩甲属(Conoderus spp)、根颈象属(Cosmopolites spp.)、绿金龟(Cotinisnitida)、象虫属(Curculio spp.)、圆头犀金龟属(Cyclocephala spp)、圆头犀金龟属(Dermestes spp.)、根萤叶甲属(Diabroticaspp.)、阿根廷兜虫(Diloboderus abderus)、食植瓢虫属(Epilachna spp.)、Eremnus属、黑异爪蔗金龟(Heteronychus arator)、咖啡果小蠹(Hypothenemus hampei)、Lagriavilosa、马铃薯甲虫(Leptinotarsa decemLineata)、稻水象属(Lissorhoptrus spp.)、Liogenys属、Maecolaspis属、栗色绒金龟(Maladera castanea)、美洲叶甲亚种(Megascelis spp)、油菜花露尾甲(Melighetes aeneus)、金龟属(Melolontha spp.)、Myochrous armatus、锯谷盗属(Orycaephilus spp.)、耳喙象属(Otiorhynchus spp.)、鳃角金龟属(Phyllophaga spp)、斑象属(Phlyctinus spp.)、丽金龟属(Popillia spp.)、油菜跳甲属(Psylliodes spp.)、Rhyssomatus aubtilis、劫根蠹属(Rhizopertha spp.)、金龟子科(Scarabeidae)、米象属(Sitophilus spp.)、麦蛾属(Sitotroga spp.)、伪切根虫属(Somaticus spp)、Sphenophorus属、大豆茎象(Sternechus subsignatus)、拟步行虫属(Tenebrio spp.)、拟谷盗属(Tribolium spp.)以及斑皮蠹属(Trogoderma spp.);
来自双翅目,例如
伊蚊属(Aedes spp.)、疟蚊属(Anopheles spp)、高梁芒蝇(Antherigonasoccata.)、橄榄果实蝇(Bactrocea oleae)、花园毛蚊(Bibio hortulanus)、迟眼蕈蚊属(Bradysia spp.)、红头丽蝇(Calliphora erythrocephala)、小条实蝇属(Ceratitisspp.)、金蝇属(Chrysomyia spp.)、库蚊属(Culex spp.)、黄蝇属(Cuterebra spp.)、寡鬃实蝇属(Dacus spp.)、地种蝇属(Delia spp)、黑腹果蝇(Drosophilamelanogaster)、厕蝇属(Fannia spp.)、胃蝇属(Gastrophilus spp.)、Geomyza tripunctata、舌蝇属(Glossinaspp.)、皮蝇属(Hypoderma spp.)、虱蝇属(Hyppobosca spp.)、斑潜蝇属(Liriomyzaspp.)、绿蝇属(Lucilia spp.)、潜蝇属(Melanagromyza spp.)、家蝇属(Musca spp.)、狂蝇属(Oestrus spp.)、瘿蚊属(Orseolia spp.)、瑞典麦秆蝇(Oscinella frit)、藜泉蝇(Pegomyia hyoscyami)、草种蝇属(Phorbia spp.)、绕实蝇属(Rhagoletis spp)、Riveliaquadrifasciata、Scatella属、蕈蚊属(Sciara spp.)、刺蝇属(Stomoxys spp.)、虻属(Tabanus spp.)、绦虫属(Tannia spp.)以及大蚊属(Tipula spp.);
来自半翅目,例如
瘤缘蝽(Acanthocoris scabrator)、绿蝽属、苜蓿盲蝽、Amblypeltanitida、海虾盾缘蝽(Bathycoelia thalassina)、土长蝽属、臭虫属、Clavigralla tomentosicollis、盲蝽属(Creontiades spp.)、可可瘤盲蝽、Dichelops furcatus、棉红蝽属、Edessa属、美洲蝽属(Euchistus spp.)、六斑菜蝽(Eurydema pulchrum)、扁盾蝽属、茶翅蝽、具凹巨股长蝽(Horciasnobilellus)、稻缘蝽属、草盲蝽属、热带硕蚧属、卷心菜斑色蝽(Murgantiahistrionic)、Neomegalotomus属、烟盲蝽(Nesidiocoris tenuis)、绿蝽属、拟长蝽(Nysiussimulans)、Oebalus insularis、皮蝽属、壁蝽属、红猎蝽属、可可盲蝽象、Scaptocoriscastanea、黑蝽属(Scotinophara spp.)、Thyanta属、锥鼻虫属、木薯网蝽(Vatigailludens);
无网长管蚜属、Adalges spp.、Agalliana ensigera、Agonoscena targionii、粉虱属(Aleurodicus spp.)、Aleurocanthus spp.、甘蔗穴粉虱、软毛粉虱(Aleurothrixusfloccosus)、甘蓝粉虱(Aleyrodes brassicae)、棉叶蝉(Amarasca biguttula)、Amritodusatkinson、肾圆盾蚧属、蚜科、蚜属、蚧属(Aspidiotus spp.)、茄沟无网蚜、Bactericeracockerelli、小粉虱属、Brachycaudus spp.、甘蓝蚜、喀木虱属、双尾蚜(Cavariellaaegopodii Scop.)、蜡蚧属、褐圆蚧、网籽草叶圆蚧、Cicadella spp.、大白叶蝉(Cofanaspectra)、隐瘤蚜属、Cicadulina spp.、褐软蚧、玉米黄翅叶蝉、裸粉虱属、柑橘木虱、麦双尾蚜、西圆尾蚜属、小绿叶蝉属、苹果绵蚜、葡萄斑叶蝉属、蜡蛤属、赤桉木虱(Glycaspisbrimblecombei)、菜缢管蚜、Hyalopterus spp.、超瘤蚜种、檬果绿叶蝉(Idioscopusclypealis)、Jacobiasca lybica、灰飞虱属、球坚蚧、蛎盾蚧属、萝卜蚜(Lopaphiserysimi)、Lyogenys maidis、长管蚜属、Mahanarva spp.、蛾蜡蝉科(Metcalfa pruinosa)、麦无网蚜、Myndus crudus、瘤蚜属、台湾韭蚜、黑尾叶蝉属、褐飞虱属(Nilaparvata spp.)、梨大绿蚜、Odonaspis ruthae、寄生甘蔗绵蚜、杨梅缘粉虱、考氏木虱、片盾蚧属、瘿绵蚜属、玉米蜡蝉、扁角飞虱属、忽布疣蚜、根瘤蚜属、动性球菌属、白盾蚧属、粉蚧属、棉盲蝽(Pseudatomoscelis seriatus)、木虱属、棉蚧(Pulvinaria aethiopica)、笠圆盾蚧属、Quesada gigas、电光叶蝉(Recilia dorsalis)、缢管蚜属、黑盔蚧属、带叶蝉属、二叉蚜属、麦蚜属(Sitobion spp.)、白背飞虱、Spissistilus festinus、条斑飞虱(TarophagusProserpina)、声蚜属、粉虱属、Tridiscus sporoboli、葵粉蚧属(Trionymus spp.)、非洲木虱、桔矢尖蚧、Zygina flammigera、Zyginidia scutellaris;
来自膜翅目,例如
顶切叶蚁属(Acromyrmex)、三节叶蜂属(Arge spp.)、布切叶白蚁属(Atta spp.)、茎叶蜂属(Cephus spp.)、松叶蜂属(Diprion spp.)、锯角叶蜂科(Diprionidae)、松叶蜂(Gilpinia polytoma)、梨实蜂属(Hoplocampa spp.)、毛蚁属(Lasius spp.)、小黄家蚁(Monomorium pharaonis)、新松叶蜂属(Neodiprion spp.)、农蚁属(Pogonomyrmex spp)、Slenopsis invicta、水蚁属(Solenopsis spp.)以及胡蜂属(Vespa spp.);
来自等翅目,例如
家白蚁属、白蚁(Corniternes cumulans)、楹白蚁属、大白蚁属、澳白蚁属、小白蚁属、散白蚁属;热带火蚁
来自鳞翅目,例如
长翅卷蛾属、褐带卷蛾属、透翅蛾属、地夜蛾属、棉叶虫、Amylois spp.、黎豆夜蛾、黄卷蛾属、银蛾属(Argyresthia spp.)、带卷蛾属、丫纹夜蛾属、棉潜蛾、玉米楷夜蛾、粉斑螟蛾、桃蛀果蛾、禾草螟属、卷叶蛾属、越蔓枯草螟(Chrysoteuchia topiaria)、葡萄果蠹蛾、卷叶螟属、云卷蛾属、纹卷蛾属、鞘蛾属、磷翅目粉蝶、Cosmophila flava、草螟属、大菜螟、苹果异形小卷蛾、黄杨木蛾、小卷蛾属、黄杨绢野螟、杆草螟属、苏丹棉铃虫、金刚钻属、非洲茎螟、粉螟属、叶小卷蛾属(Epinotia spp)、细斑灯蛾、Etiella zinckinella、花小卷蛾属、环针单纹蛾、黄毒蛾属、切根虫属、Feltia jaculiferia、Grapholita spp.、绿青虫蛾、实夜蛾属、菜螟、切叶野螟属(Herpetogramma spp)、美国白蛾、番茄蠹蛾、Lasmopalpuslignosellus、旋纹潜叶蛾、潜叶细蛾属、葡萄花翅小卷蛾、Loxostege bifidalis、毒蛾属、潜蛾属、幕枯叶蛾属、甘蓝夜蛾、烟草天蛾、Mythimna spp、夜蛾属、秋尺蛾属、Orniodesindica、欧洲玉米螟、超小卷蛾属、褐卷蛾属、小眼夜蛾、蛀茎夜蛾、Pectinophora gossypi-ela、咖啡潜叶蛾、一星黏虫、马铃薯麦蛾、菜粉蝶、粉蝶属、小菜蛾、芽蛾属、尺叶蛾属、薄荷灰夜蛾、西方豆地香(Richia albicosta)、白禾螟属(Scirpophaga spp.)、蛀茎夜蛾属、长须卷蛾属、灰翅夜蛾属、棉大卷叶螟、兴透翅蛾属、异舟蛾属、卷叶蛾属、粉纹夜蛾、番茄斑潜蝇、以及巢蛾属
来自食毛目,例如
畜虱属(Damalinea spp.)和啮毛虱属;
来自直翅目,例如
蠊属、小蠊属、蝼蛄属、马德拉蜚蠊、飞蝗属、北痣蟋蟀(Neocurtillahexadactyla)、大蠊属、痣蟋蟀属(Scapteriscus spp.)、以及沙漠蝗属;
来自啮虫目,例如
虱啮属(Liposcelis spp.);
来自蚤目,例如
角叶蚤属、栉头蚤属和开皇客蚤;
来自缨翅目,例如
Calliothrips phaseoli、花蓟马属、阳蓟马属、褐带蓟马属、单亲蓟马属(Parthenothrips spp.)、非洲桔硬蓟马(Scirtothrips aurantii)、大豆蓟马(Sericothrips variabilis)、带蓟马属、蓟马属;
来自缨尾目,例如衣鱼(Lepisma saccharina)。
根据本发明的活性成分可用于控制、也就是遏制或破坏上述类型的有害生物,这些有害生物特别出现在植物上,尤其是在农业中、在园艺中以及在林业中的有用的植物和观赏植物上,或者在这些植物的器官上,例如果实、花、叶、茎、块茎或根,并且在一些情况下,甚至在一个随后的时间点形成的植物器官仍保持受保护抵抗这些有害生物。
适宜的目标作物具体是,谷物,如小麦、大麦、黑麦、燕麦、稻、玉米或高梁;甜菜,如糖用甜菜或饲料甜菜;水果,例如梨果、核果或无核小果,如苹果、梨、李子、桃、杏、樱桃或浆果,例如草莓、覆盆子或黑莓;豆科作物,如菜豆、小扁豆、豌豆或大豆;油料作物,如油菜、芥菜、罂粟、橄榄、向日葵、椰子、蓖麻、可可豆或落花生;瓜类作物,如南瓜、黄瓜或甜瓜;纤维植物,如棉花、亚麻、大麻或黄麻;柑橘类水果,如橙子、柠檬、葡萄柚或橘子;蔬菜,如菠菜、莴苣、芦笋、卷心菜、胡萝卜、洋葱、番茄、马铃薯或灯笼椒;樟科,如鳄梨、肉桂或樟脑;以及还有烟草、坚果、咖啡、茄子、甘蔗、荼、胡椒、葡萄藤、蛇麻草、车前草科以及乳胶植物。
本发明的组合物和/或方法还可以用在任何观赏植物和/或蔬菜作物(包括花、灌木、阔叶树和常绿植物)上。
例如,本发明可以用在任何以下观赏植物物种上:藿香蓟属、假面花属(Alonsoaspp.)、银莲花属、南非葵、春黄菊属、金鱼草属、紫菀属、秋海棠属(例如丽格海棠、四季秋海棠、球根秋海棠(B.tubéreux))、叶子花属、雁河菊属(Brachycome spp.)、芸苔属(观赏植物)、蒲包草属、辣椒、长春花、美人蕉属、矢车菊属、菊属、瓜叶菊属(银叶菊)、金鸡菊属、青锁龙(Crassula coccinea)、火红萼距花(Cuphea ignea)、大丽花属、翠雀属、荷包牡丹、彩虹菊属(Dorotheantus spp.)、洋桔梗、连翘属、倒挂金钟属、鼠曲草老颧草(Geraniumgnaphalium)、大丁草属、千日红、天芥菜属、向日葵属、木槿属、绣球花属、绣球属、嫣红蔓、凤仙花属(非洲凤仙花)、血苋属(Iresines spp.)、伽蓝菜属、马缨丹、三月花葵、狮耳花、百合属、日中花属、沟酸浆属、美国薄荷属、龙面花属、万寿菊属、石竹属(康乃馨)、美人蕉属、酢浆草属、雏菊属、天竺葵属(盾叶天竺葵、马蹄纹天竺葵)、堇菜属(三色堇)、碧冬茄属、草夹竹桃属、香茶菜属(Plecthranthus spp.)、一品红属、爬山虎属(五叶爬山虎、爬山虎)、报春花属、毛茛属、杜鹃花属、蔷薇属(玫瑰)、黄雏菊属、非洲堇属、鼠尾草属、紫扇花(Scaevola aemola)、蛾蝶花(Schizanthus wisetonensis)、景天属、茄属、苏非尼亚矮牵牛属(Surfinia spp.)、万寿菊属、烟草属、马鞭草属、百日草属以及其他花坛植物。
例如,本发明可以用在任何以下蔬菜物种上:葱属(大蒜、洋葱、火葱(A.oschaninii)、韭葱、小葱、大葱)、有喙欧芹、旱芹、芦笋、甜菜、芸苔属(甘蓝、大白菜、芜菁)、辣椒、鹰嘴豆、苦苣、菊苣属(菊苣、苦苣)、西瓜、黄瓜属(黄瓜、甜瓜)、南瓜属(西葫芦、印度南瓜)、菜蓟属(朝鲜蓟、刺苞菜蓟)、胡萝卜、茴香、金丝桃属、莴苣、番茄属(番茄、樱桃番茄)、薄荷属、罗勒、香芹、菜豆属(菜豆、荷包豆)、豌豆、萝卜、食用大黄、迷迭香属、鼠尾草属、黑婆罗门参、茄子、菠菜、新缬草属(莴苣缬草、V.eriocarpa)以及蚕豆。
优选的观赏植物物种包括非洲堇、秋海棠属、大丽花属、大丁草属、绣球属、马鞭草属、蔷薇属、伽蓝菜属、一品红属、紫菀属、矢车菊属、金鸡菊属、翠雀属、美国薄荷属、草夹竹桃属、黄雏菊属、景天属、碧冬茄属、堇菜属、凤仙花属、老鹳草属、菊属、毛茛属、倒挂金钟属、鼠尾草属、绣球花属、迷迭香、鼠尾草、圣约翰草、薄荷、甜椒、番茄和黄瓜。
根据本发明所述的活性成分尤其适合于控制棉花、蔬菜、玉米、水稻以及大豆作物上的扁豆蚜、黄瓜条叶甲、烟芽夜蛾、桃蚜、小菜蛾以及海灰翅夜蛾。根据本发明所述的活性成分另外尤其适合于控制甘蓝夜蛾(优选地在蔬菜上)、苹果蠹蛾(优选地在苹果上)、小绿叶蝉(优选地在蔬菜、葡萄园里)、马铃薯叶甲(优选地在马铃薯上)以及二化螟(优选地在水稻上)。
在另一个方面,本发明还可以涉及控制由植物寄生的线虫(内寄生的-、半内寄生的-以及外寄生的线虫)对植物或其部分引起损害的方法,尤其是以下植物寄生的线虫,如根结线虫(root knot nematodes)、北方根结线虫(Meloidogyne hapla)、南方根结线虫(Meloidogyne incognita)、爪哇根结线虫(Meloidogyne javanica)、花生根结线虫(Meloidogyne arenaria)以及其他根结线虫属种类(Meloidogyne species);孢囊形成线虫(cyst-forming nematodes)、马铃薯金线虫(Globodera rostochiensis)以及其他球孢囊线虫属种类(Globodera species);禾谷孢囊线虫(Heterodera avenae)、大豆胞囊线虫(Heterodera glycines)、甜菜胞囊线虫(Heterodera schachtii)、红三叶异皮线虫(Heterodera trifolii)、以及其他异皮线虫属种类(Heterodera species);种瘿线虫(Seed gall nematodes)、粒线虫属种类(Anguina species);茎及叶面线虫(Stem andfoliar nematodes)、滑刃线虫属种类(Aphelenchoides species);刺毛线虫(Stingnematodes)、长尾刺线虫(Belonolaimus longicaudatus)以及其他刺线虫属种类;松树线虫(Pine nematodes)、松材线虫(Bursaphelenchus xylophilus)以及其他伞滑刃属种类(Bursaphelenchus species);环形线虫(Ring nematodes)、环线虫属种类(Criconemaspecies)、小环线虫属种类(Criconemella species)、轮线虫属种类(Criconemoidesspecies)、中环线虫属种类(Mesocriconema species);茎及鳞球茎线虫(Stem and bulbnematodes)、腐烂茎线虫(Ditylenchus destructor)、鳞球茎茎线虫(Ditylenchusdipsaci)以及其他茎线虫属种类(Ditylenchus species);锥线虫(Awl nematodes)、锥线虫属种类(Dolichodorus species);螺旋线虫(Spiral nematodes)、多头螺旋线虫(Heliocotylenchus multicinctus)以及其他螺旋线虫属种类(Helicotylenchusspecies);鞘及鞘形线虫(Sheath and sheathoid nematodes)、鞘线虫属种类(Hemicycliophora species)以及半轮线虫属种类(Hemicriconemoides species);潜根线虫属种类(Hirshmanniella species);支线虫(Lance nematodes)、冠线虫属种类(Hoploaimus species);假根结线虫(false rootknot nematodes)、珍珠线虫属种类(Nacobbus species);针状线虫(Needle nematodes)、横带长针线虫(Longidoruselongatus)以及其他长针线虫属种类(Longidorus species);大头针线虫(Pinnematodes)、短体线虫属种类(Pratylenchus species);腐线虫(Lesion nematodes)、花斑短体线虫(Pratylenchus neglectus)、穿刺短体线虫(Pratylenchus penetrans)、弯曲短体线虫(Pratylenchus curvitatus)、古氏短体线虫(Pratylenchus goodeyi)以及其他短体线虫属种类(Pratylenchus species);柑桔穿孔线虫(Burrowing nematodes)、香蕉穿孔线虫(Radopholus similis)以及其他内侵线虫属种类(Radopholus species);肾形线虫(Reniform nematodes)、罗柏氏盘旋线虫(Rotylenchus robustus)、肾形盘旋线虫(Rotylenchus reniformis)以及其他盘旋线虫属种类(Rotylenchus species);盾线虫属种类(Scutellonema species);短粗根线虫(Stubby root nematodes)、原始毛刺线虫(Trichodorus primitivus)以及其他毛刺线虫属种类(Trichodorus species)、拟毛刺线虫属种类(Paratrichodorus species);矮化线虫(Stunt nematodes)、马齿苋矮化线虫(Tylenchorhynchus claytoni)、顺逆矮化线虫(Tylenchorhynchus dubius)以及其他矮化线虫属种类(Tylenchorhynchus species);柑桔线虫(Citrus nematodes)、穿刺线虫属种类(Tylenchulus species);短剑线虫(Dagger nematodes)、剑线虫属种类(Xiphinemaspecies);以及其他植物寄生的线虫种类,如亚粒线虫属(Subanguina spp.)、Hypsoperine属、大刺环线虫属(Macroposthonia spp.)、Melinius属、刻点胞囊属(Punctodera spp.)、以及五沟线虫属(Quinisulcius spp.)。
本发明所述的化合物还具有针对软体动物的活性。这些软体动物的实例包括例如苹果螺科;阿勇蛞蝓属(Arion)(灰黑阿勇蛞蝓(A.ater)、环斑阿勇蛞蝓(A.circumscriptus)、庭院阿勇蛞蝓(A.hortensis)、红棕阿勇蛞蝓(A.rufus));巴蜗牛科(灌木巴蜗牛(Bradybaena fruticum));蜗牛属(庭院蜗牛(C.hortensis)、森林蜗牛(C.Nemoralis));ochlodina;灰蛞蝓属(Deroceras)(野灰蛞蝓(D.agrestis)、D.empiricorum、田灰蛞蝓(D.laeve)、庭园灰蛞蝓(D.reticulatum));圆盘螺属(Discus)(D.rotundatus);Euomphalia;土蜗属(Galba)(截形土蜗(G.trunculata));小蜗牛属(Helicelia)(伊塔拉小蜗牛(H.itala)、布维小蜗牛(H.obvia));大蜗牛科Helicigonaarbustorum);Helicodiscus;大蜗牛属(Helix)(开放大蜗牛(H.aperta));蛞蝓属(Limax)(灰黑蛞蝓(L.cinereoniger)、黄蛞蝓(L.flavus)、边缘蛞蝓(L.marginatus)、大蛞蝓(L.maximus)、柔蛞蝓(L.tenellus));椎实螺属(Lymnaea);Milax(M.gagates、M.marginatus、M.sowerbyi);钻螺属(Opeas);瓶螺属(Pomacea)(P.canaticulata);瓦娄蜗牛属(Vallonia)和Zanitoides。
术语“作物”应理解为还包括已经通过使用重组DNA技术而被这样转化使其能够合成一种或多种选择性作用毒素的作物植物,这些毒素如已知,例如来自产毒素的细菌,尤其是芽孢杆菌属的那些。
可以通过此类转基因植物表达的毒素包括例如杀昆虫蛋白,例如来自于蜡样芽孢杆菌或日本甲虫芽孢杆菌的杀昆虫蛋白;或来自于苏云金芽孢杆菌的杀昆虫蛋白,如δ-内毒素,例如Cry1Ab、Cry1Ac、Cry1F、Cry1Fa2、Cry2Ab、Cry3A、Cry3Bb1或Cry9C,或营养期杀虫蛋白(Vip),例如Vip1、Vip2、Vip3或Vip3A;或线虫寄生性细菌的杀虫蛋白,例如光杆状菌属或致病杆菌属,如发光光杆状菌、嗜线虫致病杆菌;由动物产生的毒素,如蝎毒素、蜘蛛毒素、黄蜂毒素和其他昆虫特异性神经毒素;由真菌产生的毒素,如链霉菌毒素;植物凝集素,如豌豆凝集素、大麦凝集素或雪花莲凝集素;凝集素类;蛋白酶抑制剂,如胰蛋白酶抑制剂、丝氨酸蛋白酶抑制剂、马铃薯贮存蛋白(patatin)、半胱氨酸蛋白酶抑制剂、木瓜蛋白酶抑制剂;核糖体失活蛋白(RIP),如蓖麻蛋白、玉米-RIP、相思豆毒蛋白、丝瓜籽毒蛋白、皂草毒素蛋白或异株泻根毒蛋白;类固醇代谢酶,如3-羟基类固醇氧化酶、蜕皮类固醇-UDP-糖基-转移酶、胆固醇氧化酶、蜕皮激素抑制剂、HMG-COA-还原酶,离子通道阻断剂,如钠通道或钙通道阻断剂,保幼激素酯酶,利尿激素受体、茋合酶、联苄合酶、几丁质酶和葡聚糖酶。
在本发明的上下文中,δ-内毒素例如Cry1Ab、Cry1Ac、Cry1F、Cry1Fa2、Cry2Ab、Cry3A、Cry3Bb1或Cry9C,或营养期杀虫蛋白(Vip)例如Vip1、Vip2、Vip3或Vip3A应理解为显然还包括混合型毒素、截短的毒素和经修饰的毒素。混合型毒素是通过那些蛋白的不同结构域的新组合重组产生的(参见例如,WO 02/15701)。截短的毒素例如截短的Cry1Ab是已知的。在经修饰毒素的情况下,天然存在的毒素的一个或多个氨基酸被置换。在这样的氨基酸置换中,优选将非天然存在的蛋白酶识别序列插入毒素中,例如像在Cry3A055的情况下,组织蛋白酶-G-识别序列被插入Cry3A毒素中(参见WO 03/018810)。
这样的毒素或能够合成这样的毒素的转基因植物的实例披露于例如EP-A-0 374753、WO 93/07278、WO 95/34656、EP-A-0427 529、EP-A-451 878以及WO 03/052073中。
用于制备这样的转基因植物的方法对于本领域技术人员是已知的并且描述在例如以上提及的公开物中。CryI型脱氧核糖核酸及其制备例如从WO 95/34656、EP-A-0 367474、EP-A-0401 979以及WO 90/13651中已知。
包括在转基因植物中的毒素使得植物对有害昆虫有耐受性。这样的昆虫可以存在于任何昆虫分类群,但尤其常见于甲虫(鞘翅目)、双翅昆虫(双翅目)和蛾(鳞翅目)。
包含一个或多个编码杀虫剂抗性并且表达一种或多种毒素的基因的转基因植物是已知的并且其中一些是可商购的。此类植物的实例为:(玉米品种,表达Cry1Ab毒素);YieldGard(玉米品种,表达Cry3Bb1毒素);YieldGard(玉米品种,表达Cry1Ab以及Cry3Bb1毒素);(玉米品种,表达Cry9C毒素);(玉米品种,表达Cry1Fa2毒素以及实现对除草剂草丁膦铵的耐受性的酶膦丝菌素N-乙酰转移酶(PAT));(棉花品种,表达Cry1Ac毒素);(棉花品种,表达Cry1Ac毒素);(棉花品种,表达CrylAc和Cry2Ab毒素);(棉花品种,表达Vip3A和Cry1Ab毒素); (马铃薯品种,表达Cry3A毒素);GT Advantage(GA21耐草甘膦性状),CB Advantage(Bt11玉米螟(CB)性状)以及
这样的转基因作物的其他实例是:
1.Bt11玉米,来自先正达种子公司,霍比特路27,F-31 790圣苏维尔,法国,登记号C/FR/96/05/10。遗传修饰的玉蜀黍,通过转基因表达截短的Cry1Ab毒素,使之能抵抗欧洲玉米螟(玉米螟和粉茎螟)的侵袭。Bt11玉米还转基因地表达PAT酶以达到对除草剂草丁膦铵的耐受性。
2.Bt176玉米,来自先正达种子公司,霍比特路27,F-31 790圣苏维尔,法国,登记号C/FR/96/05/10。遗传修饰的玉蜀黍,通过转基因表达Cry1Ab毒素,使之能抵抗欧洲玉米螟(玉米螟和粉茎螟)的侵袭。Bt176玉米还转基因表达PAT酶以实现对除草剂草丁膦铵盐的耐受性。
3.MIR604玉米,来自先正达种子公司,霍比特路27,F-31 790圣苏维尔,法国,登记号C/FR/96/05/10。通过转基因表达经修饰的Cry3A毒素使之具有昆虫抗性的玉米。此毒素是通过插入组织蛋白酶-G-蛋白酶识别序列而经修饰的Cry3A055。此类转基因玉米植物的制备描述于WO 03/018810中。
4.MON 863玉米,来自孟山都欧洲公司(Monsanto Europe S.A.),270-272特弗伦大道(Avenue de Tervuren),B-1150布鲁塞尔,比利时,登记号C/DE/02/9。MON 863表达Cry3Bb1毒素,并且对某些鞘翅目昆虫有抗性。
5.IPC 531棉花,来自孟山都欧洲公司,270-272特弗伦大道,B-1150布鲁塞尔,比利时,登记号C/ES/96/02。
6.1507玉米,来自先锋海外公司(Pioneer Overseas Corporation),特德斯科大道(Avenue Tedesco),7B-1160布鲁塞尔,比利时,登记号C/NL/00/10。遗传改性的玉米,表达蛋白质Cry1F以获得对某些鳞翅目昆虫的抗性,并且表达PAT蛋白质以获得对除草剂草丁膦铵的耐受性。
7.NK603×MON 810玉米,来自孟山都欧洲公司,270-272特弗伦大道,B-1150布鲁塞尔,比利时,登记号C/GB/02/M3/03。通过将遗传修饰的品种NK603和MON810杂交,由常规育种的杂交玉米品种构成。NK603×MON 810玉米转基因地表达由土壤杆菌属菌株CP4获得的蛋白质CP4 EPSPS,使之耐除草剂(含有草甘膦),以及由苏云金芽孢杆菌库尔斯塔克亚种获得的Cry1Ab毒素,使之耐某些鳞翅目昆虫,包括欧洲玉米螟。
抗昆虫的植物的转基因作物还描述于BATS(生物安全与可持续发展中心(Zentrumfür Biosicherheit und Nachhaltigkeit),BATS中心(Zentrum BATS),克拉斯崔舍(Clarastrasse)13,巴塞尔(Basel)4058,瑞士)报告2003(http://bats.ch)中。
术语“作物”应理解为还包括已经通过使用重组DNA技术而被这样转化使其能够合成具有选择性作用的抗病原物质的作物,这些抗病原物质是例如像所谓的“病程相关蛋白”(PRP,参见例如EP-A-0 392 225)。这样的抗病原物质和能够合成这样的抗病原物质的转基因植物的实例例如从EP-A-0 392 225、WO 95/33818和EP-A-0 353 191是已知的。生产这样的转基因植物的方法对于本领域的普通技术人员而言通常是已知的并且描述于例如以上提及的公开物中。
可以由此类转基因植物表达的抗病原物质包括,例如,离子通道阻断剂(例如钠和钙通道阻断剂,像病毒的KP1、KP4或KP6毒素);茋合酶;联苄合酶;几丁质酶;葡聚糖酶;所谓的“病程相关蛋白”(PRPs,参见例如EP-A-0 392 225);由微生物产生的抗病原物质,例如涉及植物病原体防御的肽抗生素或杂环类抗生素(参见例如WO 95/33818)或蛋白质或多肽因子(所谓的“植物疾病抗性基因”,如描述于WO 03/000906中的)。
根据本发明的组合物的其他使用范围是保护所储存的货物和储藏室以及保护原材料,如木材、纺织品、地板或建筑物,以及在卫生领域中,尤其是保护人类、家畜以及多产的牲畜免遭所提及类型的有害生物。
本发明还提供了用于控制害虫(如蚊科和其他的疾病媒介物)的方法;也可参见http://www.who.int/malaria/vector_control/irs/en/)的方法。在一个实施例中,用于控制有害生物的方法包括通过涂刷、滚涂(rolling)、喷雾、涂布或浸渍,向目标有害生物、它们的场所或表面或基质施用本发明的组合物。通过举例,通过本发明的方法预期了表面(如墙、天花板或地板表面)的IRS(室内滞留喷雾)施用。在另一个实施例中,考虑到了将此类组合物施用于如下基底,如无纺或织物材料,该材料处于网织品、被覆物、被褥、窗帘以及帐篷的形式(或可以用于在这些物品的制造中使用)。
在一个实施例中,用于控制这样的有害生物的方法包括向目标有害生物、它们的场所或表面或基质施用杀有害生物有效量的本发明的组合物,以便于在该表面或基质上提供有效的滞留的杀有害生物活性。这样的施用可以通过涂刷、滚涂、喷雾、涂布或浸渍本发明的杀有害生物组合物来进行。通过举例,通过本发明的方法预期了表面(如墙、天花板或地板表面)的IRS施用,以便于在该表面上提供有效的滞留的杀有害生物活性。在另一个实施例中,考虑了施用这样的组合物以用于在基底上的有害生物的残留控制,该基底是如处于网织品、被覆物、被褥、窗帘以及帐篷的形式(或可以用于在这些物品的制造中)的织物材料。
待处理的基质(包括无纺物、织物或网织品)可以由天然纤维,如棉花、拉菲亚树叶纤维、黄麻、亚麻、剑麻、粗麻布或羊毛,或者合成纤维,如聚酰胺、聚酯、聚丙烯、聚丙烯腈等等制成。聚酯是特别适合的。纺织品处理的方法是已知的,例如WO 2008/151984、WO 2003/034823、US 5631072、WO 2005/64072、WO 2006/128870、EP 1724392、WO2005/113886或WO2007/090739。
根据本发明的组合物的其他使用范围是针对所有观赏树木连同所有种类的果树和坚果树的树木注射/树干处理领域。
在树木注射/树干处理领域中,根据本发明的这些化合物特别适合于对抗来自上述的鳞翅目和来自鞘翅目的钻木昆虫,尤其是对抗下表A和B中列出的钻木虫:
表A.具有经济重要性的外来钻木虫的实例.
表B.具有经济重要性的本地钻木虫的实例。
本发明也可以用于控制任何可以存在于草坪草中的昆虫有害生物,包括例如甲虫、毛虫、火蚁、地面珍珠(ground pearl)、千足虫、潮虫、螨虫、蝼蛄、介壳虫、粉蚧蜱、沫蝉、南方麦小蝽以及蛴螬。本发明可以用于控制处于其生命周期的各个阶段的昆虫有害生物,包括卵、幼虫、若虫和成虫。
具体而言,本发明可以用于控制取食草坪草的根部的昆虫有害生物,这些昆虫有害生物包括蛴螬(如圆头犀金龟属(Cyclocephala spp.)(例如蒙面金龟子,C.lurida)、Rhizotrogus属(例如欧洲金龟子,欧洲切根鳃金龟(R.majalis))、黄栌属(Cotinus spp.)(例如绿六月甲虫(Green June beetle),C.nitida)、弧丽金龟属(Popillia spp.)(例如日本甲虫,龟纹瓢虫(P.japonica))、鳃角金龟属(Phyllophaga spp.)(例如五月/六月甲虫)、Ataenius属(例如草坪草黑金龟(Black turfgrass ataenius),A.spretulus)、绒毛金龟属(Maladera spp.)(例如亚洲花园甲虫(Asiatic garden beetle),M.castanea)以及Tomarus属),地面珍珠(硕蚧属(Margarodes spp.)),蝼蛄(褐黄色的、南方的、以及短翅的;痣蟋蟀属(Scapteriscus spp.),非洲蝼蛄(Gryllotalpa africana))以及大蚊幼虫(leatherjackets)(欧洲大蚊(European crane fly),大蚊属(Tipula spp.))。
本发明还可以用于控制茅草住宅的草坪草的昆虫有害生物,这些昆虫有害生物包括粘虫(如秋夜蛾(fall armyworm)草地贪夜蛾(Spodoptera frugiperda),和常见夜蛾一星黏虫(Pseudaletia unipuncta))、切根虫,象鼻虫(尖隐喙象属(Sphenophorus spp.),如S.venatus verstitus和牧草长喙象(S.parvulus))以及草地螟(如草螟属(Crambus spp.)和热带草地螟,Herpetogramma phaeopteralis)。
本发明还可以用于控制在地上生活并取食草坪草叶子的草坪草中的昆虫有害生物,这些昆虫有害生物包括麦小蝽(如南方麦小蝽,南方杆长蝽(Blissus insularis))、狗牙根螨(Bermudagrass mite)(Eriophyes cynodoniensis)、盖氏虎尾草粉蚧(草竹粉蚧(Antonina graminis))、两线沫蝉(Propsapia bicincta)、叶蝉、切根虫(夜蛾科)、以及麦二叉蚜。
本发明还可以用于控制草坪草中的其他有害生物,如在草坪中创建蚁巢的外引红火蚁(红火蚁(Solenopsis invicta))。
在卫生领域中,根据本发明的组合物是有效地对抗外寄生虫如硬蜱、软蜱、疥螨、秋螨、蝇(叮咬和舔舐)、寄生性蝇幼虫,虱、发虱、鸟虱和跳蚤。
这样的寄生虫的实例是:
虱目:血虱属、长颚虱属、人虱属和阴虱属、盲虱属。
食毛目:毛羽虱属、短角鸟虱属、鸭虱属、牛羽虱属、Werneckiella属、Lepikentron属、畜虱属、啮毛虱属以及猫羽虱属。
双翅目及长角亚目和短角亚目,例如伊蚊属、按蚊属、库蚊属、蚋属、真蚋属、白蛉属、罗蛉属、库蠓属、斑虻属、驼背虻属、黄虻属、虻属、麻虻属、Philipomyia属、蜂虱蝇属、家蝇属、齿股蝇属、螫蝇属、黑角蝇属、莫蝇属、厕蝇属、舌蝇属、丽蝇属、绿蝇属、金蝇属、污蝇属、麻蝇属、狂蝇属、皮蝇属、胃蝇属、虱蝇属、羊虱蝇属和蜱蝇属。
蚤目,例如蚤属、栉头蚤属、客蚤属、角叶蚤属。
异翅目,例如臭虫属、锥鼻虫属属、红猎蝽属、锥蝽属。
蜚蠊目,例如东方蜚蠊、美洲大蠊、德国小蠊以及夏柏拉蟑螂属。
蜱螨亚纲(螨科)和后气门目和中气门目,例如锐缘蜱属、钝缘蜱属、耳蜱属、硬蜱属、钝眼蜱属、牛蜱属、革蜱属、血蜱属、璃眼蜱属、扇头蜱属、皮刺螨属、刺利螨属、肺刺螨属、胸刺螨属和瓦螨属。
轴螨目(前气门亚目)和粉螨目(无气门亚目),例如蜂盾螨属、姬螯属、禽螯螨属、肉螨属、疮螨属、蠕形螨属、恙螨属、牦螨属、粉螨属、食酪螨属、嗜木螨属、颈下螨属、翅螨属、痒螨属、皮螨属、耳疥螨属、疥螨属、耳螨属、鸟疥螨属、胞螨属以及鸡雏螨属。
根据本发明的组合物还适用于保护材料如木材、纺织品、塑料、粘合剂、胶、漆料、纸张和卡片、皮革、地板和建筑等免受昆虫侵染。
根据本发明的组合物可以用于例如对抗以下有害生物:甲虫,如北美家天牛、长毛天牛、家具窃蠹、红毛窃蠹、梳角细脉窃蠹、石斛、松芽枝窃蠹、松产品窃蠹、褐粉蠹、非洲粉蠹、南方粉蠹、栎粉蠹、柔毛粉蠹、胸粉蠹、鳞毛粉蠹、材小蠹属、条木小蠹属、咖啡黑长蠹、树长蠹、棕异翅长蠹、双棘长蠹属与竹长蠹;以及膜翅类昆虫,如蓝黑树蜂、云杉大树蜂、泰加大树蜂与大树蜂;以及白蚁,如欧洲木白蚁、麻头堆砂白蚁、印巴结构木异白蚁、黄胸散白蚁、桑特散白蚁、散白蚁、达尔文澳白蚁、内华达古白蚁与家白蚁;以及蛀虫,如衣鱼。
根据本发明的化合物可以按未经修饰的形式用作杀有害生物剂,但它们通常以多种方式使用配制佐剂(如载体、溶剂以及表面活性物质)被配制成组合物。这些配制品可以处于不同的实体形式,例如,处于以下形式:撒粉剂、凝胶、可湿性粉剂、水可分散性颗粒剂、水可分散性片剂、泡腾压缩片剂、可乳化的浓缩物、微可乳化浓缩物、水包油乳剂、可流动油、水性分散体、油性分散体、悬乳剂、胶囊悬浮液、可乳化的颗粒剂、可溶性液体、水可溶性浓缩物(以水或水混溶性有机溶剂作为载体)、浸渍的聚合物膜或处于已知的其他形式,例如从关于杀有害生物剂的FAO和WHO标准的发展和使用的手册(Manual on Developmentand Use of FAO and WHO Specifications for Pesticides),联合国,第1版,二次修订(2010)中已知的。此类配制品可以直接使用或者可以使用前稀释再使用。可以利用例如水、液体肥料、微量营养素、生物有机体、油或溶剂来稀释。
可以通过例如将活性成分与配制品佐剂混合来制备这些配制品以便获得处于精细分散固体、颗粒、溶液、分散体或乳剂形式的组合物。这些活性成分还可以与其他佐剂(例如精细分散固体、矿物油、植物或动物的油、改性的植物或动物的油、有机溶剂、水、表面活性物质或它们的组合)来一起配制。
这些活性成分还可以被包含于非常精细的微胶囊中。微胶囊在多孔载体中含有活性成分。这使活性成分能以受控的量值(例如,缓慢释放)释放到环境中。微胶囊的直径范围通常为0.1微米至500微米。它们包含的活性成分的量按重量计是胶囊重量的约从25%至95%。这些活性成分可以处于整体性的固体的形式、处于固体或液体分散体中的精细颗粒的形式或处于合适溶液的形式。包囊的膜可以包括例如天然的或合成的橡胶、纤维素、苯乙烯/丁二烯共聚物、聚丙烯腈、聚丙烯酸酯、聚酯、聚酰胺、聚脲、聚氨酯或化学改性的聚合物以及淀粉黄原酸盐、或本领域技术人员已知的其他聚合物。可替代地,可以形成非常精细的微胶囊,其中活性成分在基础物质的固体基质中是以精细分散颗粒的形式被包含的,但这些微胶囊本身未经包裹。
适合于制备根据本发明所述的这些组合物的配制佐剂本身是已知的。作为液体载体可以使用:水、甲苯、二甲苯、石油醚、植物油、丙酮、甲基乙基酮、环己酮、酸酐、乙腈、乙酰苯、乙酸戊酯、2-丁酮、碳酸丁烯酯、氯苯、环己烷、环己醇、乙酸烷基酯的乙酸、二丙酮醇、1,2-二氯丙烷、二乙醇胺、对-二乙基苯、二甘醇、松脂酸二乙二醇酯、二甘醇乙醚、二甘醇乙基醚、二甘醇甲醚、N,N-二甲基甲酰胺、二甲基亚砜、1,4-二噁烷、二丙二醇、二丙二醇甲基醚、双丙甘醇二苯甲酸酯、二丙二醇、烷基吡咯烷酮、乙酸乙酯、2-乙基己醇、碳酸乙烯酯、1,1,1-三氯乙烷、2-庚酮、α-蒎烯、d-苧烯、乳酸乙酯、乙二醇、乙二醇丁基醚、乙二醇甲基醚、γ-丁内酯、丙三醇、乙酸甘油酯、二乙酸甘油酯、三乙酸甘油酯、十六烷、己二醇、乙酸异戊基酯、乙酸异冰片基酯、异辛烷、异佛尔酮、异丙苯、肉豆蔻酸异丙酯、乳酸、月桂胺、异亚丙基丙酮、甲氧基丙醇、甲基异戊基酮、甲基异丁基酮、月桂酸甲酯、辛酸甲酯、油酸甲酯、二氯甲烷、间二甲苯、正己烷、正辛胺、十八烷酸、辛胺乙酸酯、油酸、油烯基胺、邻二甲苯、苯酚、聚乙二醇、丙酸、乳酸丙酯、碳酸亚丙酯、丙二醇、丙二醇甲基醚、对-二甲苯、甲苯、磷酸三乙酯、三乙二醇、二甲苯磺酸、石蜡、矿物油、三氯乙烯、全氯乙烯、乙酸乙酯、乙酸戊酯、乙酸丁酯、丙二醇甲基醚、二乙二醇甲基醚、甲醇、乙醇、异丙醇以及更高分子量的醇,例如戊醇、四氢呋喃醇、己醇、辛醇、乙二醇、丙二醇、甘油、N-甲基-2-吡咯烷酮等。
适合的固体载体是,例如滑石、二氧化钛、叶蜡石粘土、硅石、凹凸棒石粘土、硅藻土、石灰石、碳酸钙、膨润土、钙蒙脱土、棉籽壳、小麦粉、大豆粉、浮石、木粉、胡桃壳粉、木素和类似的物质。
许多表面活性物质可以有利地用在固体和液体配制品两者中,尤其是在使用前可被载体稀释的那些配制品中。表面活性物质可以是阴离子的、阳离子的、非离子的或聚合的并且它们可以用作乳化剂、湿润剂或悬浮剂或用于其他目的。典型的表面活性物质包括例如烷基硫酸酯的盐,如十二烷基硫酸二乙醇铵;烷基芳基磺酸酯的盐,如十二烷基苯磺酸钙;烷基酚/氧化烯加成产物,如乙氧基化壬基苯酚;醇/氧化烯加成产物,如乙氧基化十三烷醇;皂,如硬脂酸钠;烷基萘磺酸酯的盐,如二丁基萘磺酸钠;磺基丁二酸盐的二烷基酯,如二(2-乙基己基)磺基丁二酸钠;山梨糖醇酯,如山梨糖醇油酸酯;季铵,如氯化十二烷基三甲基铵;脂肪酸的聚乙二醇酯,如聚乙二醇硬脂酸酯;环氧乙烷和环氧丙烷的嵌段共聚物;以及磷酸单-和二-烷酯的盐;以及还有其他物质,例如描述于:McCutcheon′sDetergents and Emulsifiers Annual,MC Publishing Corp.,Ridgewood New Jersey[麦卡琴清洁剂和乳化剂年鉴,MC出版公司,里奇伍德,新泽西州](1981)。
可以用于杀有害生物配制品的其他佐剂包括结晶作用抑制剂、粘度改性剂、悬浮剂、染料、抗氧化剂、发泡剂、光吸收剂、混合助剂、消泡剂、络合剂、中和或改变pH的物质与缓冲液、腐蚀抑制剂、香料、湿润剂、吸收增强剂、微量营养素、增塑剂、助流剂、润滑剂、分散剂、增稠剂、防冻剂、杀微生物剂、以及液体与固体肥料。
根据本发明的组合物可以包括添加剂,该添加剂包括植物或动物来源的油、矿物油、此类油的烷基酯或此类油与油衍生物的混合物。在根据本发明的组合物中的油添加剂的量通常是该待施用的混合物的0.01%到10%。例如,可以在喷雾混合物已经制备以后将该油添加剂以所希望的浓度加入喷雾罐中。优选的油添加剂包括矿物油或植物来源的油,例如菜籽油、橄榄油或葵花籽油;乳化的植物油;植物来源的油的烷基酯,例如甲基衍生物;或动物来源的油,如鱼油或牛脂。优选的油添加剂包括C8-C22脂肪酸的烷基酯,尤其是C12-C18脂肪酸的甲基衍生物,例如月桂酸、棕榈酸以及油酸的甲基酯(分别为月桂酸甲酯、棕榈酸甲酯和油酸甲酯)。许多油衍生物获知于以下文献:Compendium of HerbicideAdjuvants,10th Edition,Southern Illinois University,2010[除草剂佐剂纲要,第10版,南伊利诺伊大学,2010]。
这些本发明组合物总体上包括按重量计从0.1%至99%,尤其是按重量计从0.1%至95%的本发明的化合物以及按重量计从1%至99.9%的配制佐剂,该配制佐剂优选地包括按重量计从0至25%的表面活性物质。而商用产品可以优选地被配制为浓缩物,最终使用者将通常使用稀释配制品。
施用量在宽范围之内变化并且取决于土壤的性质、施用方法、作物植物、待控制的有害生物、主要气候条件、以及受施用方法支配的其他因素、施用时间以及目标作物。一般来讲,可以将化合物以从1 l/ha至2000 l/ha,尤其是从10 l/ha到1000 l/ha的比率施用。
优选的配制品可以具有以下成分(重量%):
可乳化的浓缩物:
活性成分: 1%至95%,优选60%至90%
表面活性剂: 1%至30%,优选5%至20%
液体载体: 1%至80%,优选1%至35%
尘剂:
活性成分: 0.1%至10%,优选0.1%至5%
固体载体: 99.9%至90%,优选99.9%至99%
悬浮液浓缩物:
活性成分: 5%至75%,优选10%至50%
水: 94%至24%,优选88%至30%
表面活性剂: 1%至40%,优选2%至30%
可湿性粉剂:
活性成分: 0.5%至90%,优选1%至80%
表面活性剂: 0.5%至20%,优选1%至15%
固体载体: 5%至95%,优选15%至90%
颗粒剂:
活性成分:0.1%至30%,优选0.1%至15%
固体载体:99.5%至70%,优选97%至85%
以下实例进一步展示了(但不限制)本发明。
可湿性粉剂 | a) | b) | c) |
活性成分 | 25% | 50% | 75% |
木质素磺酸钠 | 5% | 5% | - |
月桂基硫酸钠 | 3% | - | 5% |
二异丁基萘磺酸钠 | - | 6% | 10% |
苯酚聚乙二醇醚(7-8mol的环氧乙烷) | - | 2% | - |
高度分散的硅酸 | 5% | 10% | 10% |
高岭土 | 62% | 27% | - |
将该组合与这些佐剂充分混合并且将混合物在适当的研磨机中充分研磨,从而获得了可以用水稀释而给出所希望的浓度的悬浮液的可湿性粉剂。
干种子处理用的粉剂 | a) | b) | c) |
活性成分 | 25% | 50% | 75% |
轻质矿物油 | 5% | 5% | 5% |
高度分散的硅酸 | 5% | 5% | - |
高岭土 | 65% | 40% | - |
滑石 | - | - | 20 |
将该组合与佐剂充分混合并且将该混合物在适合的研磨机中充分研磨,从而提供可以直接用于种子处理的粉剂。
可乳化浓缩物 | |
活性成分 | 10% |
辛基苯酚聚乙二醇醚(4-5mol的环氧乙烷) | 3% |
十二烷基苯磺酸钙 | 3% |
蓖麻油聚乙二醇醚(35mol环氧乙烷) | 4% |
环己酮 | 30% |
二甲苯混合物 | 50% |
在植物保护中可以使用的具有任何所要求的稀释度的乳液可以通过用水稀释从这种浓缩物获得。
尘剂 | a) | b) | c) |
活性成分 | 5% | 6% | 4% |
滑石 | 95% | - | - |
高岭土 | - | 94% | - |
矿物填充剂 | - | - | 96% |
通过将该组合与载体混合并且将混合物在适当的研磨机中研磨获得立即可用的尘剂。此类粉剂还可以用于种子的干拌种。
挤出机颗粒剂 | |
活性成分 | 15% |
木质素磺酸钠 | 2% |
羧甲基纤维素 | 1% |
高岭土 | 82% |
将该组合与这些佐剂混合并且研磨,并且将混合物用水湿润。将混合物挤出并且然后在空气流中干燥。
包衣的颗粒剂 | |
活性成分 | 8% |
聚乙二醇(mol.wt.200) | 3% |
高岭土 | 89% |
将这种精细研磨的组合在混合器中均匀地施用于用聚乙二醇湿润的高岭土中。以此方式获得无尘的包衣的颗粒剂。
悬浮液浓缩物
活性成分 | 40% |
丙二醇 | 10% |
壬基酚聚乙二醇醚(15mol的环氧乙烷) | 6% |
木质素磺酸钠 | 10% |
羧甲基纤维素 | 1% |
硅油(处于在水中75%的乳剂的形式) | 1% |
水 | 32% |
将精细研磨的组合与佐剂密切混合,从而给出悬浮液浓缩剂,可以通过使用水稀释从该浓缩物获得任何所希望稀释度的悬浮液。使用这样的稀释物,可以对活的植物连同植物繁殖材料进行处理并且对其针对微生物侵染通过喷洒、倾倒或浸渍进行保护。
种子处理用的可流动性浓缩剂
活性成分 | 40% |
丙二醇 | 5% |
共聚物丁醇PO/EO | 2% |
三苯乙烯酚,具有10-20摩尔EO | 2% |
1,2-苯并异噻唑啉-3-酮(处于在水中20%的溶液形式) | 0.5% |
单偶氮-颜料钙盐 | 5% |
硅油(处于在水中75%的乳剂的形式) | 0.2% |
水 | 45.3% |
将精细研磨的组合与佐剂密切混合,从而给出悬浮液浓缩剂,可以通过使用水稀释从该浓缩物获得任何所希望稀释度的悬浮液。使用这样的稀释物,可以对活的植物连同植物繁殖材料进行处理并且对其针对微生物侵染通过喷洒、倾倒或浸渍进行保护。
缓释的胶囊悬浮液
将28份的组合与2份的芳香族溶剂以及7份的甲苯二异氰酸酯/多亚甲基-聚苯基异氰酸酯-混合物(8∶1)进行混合。将此混合物在1.2份的聚乙烯醇、0.05份的消泡剂以及51.6份的水的混合物中进行乳化直至达到所希望的颗粒尺寸。向此乳剂中添加在5.3份的水中的2.8份的1,6-己二胺混合物。将该混合物搅拌直至聚合反应完成。将获得的胶囊悬浮液通过添加0.25份的增稠剂以及3份的分散剂进行稳定。该胶囊悬浮液配制品包含28%的活性成分。该介质胶囊的直径是8微米-15微米。将所得配制品作为适用于此目的装置中的水性悬浮液施用到种子上。
配制品类型包括乳液浓缩剂(EC)、悬浮液浓缩物(SC)、悬乳剂(SE)、胶囊悬浮剂(CS)、水可分散性颗粒剂(WG)、可乳化性颗粒剂(EG)、油包水型乳液(EO)、水包油型乳液(EW)、微乳液(ME)、油分散体(OD)、油悬剂(OF)、油溶性液剂(OL)、可溶性浓缩剂(SL)、超低容量悬浮剂(SU)、超低容量液剂(UL)、母药(TK)、可分散性浓缩剂(DC)、可湿性粉剂(WP)、可溶性颗粒剂(SG)或与农业上可接受的佐剂组合的任何技术上可行的配制品。
制备实例:
“Mp”是指以℃计的熔点。自由基表示甲基基团。1H NMR测量值在Brucker 400MHz分光计上记录,化学位移相对于TMS标准品以ppm给出。光谱在如指定的氘代溶剂中测量。常见缩写:aq=水性,min=分钟,h=小时,sat=饱和的,Rt=滞留时间,mCPBA=间氯过氧苯甲酸,MeOH=甲醇,NaHCO3=碳酸氢钠,Na2CO3=碳酸钠,HCl=氯化氢,NBS=N-溴代琥珀酰亚胺,PdCl2(dppf)=[1,1-双(二苯基膦)二茂铁]二氯钯(II)。用以下LCMS或GCMS方法中的任一种来表征这些化合物。对于每种化合物获得的特征LCMS/GCMS值是保留时间(“Rt”以分钟为单位记录)和测量的分子离子(M)+或(M+H)+。
LCMS或GCMS方法:
方法1:
SC_BASE,仪器:Agilent 1100Bin。泵:G1312A,脱气装置;自动进样器,ColCom,DAD:Agilent G1315B,220-320nm,MSD:Agilent LC/MSD G6130B ESI,阳性/阴性100-800;ELSD PL-ELS2100气体流量1.1ml/min,气体温度:50℃;柱:沃特斯XSelectTMC18,30x2.1mm,3.5μ,温度:25℃,流量:1mL/min,梯度:t0=2%A,t1.6min=98%A,t3min=98%A,用时:1.3min,洗脱液A:在水中在乙腈中的95%乙腈+5%10mM碳酸氢铵,洗脱液B:在水中的10mM碳酸氢铵(pH=9.5)。
方法2:
AN_BASE,仪器:Agilent 1100Bin。泵:G1312A,脱气装置;自动进样器,ColCom,DAD:Agilent G1315B,220-320nm,MSD:Agilent LC/MSD G6130B ESI,阳性/阴性100-800;ELSD PL-ELS2100气体流量1.1ml/min,气体温度:50℃;柱:沃特斯XSelectTM C18,50×2.1mm,3.5μ,温度:25℃,流量:0.8mL/min,梯度:t0=2%A,t3.5min=98%A,t6min=98%A,用时:2min,洗脱液A:在水中在乙腈中的95%乙腈+5%10mM碳酸氢铵,洗脱液B:在水中的10mM碳酸氢铵(pH=9.5)。
方法3:
40S20,仪器:GC:Agilent 6890N和MS:5973MSD,EI-阳性,检测器度温度:280℃,质量范围:50-550;柱:RXi-5MS 20m,ID 180μm,df0.18μm;平均速度:50cm/s;注射体积:1μl;注射器温度:250℃;分流比:100/l;载体气体:He;初始温度:40℃;初始时间:1.5min;溶剂延迟:1.0min;速率40℃/min;最终温度250℃;最后时间2.0min。
方法4:
C20,仪器:GC:Agilent 6890N和MS:5973MSD,EI-阳性,检测器度温度:280℃,质量范围:50-550;柱:RXi-5MS 20m,ID 180μm,df0.18μm;平均速度:50cm/s;注射体积:1μl;注射器温度:250℃;分流比:100/1;载体气体:He;初始温度:100℃;初始时间:1.0min;溶剂延迟:1.0min;速率75℃/min;最终温度280℃;最后时间4.3min。
方法5:
在来自沃特斯(Waters)的质谱仪(ZQ单四极杆质谱仪)上记录光谱,该质谱仪配备有电喷射源(极性:正离子或负离子,毛细管:3.00kV,锥孔范围:30V-60V,萃取器:2.00V,源温度:150℃,去溶剂化温度:350℃,锥孔气体流量:0L/Hr,去溶剂化气体流量:650L/Hr;质量范围:100Da至900Da)以及一个来自沃特斯(Waters)的Acquity UPLC:二元泵、加热管柱室以及二极管阵列检测器)。溶剂脱气装置,二元泵,加热管柱室以及二极管阵列检测器。柱:沃特斯UPLC HSS T3,1.8μm,30×2.1mm,温度:60℃;DAD波长范围(nm):210至500,溶剂梯度:A=水+5%MeOH+0.05%HCOOH,B=乙腈+0.05%HCOOH;梯度:0min 0%B,100%A;1.2-1.5min 100%B;流量(ml/min)0.85。
实例P1:3-乙基磺酰基-2-[1-甲基-5-[6-(三氟甲基)-3-吡啶基]咪唑-2-基]-5- [4-(三氟甲基)苯基]吡啶(化合物P1)的制备
步骤1:5-溴-3-乙基硫烷基-吡啶-2-甲腈的制备
在氮气气氛下,将5-溴-3-氟-吡啶-2-甲腈(1.005g,5.00mmol)在干N,N-二甲基甲酰胺(15ml)中的溶液冷却至-50℃并向此中逐滴添加新鲜制备的乙硫醇钠(0.429g,5.10mmol)在干N,N-二甲基甲酰胺(5ml)中的溶液。在-50℃下搅拌30分钟之后,将冷却浴去除并允许混合物加温至室温。添加水和盐水并将水性混合物用乙酸乙酯萃取。在分离之后,将有机层用盐水洗涤两次,经硫酸钠干燥并浓缩。将粗产物通过二氧化硅快速柱层析(庚烷中的0至40%乙酸乙酯的梯度)纯化,以提供呈固体的标题化合物(0.93g)。GCMS(方法3):242/244(M)+,保留时间6.33min。1H-NMR(CDCl3,ppm)1.41(3H),3.06(2H),7.82(1H),8.49(1H)。
可替代的制备方法:
在氮气气氛下,将5-溴-3-硝基-吡啶-2-甲腈(45.35g,199mmol)在干N,N-二甲基甲酰胺(500ml)中的溶液冷却至-50℃并向此中逐滴添加新鲜制备的乙硫醇钠(17.4g,207mmol)在干N,N-二甲基甲酰胺(200ml)中的溶液(不是完全澄清的溶液)。添加完成之后,在-50℃下继续搅拌30分钟。添加水和盐水并将冷却浴去除。将水性混合物用乙酸乙酯萃取。在分离之后,将水层再一次用乙酸乙酯萃取。将合并的有机层用盐水洗涤两次,经硫酸钠干燥并浓缩。将粗产物通过二氧化硅快速柱层析(庚烷中的0至25%乙酸乙酯的梯度)纯化,以提供呈固体的标题化合物(33.9g)。
步骤2:5-溴-3-乙基硫烷基-2-(1H-咪唑-2-基)吡啶的制备
向5-溴-3-乙基硫烷基-吡啶-2-甲腈(10.0g,41.1mmol)在甲醇(80ml)中的悬浮液中添加甲醇钠在甲醇(2.132mmol,0.40ml,30wt%)的溶液并且将混合物在环境温度下搅拌过夜。获得透明的橙色溶液。
添加2,2-二乙氧基-乙胺(5.95g,44.7mmol,6.5ml)和乙酸(5.25g,87mmol,5.0ml)并将反应混合物在回流温度下加热45min。添加6N HCl(水性)(22ml)并且将混合物在回流温度下加热2.5h。将该反应混合物浓缩。向残余物中添加饱和碳酸氢钠水溶液以使水层变为稍微碱性。将该水性混合物用乙酸乙酯萃取两次。将合并的有机层经硫酸钠干燥并浓缩。将粗产物通过二氧化硅快速柱层析(庚烷中的10至100%乙酸乙酯的梯度)纯化,以提供呈固体的标题化合物(2.63g)。LCMS(方法1):284/286(M+H)+,保留时间2.08min。1H-NMR(DMSO-d6,ppm)1.47(3H),3.00(2H),7.15(1H),7.38(1H),7.70(1H),8.31(1H)。
步骤3:5-溴-3-乙基硫烷基-2-(1-甲基咪唑-2-基)吡啶(化合物P2.1)的制备
在氮气下,将5-溴-3-乙基硫烷基-2-(1H-咪唑-2-基)吡啶(11.06g,38.9mmol)在干燥的四氢呋喃(300ml)中的溶液在冰中冷却。向其中添加氢化钠(2.335g,58.4mmol,60%)(剧烈的气体逸出)。当气体逸出停止时,除去冷却浴并在环境温度下继续搅拌15分钟。添加碘代甲烷(10.44g,73.6mmol,4.6ml)并将混合物在环境温度下搅拌6小时。获得几乎透明的棕色溶液。小心地添加水,接着用盐水洗涤,并且将水性混合物用乙酸乙酯萃取两次。将合并的有机层经硫酸钠干燥并浓缩。将粗产物通过二氧化硅快速柱层析(庚烷中的10至100%乙酸乙酯的梯度)纯化,以提供呈固体的标题化合物(10.5g)。LCMS(方法1):298/300(M+H)+,保留时间2.04min。1H-NMR(CDCl3,ppm)1.37(3H),2.92(2H),3.85(3H),6.99(1H),7.22(1H),7.73(1H),8.41(1H)。
步骤4:5-溴-3-乙基磺酰基-2-(1-甲基咪唑-2-基)吡啶(化合物P2.2)的制备
将5-溴-3-甲基硫烷基-2-(1-甲基咪唑-2-基)吡啶(10.5g,35.2mmol)在二氯甲烷(300ml)中的溶液在冰中冷却并且向其逐份添加mCPBA(18.23g,73.9mmol,70%)。在添加完成后,将混合物在0℃下搅拌15分钟,然后在室温下搅拌4小时。用二氯甲烷稀释反应混合物,用饱和NaHCO3水溶液洗涤三次(首先洗涤含有一些硫代硫酸钠以破坏过量的mCPBA),用硫酸钠干燥并浓缩。将粗产物通过二氧化硅快速柱层析(在庚烷中10%至100%乙酸乙酯的梯度)进行纯化以得到呈固体的标题化合物(10.1g),mp 135-136.5℃。LCMS(方法2):330/332(M+H)+,保留时间2.89min。1H-NMR(CDCl3,ppm)1.35(3H),3.69(3H),3.94(2H),7.05(1H),7.14(1H),8.60(1H),8.93(1H)。
步骤5:3-乙基磺酰基-2-(1-甲基咪唑-2-基)-5-[4-(三氟甲基)苯基]吡啶(化合物P2.3)的制备
在微波小瓶中,将5-溴-3-乙基磺酰基-2-(1-甲基咪唑-2-基)吡啶(330mg,0.999mmol)、4-(三氟甲基)苯基)硼酸(285mg,1.499mmol)和碳酸钾(414mg,3.00mmol)在1,2-二甲氧基乙烷(10ml)和水(2.5ml)中的混合物用氩气冲洗5分钟。向其中添加PdCl2(dppf)(36.6mg,0.050mmol),将该小瓶封闭并将混合物在微波中在120℃下加热30分钟。将粗反应混合物在乙酸乙酯和水/盐水(1/3)之间分配。洗涤并分离后,将有机层经硫酸钠干燥并浓缩。将粗产物通过二氧化硅快速柱层析(在二氯甲烷中0%至4%甲醇的梯度)进行纯化以得到呈固体的标题化合物(329mg),mp 167-169℃。LCMS(方法2):396(M+H+),保留时间:3.61min。1H-NMR(CDCl3,ppm)1.37(3H),3.74(3H),3.96(2H),7.08(1H),7.17(1H),7.82(4H),8.67(1H),9.11(1H)。
步骤6:2-(5-溴-1-甲基-咪唑-2-基)-3-乙基磺酰基-5-[4-(三氟甲基)苯基]吡啶(化合物P2.5)的制备
向3-乙基磺酰基-2-(1-甲基咪唑-2-基)-5-[4-(三氟甲基)苯基]吡啶(568mg,1.437mmol)在氯仿(15ml)中的溶液中添加NBS(261mg,1.465mmol)并将混合物在60℃(油浴温度)下加热1小时。将反应混合物浓缩并且将粗产物通过二氧化硅快速柱层析(在庚烷中10%至100%乙酸乙酯的梯度)进行纯化以得到呈固体的标题化合物(527mg),mp 182-184℃。LCMS(方法2):474/476(M+H)+,保留时间4.08min。1H-NMR(CDCl3,ppm)1.37(3H),3.68(3H),3.93(2H),7.17(1H),7.82(4H),8.67(1H),9.12(1H)。
步骤7:3-乙基磺酰基-2-[1-甲基-5-[6-(三氟甲基)-3-吡啶基]咪唑-2-基]-5-[4-(三氟甲基)苯基]吡啶(化合物P1)的制备
在微波小瓶中,将2-(5-溴-1-甲基-咪唑-2-基)-3-乙基磺酰基-5-[4-(三氟甲基)苯基]吡啶(450mg,0.949mmol)、(6-(三氟甲基)吡啶-3-基)硼酸(272mg,1.423mmol)和碳酸钾(393mg,2.85mmol)在1,2-二甲氧基乙烷(10ml)和水(2.5ml)中的混合物用氩气冲洗5分钟。向其中添加PdCl2(dppf)(34.7mg,0.047mmol),将该小瓶封闭并将混合物在微波中在120℃下加热1小时。将该粗反应混合物用乙酸乙酯稀释,用水/盐水(1/3)洗涤,经硫酸钠干燥并浓缩。将粗产物通过二氧化硅快速柱层析(在庚烷中20至100%乙酸乙酯的梯度)进行纯化以得到呈固体的标题化合物P1(319mg),mp 182-184℃。LCMS(方法2):541(M+H+),保留时间:4.09min。1H-NMR(CDCl3,ppm)1.41(3H),3.71(3H),3.98(2H),7.38(1H),7.82(1H),8.01(1H),8.70(1H),8.91(1H),9.16(1H)。
实例P2:3-乙基磺酰基-2-[1-甲基-5-[4-(三氟甲基)苯基]咪唑-2-基]-5-[4-(三 氟甲基)苯基]吡啶(化合物P2)的制备
步骤1:5-溴-2-(5-溴-1-甲基-咪唑-2-基)-3-乙基磺酰基-吡唑(化合物P2.4)的制备
向5-溴-3-乙基磺酰基-2-(1-甲基咪唑-2-基)吡啶(660mg,1.999mmol)在氯仿(10ml)中的溶液中添加NBS(363mg,2.039mmol)并且将混合物在60℃(油浴温度)下加热一小时。将反应混合物浓缩并且将粗产物通过二氧化硅快速柱层析(在庚烷中10%至75%乙酸乙酯的梯度)进行纯化以得到呈固体的标题化合物(643mg),mp 115-118℃。GCMS(方法4):407/409/411(M)+,保留时间4.80min。1H-NMR(CDCl3,ppm)1.35(3H),3.62(3H),3.89(2H),7.14(1H),8.60(1H),8.94(1H)。
步骤2:2-(5-溴-1-甲基-咪唑-2-基)-3-乙基磺酰基-5-[4-(三氟甲基)苯基]吡啶(化合物P2.5)的制备
在反应小瓶中,将5-溴-2-(5-溴-1-甲基-咪唑-2-基)-3-乙基磺酰基-吡啶(205mg,0.501mmol)、(4-(三氟甲基)苯基)硼酸(105mg,0.551mmol)和碳酸钾(208mg,1.503mmol)在1,2-二甲氧基乙烷(4ml)和水(1ml)中的混合物用氩气冲洗5分钟。向其添加PdCl2(dppf)(14mg,0.019mmol),将小瓶封闭并且将混合物在60℃(油浴温度)下加热90分钟。将粗反应混合物在乙酸乙酯和水/盐水(1/3)之间分配。洗涤并分离后,将有机层经硫酸钠干燥并浓缩。将粗产物通过二氧化硅快速柱层析(在庚烷中10%至75%乙酸乙酯的梯度)进行纯化以得到呈固体的标题化合物(191mg),mp 182-184℃。LCMS(方法2):474/476(M+H)+,保留时间4.01min。1H-NMR(CDCl3,ppm)1.37(3H),3.68(3H),3.93(2H),7.17(1H),7.82(4H),8.67(1H),9.12(1H)。
步骤3:3-乙基磺酰基-2-[1-甲基-5-[4-(三氟甲基)苯基]咪唑-2-基]-5-[4-(三氟甲基)苯基]吡啶(标题化合物P2)的制备
在反应小瓶中,将2-(5-溴-1-甲基-咪唑-2-基)-3-乙基磺酰基-5-[4-(三氟甲基)苯基]吡啶(182mg,0.384mmol)、(4-(三氟甲基)苯基)硼酸(100mg,0.527mmol)和碳酸钾(159mg,1.151mmol)在1,2-二甲氧基乙烷(3ml)和水(0.75ml)中的混合物用氩气冲洗5分钟。向其添加PdCl2(dppf)(14mg,0.019mmol),将小瓶封闭并且将混合物在90℃(油浴温度)下加热90分钟。将粗反应混合物在乙酸乙酯和水/盐水(1/3)之间分配。洗涤并分离后,将有机层经硫酸钠干燥并浓缩。将粗产物通过二氧化硅快速柱层析(在庚烷中10至75%乙酸乙酯的梯度)进行纯化以得到呈固体的标题化合物P2(115mg),mp 188-190℃。LCMS(方法2):540(M+H+),保留时间:4.25min。1H-NMR(CDCl3,ppm)1.40(3H),3.69(3H),3.99(2H),7.29(1H),7.63(2H),7.75(2H),7.84(4H),8.70(1H),9.15(1H)。
实例P3:3-乙基磺酰基-5-(4-氟苯基)-2-[1-甲基-5-[6-(三氟甲基)-3-吡啶基]咪唑-2-基]吡啶(化合物P3)的制备
一锅两步骤法:在反应小瓶中,将5-溴-2-(5-溴-1-甲基-咪唑-2-基)-3-乙基磺酰基-吡啶(307mg,0.750mmol)、(4-氟苯基)硼酸(116mg,0.825mmol)和碳酸钾(311mg,2.251mmol)在1,2-二甲氧基乙烷(6ml)和水(1.5ml)中的混合物用氩气冲洗5分钟。向其添加PdCl2(dppf)(21.96mg,0.030mmol),将小瓶封闭并且将混合物在60℃(油浴温度,反应在室温下开始)下加热1小时。添加(6-(三氟甲基)吡啶-3-基)硼酸(201mg,1.051mmol),再次将小瓶封闭并且将混合物在90℃(油浴温度)下加热1小时。将粗反应混合物在乙酸乙酯和水/盐水(1/3)之间分配。洗涤并分离后,将有机层干燥并浓缩。将粗产物通过二氧化硅快速柱层析(在庚烷中10%至100%乙酸乙酯的梯度)进行纯化。将包含产物的级分合并并浓缩。将产物再次通过二氧化硅快速柱层析(在庚烷中25%至100%乙酸乙酯的梯度,接着通过100%乙酸乙酯)进行纯化以得到呈固体的标题化合物P3(130mg),mp 207-209℃。LCMS(方法2):491(M+H+),保留时间:3.73min。1H-NMR(CDCl3,ppm)1.40(3H),3.69(3H),3.94(2H),7.27(2H),7.37(1H),7.70(2H),7.82(1H),8.01(1H),8.63(1H),8.90(1H),9.11(1H)。
表P:具有式(I)的化合物的实例
实例P4:中间体化合物5-氯-2-[5-乙基磺酰基-6-(1-甲基咪唑-2-基)-3-吡啶基] 嘧啶(化合物P2.7)的制备
一锅两步骤法:将5-溴-3-乙基磺酰基-2-(1-甲基咪唑-2-基)吡啶(600mg,1.817mmol)、双(频哪醇并)二硼(508mg,1.999mmol)和乙酸钾(535mg,5.45mmol)在二甲亚砜(16ml)中的溶液/悬浮液用氩气冲洗5分钟。向其添加PdCl2(dppf)(60mg,0.082mmol)并且将反应混合物在80℃(油浴温度)下在在氩气下加热90分钟。添加2-溴-5-氯嘧啶(527mg,2.73mmol)、水(4ml)(在添加前用氩气冲洗)和碳酸钾(753mg,5.45mmol)并且将混合物在80℃下在氩气下加热2小时。使反应混合物冷却至室温,并在乙酸乙酯和水/盐水(约1/3)之间分配。洗涤并分离后,将有机层用盐水洗涤两次,经硫酸钠干燥并浓缩。将粗产物通过二氧化硅快速柱层析(在CH2Cl2中的0%至4%MeOH的梯度)进行纯化。将包含产物的级分合并并浓缩。将产物再次通过二氧化硅快速柱层析(在庚烷中20至100%乙酸乙酯的梯度,接着通过100%的乙酸乙酯)进行纯化以得到呈固体的中间体化合物P2.7(393mg),mp 228-229.5℃。LCMS(方法2):364/366(M+H)+,保留时间3.40min。1H-NMR(CDCl3,ppm)1.38(3H),3.75(3H),3.98(2H),7.08(1H),7.17(1H),8.84(2H),9.42(1H),9.83(1H)。
表P2:具有式(IIIa)、(IVa)和(XVIII)的中间体的实例
通过添加其他有杀昆虫、杀螨和/或杀真菌活性的成分,根据本发明的组合物的活性可以显著地加宽,并且适合于当时的环境。具有式I的化合物与其他具有杀昆虫、杀螨和/或杀真菌活性的成分的混合物还可以具有另外的意料之外的优点,这些优点还可以在更宽的意义上描述为协同活性。例如,植物对其更好的耐受性、降低的植物毒性,昆虫可以在它们的不同发育阶段得到控制或者在它们的生产期间(例如,在研磨或者混合过程中,在它们的储藏或它们的使用过程中)更好的行为。
在这里,合适的活性成分的添加物是例如下面类别的活性成分的代表物:有机磷化合物、硝基苯酚衍生物、硫脲、保幼激素、甲脒、二苯甲酮衍生物、脲类、吡咯衍生物、氨基甲酸酯、拟除虫菊酯、氯化烃、酰基脲、吡啶基亚甲基氨基衍生物、大环内酯类、新烟碱以及苏云金杆菌制剂。
以下具有式I的化合物与活性成分的混合物是优选的(缩写“TX”意为“选自下组的化合物,该组由描述于本发明的表1至6以及P中的化合物组成”):
佐剂,该佐剂选自由以下物质组成的组:石油(628)+TX,
杀螨剂,该杀螨剂选自由以下物质组成的组:1,1-双(4-氯苯基)-2-乙氧基乙醇(IUPAC名称)(910)+TX、2,4-二氯苯基苯磺酸酯(IUPAC/化学文摘名)(1059)+TX、2-氟-N-甲基-N-1-萘乙酰胺(IUPAC名称)(1295)+TX、4-氯苯基苯基砜(IUPAC名称)(981)+TX、阿维菌素(1)+TX、灭螨醌(3)+TX、乙酰虫腈[CCN]+TX、氟丙菊酯(9)+TX、涕灭威(16)+TX、涕灭砜威(863)+TX、α-氯氰菊酯(202)+TX、赛硫磷(870)+TX、磺胺螨酯[CCN]+TX、氨基硫代盐(872)+TX、胺吸磷(875)+TX、胺吸磷草酸氢盐(875)+TX、双甲脒(24)+TX、杀螨特(881)+TX、三氧化二砷(882)+TX、AVI 382(化合物代码)+TX、AZ 60541(化合物代码)+TX、益棉磷(44)+TX、保棉磷(azinphos-methyl)(45)+TX、偶氮苯(IUPAC名称)(888)+TX、三唑锡(azacyclotin)(46)+TX、偶氮磷(azothoate)(889)+TX、苯茵灵(62)+TX、苯诺沙磷(benoxafos)[CCN]+TX、苯螨特(benzoximate)(71)+TX、苯甲酸苄酯(IUPAC名称)[CCN]+TX、联苯肼酯(74)+TX、氟氯菊酯(76)+TX、乐杀螨(907)+TX、溴灭菊酯+TX、溴烯杀(bromocyclene)(918)+TX、溴硫磷(920)+TX、乙基溴硫磷(921)+TX、溴螨酯(bromopropylate)(94)+TX、噻嗪酮(99)+TX、丁酮威(103)+TX、丁酮砜威(104)+TX、丁酮威(butylpyridaben)+TX、石硫合剂(calciumpolysulfide)(IUPAC名称)(111)+TX、毒杀芬(campheechlor)(941)+TX、氯灭杀威(carbanolate)(943)+TX、甲萘威(115)+TX、克百威(carbofuran)(118)+TX、卡波硫磷(947)+TX、CGA 50’439(研究代码)(125)+TX、灭螨猛(chinomethionat)(126)+TX、杀螨醚(chlorbenside)(959)+TX、杀虫脒(964)+TX、杀虫脒盐酸盐(964)+TX、溴虫腈(130)+TX、敌螨(968)+TX、杀螨酯(chlorfenson)(970)+TX、敌螨特(chlorfensulfide)(971)+TX、氯芬磷(131)+TX、乙酯杀螨醇(chlorobenzilate)(975)+TX、伊托明(chloromebuform)(977)+TX、灭虫脲(chloromethiuron)(978)+TX、丙酯杀螨醇(chloropropylate)(983)+TX、毒死蜱(145)+TX、甲基毒死蜱(146)+TX、虫螨磷(chlorthiophos)(994)+TX、瓜菊酯(cinerin)I(696)+TX、瓜菊酯11(696)+TX、瓜叶菊素(cinerins)(696)+TX、四螨嗪(158)+TX、氯氰碘柳胺[CCN]+TX、库马磷(174)+TX、克罗米通[CCN]+TX、巴毒磷(crotoxyphos)(1010)+TX、硫杂灵(1013)+TX、果虫磷(cyanthoate)(1020)+TX、丁氟螨酯(CAS登记号:400882-07-7)+TX、三氯氟氰菊酯(196)+TX、三环锡(199)+TX、氯氰菊酯(201)+TX、DCPM(1032)+TX、DDT(219)+TX、田乐磷(demephion)(1037)+TX、田乐磷-O(1037)+TX、田乐磷-S(1037)+TX、内吸磷(demeton)(1038)+TX、甲基内吸磷(224)+TX、内吸磷-O(1038)+TX、甲基内吸磷-O(224)+TX、内吸磷-S(1038)+TX、甲基内吸磷-S(224)+TX、内吸磷-S-甲基磺隆(demeton-S-methylsulfon)(1039)+TX、杀螨隆(226)+TX、氯亚胺硫磷(dialifos)(1042)+TX、二嗪磷(227)+TX、苯氟磺胺(230)+TX、敌敌畏(236)+TX、甲氟磷(dicliphos)+TX、开乐散(242)+TX、百治磷(243)+TX、遍地克(1071)+TX、甲氟磷(dimefox)(1081)+TX、乐果(262)+TX、二甲杀螨霉素(dinactin)(653)+TX、消螨酚(dinex)(1089)+TX、消螨酚(dinex-diclexine)(1089)+TX、消螨通(dinobuton)(269)+TX、敌螨普(dinocap)(270)+TX、敌螨普-4[CCN]+TX、敌螨普-6[CCN]+TX、二硝酯(1090)+TX、硝戊酯(dinopenton)(1092)+TX、硝辛酯(dinosulfon)(1097)+TX、硝丁酯(dinoterbon)(1098)+TX、敌恶磷(1102)+TX、二苯砜(IUPAC名称)(1103)+TX、双硫仑[CCN]+TX、乙拌磷(278)+TX、DNOC(282)+TX、苯氧炔螨(dofenapyn)(1113)+TX、多拉克汀[CCN]+TX、硫丹(294)+TX、因毒磷(endothion)(1121)+TX、EPN(297)+TX、依立诺克丁[CCN]+TX、乙硫磷(309)+TX、益硫磷(ethoate-methyl)(1134)+TX、乙螨唑(etoxazole)(320)+TX、乙嘧硫磷(etrimfos)(1142)+TX、抗螨唑(fenazaflor)(1147)+TX、喹螨醚(328)+TX、苯丁锡(fenbutatin oxide)(330)+TX、苯硫威(fenothiocarb)(337)+TX、甲氰菊酯(342)+TX、吡螨胺(fenpyrad)+TX、唑螨酯(fenpyroximate)(345)+TX、芬螨酯(fenson)(1157)+TX、氟硝二苯胺(fentrifanil)(1161)+TX、氰戊菊酯(349)+TX、氟虫腈(354)+TX、嘧螨酯(fluacrypyrim)(360)+TX、氟佐隆(1166)+TX、氟螨噻(flubenzimine)(1167)+TX、氟螨脲(366)+TX、氟氰戊菊酯(flucythrinate)(367)+TX、联氟螨(fluenetil)(1169)+TX、氟虫脲(370)+TX、氟氯苯菊酯(flumethrin)(372)+TX、氟杀螨(fluorbenside)(1174)+TX、氟胺氰菊酯(fluvalinate)(1184)+TX、FMC 1137(研究代码)(1185)+TX、抗螨脒(405)+TX、抗螨脒盐酸盐(405)+TX、安硫磷(formothion)(1192)+TX、胺甲威(formparanate)(1193)+TX、γ-HCH(430)+TX、果绿啶(glyodin)(1205)+TX、苄螨醚(halfenprox)(424)+TX、庚烯醚(heptenophos)(432)+TX、十六碳烷基环丙烷羧酸酯(IUPAC/化学文摘名)(1216)+TX、噻螨酮(441)+TX、碘甲烷(IUPAC名称)(542)+TX、水胺硫磷(isocarbophos)(473)+TX、异丙基O-(甲氧基氨基硫代磷酰基)水杨酸酯(IUPAC名称)(473)+TX、伊维菌素[CCN]+TX、茉莉菊酯(jasmolin)I(696)+TX、茉莉菊酯II(696)+TX、碘硫磷(jodfenphos)(1248)+TX、林丹(430)+TX、虱螨脲(490)+TX、马拉硫磷(492)+TX、苄丙二腈(malonoben)(1254)+TX、灭蚜磷(mecarbam)(502)+TX、地胺磷(mephosfolan)(1261)+TX、甲硫芬[CCN]+TX、虫螨畏(methacrifos)(1266)+TX、甲胺磷(527)+TX、杀扑磷(529)+TX、灭虫威(530)+TX、灭多虫(531)+TX、溴甲烷(537)+TX、速灭威(metolcarb)(550)+TX、速灭磷(556)+TX、自克威(mexacarbate)(1290)+TX、米尔螨素(557)+TX、杀螨茵素肟(milbemycin oxime)[CCN]+TX、丙胺氟磷(mipafox)(1293)+TX、久效磷(561)+TX、茂硫磷(morphothion)(1300)+TX、莫昔克丁[CCN]+TX、二溴磷(naled)(567)+TX、NC-184(化合物代码)+TX、NC-152(化合物代码)+TX、氟蚊灵(nifluridide)(1309)+TX、尼柯霉素[CCN]+TX、戊氰威(nitrilacarb)(1313)+TX、戊氰威(nitrilacarb)1∶1氯化锌络合物(1313)+TX、NNI-0101(化合物代码)+TX、NNI-0250(化合物代码)+TX、氧乐果(氧乐果)(594)+TX、杀线威(602)+TX、亚异砜磷(oxydeprofos)(1324)+TX、砜拌磷(oxydisulfoton)(1325)+TX、pp’-DDT(219)+TX、对硫磷(615)+TX、氯菊酯(626)+TX、石油(628)+TX、芬硫磷(1330)+TX、稻丰散(631)+TX、甲拌磷(636)+TX、伏杀硫磷(637)+TX、硫环磷(phosfolan)(1338)+TX、亚胺硫磷(638)+TX、磷胺(639)+TX、辛硫磷(642)+TX、甲基嘧啶磷(652)+TX、氯化松节油(polychloroterpenes)(传统名称)(1347)+TX、杀螨霉素(polynactins)(653)+TX、丙氯诺(1350)+TX、丙溴磷(662)+TX、蜱虱威(promacyl)(1354)+TX、克螨特(671)+TX、胺丙畏(propetamphos)(673)+TX、残杀威(678)+TX、乙噻唑磷(prothidathion)(1360)+TX、发硫磷(prothoate)(1362)+TX、除虫菊酯I(696)+TX、除虫菊酯II(696)+TX、除虫菊素(pyrethrins)(696)+TX、哒螨灵(699)+TX、哒嗪硫磷(pyridaphenthion)(701)+TX、嘧螨醚(pyrimidifen)(706)+TX、嘧硫磷(1370)+TX、喹硫磷(quinalphos)(711)+TX、喹硫磷(quintiofos)(1381)+TX、R-1492(研究代码)(1382)+TX、RA-17(研究代码)(1383)+TX、鱼藤酮(722)+TX、八甲磷(schradan)(1389)+TX、硫线磷(sebufos)+TX、塞拉菌素(selamectin)[CCN]+TX、SI-0009(化合物代码)+TX、苏硫磷(sophamide)(1402)+TX、季酮螨酯(738)+TX、螺甲螨酯(739)+TX、SSI-121(研究代码)(1404)+TX、舒非仑[CCN]+TX、氟虫胺(sulfluramid)(750)+TX、治螟磷(sulfotep)(753)+TX、硫黄(754)+TX、S21-121(研究代码)(757)+TX、氟胺氰菊酯(398)+TX、吡螨胺(763)+TX、TEPP(1417)+TX、叔丁威(terbam)+TX、司替罗磷(777)+TX、三氯杀螨砜(tetradifon)(786)+TX、杀螨霉素(tetranactin)(653)+TX、杀螨硫醚(tetrasul)(1425)+TX、久效威(thiafenox)+TX、抗虫威(thiocarboxime)(1431)+TX、久效威(thiofanox)(800)+TX、甲基乙拌磷(thiometon)(801)+TX、克杀螨(1436)+TX、苏力菌素(thuringiensin)[CCN]+TX、威茵磷(triamiphos)(1441)+TX、苯噻螨(triarathene)(1443)+TX、三唑磷(820)+TX、唑呀威(triazuron)+TX、敌百虫(824)+TX、氯苯乙丙磷(trifenofos)(1455)+TX、甲杀螨霉素(trinactin)(653)+TX、灭蚜硫磷(847)+TX、氟吡唑虫(vaniliprole)[CCN]和YI-5302(化合物代码)+TX,
杀藻剂,该杀藻剂选自由以下物质组成的组:贝斯氧杂嗪(bethoxazin)[CCN]+TX、二辛酸铜(IUPAC名称)(170)+TX、硫酸铜(172)+TX、cybutryne[CCN]+TX、二氢萘醌(dichlone)(1052)+TX、双氯酚(232)+TX、茵多酸(295)+TX、三苯锡(fentin)(347)+TX、熟石灰[CCN]+TX、代森钠(nabam)(566)+TX、灭藻醌(quinoclamine)(714)+TX、醌萍胺(quinonamid)(1379)+TX、西玛津(730)+TX、三苯锡乙酸盐(IUPAC名称)(347)和氢氧化三苯锡(IUPAC名称)(347)+TX,
驱蠕虫剂,该驱蠕虫剂选自由以下物质组成的组:阿巴美丁(1)+TX、克芦磷酯(1011)+TX、多拉克汀[CCN]+TX、依马克丁(291)+TX、依马克丁苯甲酸酯(291)+TX、依立诺克丁[CCN]+TX、伊维菌素[CCN]+TX、米尔倍霉素[CCN]+TX、莫昔克丁[CCN]+TX、哌嗪[CCN]+TX、塞拉菌素(selamectin)[CCN]+TX、多杀菌素(737)和硫菌灵(thiophanate)(1435)+TX,
杀鸟剂,该杀鸟剂选自由以下物质组成的组:氯醛糖(127)+TX、异狄氏剂(1122)+TX、倍硫磷(346)+TX、吡啶-4-胺(IUPAC名称)(23)和士的宁(745)+TX,
杀细菌剂,该杀细菌剂选自由以下物质组成的组:1-羟基-1H-吡啶-2-硫酮(IUPAC名称)(1222)+TX、4-(喹喔啉-2-基氨基)苯磺酰胺(IUPAC名称)(748)+TX、8-羟基喹啉硫酸盐(446)+TX、溴硝醇(97)+TX、二辛酸铜(IUPAC名称)(170)+TX、氢氧化铜(IUPAC名称)(169)+TX、甲酚[CCN]+TX、双氯酚(232)+TX、双吡硫翁(1105)+TX、多地辛(1112)+TX、敌磺钠(fenaminosulf)(1144)+TX、甲醛(404)+TX、汞加芬[CCN]+TX、春雷霉素(483)+TX、春雷霉素盐酸盐水合物(483)+TX、二(二甲基二硫代氨基甲酸盐)镍(IUPAC名称)(1308)+TX、三氯甲基吡啶(nitrapyrin)(580)+TX、辛噻酮(octhilinone)(590)+TX、奥索利酸(606)+TX、土霉素(611)+TX、羟基喹啉硫酸钾(446)+TX、烯丙苯噻唑(probenazole)(658)+TX、链霉素(744)+TX、链霉素倍半硫酸盐(744)+TX、叶枯酞(766)+TX、和硫柳汞[CCN]+TX,
生物试剂,该生物试剂选自由以下物质构成的组:棉褐带卷蛾颗粒体病毒(Adoxophyes orana GV)(12)+TX、放射形土壤杆菌(13)+TX、捕食螨(Amblyseius spp.)(19)+TX、芹菜夜蛾核多角体病毒(Anagrapha falcifera NPV)(28)+TX、Anagrus atomus(29)+TX、短距蚜小蜂(Aphelinus abdominalis)(33)+TX、棉蚜寄生蜂(Aphidiuscolemani)(34)+TX、食蚜瘿蚊(Aphidoletes aphidimyza)(35)+TX、苜蓿银纹夜蛾核多角体病毒(Autographa californica NPV)(38)+TX、坚硬芽孢杆菌(Bacillus firmus)(48)+TX、球形芽孢杆菌(Bacillus sphaericus Neide)(学名)(49)+TX、苏云金芽孢杆菌(Bacillusthuringiensis Berliner)(学名)(51)+TX、苏云金芽孢杆菌鲇泽亚种(Bacillusthuringiensis subsp.aizawai)(学名)(51)+TX、苏云金芽孢杆菌以色列亚种(Bacillusthuringiensis subsp.israelensis)(学名)(51)+TX、苏云金芽孢杆菌日本亚种(Bacillusthuringiensis subsp.japonensis)(学名)(51)+TX、苏云金芽孢杆菌库尔斯塔克亚种(Bacillus thuringiensis subsp.kurstaki)(学名)(51)+TX、苏云金芽孢杆菌拟步行甲亚种(Bacillus thuringiensis subsp.tenebrionis)(学名)(51)+TX、球孢白僵茵(Beauveria bassiana)(53)+TX、布氏白僵茵(Beauveria brongniartii)(54)+TX、草蜻蛉(Chrysoperla carnea)(151)+TX、孟氏隐唇瓢虫(Cryptolaemus montrouzieri)(178)+TX、苹果蠹蛾颗粒体病毒(Cydia pomonella GV)(191)+TX、西伯利亚离颚茧蜂(Dacnusasibirica)(212)+TX、豌豆潜叶蝇姬小蜂(Diglyphus isaea)(254)+TX、丽蚜小蜂(Enearsiaformosa)(学名)(293)+TX、桨角蚜小蜂(Eretmocerus eremicus)(300)+TX、玉米穗夜蛾核多角体病毒(Helicoverpa zea NPV)(431)+TX、嗜茵异小杆线虫(Heterorhabditisbacteriophora)和H.megidis(433)+TX、会聚长足瓢虫(Hippodamia convergens)(442)+TX、橘粉介壳虫寄生蜂(Leptomastix dactylopii)(488)+TX、盲蝽(Macrolophuscaliginosus)(491)+TX、甘蓝夜蛾核多角体病毒(Mamestra brassicae NPV)(494)+TX、Metaphycus helvolus(522)+TX、黄绿绿僵茵(Metarhizium anisopliae var.acridum)(学名)(523)+TX、金龟子绿僵菌小孢变种(Metarhizium anisopliae var.anisopliae)(学名)(523)+TX、松黄叶蜂(Neodiprion sertifer)核多角体病毒和红头松树叶蜂(N.lecontei)核多角体病毒(575)+TX、小花蝽(596)+TX、玫烟色拟青霉(Paecilomyces fumosoroseus)(613)+TX、智利捕植螨(Phytoseiulus persimilis)(644)+TX、甜菜夜蛾(Spodopteraexigua multicapsid)多核衣壳核多角体病毒(学名)(741)+TX、毛蚊线虫(Steinernemabibionis)(742)+TX、小卷蛾斯氏线虫(Steinernema carpocapsae)(742)+TX、夜蛾斯氏线虫(742)+TX、Steinernema glaseri(742)+TX、Steinernema riobrave(另名)(742)+TX、Steinernema riobrayis(742)+TX、Steinernema scapterisci(742)+TX、斯氏线虫属(Steinernema spp.)(742)+TX、赤眼蜂属(826)+TX、西方盲走螨(Typhlodromusoccidentalis)(844)和蜡蚧轮枝茵(Verticillium lecanii)(848)+TX,
土壤消毒剂,该土壤消毒剂选自由以下物质组成的组:碘甲烷(IUPAC名称)(542)和甲基溴(537)+TX,
化学不育剂,该化学不育剂选自由以下物质组成的组:唑磷嗪(apholate)[CCN]+TX、双(氮丙啶)甲氨基膦硫化物(bisazir)[CCN]+TX、白消安[CCN]+TX、除虫脲(250)+TX、迪麦替夫(dimatif)[CCN]+TX、六甲蜜胺(hemel)[CCN]+TX、六甲磷(hempa)[CCN]+TX、甲基涕巴(metepa)[CCN]+TX、甲硫涕巴(methiotepa)[CCN]+TX、不育特(methyl apholate)[CCN]+TX、不孕啶(morzid)[CCN]+TX、氟幼脲(penfluron)[CCN]+TX、涕巴(tepa)[CCN]+TX、硫代六甲磷(thiohempa)[CCN]+TX、硫涕巴[CCN]+TX、曲他胺[CCN]和尿烷亚胺[CCN]+TX,
昆虫信息素,该昆虫信息素选自由以下物质组成的组:(E)-癸-5-烯-1-基乙酸酯与(E)-癸-5-烯-1-醇(IUPAC名称)(222)+TX、(E)-十三碳-4-烯-1-基乙酸酯(IUPAC名称)(829)+TX、(E)-6-甲基庚-2-烯-4-醇(IUPAC名称)(541)+TX、(E,Z)-十四碳-4,10-二烯-1-基乙酸酯(IUPAC名称)(779)+TX、(Z)-十二碳-7-烯-1-基乙酸酯(IUPAC名称)(285)+TX、(Z)-十六碳-11-烯醛(IUPAC名称)(436)+TX、(Z)-十六碳-11-烯-1-基乙酸酯(IUPAC名称)(437)+TX、(Z)-十六碳-13-烯-11-炔-1-基乙酸酯(IUPAC名称)(438)+TX、(Z)-二十-13-烯-10-酮(IUPAC名称)(448)+TX、(Z)-十四碳-7-烯-1-醛(IUPAC名称)(782)+TX、(Z)-十四碳-9-烯-1-醇(IUPAC名称)(783)+TX、(Z)-十四碳-9-烯-1-基乙酸酯(IUPAC名称)(784)+TX、(7E,9Z)-十二碳-7,9-二烯-1-基乙酸酯(IUPAC名称)(283)+TX、(9Z,11E)-十四碳-9,11-二烯-1-基乙酸酯(IUPAC名称)(780)+TX、(9Z,12E)-十四碳-9,12-二烯-1-基乙酸酯(IUPAC名称)(781)+TX、14-甲基十八-1-烯(IUPAC名称)(545)+TX、4-甲基壬醛-5-醇与4-甲基壬醛-5-酮(IUPAC名称)(544)+TX、α-多纹素(multistriatin)[CCN]+TX、西部松小蠹集合信息素(brevicomin)[CCN]+TX、十二碳二烯醇(codlelure)[CCN]+TX、十二碳二烯醇(codlemone)(167)+TX、诱蝇酮(cuelure)(179)+TX、环氧十九烷(disparlure)(277)+TX、十二碳-8-烯-1基乙酸酯(IUPAC名称)(286)+TX、十二碳-9-烯-1-基乙酸酯(IUPAC名称)(287)+TX、十二碳-8+TX、10-二烯-1-基乙酸酯(IUPAC名称)(284)+TX、dominicalure[CCN]+TX、4-甲基辛酸乙酯(IUPAC名称)(317)+TX、丁香酚[CCN]+TX、南部松小蠹集合信息素(frontalin)[CCN]+TX、诱虫十六酯(gossyplure)(420)+TX、诱杀烯混剂(grandlure)(421)+TX、诱杀烯混剂I(421)+TX、诱杀烯混剂II(421)+TX、诱杀烯混剂III(421)+TX、诱杀烯混剂IV(421)+TX、醋酸十六烯酯(hexalure)[CCN]+TX、齿小蠹二烯醇(ipsdienol)[CCN]+TX、小蠢烯醇(ipsenol)[CCN]+TX、金龟子性诱剂(japonilure)(481)+TX、lineatin[CCN]+TX、litlure[CCN]+TX、粉纹夜蛾性诱剂(looplure)[CCN]+TX、诱杀酯(medlure)[CCN]+TX、megatomoic acid[CCN]+TX、诱虫醚(methyl eugenol)(540)+TX、诱虫烯(muscalure)(563)+TX、十八-2,13-二烯-1-基乙酸酯(IUPAC名称)(588)+TX、十八-3,13-二烯-1-基乙酸酯(IUPAC名称)(589)+TX、贺康彼(orfralure)[CCN]+TX、oryctalure(317)+TX、非乐康(ostramone)[CCN]+TX、诱虫环(siglure)[CCN]+TX、sordidin(736)+TX、食菌甲诱醇(sulcatol)[CCN]+TX、十四-11-烯-1-基乙酸酯(IUPAC名称)(785)+TX、特诱酮(839)+TX、特诱酮A(839)+TX、特诱酮B1(839)+TX、特诱酮B2(839)+TX、特诱酮C(839)和trunc-call[CCN]+TX,
昆虫驱避剂,该昆虫驱避剂选自以下物质组成的组:2-(辛基硫代)乙醇(IUPAC名称)(591)+TX、避蚊酮(butopyronoxyl)(933)+TX、丁氧基(聚丙二醇)(936)+TX、己二酸二丁酯(IUPAC名称)(1046)+TX、邻苯二甲酸二丁酯(1047)+TX、丁二酸二丁酯(IUPAC名称)(1048)+TX、避蚊胺[CCN]+TX、避蚊胺[CCN]+TX、驱蚊酯(dimethyl carbate)[CCN]+TX、乙基己二醇(1137)+TX、己脲[CCN]+TX、甲喹丁(methoquin-butyl)(1276)+TX、甲基新癸酰胺[CCN]+TX、氨羰基甲酸酯(oxamate)[CCN]和羟哌酯[CCN]+TX,
杀昆虫剂,该杀昆虫剂选自由以下物质组成的组:1-二氯-1-硝基乙烷(IUPAC/化学文摘名称)(1058)+TX、1,1-二氯-2,2-二(4-乙基苯基)乙烷(IUPAC名称)(1056)+TX、1,2-二氯丙烷(IUPAC/化学文摘名称)(1062)+TX、带有1,3-二氯丙烯的1,2-二氯丙烷(IUPAC名称)(1063)+TX、1-溴-2-氯乙烷(IUPAC/化学文摘名称)(916)+TX、乙酸2,2,2-三氯-1-(3,4-二氯苯基)乙基酯(IUPAC名称)(1451)+TX、2,2-二氯乙烯基2-乙基亚磺酰基乙基甲基磷酸酯(IUPAC名称)(1066)+TX、二甲基氨基甲酸2-(1,3-二硫杂环戊烷-2-基)苯基酯(IUPAC/化学文摘名称)(1109)+TX、硫氰酸2-(2-丁氧基乙氧基)乙基酯(IUPAC/化学文摘名称)(935)+TX、甲基氨基甲酸2-(4,5-二甲基-1,3-二氧环戊烷-2-基)苯基酯(IUPAC/化学文摘名称)(1084)+TX、2-(4-氯-3,5-二甲苯基氧基)乙醇(IUPAC名称)(986)+TX、2-氯乙烯基二乙基磷酸酯(IUPAC名称)(984)+TX、2-咪唑啉酮(IUPAC名称)(1225)+TX、2-异戊酰基茚满-1,3-二酮(IUPAC名称)(1246)+TX、甲基氨基甲酸2-甲基(丙-2-炔基)氨基苯基酯(IUPAC名称)(1284)+TX、月桂酸2-硫氰基乙基酯(IUPAC名称)(1433)+TX、3-溴-1-氯丙-1-烯(IUPAC名称)(917)+TX、二甲基氨基甲酸3-甲基-1-苯基吡唑-5-基酯(IUPAC名称)(1283)+TX、甲基氨基甲酸4-甲基(丙-2-炔基)氨基-3,5-二甲苯基酯(IUPAC名称)(1285)+TX、二甲基氨基甲酸5,5-二甲基-3-氧代环己-1-烯基酯(IUPAC名称)(1085)+TX、阿维菌素(1)+TX、乙酰甲胺磷(2)+TX、啶虫脒(4)+TX、家蝇磷[CCN]+TX、乙酰虫腈[CCN]+TX、氟丙菊酯(9)+TX、丙烯腈(IUPAC名称)(861)+TX、棉铃威(15)+TX、涕灭威(16)+TX、涕灭砜威(863)+TX、氯甲桥萘(864)+TX、烯丙菊酯(17)+TX、阿洛氨菌素[CCN]+TX、除害威(866)+TX、α-氯氰菊酯(202)+TX、α-蜕皮激素[CCN]+TX、磷化铝(640)+TX、赛硫磷(870)+TX、硫代酰胺(872)+TX、灭害威(873)+TX、胺吸磷(875)+TX、胺吸磷草酸氢盐(875)+TX、双甲脒(24)+TX、新烟碱(877)+TX、乙基杀扑磷(883)+TX、AVI 382(化合物代码)+TX、AZ 60541(化合物代码)+TX、印楝素(41)+TX、甲基吡啶磷(42)+TX、谷硫磷-乙基(44)+TX、谷硫磷-甲基(45)+TX、偶氮磷(889)+TX、苏云金芽孢杆菌δ内毒素类(52)+TX、六氟硅酸钡[CCN]+TX、多硫化钡(IUPAC/化学文摘名称)(892)+TX、熏菊酯[CCN]+TX、Bayer 22/190(研究代码)(893)+TX、Bayer 22408(研究代码)(894)+TX、噁虫威(58)+TX、丙硫克百威(60)+TX、杀虫磺(66)+TX、β氟氯氰菊酯(194)+TX、β-氯氰菊酯(203)+TX、联苯菊酯(76)+TX、生物烯丙菊酯(78)+TX、生物烯丙菊酯S-环戊烯基异构体(79)+TX、戊环苄呋菊酯(bioethanomethrin)[CCN]+TX、生物氯菊酯(908)+TX、除虫菊酯(80)+TX、二(2-氯乙基)醚(IUPAC名称)(909)+TX、双三氟虫脲(83)+TX、硼砂(86)+TX、溴灭菊酯+TX、溴苯烯磷(914)+TX、溴杀烯(918)+TX、溴-DDT[CCN]+TX、溴硫磷(920)+TX、溴硫磷-乙基(921)+TX、合杀威(924)+TX、噻嗪酮(99)+TX、畜虫威(926)+TX、脱甲基丁嘧啶磷(butathiofos)(927)+TX、丁酮威(103)+TX、丁酯膦(932)+TX、丁酮砜威(104)+TX、丁基哒螨灵+TX、硫线磷(109)+TX、砷酸钙[CCN]+TX、氰化钙(444)+TX、多硫化钙(IUPAC名称)(111)+TX、毒杀芬(941)+TX、氯灭杀威(943)+TX、甲萘威(115)+TX、克百威(118)+TX、二硫化碳(IUPAC/化学文摘名称)(945)+TX、四氯化碳(IUPAC名称)(946)+TX、三硫磷(947)+TX、丁硫克百成(119)+TX、杀螟丹(123)+TX、杀螟丹盐酸盐(123)+TX、西伐丁(725)+TX、冰片丹(960)+TX、氯丹(128)+TX、开蓬(963)+TX、杀虫脒(964)+TX、杀虫脒盐酸盐(964)+TX、氯氧磷(129)+TX、溴虫腈(130)+TX、毒虫畏(131)+TX、定虫隆(132)+TX、氯甲磷(136)+TX、氯仿[CCN]+TX、三氯硝基甲烷(141)+TX、氯辛硫磷(989)+TX、灭虫吡啶(990)+TX、毒死蜱(145)+TX、毒死蜱-甲基(146)+TX、虫螨磷(994)+TX、环虫酰肼(150)+TX、灰菊素I(696)+TX、灰菊素II(696)+TX、灰菊素类(696)+TX、顺式苄呋菊酯(cis-resmethrin)+TX、顺式苄呋菊酯(cismethrin)(80)+TX、功夫菊酯+TX、除线威(999)+TX、氯氰碘柳胺[CCN]+TX、噻虫胺(165)+TX、乙酰亚砷酸铜[CCN]+TX、砷酸铜[CCN]+TX、油酸铜[CCN]+TX、蝇毒磷(174)+TX、畜虫磷(1006)+TX、克罗米通[CCN]+TX、巴毒磷(1010)+TX、克芦磷酯(1011)+TX、冰晶石(177)+TX、CS 708(研究代码)(1012)+TX、苯腈膦(1019)+TX、杀螟睛(184)+TX、果虫磷(1020)+TX、环虫菊酯[CCN]+TX、乙氰菊酯(188)+TX、氟氯氰菊酯(193)+TX、三氯氟氰菊酯(196)+TX、氯氰菊酯(201)+TX、苯氰菊酯(206)+TX、环丙马秦(209)+TX、畜蜱磷[CCN]+TX、d-柠檬烯[CCN]+TX、d-四甲菊酯(788)+TX、DAEP(1031)+TX、棉隆(216)+TX、DDT(219)+TX、单甲基克百威(decarbofuran)(1034)+TX、溴氰菊酯(223)+TX、田乐磷(1037)+TX、田乐磷-O(1037)+TX、田乐磷-S(1037)+TX、内吸磷(1038)+TX、内吸磷-甲基(224)+TX、内吸磷-O(1038)+TX、内吸磷-O-甲基(224)+TX、内吸磷-S(1038)+TX、内吸磷-S-甲基(224)+TX、内吸磷-S-甲基砜(1039)+TX、丁醚脲(226)+TX、氯亚胺硫磷(1042)+TX、二胺磷(1044)+TX、二嗪磷(227)+TX、异氯磷(1050)+TX、除线磷(1051)+TX、敌敌畏(236)+TX、迪克力弗斯(dicliphos)+TX、迪克莱赛尔(dicresyl)[CCN]+TX、百治磷(243)+TX、地昔尼尔(244)+TX、狄氏刑(1070)+TX、二乙基5-甲基吡唑-3-基磷酸酯(IUPAC名称)(1076)+TX、除虫脲(250)+TX、二羟丙茶碱(dilor)[CCN]+TX、四氟甲醚菊酯[CCN]+TX、甲氟磷(1081)+TX、地麦威(1085)+TX、乐果(262)+TX、苄菊酯(1083)+TX、甲基毒虫畏(265)+TX、敌蝇威(1086)+TX、消螨酚(1089)+TX、消螨酚(dinex-diclexine)(1089)+TX、丙硝酚(1093)+TX、戊硝酚(1094)+TX、达诺杀(1095)+TX、呋虫胺(271)+TX、苯虫醚(1099)+TX、蔬果磷(1100)+TX、二氧威(1101)+TX、敌恶磷(1102)+TX、乙拌磷(278)+TX、苯噻乙双硫磷(dithicrofos)(1108)+TX、DNOC(282)+TX、多拉克汀[CCN]+TX、DSP(1115)+TX、蜕皮激素[CCN]+TX、EI 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25475(研究代码)(1386)+TX、尼亚那(ryania)(1387)+TX、利阿诺定(传统名称)(1387)+TX、沙巴藜芦(725)+TX、八甲磷(1389)+TX、硫线磷+TX、塞拉菌素[CCN]+TX、SI-0009(化合物代码)+TX、SI-0205(化合物代码)+TX、SI-0404(化合物代码)+TX、SI-0405(化合物代码)+TX、氟硅菊酯(728)+TX、SN72129(研究代码)(1397)+TX、亚砷酸钠[CCN]+TX、氰化钠(444)+TX、氟化钠(IUPAC/化学文摘名称)(1399)+TX、六氟硅酸钠(1400)+TX、五氯酚钠(623)+TX、硒酸钠(IUPAC名称)(1401)+TX、硫氰酸钠[CCN]+TX、苏硫磷(1402)+TX、多杀菌素(737)+TX、螺甲螨酯(739)+TX、螺虫乙酯(CCN)+TX、萨尔科福隆(sulcofuron)(746)+TX、萨尔科福隆钠(sulcofuron-sodium)(746)+TX、氟虫胺(750)+TX、治螟磷(753)+TX、磺酰氟(756)+TX、硫丙磷(1408)+TX、焦油类(758)+TX、τ-氟胺氰菊酯(398)+TX、噻螨威(1412)+TX、TDE(1414)+TX、虫酰肼(762)+TX、吡螨胺(763)+TX、丁基嘧啶磷(764)+TX、氟苯脲(768)+TX、七氟菊酯(769)+TX、双硫磷(770)+TX、TEPP(1417)+TX、环戊烯丙菊酯(1418)+TX、叔丁威(terbam)+TX、特丁硫磷(773)+TX、四氯乙烷[CCN]+TX、杀虫畏(777)+TX、四甲菊酯(787)+TX、θ氯氰菊酯(204)+TX、噻虫啉(791)+TX、塞芬诺克斯(thiafenox)+TX、噻虫嗪(792)+TX、苯噻硫磷(thicrofos)(1428)+TX、克虫威(1431)+TX、杀虫环(798)+TX、杀虫环草酸氢盐(798)+TX、硫双威(799)+TX、久效威(800)+TX、甲基乙拌磷(801)+TX、虫线磷(1434)+TX、杀虫单(thiosultap)(803)+TX、杀虫双(thiosultap-sodium)(803)+TX、苏云金素[CCN]+TX、唑虫酰胺(809)+TX、四溴菊酯(812)+TX、四氟苯菊酯(813)+TX、反式苄氯菊酯(transpermethrin)(1440)+TX、威菌磷(1441)+TX、唑蚜威(818)+TX、三唑磷(820)+TX、唑呀威+TX、敌百虫(824)+TX、三氯偏磷酸-3(trichlormetaphos-3)[CCN]+TX、毒壤膦(1452)+TX、三氯丙氧磷(1455)+TX、杀铃脲(835)+TX、混杀威(840)+TX、烯虫硫酯(1459)+TX、蚜灭磷(847)+TX、甲烯氟虫腈(vaniliprole)[CCN]+TX、藜芦定(725)+TX、藜芦碱(725)+TX、XMC(853)+TX、灭杀威(854)+TX、YI-5302(化合物代码)+TX、ζ-氯氰菊酯(205)+TX、泽塔米林(zetamethrin)+TX、磷化锌(640)+TX、丙硫恶唑磷(zolaprofos)(1469)以及ZXI 8901(研究代码)(858)+TX、氰虫酰胺[736994-63-19]+TX、氯虫酰胺[500008-45-7]+TX、唑螨氰(cyenopyrafen)[560121-52-0]+TX、丁氟螨酯[400882-07-7]+TX、氟虫吡喹(pyrifluquinazon)[337458-27-2]+TX、乙基多杀菌素(spinetoram)[187166-40-1+187166-15-0]+TX、螺虫乙酯[203313-25-1]+TX、砜虫啶(sulfoxaflor)[946578-00-3]+TX、丁虫腈(flufiprole)[704886-18-0]+TX、氯氟醚菊酯[915288-13-0]+TX、四氟醚菊酯(tetramethylfluthrin)[84937-88-2]+TX、triflumezopyrim(披露于WO 2012/092115中)+TX、fluxametamide(WO 2007/026965)+TX、ε-美特宁(epsilon-metofluthrin)[240494-71-7]+TX、ε-momfluorothrin[1065124-65-3]+TX、氟炔丙菊酯(fluazaindolizine)[1254304-22-7]+TX、氯炔丙菊酯(chloroprallethrin)[399572-87-3]+TX、fluxametamide[928783-29-3]+TX、氯氟氰虫酰胺(cyhalodiamide)[1262605-53-7]+TX、tioxazafen[330459-31-9]+TX、双酰胺杀虫剂(broflanilide)[1207727-04-5]+TX、丁烯氟虫腈[704886-18-0]+TX、环溴虫酰胺[1031756-98-5]+TX、氟氰虫酰胺(tetraniliprole)[1229654-66-3]+TX、戊吡虫胍(描述在WO2010/060231中)+TX、环氧虫啶(描述在WO2005/077934中)+TX,
杀软体动物剂,该杀软体动物剂选自由以下物质组成的组:二(三丁基锡)氧化物(IUPAC名称)(913)+TX、溴乙酰胺[CCN]+TX、砷酸钙[CCN]+TX、除线威(cloethocarb)(999)+TX、乙酰亚砷酸铜[CCN]+TX、硫酸铜(172)+TX、三苯锡(347)+TX、磷酸铁(IUPAC名称)(352)+TX、四聚乙醛(518)+TX、灭虫威(530)+TX、氯硝柳胺(576)+TX、氯硝柳胺乙醇胺盐(576)+TX、五氯酚(623)+TX、五氯苯氧化钠(623)+TX、噻螨威(tazimcarb)(1412)+TX、硫双威(799)+TX、三丁基氧化锡(913)+TX、杀螺吗啉(trifenmorph)(1454)+TX、混杀威(trimethacarb)(840)+TX、乙酸三苯基锡(IUPAC名称)(347)和三苯基氢氧化锡(IUPAC名称)(347)+TX、皮瑞普(pyriprole)[394730-71-3]+TX,
杀线虫剂,该杀线虫剂选自由以下物质组成的组:AKD-3088(化合物代码)+TX、1,2-二溴-3-氯丙烷(IUPAC/化学文摘名)(1045)+TX、1,2-二氯丙烷(IUPAC/化学文摘名)(1062)+TX、1,2-二氯丙烷与1,3-二氯丙烯(IUPAC名称)(1063)+TX、1,3-二氯丙烯(233)+TX、3,4-二氯四氢噻吩1,1-二氧化物(IUPAC/化学文摘名)(1065)+TX、3-(4-氯苯基)-5-甲基绕丹宁(IUPAC名称)(980)+TX、5-甲基-6-硫代-1,3,5-噻二嗪烷-3-基乙酸(IUPAC名称)(1286)+TX、6-异戊烯基氨基嘌呤(210)+TX、阿巴美丁(1)+TX、乙酰虫腈[CCN]+TX、棉铃威(15)+TX、涕灭威(aldicarb)(16)+TX、涕灭砜威(aldoxycarb)(863)+TX、AZ 60541(化合物代码)+TX、benclothiaz[CCN]+TX、苯茵灵(62)+TX、丁基哒螨酮(butylpyridaben)+TX、硫线磷(cadusafos)(109)+TX、克百威(carbofuran)(118)+TX、二硫化碳(945)+TX、丁硫克百威(119)+TX、氯化苦(141)+TX、毒死蜱(145)+TX、除线威(cloethocarb)(999)+TX、细胞分裂素(cytokinins)(210)+TX、棉隆(216)+TX、DBCP(1045)+TX、DCIP(218)+TX、除线特(diamidafos)(1044)+TX、除线磷(dichlofenthion)(1051)+TX、二克磷(dicliphos)+TX、乐果(262)+TX、依马克丁[CCN]+TX、苯甲酸依马克丁(291)+TX、依立诺克丁(291)+TX、[CCN]+TX、灭线磷(312)+TX、二溴乙烷(316)+TX、苯线磷(角namiphos)(326)+TX、吡螨胺+TX、丰索磷(fenpyrad)(1158)+TX、噻唑磷(fosthiazate)(408)+TX、丁硫环磷(fosthietan)(1196)+TX、糠醛[CCN]+TX、GY-81(研究代码)(423)+TX、速杀硫磷(heterophos)[CCN]+TX、碘甲烷(IUPAC名称)(542)+TX、isamidofos(1230)+TX、氯唑磷(isazofos)(1231)+TX、激动素(kinetin)[CCN]+TX、糠氨基嘌呤(mecarphon)(210)+TX、甲基灭蚜磷(mecarphon)(1258)+TX、威百亩(519)+TX、威百亩钾盐(519)+TX、威百亩钠盐(519)+TX、甲基溴(537)+TX、异硫氰酸甲酯(543)+TX、杀螨菌素肟(milbemycin oxime)[CCN]+TX、莫昔克丁(剔名)[CCN]+TX、疣孢漆斑茵(Myrothecium verrucaria)组分(565)+TX、NC-184(化合物代码)+TX、杀线威(602)+TX、甲拌磷(636)+TX、磷胺(639)+TX、磷虫威(phosphocarb)[CCN]+TX、硫线磷(sebufos)+TX、塞拉菌素(selamectin)[CCN]+TX、多杀菌素(737)+TX、叔丁威(terbam)+TX、特丁磷(terbufos)(773)+TX、四氯噻吩(IUPAC/化学文摘名)(1422)+TX、thiaf enox+TX、虫线磷(thionazin)(1434)+TX、三唑磷(triazophos)(820)+TX、triazuron+TX、二甲苯酚[CCN]+TX、YI-5302(化合物代码)和玉米素(210)+TX、fluensulfone[318290-98-1]+TX,
硝化作用抑制剂,该硝化作用抑制剂选自由以下物质组成的组:乙基黄原酸钾[CCN]以及氯啶(nitrapyrin)(580)+TX,
植物激活剂,该植物激活剂选自由以下物质组成的组:噻二唑素(acibenzolar)(6)+TX、噻二唑素-S-甲基(6)+TX、烯丙苯噻唑(probenazole)(658)和大虎杖(Reynoutriasachalinensis)提取物(720)+TX,
杀鼠剂,该杀鼠剂选自由以下物质组成的组:2-异戊酰茚满-1,3-二酮(IUPAC名称)(1246)+TX、4-(喹喔啉-2-基氨基)苯磺酰胺(IUPAC名称)(748)+TX、α-氯代醇[CCN]+TX、磷化铝(640)+TX、安妥(880)+TX、三氧化二砷(882)+TX、碳酸钡(891)+TX、双鼠脲(912)+TX、溴鼠隆(89)+TX、溴敌隆(91)+TX、溴鼠胺(92)+TX、氰化钙(444)+TX、氮醛糖(127)+TX、氯鼠酮(140)+TX、维生素D3(850)+TX、氯灭鼠灵(1004)+TX、克灭鼠(1005)+TX、杀鼠萘(175)+TX、杀鼠嘧啶(1009)+TX、鼠得克(246)+TX、噻鼠灵(249)+TX、敌鼠钠(273)+TX、维生素D2(301)+TX、氟鼠灵(357)+TX、氟乙酰胺(379)+TX、鼠朴定(1183)+TX、盐酸鼠朴定(1183)+TX、γ-HCH(430)+TX、HCH(430)+TX、氢氰酸(444)+TX、碘甲烷(IUPAC名称)(542)+TX、林旦(430)+TX、磷化镁(IUPAC名称)(640)+TX、甲基溴(537)+TX、鼠特灵(1318)+TX、毒鼠磷(1336)+TX、磷化氢(IUPAC名称)(640)+TX、磷[CCN]+TX、杀鼠酮(1341)+TX、亚砷酸钾[CCN]+TX、灭鼠优(1371)+TX、海葱糖苷(1390)+TX、亚砷酸钠[CCN]+TX、氰化钠(444)+TX、氟乙酸钠(735)+TX、士的宁(745)+TX、硫酸铊[CCN]+TX、杀鼠灵(851)以及磷化锌(640)+TX,
增效剂,该增效剂选自由以下物质组成的组:2-(2-丁氧基乙氧基)乙基胡椒基酯(IUPAC名称)(934)+TX、5-(1,3-苯并二氧杂环戊烯-5-基)-3-己基环己-2-烯酮(IUPAC名称)(903)+TX、具有橙花叔醇的法呢醇(324)+TX、MB-599(研究代码)(498)+TX、MGK 264(研究代码)(296)+TX、增效醚(piperonyl butoxide)(649)+TX、增效醛(piprotal)(1343)+TX、增效酯(propyl isomer)(1358)+TX、S421(研究代码)(724)+TX、增效散(sesamex)(1393)+TX、芝麻林素(sesasmolin)(1394)和亚砜(1406)+TX,
动物驱避剂,该动物驱避剂选自由以下物质组成的组:蒽醌(32)+TX、氯醛糖(127)+TX、环烷酸铜[CCN]+TX、王铜(171)+TX、二嗪磷(227)+TX、二环戊二烯(化学名称)(1069)+TX、双胍盐(guazatine)(422)+TX、双胍醋酸盐(422)+TX、灭虫威(530)+TX、吡啶-4-胺(IUPAC名称)(23)+TX、塞仑(804)+TX、混杀威(trimethacarb)(840)+TX、环烷酸锌[CCN]和福美锌(856)+TX,
杀病毒剂,该杀病毒剂选自由以下物质组成的组:衣马宁[CCN]和利巴韦林[CCN]+TX,
创伤保护剂,该创伤保护剂选自由以下物质组成的组:氧化汞(512)+TX、辛噻酮(590)和甲基硫茵灵(802)+TX,
以及生物活性化合物,这些化合物选自由以下物质组成的组:阿扎康唑[60207-31-0]+TX、联苯三唑醇[70585-36-3]+TX、糠菌唑[116255-48-2]+TX、环唑醇[94361-06-5]+TX、苯醚甲环唑[119446-68-3]+TX、烯唑醇[83657-24-3]+TX、氟环唑[106325-08-0]+TX、腈苯唑[114369-43-6]+TX、氟喹唑[136426-54-5]+TX、氟硅唑[85509-19-9]+TX、粉唑醇[76674-21-0]+TX、己唑醇[79983-71-4]+TX、抑霉唑[35554-44-0]+TX、亚胺唑[86598-92-7]+TX、种菌唑[125225-28-7]+TX、叶菌唑[125116-23-6]+TX、腈菌唑[88671-89-0]+TX、稻瘟酯[101903-30-4]+TX、戊菌唑[66246-88-6]+TX、丙硫菌唑[178928-70-6]+TX、啶斑肟(pyrifenox)[88283-41-4]+TX、丙氯灵[67747-09-5]+TX、丙环唑[60207-90-1]+TX、硅氟唑(simeconazole)[149508-90-7]+TX、戊唑醇[107534-96-3]+TX、氟醚唑[112281-77-3]+TX、三唑酮[43121-43-3]+TX、三唑酮[55219-65-3]+TX、氟菌唑[99387-89-0]+TX、灭菌唑[131983-72-7]+TX、三环苯嘧醇[12771-68-5]+TX、氯苯嘧啶醇[60168-88-9]+TX、氟氯苯嘧啶醇[63284-71-9]+TX、乙嘧酚磺酸酯(bupirimate)[41483-43-6]+TX、甲菌定(dimethirimol)[5221-53-4]+TX、乙菌定(ethirimol)[23947-60-6]+TX、十二环吗啉[1593-77-7]+TX、苯锈啶(fenpropidine)[67306-00-7]+TX、丁苯吗啉[67564-91-4]+TX、螺环菌胺[118134-30-8]+TX、十三吗啉[81412-43-3]+TX、嘧菌环胺[121552-61-2]+TX、嘧菌胺[110235-47-7]+TX、嘧霉胺(pyrimethanil)[53112-28-0]+TX、拌种咯[74738-17-3]+TX、咯菌腈(fludioxonil)[131341-86-1]+TX、苯霜灵(benalaxyl)[71626-11-4]+TX、呋霜灵(furalaxyl)[57646-30-7]+TX、甲霜灵[57837-19-1]+TX、R甲霜灵[70630-17-0]+TX、呋酰胺[58810-48-3]+TX、恶霜灵(Oxadixyl)[77732-09-3]+TX、苯菌灵[17804-35-2]+TX、多菌灵[10605-21-7]+TX、咪菌威(debacarb)[62732-91-6]+TX、麦穗宁[3878-19-1]+TX、噻苯达唑[148-79-8]+TX、乙菌利(chlozolinate)[84332-86-5]+TX、菌核利(dichlozoline)[24201-58-9]+TX、异菌脲(Iprodione)[36734-19-7]+TX、甲菌利(myclozoline)[54864-61-8]+TX、腐霉利(procymidone)[32809-16-8]+TX、乙烯菌核利(vinclozoline)[50471-44-8]+TX、啶酰菌胺(boscalid)[188425-85-6]+TX、萎锈灵[5234-68-4]+TX、甲呋酰苯胺[24691-80-3]+TX、氟酰胺(Flutolanil)[66332-96-5]+TX、灭锈胺[55814-41-0]+TX、氧化萎锈灵[5259-88-1]+TX、吡噻菌胺(penthiopyrad)[183675-82-3]+TX、噻呋菌胺[130000-40-7]+TX、双胍盐[108173-90-6]+TX、多果定(dodine)[2439-10-3][112-65-2](游离碱)+TX、双胍辛胺(iminoctadine)[13516-27-3]+TX、嘧菌酯[131860-33-8]+TX、醚菌胺[149961-52-4]+TX、烯肟菌酯{Proc.BCPC,Int.Congr.,Glasgow.2003,1,93}+TX、氟嘧菌酯[361377-29-9]+TX、甲基醚菌酯[143390-89-0]+TX、苯氧菌胺[133408-50-1]+TX、肟菌酯[141517-21-7]+TX、肟醚菌胺[248593-16-0]+TX、啶氧菌酯[117428-22-5]+TX、唑菌胺酯[175013-18-0]+TX、福美铁[14484-64-1]+TX、代森锰锌[8018-01-7]+TX、代森锰[12427-38-2]+TX、代森联[9006-42-2]+TX、甲代森锌(propineb)[12071-83-9]+TX、塞仑[137-26-8]+TX、代森锌[12122-67-7]+TX、福美锌[137-30-4]+TX、敌菌丹(captafol)[2425-06-1]+TX、克菌丹[133-06-2]+TX、苯氟磺胺[1085-98-9]+TX、唑啶草(fluoroimide)[41205-21-4]+TX、灭菌丹[133-07-3]+TX、甲苯氟磺胺[731-27-1]+TX、波尔多(bordeaux)混合物[8011-63-0]+TX、氢氧化铜(copperhydroxid)[20427-59-2]+TX、氯化铜(copperoxychlorid)[1332-40-7]+TX、硫酸铜(coppersulfat)[7758-98-7]+TX、氧化铜(copperoxid)[1317-39-1]+TX、代森锰铜(mancopper)[53988-93-5]+TX、喹啉铜(oxine-copper)[10380-28-6]+TX、敌螨普(dinocap)[131-72-6]+TX、酞菌酯(硝基thal-isopropyl)[10552-74-6]+TX、克瘟散[17109-49-8]+TX、异稻瘟净(iprobenphos)[26087-47-8]+TX、稻瘟灵(isoprothiolane)[50512-35-1]+TX、氯瘟磷(phosdiphen)[36519-00-3]+TX、克菌磷(pyrazophos)[13457-18-6]+TX、甲基托氯磷(tolclofos-methyl)[57018-04-9]+TX、苯并噻二唑(acibenzolar-S-methyl)[135158-54-2]+TX、敌菌灵[101-05-3]+TX、苯噻菌胺[413615-35-7]+TX、灭瘟素(blasticidin)-S[2079-00-7]+TX、灭螨猛(chinomethionat)[2439-01-2]+TX、地茂散(chloroneb)[2675-77-6]+TX、百菌清[1897-45-6]+TX、环氟菌胺[180409-60-3]+TX、霜脲氰[57966-95-7]+TX、二氯萘醌(dichlone)[117-80-6]+TX、双氯氰菌胺(diclocymet)[139920-32-4]+TX、哒菌酮(diclomezine)[62865-36-5]+TX、氯硝胺(dicloran)[99-30-9]+TX、乙霉威(diethofencarb)[87130-20-9]+TX、烯酰吗啉[110488-70-5]+TX、SYP LI90(Flumorph)[211867-47-9]+TX、二噻农(dithianon)[3347-22-6]+TX、噻唑菌胺(ethaboxam)[162650-77-3]+TX、土菌灵(etridiazole)[2593-15-9]+TX、恶唑菌酮[131807-57-3]+TX、咪唑菌酮(fenamidone)[161326-34-7]+TX、稻瘟酰胺(Fenoxanil)[115852-48-7]+TX、三苯锡(fentin)[668-34-8]+TX、嘧菌腙(ferimzone)[89269-64-7]+TX、氟啶胺(fluazinam)[79622-59-6]+TX、氟吡菌胺(fluopicolide)[239110-15-7]+TX、磺菌胺(flusulfamide)[106917-52-6]+TX、环酰菌胺[126833-17-8]+TX、福赛得(fosetyl-aluminium)[39148-24-8]+TX、恶霉灵(hymexazol)[10004-44-1]+TX、丙森锌[140923-17-7]+TX、IKF 916(赛座灭(Cyazofamid))[120116-88-3]+TX、春雷霉素(kasugamycin)[6980-18-3]+TX、磺菌威(methasulfocarb)[66952-49-6]+TX、苯菌酮[220899-03-6]+TX、戊菌隆(pencycuron)[66063-05-6]+TX、苯酞[27355-22-2]+TX、多氧霉素(polyoxins)[11113-80-7]+TX、噻菌灵(probenazole)[27605-76-1]+TX、百维威(propamocarb)[25606-41-1]+TX、碘喹唑酮(proquinazid)[189278-12-4]+TX、乐喹酮(pyroquilon)[57369-32-1]+TX、喹氧灵[124495-18-7]+TX、五氯硝苯[82-68-8]+TX、硫[7704-34-9]+TX、噻酰菌胺[223580-51-6]+TX、咪唑嗪(triazoxide)[72459-58-6]+TX、三环唑[41814-78-2]+TX、嗪氨灵[26644-46-2]+TX、有效霉素[37248-47-8]+TX、苯酰菌胺(zoxamide)(RH7281)[156052-68-5]+TX、双炔酰菌胺(mandipropamid)[374726-62-2]+TX、吡蚜酮(isopyrazam)[881685-58-1]+TX、塞德因(sedaxane)[874967-67-6]+TX、3-二氟甲基-1-甲基-1H-吡唑-4-羧酸(9-二氯亚甲基-1,2,3,4-四氢-1,4-桥亚甲基-萘-5-基)-酰胺(披露于WO 2007/048556中)+TX、3-二氟甲基-1-甲基-1H-吡唑-4-羧酸(3’,4’,5’-三氟-联苯基-2-基)-酰胺(披露于WO 2006/087343中)+TX、[(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-3-[(环丙基羰基)氧基]-1,3,4,4a,5,6,6a,12,12a,12b-十氢-6,12-二羟基-4,6a,12b-三甲基-11-氧代-9-(3-吡啶基)-2H,11H萘并[2,1-b]吡喃并[3,4-e]吡喃-4-基]甲基-环丙甲酸酯[915972-17-7]+TX、1,3,5-三甲基-N-(2-甲基-1-氧丙基)-N-[3-(2-甲基丙基)-4-[2,2,2-三氟-1-甲氧基-1-(三氟甲基)乙基]苯基]-1H-吡唑-4-甲酰胺[926914-55-8]+TX、lancotrione[1486617-21-3]+TX;氯氟吡啶酯[943832-81-3]+TX;ipfentrifluconazole[1417782-08-1]+TX;mefentrifluconazole[1417782-03-6]+TX;quinofumelin[861647-84-9]+TX;右旋反式氯丙炔菊酯[399572-87-3]+TX;氯氟氰虫酰胺[1262605-53-7]+TX;三氟咪啶酰胺[1254304-22-7]+Tx;fluxametamide[928783-29-3]+TX;ε-甲氧苄氟菊酯[240494-71-7]+TX;ε-momfluorothrin[1065124-65-3]+TX;氟唑菌酰羟胺(pydiflumetofen)[1228284-64-7]+TX;κ-联苯菊酯[439680-76-9]+TX;broflanilide[1207727-04-5]+TX;dicloromezotiaz[1263629-39-5]+TX;dipymetitrone[16114-35-5]+Tx;pyraziflumid[942515-63-1]+Tx;和κ-七氟菊酯[391634-71-2]+TX;以及
微生物剂,包括:鲁氏不动杆菌+TX、交替枝顶孢(Acremonium alternatum)+TX+TX、顶头孢霉(Acremonium cephalosporium)+TX+TX、Acremonium diospyri+TX、Acremonium obclavatum+TX、棉褐带卷蛾颗粒体病毒(AdoxGV)+TX、放射形土壤杆菌菌株K84+TX、互隔链格孢+TX、决明链格孢(Alternaria cassia)+TX、损毁链格孢+TX、白粉寄生孢+TX、黄曲霉AF36+TX、黄曲霉NRRL 21882+TX、曲霉属+TX、出芽短梗霉+TX、固氮螺菌属+TX、(+TX、)+TX、固氮菌属+TX、圆褐固氮菌+TX、孢囊固氮菌(BionaturalBlooming)+TX、解淀粉芽孢杆菌+TX、蜡样芽孢杆菌+TX、原生祛病芽孢杆菌(Bacillus chitinosporus)菌株CM-1+TX、原生祛病芽孢杆菌菌株AQ746+TX、地衣芽孢杆菌菌株HB-2(BiostartTM )+TX、地衣芽孢杆菌菌株3086(+TX、Green)+TX、环状芽孢杆菌+TX、坚硬芽孢杆菌(+TX、+TX、)+TX、坚硬芽孢杆菌菌株I-1582+TX、浸麻芽孢杆菌+TX、Bacillus marismortui+TX、巨大芽孢杆菌+TX、蕈状芽孢杆菌菌株AQ726+TX、日本甲虫芽孢杆菌(Milky Spore)+TX、短小芽孢杆菌属+TX、短小芽孢杆菌菌株GB34(Yield)+TX、短小芽孢杆菌菌株AQ717+TX、短小芽孢杆菌菌株QST 2808(+TX、Ballad)+TX、球形芽孢杆菌+TX、芽孢杆菌属+TX、芽孢杆菌属菌株AQ175+TX、芽孢杆菌属菌株AQ177+TX、芽孢杆菌属菌株AQ178+TX、枯草芽孢杆菌菌株QST 713(+TX、+TX、)+TX、枯草芽孢杆菌菌株QST 714+TX、枯草芽孢杆菌菌株AQ153+TX、枯草芽孢杆菌菌株AQ743+TX、枯草芽孢杆菌菌株QST3002+TX、枯草芽孢杆菌菌株QST3004+TX、枯草芽孢杆菌解淀粉变种菌株FZB24(+TX、)+TX、苏云金芽孢杆菌Cry 2Ae+TX、苏云金芽孢杆菌Cry1Ab+TX、苏云金芽孢杆菌鲇泽亚种(Bacillus thuringiensis aizawai)GC 91+TX、苏云金芽孢杆菌以色列亚种(Bacillus thuringiensis israelensis)(+TX、+TX、)+TX、苏云金芽孢杆菌库尔斯塔克亚种(Bacillus thuringiensis kurstaki)(+TX、+TX、+TX、+TX、Scutella+TX、Turilav+TX、+TX、Dipel+TX、+TX、)+TX、苏云金芽孢杆菌库尔斯塔克亚种BMP 123+TX、苏云金芽孢杆菌库尔斯塔克亚种HD-1(Bioprotec-CAF/)+TX、苏云金芽孢杆菌菌株BD#32+TX、苏云金芽孢杆菌菌株AQ52+TX、苏云金芽孢杆菌鲇泽变种(+TX、)+TX、细菌属(+TX、+TX、)+TX、密执安棍状杆菌(Clavipacter michiganensis)的噬菌体+TX、+TX、球孢白僵菌(+TX、Brocaril)+TX、球孢白僵菌GHA(Mycotrol+TX、Mycotrol+TX、)+TX、布氏白僵菌(+TX、Schweizer+TX、)+TX、白僵菌属+TX、灰葡萄孢霉+TX、大豆慢生型根瘤菌+TX、短短小芽孢杆菌+TX、苏云金芽孢杆菌拟步行甲亚种(Bacillusthuringiensis tenebrionis)+TX、BtBooster+TX、洋葱伯克霍尔德菌(+TX、+TX、Blue)+TX、伯克霍尔德菌(Burkholderia gladii)+TX、唐菖蒲伯克霍尔德菌+TX、伯克霍尔德菌属+TX、加拿大蓟真菌(CBH Canadian)+TX、奶酪假丝酵母+TX、无名假丝酵母+TX、Candida fructus+TX、光滑念珠菌+TX、吉利蒙念珠菌(Candida guilliermondii)+TX、口津假丝酵母+TX、橄榄假丝酵母菌株O+TX、近平滑假丝酵母+TX、菌膜假丝酵母+TX、铁红假丝酵母+TX、拉考夫假丝酵母(Candida reukaufii)+TX、齐藤假丝酵母(Candida saitoana)(+TX、)+TX、清酒假丝酵母+TX、假丝酵母属+TX、纤细假丝酵母+TX、戴氏西地西菌(Cedeceadravisae)+TX、产黄纤维单胞菌+TX、螺卷毛壳+TX、球毛壳菌+TX、铁杉紫色杆菌(Chromobacterium subtsugae)菌株PRAA4-1T+TX、枝状枝孢菌+TX、尖孢枝孢+TX、Cladosporium chlorocephalum+TX、枝孢属+TX、极细枝孢霉+TX、粉红粘帚霉+TX、尖孢炭疽菌(Colletotrichum acutatum)+TX、盾壳霉+TX、盾壳霉属+TX、浅白隐球酵母+TX、土生隐球菌+TX、Cryptococcus infirmo-miniatus+TX、罗伦隐球酵母+TX、苹果异形小卷蛾颗粒体病毒+TX、坎平贪铜菌(Cupriavidus campinensis)+TX、苹果蠹蛾颗粒体病毒+TX、苹果蠹蛾颗粒体病毒(+TX、Madex+TX、Madex Max/)+TX、Cylindrobasidium laeve+TX、枝双孢霉属+TX、汉逊德巴利酵母+TX、Drechslera hawaiinensis+TX、阴沟肠杆菌+TX、肠杆菌科+TX、毒力虫霉+TX、黑附球菌(Epicoccum nigrum)+TX、黑附球菌(Epicoccum purpurascens)+TX、附球菌属+TX、花状线黑粉菌(Filobasidium floriforme)+TX、锐顶镰孢菌+TX、厚垣镰孢霉+TX、尖镰孢(/Biofox)+TX、层生镰孢+TX、镰孢属+TX、溶磷白地霉(Galactomyces geotrichum)+TX、链孢粘帚霉(+TX、)+TX、粉红粘帚霉+TX、粘帚霉属+TX、绿色粘帚霉+TX、颗粒体病毒属+TX、嗜盐盐芽孢杆菌(Halobacillus halophilus)+TX、沿岸盐芽孢杆菌(Halobacillus litoralis)+TX、特氏盐芽孢杆菌(Halobacillus trueperi)+TX、盐单胞菌属+TX、冰下盐单胞菌(Halomonas subglaciescola)+TX、盐弧菌变型(Halovibriovariabilis)+TX、葡萄汁有孢汉逊酵母+TX、棉铃虫核型多角体病毒+TX、玉米穗虫核型多角体病毒+TX、异黄酮-芒柄花黄素+TX、柠檬克勒克酵母+TX、克勒克酵母属+TX、大链壶菌(Lagenidium giganteum)+TX、长孢蜡蚧菌(Lecanicillium longisporum)+TX、蜡蚧轮枝菌(Lecanicilliummuscarium)+TX、舞毒蛾核多角体病毒+TX、嗜盐海球菌+TX、格氏梅拉菌(Meira geulakonigii)+TX、绿僵菌+TX、绿僵菌(Destruxin)+TX、Metschnikowia fruticola+TX、美极梅奇酵母(Metschnikowia pulcherrima)+TX、Microdochium dimerum+TX、蓝色小单孢菌(Micromonospora coerulea)+TX、Microsphaeropsis ochracea+TX、Muscodor albus 620+TX、Muscodorroseus菌株A3-5+TX、菌根属(Mycorrhizae spp.)(+TX、Root)+TX、疣孢漆斑菌菌株AARC-0255+TX、BROS+TX、Ophiostoma piliferum菌株D97+TX、粉质拟青霉(Paecilomyces farinosus)+TX、玫烟色拟青霉(+TX、)+TX、淡紫拟青霉(Paecilomyces linacinus)(Biostat)+TX、淡紫拟青霉菌株251(MeloCon)+TX、多粘类芽孢杆菌+TX、成团泛菌(BlightBan)+TX、泛菌属+TX、巴斯德氏芽菌属+TX、Pasteuria nishizawae+TX、黄灰青霉+TX、Penicillium billai(+TX、)+TX、短密青霉+TX、常现青霉+TX、灰黄青霉+TX、产紫青霉+TX、青霉菌属+TX、纯绿色肯霉+TX、大伏革菌(Phlebiopsisgigantean)+TX、解磷细菌+TX、隐地疫霉+TX、棕榈疫霉+TX、异常毕赤酵母+TX、Pichia guilermondii+TX、膜醭毕赤氏酵母+TX、指甲毕赤酵母+TX、树干毕赤酵母+TX、铜绿假单胞菌+TX、致金色假单胞菌(Pseudomonasaureofasciens)(Spot-Less)+TX、洋葱假单胞菌+TX、绿针假单胞菌+TX、皱褶假单胞菌(Pseudomonas corrugate)+TX、荧光假单胞菌菌株A506(BlightBan)+TX、恶臭假单胞菌+TX、Pseudomonas reactans+TX、假单胞菌属+TX、丁香假单胞菌+TX、绿黄假单胞菌+TX、荧光假单胞菌+TX、Pseudozyma flocculosa菌株PF-A22UL(Sporodex)+TX、纵沟柄锈菌(Pucciniacanaliculata)+TX、Puccinia thlaspeos(Wood)+TX、侧雄腐霉菌(Pythiumparoecandrum)+TX、寡雄腐霉(+TX、)+TX、缠器腐霉+TX、水生拉恩菌(Rhanella aquatilis)+TX、拉恩菌属+TX、根瘤菌(+TX、)+TX、丝核菌属+TX、球状红球菌菌株AQ719+TX、双倒卵形红冬孢酵母菌(Rhodosporidiumdiobovatum)+TX、圆红冬孢酵母菌+TX、红酵母属+TX、粘红酵母+TX、禾本红酵母+TX、胶红酵母(Rhodotorula mucilagnosa)+TX、深红酵母+TX、酿酒酵母+TX、玫瑰色盐水球菌(Salinococcus roseus)+TX、小核盘菌+TX、小核盘菌+TX、柱顶孢霉属+TX、Scytalidium uredinicola+TX、甜菜夜蛾核型多角体病毒(+TX、)+TX、粘质沙雷氏菌+TX、普城沙雷菌+TX、沙雷氏菌属+TX、粪生粪壳菌+TX、海灰翅夜蛾核型多角体病毒+TX、红掷孢酵母+TX、嗜麦芽寡养单胞菌+TX、不吸水链霉菌+TX、白丘链霉菌(Streptomyces albaduncus)+TX、脱叶链霉菌+TX、鲜黄链霉菌+TX、灰平链霉菌+TX、灰绿链霉菌+TX、利迪链霉菌+TX、利迪链霉菌WYEC-108+TX、紫色链霉菌+TX、小铁艾酵母(Tilletiopsis minor)+TX、铁艾酵母属+TX、棘孢木霉+TX、盖姆斯木霉(Trichoderma gamsii)+TX、深绿木霉+TX、钩状木霉TH 382+TX、里法哈茨木霉(Trichoderma harzianumrifai)+TX、哈茨木霉T-22(+TX、PlantShield+TX、+TX、)+TX、哈茨木霉T-39+TX、非钩木霉(Trichoderma inhamatum)+TX、康宁木霉+TX、木霉属LC 52+TX、木素木霉+TX、长柄木霉+TX、多孢木霉(Trichoderma polysporum)+TX、紫杉木霉+TX、绿色木霉+TX、绿色木霉(原来称为绿色粘帚霉GL-21)+TX、绿色木霉+TX、绿色木霉菌株ICC 080+TX、茁芽丝孢酵母+TX、毛孢子菌属+TX、单端孢属+TX、粉红单端孢+TX、Typhula phacorrhiza菌株94670+TX、Typhula phacorrhiza菌株94671+TX、黑细基格孢+TX、奥德曼细基格孢(Ulocladium oudemansii)+TX、玉蜀黍黑粉菌+TX、各种细菌和补充营养素 +TX、各种真菌(Millennium)+TX、厚垣轮枝孢菌+TX、蜡蚧轮枝菌(+TX、)+TX、Vip3Aa20+TX、Virgibaclillus marismortui+TX、野油菜黄单胞菌(Xanthomonas campestris pv.Poae)+TX、伯氏致病杆菌+TX、嗜线虫致病杆菌;以及
植物提取物,包括:松油+TX、印楝素(Plasma Neem+TX、+TX、+TX、+TX、植物IGR(+TX、)+TX、菜籽油(Lilly Miller)+TX、土荆芥附近荆芥(Chenopodium ambrosioidesnear ambrosioides)+TX、菊花浓汁(Chrysanthemum extract)+TX、提取印楝油(extract ofneem oil)+TX、唇形科的精油+TX、丁香迷迭香薄荷的提取物和百里香精油(Garden insect)+TX、甜菜碱+TX、大蒜+TX、柠檬草精油+TX、印度楝树精油+TX、猫薄荷(薄荷精油)+TX、荆芥卡塔琳娜州(Nepeta catarina)+TX、尼古丁+Tx、牛至精油+TX、胡麻科精油+TX、除虫菊+TX、皂皮树()+TX、大虎杖(Reynoutriasachalinensis)(+TX、)+TX、鱼藤酮(Eco)+TX、芸香料植物提取物+TX、豆油(Ortho)+TX、茶树精油(Timorex)+TX、百里香精油+TX、MMF+TX、+TX、迷迭香芝麻薄荷百里香和肉桂提取物的混合物+TX、丁香迷迭香和薄荷提取物的混合物+TX、丁香薄荷大蒜油和薄菏的混合物+TX、高岭土+TX、储存葡萄糖的褐藻以及
信息素,包括:黑头萤火虫信息素(3M喷洒型黑头萤火虫信息素)+TX、苹果蠹蛾信息素(派拉蒙分配器(Paramount dispenser)-(CM)/Isomate)+TX、葡萄卷叶蛾信息素(3M MEC-GBM喷洒型信息素)+TX、卷叶虫信息素(3M MEC-LR喷洒型信息素)+TX、家蝇信息素(Snip7Fly+TX、Starbar Premium Fly)+TX、梨小食心虫信息素(3M梨小食心虫喷洒型信息素)+TX、桃树钻心虫信息素+TX、番茄蛲虫信息素(3M喷洒型信息素)+TX、Entostat粉(来自棕榈树的提取物)(Exosex)+TX、(E+TX,Z+TX,Z)-3+TX,8+TX、,11十四烷三烯基乙酸酯+TX、(Z+TX,Z+TX,E)-7+TX,11+TX、13-十六碳三烯醛+TX、(E+TX,Z)-7+TX、9-十二碳二烯-1-基乙酸酯+TX、2-甲基-1-丁醇+TX、乙酸钙+TX、+TX、+TX、+TX、薰衣草千里酸酯;以及
宏生物剂,包括:短距蚜小蜂+TX、阿尔蚜茧蜂(Aphidius ervi)+TX、Acerophagus papaya+TX、二星瓢虫+TX、二星瓢虫+TX、二星瓢虫+TX、串茧跳小蜂(Ageniaspis citricola)+TX、巢蛾多胚跳小蜂+TX、安氏钝绥螨(Amblyseius andersoni)(+TX、)+TX、加州钝绥螨(Amblyseius californicus)(+TX、)+TX、胡瓜钝绥螨(+TX、Bugline)+TX、伪钝绥螨+TX、斯氏钝绥螨(Bugline+TX、)+TX、奥氏钝绥螨+TX、粉虱细蜂(Amitus hesperidum)+TX、原缨翅缨小蜂(Anagrus atomus)+TX、暗腹长索跳小蜂(Anagyrus fusciventris)+TX、卡玛长索跳小蜂(Anagyrus kamali)+TX、Anagyrusloecki+TX、粉蚧长索跳小蜂(Anagyrus pseudococci)+TX、红蜡蚧扁角跳小蜂(Anicetus benefices)+TX、金小蜂(Anisopteromalus calandrae)+TX、林地花蝽(Anthocoris nemoralis)+TX、短距蚜小蜂(+TX、)+TX、短翅蚜小蜂(Aphelinus asychis)+TX、科列马·阿布拉小蜂(Aphidiuscolemani)+TX、阿尔蚜茧蜂+TX、烟蚜茧蜂+TX、桃赤蚜蚜茧蜂+TX、食蚜瘿蚊+TX、食蚜瘿蚊+TX、岭南蚜小蜂+TX、印巴黄金蚜小蜂+TX、蠊卵长尾啮小蜂(Aprostocetus hagenowii)+TX、隐翅虫(Athetacoriaria)+TX、熊蜂属+TX、欧洲熊蜂(Natupol)+TX、欧洲熊蜂(+TX、)+TX、Cephalonomia stephanoderis+TX、黑背红瓢虫(Chilocorusnigritus)+TX、普通草蛉(Chrysoperla carnea)+TX、普通草蛉+TX、红通草蛉(Chrysoperla rufilabris)+TX、Cirrospilus ingenuus+TX、Cirrospilus quadristriatus+TX、白星橘啮小蜂(Citrostichus phyllocnistoides)+TX、Closterocerus chamaeleon+TX、Closterocerus属+TX、Coccidoxenoides perminutus+TX、Coccophagus cowperi+TX、赖食蚧蚜小蜂(Coccophagus 1ycimnia)+TX、螟黄足盘绒茧蜂+TX、菜蛾盘绒茧蜂+TX、孟氏隐唇瓢虫(+TX、)+TX、日本方头甲+TX、西伯利亚离颚茧蜂+TX、西伯利亚离颚茧蜂+TX、豌豆潜蝇姬小蜂+TX、小黑瓢虫(Delphastus catalinae)+TX、Delphastuspusillus+TX、Diachasmimorpha krausii+TX、长尾潜蝇茧蜂+TX、Diaparsis jucunda+TX、阿里食虱跳小蜂(Diaphorencyrtus aligarhensis)+TX、豌豆潜叶蝇姬小蜂+TX、豌豆潜叶蝇姬小蜂(+TX、)+TX、西伯利亚离颚茧蜂(+TX、)+TX、歧脉跳小蜂属+TX、盾蚧长缨蚜小蜂+TX、丽蚜小蜂(Encarsia+TX、+TX、)+TX、浆角蚜小蜂(Eretmocerus eremicus)+TX、哥德恩蚜小蜂(Encarsia guadeloupae)+TX、海地恩蚜小蜂(Encarsia haitiensis)+TX、细扁食蚜蝇+TX、Eretmoceris siphonini+TX、浆角蚜小蜂(Eretmoceruscalifornicus)+TX、浆角蚜小蜂(Eretmocerus eremicus)(+TX、)+TX、浆角蚜小蜂(Eretmocerus eremicus)+TX、海氏桨角蚜小蜂+TX、蒙氏桨角蚜小蜂(+TX、Eretline)+TX、Eretmocerus siphonini+TX、四斑光缘瓢虫(Exochomus quadripustulatus)+TX、食螨瘿蚊(Feltiella acarisuga)+TX、食螨瘿蚊+TX、阿里山潜蝇茧蜂+TX、Fopius ceratitivorus+TX、芒柄花黄素(Wirless)+TX、细腰凶蓟马+TX、西方静走螨(Galendromusoccidentalis)+TX、莱氏棱角肿腿蜂(Goniozus legneri)+TX、麦蛾柔茧蜂+TX、异色瓢虫+TX、异小杆线虫属(Lawn)+TX、嗜菌异小杆线虫(+TX、+TX、+TX、+TX、+TX、+TX、+TX、)+TX、大异小杆线虫(Heterorhabditis megidis)(Nemasys+TX、BioNem+TX、Exhibitline+TX、)+TX、集栖瓢虫(Hippodamia convergens)+TX、尖狭下盾螨(Hypoaspisaculeifer)(+TX、)+TX、兵下盾螨(Hypoaspis miles)(+TX、)+TX、黑色枝跗瘿蜂+TX、Lecanoideus floccissimus+TX、Lemophagus errabundus+TX、三色丽突跳小蜂(Leptomastidea abnormis)+TX、Leptomastix dactylopii+TX、长角跳小蜂(Leptomastix epona)+TX、Lindorus lophanthae+TX、Lipolexis oregmae+TX、叉叶绿蝇+TX、茶足柄瘤蚜茧蜂+TX、暗黑长脊盲蝽(Macrolophus caliginosus)(+TX、+TX、)+TX、Mesoseiulus longipes+TX、黄色阔柄跳小蜂(Metaphycus flavus)+TX、Metaphycus lounsburyi+TX、角纹脉褐蛉+TX、黄色花翅跳小蜂(Microterys flavus)+TX、Muscidifurax raptorellus和Spalangia cameroni+TX、Neodryinus typhlocybae+TX、加州新小绥螨+TX、胡瓜钝绥螨+TX、虚伪新小绥螨(Neoseiulus fallacis)+TX、Nesideocoris tenuis(+TX、)+TX、古铜黑蝇+TX、狡小花蝽(Orius insidiosus)(+TX、)+TX、无毛小花蝽(Orius laevigatus)(+TX、)+TX、大型小花蝽(Orius majusculus)+TX、小黑花椿象+TX、Pauesiajuniperorum+TX、酸酱瓢虫腹柄姬小蜂(Pediobius foveolatus)+TX、Phasmarhabditishermaphrodita+TX、Phymastichus coffea+TX、Phytoseiulus macropilus+TX、智利小植绥螨(+TX、)+TX、斑腹刺益蝽+TX、Pseudacteon curvatus+TX、Pseudacteon obtusus+TX、Pseudacteon tricuspis+TX、Pseudaphycus maculipennis+TX、Pseudleptomastix mexicana+TX、具毛嗜木虱跳小蜂(Psyllaephagus pilosus)+TX、同色短背茧蜂(Psyttalia concolor)(complex)+TX、胯姬小蜂属+TX、Rhyzobius lophanthae+TX、澳洲瓢虫+TX、Rumina decollate+TX、Semielacherpetiolatus+TX、麦长管蚜+TX、小卷蛾斯氏线虫(Nematac+TX、+TX、+TX、+TX、+TX、)+TX、夜蛾斯氏线虫(+TX、Nemasys+TX、+TX、+TX、+TX、+TX、+TX、+TX、)+TX、锯蜂线虫(Steinernema kraussei)(+TX、+TX、)+TX、里奥布拉夫线虫(Steinernema riobrave)(+TX、)+TX、蝼蛄斯氏线虫(Steinemema scapterisci)+TX、斯氏线虫属+TX、Steinemematid属(Guardian)+TX、深点食螨瓢虫+TX、亮腹釉小蜂+TX、Tetrastichus setifer+TX、Thrpobiussemiluteus+TX、中华长尾小蜂(Torymus sinensis)+TX、甘蓝夜蛾赤眼蜂+TX、甘蓝夜蛾赤眼蜂+TX、广赤眼蜂+TX、微小赤眼蜂+TX、玉米螟赤眼蜂+TX、宽脉赤眼蜂(Trichogrammaplatneri)+TX、短管赤眼蜂+TX、螟黑点瘤姬蜂;以及
其他生物剂,包括:脱落酸+TX、+TX、银叶菌(Chondrostereumpurpureum)(Chontrol)+TX、盘长孢状刺盘孢+TX、辛酸铜盐+TX、δ陷阱(Delta trap)+TX、解淀粉欧文氏菌(Hatpin)(+TX、Ni-HIBIT Gold)+TX、磷酸高铁+TX、漏斗陷阱+TX、+TX、Grower’s+TX、高油菜素内酯+TX、磷酸铁(Lilly Miller Worry FreeFerramolSlug&Snail)+TX、MCP冰雹陷阱+TX、Microctonus hyperodae+TX、Mycoleptodiscus terrestris+TX、+TX、+TX、+TX、信息素陷阱(Thripline)+TX、碳酸氢钾+TX、脂肪酸的钾盐+TX、硅酸钾溶液+TX、碘化钾+硫氰酸钾+TX、+TX、蜘蛛毒+TX、蝗虫微孢子虫(Semaspore Organic Grasshopper)+TX、粘着陷阱(Trapline+TX、Rebell)+TX以及陷阱+TX。
在活性成分之后的括号中的参考例如[3878-19-1]是指化学文摘登记号。以上描述的混合配对物是已知的。当这些活性成分包括在“The Pesticide Manual[杀有害生物剂手册]”[The Pesticide Manual-A World Compendium[杀有害生物剂手册-全球概览];第13版;编著:C.D.S.TomLin;英国农作物保护委员会(The British Crop ProtectionCouncil)]中时,它们在上文对于特定化合物在圆括号内给定的条目编号之下描述于该手册中;例如,化合物“阿巴美丁”在条目编号(1)之下描述。其中“[CCN]”是对于上文的特定化合物来加上的,所述的化合物包括在“Compendium of Pesticide Common Names”(农药通 用名概要)中,它们可以在国际互联网[A.Wood;Compendium of Pesticide Common Names,1995-2004]中查到;例如,化合物“乙酰虫腈”描述于国际互联网地址http://www.alanwood.net/pesticides/acetoprole.html。
上述的活性成分中大部分在上文是通过所谓的“通用名”、相关的“ISO通用名”或在个别情况下使用的另一个“通用名”来提及。若其名称不是“通用名”,则所使用的名称种类以特定化合物的圆括号中所给出的名称来代替;在该情况下,使用IUPAC名称、IUPAC/化学文摘名、“化学名称”、“传统名称”、“化合物名”或“研究代码”,或若既不使用指定名称也不使用“通用名”,则使用别名。“CAS登记号”意指化学文摘登记号。
选自表1至6以及P的具有式I的化合物与上述活性成分的活性成分混合物包括选自表1至6以及P的化合物和上述活性成分,优选地是处于从100∶1至1∶6000的混合比率,尤其是从50∶1至1∶50,更尤其是处于从20∶1至1∶20的比率,甚至更尤其从10∶1至1∶10,非常尤其是从5∶1和1∶5,尤其优选的是从2∶1至1∶2的比率给出的,并且从4∶1至2∶1的比率同样是优选的,特别是处于1∶1,或5∶1,或5∶2,或5∶3,或5∶4,或4∶1,或4∶2,或4∶3,或3∶1,或3∶2,或2∶1,或1∶5,或2∶5,或3∶5,或4∶5,或1∶4,或2∶4,或3∶4,或1∶3,或2∶3,或1∶2,或1∶600,或1∶300,或1∶150,或1∶35,或2∶35,或4∶35,或1∶75,或2∶75,或4∶75,或1∶6000,或1∶3000,或1∶1500,或1∶350,或2∶350,或4∶350,或1∶750,或2∶750,或4∶750的比率。那些混合比率是按重量计的。
如上描述的混合物可以被用于控制有害生物的方法中,该方法包括将含如上描述的混合物的组合物施用于有害生物或其环境中,除了通过手术或疗法用于处理人或动物体的方法以及在人或动物体上实施的诊断方法之外。
包含选自表1至6以及P的具有式I的化合物以及一种或多种如上所述的活性成分的混合物可以例如以单一的“掺水即用”的形式施用,以组合的喷洒混合物(该混合物由这些单一活性成分的单独配制品构成)(例如一种“桶混制剂”)施用,并且当以顺序的方式(即,一个在另一个适度短的时期之后,例如几小时或几天)施用时组合使用这些单独活性成分来施用。施用选自表1至6以及P的这些具有式I的化合物和如上所述活性成分的顺序对于实施本发明并不是至关重要的。
根据本发明的组合物还可以包含其他固体或液体助剂,如稳定剂,例如未环氧化的或环氧化的植物油(例如环氧化的椰子油、菜籽油或大豆油),消泡剂(例如硅酮油),防腐剂,粘度调节剂,粘合剂和/或增粘剂,肥料或其他用于获得特定效果的活性成分,例如杀细菌剂、杀真菌剂、杀线虫剂、植物活化剂、杀软体动物剂或除草剂。
根据本发明的组合物是以本身已知的方式,在不存在助剂的情况下,例如通过研磨、筛选和/或压缩固体活性成分;和在至少一种助剂的存在下,例如通过紧密混合活性成分与一种或多种助剂和/或将活性成分与一种或多种助剂一起研磨来制备。用于制备组合物的这些方法和用于制备这些组合物的化合物I的用途也是本发明的主题。
这些组合物的施用方法,即是控制上述类型的有害生物的方法,如喷雾、雾化,撒粉,刷涂,包衣,撒播或浇灌-它们被选择以适于普遍情况的预期目的-并且这些组合物用于控制上述类型的有害生物的用途是本发明的其他主题。典型的浓度比是在0.1ppm与1000ppm之间,优选地在0.1ppm与500ppm之间的活性成分。每公项的施用量总体上是每公项1g到2000g活性成分,尤其是10g/ha到1000g/ha,优选地10g/ha到600g/ha。
在作物保护领域中,优选的施用方法是施用至这些植物的叶(叶施药),可能的是选择施用的频率和比率以符合所讨论的有害生物的侵染风险。可替代地,该活性成分可以通过根系统(内吸作用)到达植物,这是通过用一种液体组合物将这些植物的所在地浸透或者通过将固体形式的活性成分引入植物的所在地(例如引入土壤,例如以颗粒(土施)的形式)来实现的。在水稻作物的情况下,这样的颗粒剂可以被计量地添加淹水的稻田中。
本发明的这些化合物及其组合物还适合于植物繁殖材料的保护(例如种子,像果实、块茎或籽粒,或者苗圃植物)对抗上述类型的有害生物。可以用该化合物在种植前对该繁殖材料进行处理,例如可以在播种前对种子进行处理。可替代地,该化合物可以施用至种子籽粒(包衣),这是通过将籽粒浸渍入液体组合物中或通过施涂固体组合物层实现的。当该繁殖材料被种植在施用处时,还可能例如在条播期间将这些组合物施入种子犁沟。这些用于植物繁殖材料的处理方法和因此处理的植物繁殖材料是本发明另外的主题。典型的处理比率将取决于有待控制的植物以及有害生物/真菌,通常在每100kg种子1克至200克之间,优选在每100kg种子5克至150克之间,例如在每100kg种子10克至100克之间。
术语种子包括所有种类的种子以及植物繁殖体,包括但并不限于真正的种子、种子块、吸盘、谷粒、鳞球茎、果实、块茎、谷物、根茎、插条、切割枝条以及类似物并且在一个优选的实施例中是指真正的种子。
本发明还包括用具有式I的化合物包衣或处理的种子或含有具有式I的化合物的种子。尽管成分的更多或更少的部分可以渗透到该种子材料中,这取决于施用的方法,术语“包衣或处理和/或含有”通常表示在施用的时候,在大多数情况下,该活性成分在该种子的表面。当所述种子产物(再)种植时,它可以吸收该活性成分。在一个实施例中,本发明使得一种其上粘附有具有式(I)的化合物的植物繁殖材料可得。此外,由此可得一种包括用具有式(I)的化合物处理过的植物繁殖材料的组合物。
种子处理包括本领域中已知的所有适合的种子处理技术,例如拌种、种子包衣、种子撒粉、浸种以及种子造粒。可以通过任何已知的方法实现具有式I的化合物的种子处理施用,例如,在这些种子播种之前或播种/种植过程中喷雾或通过撒粉。
生物学实例:
实例B1:对抗海灰翅夜蛾(埃及棉叶虫)的活性:
将棉花叶圆片置于24孔微量滴定板中的琼脂上并且用从10’000ppm DMSO储备溶液中制备的水性测试溶液进行喷雾。在干燥之后,将叶圆片用五只L1期幼虫进行侵染。侵染3天之后,相比于未处理样品,针对死亡率、拒食效果以及生长抑制对这些样品进行评估。测试样品的海灰翅夜蛾的控制为在死亡率、拒食作用、以及生长抑制中的至少一种比未处理样品更高时。
以下化合物在200ppm施用率下得到至少80%的控制:P1、P2、P3、P4、P5、P6、P7、P8、P9、P10、P11、P12和P13。
实例B2:对抗海灰翅夜蛾(埃及棉叶虫)的活性
将测试化合物用移液管从10’000ppm DMSO储备溶液施用到24孔板中并且与琼脂进行混合。将莴苣种子置于琼脂上并且用另一块也包含琼脂的平板封闭该多孔板。7天之后,根已经将化合物吸收并且莴苣已经生长进入盖平板。现在将这些莴苣叶切到盖平板中。将夜蛾属卵吸移穿过潮湿凝胶印记纸上的塑料模板及其所封闭的平板。侵染6天之后,相比于未处理样品,针对死亡率、拒食效果以及生长抑制对这些样品进行评估。
以下化合物在12.5ppm测试比率处给出了这三个类别(死亡率、拒食效果、或生长抑制)中至少一个的至少80%的效果:P3、P4、P6、P8、P10和P11。
实例B3:对抗小菜蛾(Plutella xylostella)(小菜蛾(Diamond back moth))的活些
将具有人工饲料的24孔微量滴定板用从10’000 ppm DMSO储备溶液中制备的水性测试溶液通过移液进行处理。在干燥之后,用L2期幼虫对各板进行侵染(10至15只/孔)。侵染5天之后,相比于未处理样品,针对死亡率和生长抑制对这些样品进行评估。
以下化合物在200ppm施用率下给出了这两个类别(死亡率或生长抑制)中至少一个的至少80%的效果:P1、P2、P3、P4、P5、P6、P7、P8、P9、P10、P11、P12和P13。
实例B4:对抗黄瓜条叶甲(玉米根虫)的活性
将置于24孔微量滴定板中的琼脂层上的玉米芽通过喷雾用从10’000ppm DMSO储备溶液中制备的水性测试溶液进行处理。在干燥之后,用L2期幼虫对各板进行侵染(6至10只/孔)。侵染4天之后,相比于未处理样品,针对死亡率和生长抑制对这些样品进行评估。
以下化合物在200ppm施用率下给出了这两个类别(死亡率或生长抑制)中至少一个的至少80%的效果:P1、P2、P3、P4、P5、P6、P7、P8、P9、P10、P11、P12和P13。
实例B5:对抗桃蚜(Myzus persicae)(碧桃蚜(Green peach aphid))的活性
将向日葵叶圆片置于24孔微量滴定板中的琼脂上并且用从10’000 ppm DMSO储备溶液中制备的水性测试溶液进行喷雾。在干燥之后,将叶圆片用混合年龄的蚜虫群体进行侵染。侵染6天之后,针对死亡率对这些样品进行评估。
以下化合物在200ppm施用率下得到至少80%的死亡率:P3、P4、P5、P6、P8、P10和P11。
实例B6:对抗桃蚜(Myzus persicae)(碧桃蚜(Green peach aphid))的活性
将受到混合年龄的蚜虫群体侵染的豌豆幼苗的根部直接放在从10’000ppmDMSO储备溶液中制备的水性测试溶液中。将幼苗放置在测试溶液中6天之后,针对死亡率对这些样品进行评估。
以下化合物在24ppm测试率下得到至少80%的死亡率:P8和P10。
实例B7:对抗西花蓟马(西方花蓟马)的活性:
将向日葵叶圆片置于24孔微量滴定板中的琼脂上并且用从10’000 ppm DMSO储备溶液中制备的水性测试溶液进行喷雾。在干燥之后,将叶圆片用混合年龄的花蓟马种群进行侵染。侵染7天之后,针对死亡率对这些样品进行评估。
以下化合物在200ppm施用率下得到至少80%的死亡率:P1、P2、P3、P5、P6、P8、P10和P12。
实例B8:对抗烟粉虱(棉粉虱)的活性:
将棉花叶圆片置于24孔微量滴定板中的琼脂上并且用从10’000ppm DMSO储备溶液中制备的水性测试溶液进行喷雾。在干燥之后,将叶圆片用成年粉虱进行侵染。孵育6天之后,针对死亡率对这些样品进行检查。
以下化合物在200ppm施用率下得到至少80%的死亡率:P4。
实例B9:对抗大豆褐椿(Euschistus heros)(新热带褐臭蝽)的活性
将24孔微量滴定板中的琼脂上的大豆叶用从10’000ppm DMSO储备溶液中制备的水性测试溶液进行喷雾。干燥之后,将叶用N-2期若虫进行侵染。侵染5天之后,相比于未处理样品,针对死亡率和生长抑制对这些样品进行评估。
以下化合物在200ppm施用率下给出了这两个类别(死亡率或生长抑制)中至少一个的至少80%的效果:P1、P5、P8、P10和P11。
实例B10:对抗二点叶螨(二斑叶螨)的活性:
将24孔微量滴定板中的琼脂上的豆叶圆片用从10’000ppm DMSO储备溶液中制备的水性测试溶液进行喷雾。在干燥之后,将叶圆片用混合年龄的螨种群进行侵染。侵染8天之后,针对混合种群(流动平台)的死亡率对这些样品进行评估。
以下化合物在200ppm施用率下得到至少80%的死亡率:P3。
实例B11:对抗埃及伊蚊(黄热病蚊子)的活性
在乙醇中,以200ppm的施用率,将测试溶液施加到12孔组织培养皿中。一旦沉积物干燥,将五天、两天至五天大的成年雌性埃及伊蚊添加到每个孔中,并且在棉塞中保持10%的蔗糖溶液。引入后一小时,进行击倒评估,并且在引入后24小时和48小时,评估死亡率。
以下化合物在48h和/或24h后对埃及伊蚊给出至少80%的控制:P1、P2、P3、P5、P7、P9、P11和P12。
实例B12:对抗斯氏按蚊(印度疟蚊)的活性
在乙醇中,以200ppm的施用率,将测试溶液施加到12孔组织培养皿中。一旦沉积物干燥,将五天、两天至五天大的成年雌性斯氏按蚊添加到每个孔中,并且在棉塞中保持10%的蔗糖溶液。引入后一小时,进行击倒评估,并且在引入后24小时和48小时,评估死亡率。
以下化合物在48h和/或24h后对斯氏按蚊给出至少80%的控制:P3、P5、P7、P9、P11和P12。
Claims (15)
1.一种具有式I的化合物
其中
G1是氮或CR2;
G2是氮或CR3;
G3是氮或CR4;
G4是氮或CR5;
G5是氮或CR6,其前提是不多于2个氮作为G可连续出现;
R2、R3、R4、R5或R6彼此独立地是氢、卤素、C1-C4卤代烷基、
被一个或两个羟基取代的C1-C4卤代烷基、被一个或两个甲氧基取代的C1-C4卤代烷基;
被一个或两个氰基取代的C1-C4卤代烷基;或
R2、R3、R4、R5或R6彼此独立地是C1-C4卤代烷基硫烷基、C1-C4卤代烷基亚磺酰基、C1-C4卤代烷基磺酰基、C1-C4卤代烷氧基、SF5、苯基羰基硫基、氰基、巯基、
C1-C4烷氧基羰基、C1-C4烷基羰基或-C(O)C1-C4卤代烷基;或
R2、R3、R4、R5或R6彼此独立地是可以被选自下组的取代基单或多取代的C3-C6环烷基,该组由以下各项组成:卤素、氰基和C1-C4烷基;或两个相邻的Ri,其中Ri选自R2、R3、R4、R5以及R6,可以一起形成片段-OCH2O-或-OCF2O-;
R8是氢、C1-C4烷基或C1-C4卤代烷基;
R9是氢、C1-C4烷基、C1-C4卤代烷基、氰基或卤素;
R7是选自下组的基团,该组由以下各项组成:式Q1和Q2
其中箭头表示连接至咪唑环的点;
并且其中A表示CH或N;
Q是可以被选自下组的取代基单取代或多取代的苯基,该组由以下各项组成:卤素、氰基、C1-C4烷基、C1-C4卤代烷基、C1-C4卤代烷氧基、C1-C4烷氧基、C1-C4卤代烷基硫烷基、C1-C4卤代烷基亚磺酰基、C1-C4卤代烷基磺酰基和-C(O)C1-C4卤代烷基;或者
Q是五-元至十元单环的或稠合的双环的环系统,该环系统经由碳原子连接至包含基团A的环,所述环系统可以是芳香族的、部分饱和的或完全饱和的并且包含1至4个选自下组的杂原子,该组由以下各项组成:氮、氧和硫,对于每个环系统不可能包含多于2个氧原子和多于2个硫原子,所述五元至十元环系统可以被独立地选自下组的取代基单取代至多取代,该组由以下各项组成:卤素、氰基、C1-C4烷基、C1-C4卤代烷基、C1-C4卤代烷氧基、C1-C4烷氧基、C1-C4烷基硫烷基、C1-C4烷基亚磺酰基、C1-C4烷基磺酰基、-C(O)C1-C4烷基、C1-C4卤代烷基硫烷基、C1-C4卤代烷基亚磺酰基、C1-C4卤代烷基磺酰基和-C(O)C1-C4卤代烷基;或者
Q是部分饱和的或完全饱和的五元至六元芳香族环系统,该环系统经由氮原子连接至包含基团A的环,所述环系统可以被选自下组的取代基单取代或多取代,该组由以下各项组成:卤素、氰基、C1-C4烷基、C1-C4卤代烷基、C1-C4卤代烷氧基、C1-C4烷氧基、C1-C4烷基硫烷基、C1-C4烷基亚磺酰基、C1-C4烷基磺酰基、-C(O)C1-C4烷基、C1-C4卤代烷基硫烷基、C1-C4卤代烷基亚磺酰基、C1-C4卤代烷基磺酰基和
-C(O)C1-C4卤代烷基;并且所述环系统包含选自下组的1个、2个或3个杂原子,该组由以下各项组成:氮、氧和硫,其中所述环系统可以不包含多于一个氧原子和不多于一个硫原子;或者
Q是C3-C6环烷基,或被选自下组的取代基单取代或多取代的C3-C6环烷基,该组由以下各项组成:卤素、氰基、C1-C4烷基、C1-C4卤代烷基、C3-C6环烷基和苯基,其中所述苯基可以被选自下组的取代基单取代或多取代,该组由以下各项组成:卤素、氰基、C1-C4烷基、C1-C4卤代烷基、C1-C4卤代烷氧基、C1-C4烷氧基、C1-C4卤代烷基硫烷基、C1-C4卤代烷基亚磺酰基、C1-C4卤代烷基磺酰基和-C(O)C1-C4卤代烷基;或者
Q是C2-C6烯基,或被选自下组的取代基单取代或多取代的C2-C6烯基,该组由以下各项组成:卤素、氰基、C1-C4烷基、C1-C4卤代烷基、C3-C6环烷基和苯基,其中所述苯基可以被选自下组的取代基单取代或多取代,该组由以下各项组成:卤素、氰基、C1-C4烷基、C1-C4卤代烷基、C1-C4卤代烷氧基、C1-C4烷氧基、C1-C4卤代烷基硫烷基、C1-C4卤代烷基亚磺酰基、C1-C4卤代烷基磺酰基和-C(O)C1-C4卤代烷基;或者
Q是C2-C6炔基,或被选自下组的取代基单取代或多取代的C2-C6炔基,该组由以下各项组成:卤素、氰基、C1-C4烷基、C1-C4卤代烷基、C3-C6环烷基、三(C1-C4烷基)甲硅烷基和苯基,其中所述苯基可以被选自下组的取代基单取代或多取代,该组由以下各项组成:卤素、氰基、C1-C4烷基、C1-C4卤代烷基、C1-C4卤代烷氧基、C1-C4烷氧基、C1-C4卤代-烷基硫烷基、C1-C4卤代烷基亚磺酰基、C1-C4卤代烷基磺酰基和-C(O)C1-C4卤代烷基;或者
Q是C1-C6卤代烷基硫烷基、C1-C6卤代烷基亚磺酰基、C1-C6卤代烷基磺酰基、C1-C6卤代烷氧基、-C(O)C1-C4卤代烷基、C1-C6烷基硫烷基、C1-C6烷基亚磺酰基、或C1-C6烷基磺酰基;
X是S、SO或SO2;以及
R1是C1-C4烷基、C1-C4卤代烷基、C3-C6环烷基、C3-C6环烷基-C1-C4烷基;或者
R1是被选自下组的取代基单取代或多取代的C3-C6环烷基,该组由以下各项组成:卤素、氰基和C1-C4烷基;或者
R1是被选自下组的取代基单取代或多取代的C3-C6环烷基-C1-C4烷基,该组由以下各项组成:卤素、氰基和C1-C4烷基;或者
R1是C2-C6烯基、C2-C6卤代烯基或C2-C6炔基;
以及具有式I的化合物的农用化学上可接受的盐、立体异构体、对映异构体、互变异构体和N-氧化物。
2.根据权利要求1所述的具有式I的化合物,其中
Q选自下组,该组由以下杂环基团组成:
吡咯基;吡唑基;异噁唑基;呋喃基(furanyl);噻吩基;咪唑基;噁唑基;噻唑基;异噻唑基;三唑基;噁二唑基;噻二唑基;四唑基;呋喃基(furyl);吡啶基;嘧啶基;吡嗪基;哒嗪基;三嗪基,吡喃基;喹唑啉基;异喹啉基;吲嗪基;异苯并呋喃基萘啶基;喹喔啉基;噌啉基;酞嗪基;苯并噻唑基;苯并噁唑基;苯并三唑基;吲唑基;吲哚基;(1H-吡咯-1-基)-;(1H-吡咯-2-基)-;(1H-吡咯-3-基)-;(1H-吡唑-1-基)-;(1H-吡唑-3-基)-;(3H-吡唑-3-基)-;(1H-吡唑-4-基)-;(3-异噁唑基)-;(5-异噁唑基)-;(2-呋喃基)-;(3-呋喃基)-;(2噻吩基)-;(3-噻吩基)-;(1H-咪唑-2-基)-;(1H-咪唑-4-基)-;(1H-咪唑-5-基)-;(2-噁唑-2-基)-;(噁唑-4-基)-;(噁唑-5-基)-;(噻唑-2-基)-;(噻唑-4-基)-;(噻唑-5-基)-;(异噻唑-3-基)-;(异噻唑-5-基)-;(1H-1,2,3-三唑-1-基)-;(1H-1,2,4-三唑-3-基)-;(4H-1,2,4-三唑-4-基)-;(1H-1,2,4-三唑-1-基)-;(1,2,3-噁二唑-2-基)-;(1,2,4-噁二唑-3-基)-;(1,2,4-噁二唑-4-基)-;(1,2,4-噁二唑-5-基)-;(1,2,3-噻二唑-2-基)-;(1,2,4-噻二唑-3-基)-;(1,2,4-噻二唑-4-基)-;(1,3,4-噻二唑-5-基)-;(1H-四唑-1-基)-;(1H-四唑-5-基)-;(2H-四唑-5-基)-;(2-吡啶基)-;(3-吡啶基)-;(4-吡啶基)-;(2-嘧啶基)-;(4-嘧啶基)-;(5-嘧啶基)-;(2-吡嗪基)-;(3-哒嗪基)-;(4-哒嗪基)-;(1,3,5-三嗪-2-基)-;(1,2,4-三嗪-5-基)-;(1,2,4-三嗪-6-基)-;(1,2,4-三嗪-3-基)-;(呋咱-3-基)-;(2-喹啉基)-;(3-喹啉基)-;(4-喹啉基)-;(5-喹啉基)-;(6-喹啉基)-;(3-异喹啉基)-;(4-异喹啉基)-;(2-喹唑啉基)-;(2-喹喔啉基)-;(5-喹喔啉基)-;(吡啶并[2,3-b]吡嗪-7-基)-;(苯并噁唑-5-基)-;(苯并噻唑-5-基)-;(苯并[b]噻吩-2-基)-和(苯并[1,2,5]噁二唑-5-基)-;二氢吲哚基以及四氢喹啉基。
3.根据权利要求1所述的具有式I的化合物,其中
Q选自下组,该组由以下各项组成:J-0至J-48:
其中每个基团J-0至J-48被Rx单取代、二取代或三取代,其中
每个Rx独立地选自:氢、卤素、氰基、C1-C4烷基、C1-C4卤代烷基、C1-C4卤代烷氧基、C1-C4烷氧基、C1-C4烷基硫烷基、C1-C4烷基亚磺酰基、C1-C4烷基磺酰基、-C(O)C1-C4烷基、C1-C4卤代烷基硫烷基、C1-C4卤代烷基亚磺酰基、C1-C4卤代烷基磺酰基和-C(O)C1-C4卤代烷基。
4.根据权利要求1所述的具有式I的化合物,由具有式I-1的化合物表示
其中
A、Q、G1、G2、G3、G4、以及G5是如在权利要求1中的式I下所定义的;
X1是S、SO或SO2;
R11是甲基、乙基、正丙基、异丙基或环丙基甲基;
R8是如以上在权利要求1中的式I下所定义的;并且
R9是如以上在权利要求1中的式I下所定义的。
5.根据权利要求1所述的具有式I的化合物,其由具有式I-2的化合物表示
其中
A、G1、G2、G3、G4、以及G5是如在权利要求1中的式I下所定义的;
X2是S、SO或SO2;
R12是甲基、乙基、正丙基、异丙基或环丙基甲基;
R8是如以上在权利要求1中的式I下所定义的;
R9是如以上在权利要求1中的式I下所定义的;并且
Qa1选自下组,该组由以下各项组成:
其中每个基团J是被Rx单取代、二取代或三取代的,其中
每个Rx独立地选自:氢、卤素、氰基、C1-C4烷基、C1-C4卤代烷基、C1-C4卤代烷氧基、C1-C4烷氧基、C1-C4烷基硫烷基、C1-C4烷基亚磺酰基、C1-C4烷基磺酰基、-C(O)C1-C4烷基、C1-C4卤代烷基硫烷基、C1-C4卤代烷基亚磺酰基、C1-C4卤代烷基磺酰基和-C(O)C1-C4卤代烷基。
6.根据权利要求1所述的具有式I的化合物,其由具有式I-3的化合物表示
其中
A是N或CH;
R10是被独立地选自下组的取代基单取代或多取代的苯基,该组由以下各项组成:卤素、C1-C4卤代烷基、C1-C4卤代烷基硫烷基和C1-C4卤代烷基磺酰基;或者
R10是被独立地选自下组的取代基单取代或多取代的吡啶基,该组由以下各项组成:卤素和C1-C4卤代烷基;或者
R10是被独立地选自下组的取代基单取代或多取代的嘧啶基,该组由以下各项组成:卤素和C1-C4卤代烷基,具体地是氟和三氟甲基;
X3是S或SO2;
Qa2选自下组,该组由以下各项组成:
其中每个基团J被Rx单取代,二取代或三取代,其中每个Rx独立地选自氢、卤素和C1-C4卤代烷基;
R13是C1-C4烷基;
R8是C1-C4烷基;并且
R9是氢。
7.根据权利要求1所述的具有式I的化合物,其由具有式I-4的化合物表示
其中
R10’是被独立地选自下组的取代基单取代的苯基,该组由以下各项组成:卤素、C1-C4卤代烷基、C1-C4卤代烷基硫烷基和C1-C4卤代烷基磺酰基;或者
R10’是被独立地选自下组的取代基单取代的吡啶基,该组由以下各项组成:卤素和C1-C4卤代烷基;或者
R10’是被独立地选自下组的取代基单取代的嘧啶基,该组由以下各项组成:卤素和C1-C4卤代烷基;并且
Qa4选自下组,该组由以下各项组成:
其中每个Rx独立地选自氢、卤素和C1-C4卤代烷基。
8.根据权利要求1所述的具有式I的化合物,其由具有式I-5的化合物表示
其中
R10#是基团G-10至G-12,其独立地选自下组,该组由以下各项组成:
其中
箭头表示连接至咪唑环的点;并且
每个Ry独立地选自卤素、C1-C4卤代烷基、C1-C4卤代烷基硫烷基和C1-C4卤代烷基磺酰基;并且
Qa5选自下组,该组由以下各项组成:
其中每个Rx独立地选自氢、卤素和C1-C4卤代烷基。
9.一种杀有害生物组合物,该杀有害生物组合物包含至少一种根据权利要求1所述的具有式I的化合物或适当时其互变异构体作为活性成分以及至少一种助剂,该化合物在所有情况下为游离形式或农用化学上可用的盐形式。
10.一种用于控制有害生物的方法,该方法包括将根据权利要求9所述的组合物施用于这些有害生物或其环境中,除了通过手术或疗法用于处理人或动物体的方法以及在人或动物体上实施的诊断方法之外。
11.一种用于保护植物繁殖材料免受有害生物攻击的方法,该方法包括用根据权利要求9所述的组合物处理该繁殖材料或该繁殖材料所种植的场所。
12.一种根据权利要求11中所描述的方法处理的植物繁殖材料。
13.一种具有式IIIa的化合物
其中
R8和R7是如在权利要求1中的式I下所定义的;
R9是氢;并且
LG是碘或溴。
14.一种具有式IVa的化合物
其中
R8和R7是如在权利要求1中的式I下所定义的;并且
R9是氢。
15.一种具有式XVIII的化合物
其中
R8、A、X和R1是如在权利要求1中的式I下所定义的;
FG是氢、溴或碘;
R9是氢;并且
Xa是氯、溴或碘。
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CN110596070A (zh) * | 2019-10-24 | 2019-12-20 | 哈尔滨工业大学 | 比率氧传感膜在气态氧检测中的应用 |
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CN110596070A (zh) * | 2019-10-24 | 2019-12-20 | 哈尔滨工业大学 | 比率氧传感膜在气态氧检测中的应用 |
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