CN1099415C - 杀虫的1-芳基吡唑 - Google Patents
杀虫的1-芳基吡唑 Download PDFInfo
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- CN1099415C CN1099415C CN97180938A CN97180938A CN1099415C CN 1099415 C CN1099415 C CN 1099415C CN 97180938 A CN97180938 A CN 97180938A CN 97180938 A CN97180938 A CN 97180938A CN 1099415 C CN1099415 C CN 1099415C
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- Prior art keywords
- compound
- formula
- amino
- acetyl
- methyl
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- 125000004961 1-arylpyrazolyl group Chemical group 0.000 title claims description 11
- 230000000361 pesticidal effect Effects 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims description 175
- 239000000203 mixture Substances 0.000 claims description 90
- 239000000460 chlorine Substances 0.000 claims description 86
- 241000238631 Hexapoda Species 0.000 claims description 79
- 238000000034 method Methods 0.000 claims description 66
- 125000006414 CCl Chemical group ClC* 0.000 claims description 61
- 150000003839 salts Chemical class 0.000 claims description 45
- -1 aminocarboxyl Chemical group 0.000 claims description 34
- 125000000217 alkyl group Chemical group 0.000 claims description 32
- 238000002360 preparation method Methods 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 230000000590 parasiticidal effect Effects 0.000 claims description 27
- 229910052801 chlorine Inorganic materials 0.000 claims description 24
- 125000001188 haloalkyl group Chemical group 0.000 claims description 24
- 229910052736 halogen Inorganic materials 0.000 claims description 21
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 19
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 15
- 125000003545 alkoxy group Chemical group 0.000 claims description 15
- 150000002367 halogens Chemical class 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 14
- 125000005843 halogen group Chemical group 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 241001600407 Aphis <genus> Species 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
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- 230000000749 insecticidal effect Effects 0.000 claims description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 125000001118 alkylidene group Chemical group 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 150000003217 pyrazoles Chemical class 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
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- 125000004457 alkyl amino carbonyl group Chemical group 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 201000010099 disease Diseases 0.000 claims description 5
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 229910052728 basic metal Inorganic materials 0.000 claims description 4
- 150000003818 basic metals Chemical group 0.000 claims description 4
- 125000004473 dialkylaminocarbonyl group Chemical group 0.000 claims description 4
- 125000004472 dialkylaminosulfonyl group Chemical group 0.000 claims description 4
- 230000014509 gene expression Effects 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical compound O=[CH] CFHIDWOYWUOIHU-UHFFFAOYSA-N 0.000 claims description 4
- 125000003226 pyrazolyl group Chemical group 0.000 claims description 4
- GDZNYEZGJAFIKA-UHFFFAOYSA-N acetoprole Chemical class NC1=C(S(C)=O)C(C(=O)C)=NN1C1=C(Cl)C=C(C(F)(F)F)C=C1Cl GDZNYEZGJAFIKA-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical group C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 125000004193 piperazinyl group Chemical group 0.000 claims description 2
- 125000003386 piperidinyl group Chemical group 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 230000019635 sulfation Effects 0.000 claims description 2
- 238000005670 sulfation reaction Methods 0.000 claims description 2
- SLNFDZJBMXNYPT-UHFFFAOYSA-N 1-[5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfanylpyrazol-3-yl]ethanone Chemical class N1=C(C(C)=O)C(SC)=C(N)N1C1=C(Cl)C=C(C(F)(F)F)C=C1Cl SLNFDZJBMXNYPT-UHFFFAOYSA-N 0.000 claims 3
- ROEORWSJYDKMBJ-UHFFFAOYSA-N 1-[1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-5-(2-ethylsulfonylethylamino)-4-methylsulfinylpyrazol-3-yl]ethanone Chemical class CCS(=O)(=O)CCNC1=C(S(C)=O)C(C(C)=O)=NN1C1=C(Cl)C=C(C(F)(F)F)C=C1Cl ROEORWSJYDKMBJ-UHFFFAOYSA-N 0.000 claims 2
- OOKNLBZPXHVFDV-UHFFFAOYSA-N 1-[1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-5-(ethylamino)-4-methylsulfinylpyrazol-3-yl]ethanone Chemical class CCNC1=C(S(C)=O)C(C(C)=O)=NN1C1=C(Cl)C=C(C(F)(F)F)C=C1Cl OOKNLBZPXHVFDV-UHFFFAOYSA-N 0.000 claims 2
- ZNNSXDKUXLLRDP-UHFFFAOYSA-N 1-[1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-5-(methylamino)-4-methylsulfinylpyrazol-3-yl]ethanone Chemical class CNC1=C(S(C)=O)C(C(C)=O)=NN1C1=C(Cl)C=C(C(F)(F)F)C=C1Cl ZNNSXDKUXLLRDP-UHFFFAOYSA-N 0.000 claims 2
- GGYYKCPFDSZEMU-UHFFFAOYSA-N CC(=O)C1C(=C(N(N1N)C2=C(C=C(C=C2Cl)C(F)(F)F)Cl)SC(F)(F)F)S(=O)C Chemical compound CC(=O)C1C(=C(N(N1N)C2=C(C=C(C=C2Cl)C(F)(F)F)Cl)SC(F)(F)F)S(=O)C GGYYKCPFDSZEMU-UHFFFAOYSA-N 0.000 claims 2
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- RQYLOOVORNJDQX-UHFFFAOYSA-N trifluoromethyl thiohypochlorite Chemical compound FC(F)(F)SCl RQYLOOVORNJDQX-UHFFFAOYSA-N 0.000 description 1
- 210000001835 viscera Anatomy 0.000 description 1
- 208000022534 visible peristalsis Diseases 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Abstract
本发明涉及式(I)的1-苯基吡唑衍生物及它们作为杀虫剂的应用,其中,R1、R2、R3、R4和X的定义如说明书中所述。
Description
发明背景
本发明涉及可用于防治昆虫、线虫和蠕虫的3-乙酰-1-芳基吡唑衍生物和含这些衍生物的组合物。本发明的方法尤其涉及在一些工作人员容易接触到的条件下施用1-芳基吡唑衍生物。本发明还涉及一种新的改进的用具有1-苯基吡唑基团的杀虫活性物质防治昆虫、线虫或蠕虫的方法,该方法对防治蚜虫特别有用。
相关技术的描述
用具有1-芳基吡唑基团的活性物质防治昆虫、线虫或蠕虫在许多专利或专利申请(如国际专利申请No.WO93/06089及其同族的美国专利No.5,451,598,WO94/21606和WO87/03781以及欧洲专利公报No.0295117、659745、679650、201852和412849,德国专利No.DE19511269和美国专利No.5,232,940)中已有描述。
本发明的第一个目的是,提供一种对使用者和环境的安全程度得到改善的防治昆虫、线虫和蠕虫的方法。所有杀虫剂一般多少有毒性,因此,人们总是希望能降低其可能存在的毒性,即使这些毒性已相当地小并满足一般用途。由此,本发明的目的是,开发一种与已知的现有方法相比,可降低杀虫剂可能的毒性的防治方法,即使这些现有的毒性较低且合乎要求。
本发明的第二个目的是,降低对使用上述方法的工作人员的毒性。
本发明的第三个目的是,在使用上述方法的工作人员可能大量接触到杀虫剂时降低对他们的毒性。
本发明的第四个目的是,提供一种新的更好的防治蚜虫的方法。用许多杀虫活性物质防治蚜虫是已知的,但这些昆虫类能极迅速地繁殖并基本上对杀虫剂产生抗药性且出现这种抗药性的风险比其他昆虫类高。因此,非常希望能提出一些新的用与迄今使用的那些不同的杀虫剂进行防治的方法。本发明的目的是,提供一种用1-苯基吡唑类杀虫活性物质进行防治的方法,该方法具有较高的效率,若可能,其效率比迄今已知的方法更高。
本发明的第五个目的是,提供新的1-苯基吡唑衍生物,这些衍生物与已知的化合物相比,具有改善的系统杀蚜虫活性。这些化合物在系统施用以防治棉叶蚜(Aphis gossypii)和绿蚜(Schizaphis graminum)方面具有优异的性能。
本发明的这些和其他目的将通过下面的描述而变得容易理解,并能通过本发明而全部或部分达到。
发明概要
本发明提供一种改进的通过向有昆虫或预计会有昆虫的位置施用具有1-芳基吡唑基团的杀虫活性成分来防治昆虫的方法,所述施用在哺乳动物类可能接触到(尤其是大量接触到)杀虫活性成分的条件下施用,其改进在于,所述活性成分的吡唑环上有3-乙酰取代基。本发明的防治方法在工作人员可能接触到杀虫活性成分时尤其适合。
本发明还提供一种通过通过向有蚜虫或预计会有蚜虫的位置施用具有1-芳基吡唑基团的杀虫活性成分来防治昆虫的方法,其改进之处在于,所述活性成分的吡唑环上有3-乙酰取代基。
R1是S(O)mR5;
R2选自氢原子、卤原子、-NR6R7、-S(O)nR8、C(O)R8、C(O)OR9、烷基、卤代烷基、-OR9或-N=C(R10)(R11);
R3选自卤原子或氢原子;
R4选自卤原子、卤代烷基、卤代烷氧基、-S(O)pCF3或-SF5;
R5是烷基或卤代烷基;
R6和R7独立地选自氢原子、烷基、卤代烷基、-C(O)R8、C(O)OR8、-S(O)qCF3;其烷基部分可任选地被一个或多个R12取代;或R6与R7结合在一起,形成一个具有4至6个链原子的二价基团,该二价基团是亚烷基、亚烷基氧基亚烷基或亚烷基氨基亚烷基,较好的是,形成吗啉环、吡咯烷环、哌啶环或哌嗪环;
R8是烷基或卤代烷基;
R9选自烷基、卤代烷基或氢原子;
R10选自R9或烷氧基;
R11是烷基或卤代烷基;或选自苯基或杂芳基,该苯基或杂芳基可任选地被一个或多个选自羟基、卤素、烷氧基、-S(O)rR8、氰基、R8或它们的组合的基团取代;
R12选自氰基、硝基、烷氧基、卤代烷氧基、-S(O)s-烷基、-S(O)s-卤代烷基、C(O)-烷基、C(O)-卤代烷基、C(O)O-烷基、C(O)O-卤代烷基、氨基羰基、烷氨基羰基、二烷基氨基羰基、羟基、氨基磺酰基、烷氨基磺酰基或二烷基氨基磺酰基;
X选自氮原子或C-R13基团;
R13是卤原子;
m、n、p、q、r和s彼此独立地表示数值0、1或2。
“可用于杀虫的盐”是指这样一种盐,其阴离子和阳离子是已知的并可在本领域用于形成合乎杀虫剂要求的盐。这些盐最好可溶于水。由含胺基团的式(I)化合物形成的合适的酸加合盐包括具有无机酸(如盐酸、磷酸、硫酸和硝酸)的盐和具有有机酸(如乙酸)的盐。由含羧酸基团的式(I)化合物与碱形成的合适的盐包括碱金属(如钠或钾)盐、铵盐和有机胺(如二乙醇胺或吗啉)盐。发明的详细描述
除非特别指出,烷基和烷氧基具有1-4个碳原子。同样地,卤代烷基和卤代烷氧基最好具有1-4个碳原子。各种脂族烃部分,即,基团或其一部分(如烷氨基羰基和烷氨基磺酰基的烷基部分),在链中最多可有4个碳原子。
卤代烷基和卤代烷氧基可具有1个或多个卤原子。
“卤代芳基”一词是指含1-4个选自氮、氧和硫的杂原子的5-7员杂环。
“卤素”一词是指氟、氯、溴或碘。在基团名称之前的“卤代”一词是指该基团部分或全部被卤化,即,被氟、氯、溴或碘以任一组合(最好是被氟或氯)取代。
R2最好是未取代的或被一或二个选自烷基、-C(O)R8和-C(O)OR8的基团取代的氨基;其烷基部分可任选地被一个或多个R12取代。
R3最好是卤原子,尤其好的是氯原子;
R4最好选自卤原子、卤代烷基、卤代烷氧基或-SF5,尤其好的是CF3-、CF3O-和-SF5。
R5最好是甲基、乙基或丙基。
由于它们的系统杀蚜虫特性,在式(I)化合物中,特别优选具有如下取代基定义的化合物:
R2是NR6R7;
R3是卤素;
R4是CF3-、CF3O-或-SF5;
R5是烷基;
X是CR13;
R13是卤素;
m是0或1。
由于它们的系统杀蚜虫特性,在通式(I)的化合物中,更特别优选具有如下取代基定义的化合物:
R2是NR6R7;
R3是氯;
R4是CF3-、CF3O-或-SF5;
R5是烷基;
R6是氢;
R7是氢、-S(O)qCF3或可被-S(O)sR8或氨基羰基任意取代的烷基;
X是CR13;
R13是氯或溴;
m是0或1。
由于它们的系统杀蚜虫特性,在通式(I)的化合物中,更特别优选具有如下取代基定义的化合物:
R2是NR6R7;
R3是氯;
R4是CF3-或-SF5;
R5是甲基或乙基;
R6是氢;
R7是氢、或可被-S(O)sR8或氨基羰基任意取代的甲基或乙基;
R8是甲基或乙基;
R9是甲基或乙基;
X是CR13;
R13是氯或溴;
m是0或1。
可在本发明的防治昆虫的方法中使用的特别优选的吡唑衍生物包括以下这些。数字1-12是对这些化合物用来进行编号和确认的。
1.3-乙酰-5-氨基-1-(2,6-二氯-4-三氟甲基苯基)-4-甲基亚硫酰基吡唑、
2.3-乙酰-5-氨基-1-(2,6-二氯-4-三氟甲基苯基)-4-甲基硫基吡唑、
3.3-乙酰-5-氨基-1-(2,6-二氯-4-三氟甲基苯基)-4-乙基亚硫酰基吡唑、
4.3-乙酰-1-(2,6-二氯-4-三氟甲基苯基)-5-乙氨基-4-甲基亚硫酰基吡唑、
5.3-乙酰-1-(2,6-二氯-4-三氟甲基苯基)-5-甲氨基-4-甲基亚硫酰基吡唑、
6.3-乙酰-5-(2-氨基甲酰基甲基氨基)-1-(2,6-二氯-4-三氟甲基苯基)-4-甲基亚硫酰基吡唑、
7.3-乙酰-1-(2,6-二氯-4-三氟甲基苯基)-5-(2-乙基磺酰基乙氨基)-4-甲基亚硫酰基吡唑、
8.3-乙酰-1-(2,6-二氯-4-三氟甲基苯基)-5-(2-氨基甲酰基乙氨基)-4-甲基亚硫酰基吡唑、
9.3-乙酰-5-氨基-1-(2-溴-6-氯-4-三氟甲基苯基)-4-甲基亚硫酰基吡唑、
10.3-乙酰-1-(2,6-二氯-4-三氟甲基苯基)-4-甲基亚硫酰基-5-三氟甲硫基氨基吡唑、
11.3-乙酰-5-氨基-1-(2,6-二氯-4-五氟硫代苯基)-4-甲基亚硫酰基吡唑、
12.3-乙酰-5-氨基-1-(2,6-二氯-4-五氟硫代苯基)-4-甲基硫基吡唑。
优选化合物1和2。
在可用于本发明的化合物中,其中的一些是新的并成为本发明的一部分。下面的代表性的式(I)化合物也构成本发明的一部分。在下面的表中,Et表示乙基,Pr表示正丙基。在表中,未使用下标,但读者会明白,例如,SCFCl2表示的是SCFCl2。
合成方法
化合物No | R1 | R2 | R3 | R4 | X | m.p.℃(约) |
13 | SCFCl2 | NH2 | Cl | CF3 | C-Cl | 136 |
14 | SO2CF3 | NH2 | Cl | CF3 | C-Cl | 164 |
15 | SCF3 | H | Cl | CF3 | C-Cl | |
16 | SCF3 | N=CH(OEt) | Cl | CF3 | C-Cl | |
17 | SOCF3 | H | Cl | CF3 | C-Cl | 149 |
18 | SO2CF3 | H | Cl | CF3 | C-Cl | 119 |
19 | SOCH3 | NH2 | Cl | OCF3 | C-Cl | 147 |
20 | SOEt | NH2 | Cl | CF3 | N | 69 |
21 | SOCH3 | NH(CH2)2CN | Cl | CF3 | C-Cl | |
22 | SOCH3 | NH(CH2)2COCH3 | Cl | CF3 | C-Cl | |
23 | SOCH3 | NH2 | Cl | CF3 | N | 92 |
24 | SO2CH | NH2 | Cl | OCF3 | C-Cl | 211 |
25 | SCClF2 | NH2 | Cl | CF3 | C-Cl | 124 |
26 | SCH3 | NH2 | Br | CF3 | C-Cl | 99 |
27 | SO2CH3 | NH2 | Cl | CF3 | N | 165 |
28 | SOCH3 | NH2 | Br | CF3 | C-Br | |
29 | SOCH3 | NH2 | H | CF3 | C-Br | 162 |
30 | SOCH3 | NH2 | H | CF3 | C-Cl | |
31 | SCH3 | NH2 | Cl | OCF3 | C-Cl | 151 |
32 | SOCH3 | CH3 | Cl | CF3 | C-Cl | 138 |
33 | SOCH3 | NHEt | Br | CF3 | C-Cl | 124 |
34 | SOCH3 | NH2 | Cl | CF3 | C-Cl | 177 |
35 | SOEt | H | Cl | CF3 | C-Cl | 152 |
36 | SO(CH2)2F | NHCH2CONH2 | Cl | CF3 | C-Cl | 140 |
37 | SO2Et | NHCH3 | Cl | CF3 | C-Cl | 212 |
38 | SOCH3 | NH(CH2)2SO2Et | Br | CF3 | C-Cl | 58 |
39 | SOEt | NH2 | Cl | CF3 | C-Cl | 106 |
40 | SOCHF2 | NH2 | H | CF3 | C-Cl | 140 |
41 | SOPr | NH(CH2)2OCH3 | Cl | CF3 | C-Cl | 147 |
42 | SO2CH3 | NHCH2C(CH3)2OH | Cl | CF3 | C-Cl | 54 |
43 | SOCH3 | NH2 | Cl | CF3 | C-Cl | 50 |
44 | SOCH2F | NHCH3 | Cl | CF3 | C-Cl | |
45 | SOEt | H | Cl | OCF3 | C-Cl | 138 |
46 | SOCH3 | NH2 | Cl | CF3 | C-Cl | 174 |
47 | SO2CH3 | NH2 | Br | CF3 | C-Cl | 199 |
48 | SOEt | NH2 | Br | CF3 | C-Br | 176 |
49 | SOEt | N(CH3)Et | Cl | OCF3 | C-Cl | 165 |
50 | SEt | NHCH3 | Cl | CF3 | C-Cl | 78 |
51 | SEt | NHCH3 | Cl | CF3 | C-Cl | |
52 | SOEt | OEt | Cl | CF3 | C-Cl | 148 |
53 | SCH3 | SCH3 | Cl | CF3 | C-Cl | |
54 | SO2CH3 | NH2 | Cl | CF3 | C-Cl | 122 |
55 | SCH3 | NH2 | Cl | Cl | N | 110 |
56 | SO2CH3 | NH2 | Cl | Cl | N | 200 |
57 | SO2Et | NH2 | Cl | CF3 | C-Cl | 178 |
58 | SCH3 | NH2 | Br | OCF3 | C-Br | 140 |
59 | SOCH3 | NH2 | Cl | Cl | N | 160 |
60 | SEt | NH2 | Br | OCF3 | C-Br | |
61 | SOEt | NH(CH2)2SO2CH3 | Cl | CF3 | C-Cl | 123 |
62 | SPr | NH2 | Cl | CF3 | C-Cl | 89 |
63 | SCH3 | NH2 | Br | CF3 | C-Br | 110 |
64 | SCH3 | NHCOCF3 | Cl | CF3 | C-Cl | 155 |
65 | S(CH2)2Cl | NH2 | Cl | CF3 | C-Cl | 99 |
66 | SO2CH3 | NH2 | Cl | SF5 | C-Cl | 250 |
67 | SOCH3 | N=CH(OCH3) | Cl | CF3 | C-Cl | 114 |
68 | SOCH3 | N(CH3)2 | Cl | CF3 | C-Cl | 129 |
69 | SOCH3 | CH2CH2Br | Cl | CF3 | C-Cl | |
70 | SCF3 | H | Cl | CF3 | C-Cl | 88 |
式(I)化合物可用国际专利公报No.WO94/21606和WO93/06089或国际专利公报No.WO87/03781及欧洲专利公报No.0295117和Hatton等的美国专利No.5,232,940中所述的制备方法进行制备。本领域的技术人员会在这些已知的方法中选择合适的起始反应物并将这些已知的方法运用于所述反应物,从而得到相应的所需产物。应明白,在下面的方法的描述中,可以以不同的顺序在吡唑环上导入各种基团,并可采用对本领域技术人员显而易见的合适的保护基。
在下面的方法的描述中,当出现在式中的符号未具体定义时,应理解,它们表示“定义同上”,即与各符号在说明书中的第一个定义相同。
其中,R1、R2、R3、R4和X的定义同上与合适的试剂CH3M(式中,M表示碱金属,如锂;碱土金属盐,如MgBr、MgCl、MgI,在该情况下,CH3M表示格氏试剂,如溴化甲基镁、碘化甲基镁和氯化甲基镁)反应。反应可在多种溶剂(如二氯乙烷、二氯甲烷、甲苯、四氢呋喃和氯苯或它们的混合液)中于-70℃至120℃(较好的是-20℃至50℃)进行。反应可用包括路易斯酸在内的酸进行催化,所述路易斯酸的例子包括但不限于AlCl3、BBr3、TiCl4、BF3、SiCl4、BCl3、CuBr。
作为本发明的又一个方面,通式(I)化合物(式中,R1、R2、R3、R4和X的定义同上,m表示0或1)可直接通过将相应的式(III)化合物与合适的试剂R5S(O)mY(式中,m表示0或1,Y表示卤素,优选氯)反应而制得。式(III)化合物向式(I)化合物的转化可通过用合适的烷硫基卤或烷基亚硫酰基卤(如甲硫基卤或甲基亚硫酰基卤)直接硫基化或亚硫酰化而实现。烷硫基基卤和烷基亚硫酰基卤可在不同的反应罐中制备或可任选地在用于与式(III)化合物反应的介质中现场制备。通常使用惰性溶剂,如甲基·叔丁基醚、二氯乙烷、甲苯和氯苯。反应可在催化剂的存在下进行,催化剂可以是碱性的,例如是金属碳酸盐、金属氢化物(如氢化钠)或金属氢氧化物(如氢氧化钠)。反应可在约-20℃至120℃进行,最好在0℃至100℃进行。
反应在碱(如金属烷氧化物,最好是乙醇钠)的存在下于惰性溶剂(如乙醇)中在0℃至回流温度下进行。
作为本发明的又一方面,通式(I)化合物(式中,R1、R2、R3、R4和X的定义同上,m为1或2)可通过将m为0或1的相应的式(I)化合物氧化而制得。反应最好用过酸(如3-氯过苯甲酸)在惰性溶剂(如二氯甲烷)中于0℃至溶剂的回流温度下进行。
作为本发明的又一方面,通式(I)化合物(式中,R2表示-NR6R7、-S(O)nR8、C(O)OH、烷基、卤代烷基或-N=C(R10)(R11),其中,R6和/或R7表示烷基、卤代烷基、C(O)R8、C(O)OR8和S(O)qCF3;其烷基部分可任选地被一个或多个R12取代;或者,R6和R7结合在一起,形成具有4-6个链原子的二价基团)可用国际专利申请No.WO94/21606、WO93/06089和WO87/03781、欧洲专利公报No.0295117和EP511845、Hatton等的美国专利No.5,232,940、德国专利公报No.DE19511269和EP780378中的一个或多个所述的方法由R2为氨基的相应化合物制得。
作为本发明的又一部分,通式(I)化合物(式中,R1、R3、R4和X的定义同上,R2表示NR6R7,其中,R6表示氢,R7表示在2位被R12取代的乙基,R12表示氰基、硝基、-S(O)sR8、C(O)R8、C(O)OR9、氨基羰基、烷氨基羰基、二烷基氨基羰基、氨基磺酰基、烷氨基磺酰基或二烷基氨基磺酰基)可通过R2为氨基的相应的式(I)化合物与式(VI)化合物
R12-CH=CH2 (VI)(式中,R12的定义同上)反应而制得。反应可任选地在碱(如氢化钠,氢氧化钾等碱金属氢氧化物,或N-苄基·三甲基氢氧化铵等四烷基氢氧化铵)的存在下在溶剂(如甲苯、乙醇或水)中于-20℃至回流温度下进行。
作为本发明的又一方面,通式(I)化合物(式中,R1、R3、R4和X的定义同上,R2表示NR6R7,其中,R6和/或R7表示可被一个或多个R12任意取代的烷基或卤代烷基)可通过R2为氨基的相应的式(I)化合物与式(VII)化合物
R14-Y (VII)(式中,R14为可被一个或多个R12任意取代的烷基或卤代烷基,Y表示离去基团,最好是卤素,如氯)反应而制得。反应在碱(如氢氧化钾、甲醇钾、氢化钠或三乙胺)的存在下在惰性溶剂(如甲基·叔丁基醚或甲苯)中于-20℃至回流温度下进行。
作为本发明的又一部分,R2表示C(O)OR8的通式(I)化合物可通过R2为羧基的相应的式(I)化合物与式(VIII)的醇反应而制得。
R8OH (VIII)
上述反应通常在酸催化剂(如硫酸)和过量的醇的存在下或任选地在助溶剂中于0℃至回流温度下进行。或者,反应可使用偶合剂(如二环己基碳二亚胺(DCC))在惰性溶剂中进行。
作为本发明的又一方面,R2为羧基的通式(I)化合物可通过将R2被甲酰基取代的相应的式(I)化合物氧化而制得。反应通常用高锰酸钾或铬酸在水等溶剂中于0℃至回流温度下进行。
作为本发明的又一部分,通式(I)化合物(式中,R2表示RaCH(Cl)CH2-,Ra表示烷基)可通过将R2为氨基的相应的式(I)化合物重氮化并与式(IX)的化合物
RaCH=CH2 (IX)反应而制得。
反应通常使用亚硝酸烷基酯(如亚硝酸叔丁酯)在铜盐(如氯化铜)的存在下在溶剂(如乙腈)中于-10℃至50℃进行。
作为本发明的又一部分,R2表示C(O)R8的通式(I)化合物可通过将相应的式(X)化合物(式中,R1、R3、R4、R8和X的定义同上)氧化而制得。反应可使用铬酸与硫酸的混合液在溶剂(如水和丙酮)中于0℃至60℃进行。
作为本发明的又一部分,R2表示OR9的通式(I)化合物可用美国专利No.5,047,50和4,918,085中所述的方法制备。
式(II)中间体(式中,R1表示S(O)mR5,m表示1或2)可用上述由式(III)化合物制备式(I)化合物的方法通过式(XI)化合物与式R5S(O)mY(式中,Y表示卤素,优选氯)试剂反应而制得。
R2为氨基的式(III)中间体可通过式(XII)化合物的重氮化和所得的重氮盐与式(XIII)试剂的反应而制得。
式(XII)化合物的重氮化可用文献报道过的的方法进行。可用包括偶合和随后的闭环(该步骤可在同一反应器中进行)在内的二步法使重氮盐与式(XIII)化合物反应,产生R2为氨基的式(III)化合物。缩合可在合适的酸(如乙酸或盐酸)的存在下或在碱性催化剂(如乙酸钠)的存在下进行。反应可在包括醇(如乙醇)或醚(如甲基·叔丁基醚)在内的各种溶剂中,或任选地在与水的混合液中通常于约-30℃至100℃(优选0-50℃)进行。闭环步骤最好在碱催化剂的存在下在包括但不限于反应第一阶段(偶合)中所用的那些溶剂在内的合适的溶剂中进行。所用的碱催化剂可以是有机碱,如三乙胺或吡啶;脒,如1,8-二氮杂双环〔5.4.0〕十一碳-7-烯(DBU);也可以是无机碱,如氨、碳酸氢钠或氢氧化钠。反应可在约30-120℃(最好是0-100℃)进行。
式(X)中间体可通过R2被甲酰基取代的相应的式(I)化合物与式R8Q(式中,Q最好是碱金属或碱土金属,如卤化镁(格氏)试剂)的有机金属试剂反应而制得。反应可在惰性溶剂(如甲基·叔丁基醚)中于-78℃至溶剂的回流温度下进行。
R2被甲酰基取代的式(I)中间体可通过将R2表示RaCH=CH-的相应的式(I)化合物氧化而制得。反应通常用臭氧或偏过亚碘酸钠(sodiummetaperiodite)等试剂在惰性溶剂(如二氯乙烷)中于-100℃至100℃进行。
R2被RaCH=CH-取代的式(I)中间体可通过将R2表示RaCH(Cl)CH2-的相应的式(I)化合物脱去氯化氢而制得。反应通常用碱(如氢氧化钠或三乙胺)在惰性溶剂(如二氯乙烷)中于-70℃至回流温度下进行。
通式(XII)的中间体化合物的合成可用各种已知的方法进行,这些方法例如有英国专利GB 8531485和GB 9201636及Hatton等的美国专利No.5,232,940中所述的那些。
式(II)的一些化合物是新的,它们构成本发明的一个方面。式(IV)和(V)中间体是已知的,或者可用已知方法制得。
下面通过实施例对本发明作举例说明,但这些实施例不应被认为是对本发明的限定,而是为了使本领域的技术人员更好地使用本发明。
实施例1
往1-(2,6-二氯-4-三氟甲基苯基)-5-氨基-3-氰基-4-甲基亚硫酰基吡唑(2g)在甲苯中的悬浮液中加入甲基溴化镁(在甲苯/THF中的1.4M溶液7ml)。将该混合物在20℃搅拌(1小时)并用饱和的氯化铵溶液中和。将有机层干燥(硫酸钠),蒸干并用40%乙酸乙酯/己烷溶液通过色谱法进行纯化,得到3-乙酰-5-氨基-1-(2,6-二氯-4-三氟甲基苯基)-4-甲基亚硫酰基吡唑(化合物1,0.68g),熔点166℃。
用相似的方法,还得到下表所示的式(I)化合物。在表中,Et表示乙基。
实施例2
化合物No | R1 | R2 | R3 | R4 | X | m.p.℃ |
2 | SCH3 | NH2 | Cl | CF3 | C-Cl | 113 |
3 | SOEt | NH2 | Cl | CF3 | C-Cl | 189 |
4 | SOCH3 | NHEt | Cl | CF3 | C-Cl | 123 |
5 | SOCH3 | NHCH3 | Cl | CF3 | C-Cl | 126 |
6 | SOCH3 | NHCH2CONH2 | Cl | CF3 | C-Cl | 165 |
7 | SOCH3 | NH(CH2)2SO2Et | Cl | CF3 | C-Cl | 102 |
8 | SOCH3 | NH(CH2)2CONH2 | Cl | CF3 | C-Cl | 132 |
9 | SOCH3 | NH2 | Br | CF3 | C-Cl | 153 |
11 | SOCH3 | NH2 | Cl | SF5 | C-Cl | 166 |
12 | SCH3 | NH2 | Cl | SF5 | C-Cl | 150 |
在-30℃,往3-乙酰-5-氨基-1-(2,6-二氯-4-三氟甲基苯基)-4-甲基亚硫酰基吡唑(3g)在含二异丙基乙胺的二氯甲烷(1.44ml)中的溶液中加入三氟甲硫基氯(0.97ml)。搅拌该混合物(2小时)并在20℃用氮气吹洗。加水并将有机相干燥(硫酸钠),蒸干。以25%乙酸乙酯/己烷为洗脱液,用硅胶色谱法纯化残余物,得到3-乙酰-1-(2,6-二氯-4-三氟甲基苯基)-4-甲基亚硫酰基-5-三氟甲硫基氨基吡唑(化合物10,0.5g),熔点67-102℃,质谱分析M+/e=499。参考例1
往5-氨基-3-氰基-1-(2,6-二氯-4-三氟甲基苯基)-4-乙硫基吡唑(22.25g)在甲醇中的溶液中加入硫酸(1.5g)在异丙醇中的溶液。加入过氧化氢(30%水溶液6.95g)并将温度升至60℃。2小时之后,将反应液过滤并用甲醇洗涤固体。将滤出物洗涤(水)、干燥和重结晶(甲醇),得到5-氨基-3-氰基-1-(2,6-二氯-4-三氟甲基苯基)-4-乙亚硫酰基吡唑(18.4g),熔点173-174℃。参考例2
在20℃,用15分钟将硼氢化钠(0.79g)分成三份加入到1-(2,6-二氯-4-三氟甲基苯基)-3-氰基-4-甲亚硫酰基-5-〔1-甲氧基(亚乙基-亚氨基〕吡唑(6g)在甲醇中的悬浮液中,并在氮气氛中搅拌45分钟。将混合物蒸干并以15%乙酸乙酯/二氯甲烷为洗脱液,用快速硅胶柱色谱法纯化残余物,得到1-(2,6-二氯-4-三氟甲基苯基)-3-氰基-5-乙氨基-4-甲亚硫酰基吡唑(1.1g),熔点130-131℃(分解)。参考例3
在4℃,往5-氨基-1-(2,6-二氯-4-五氟硫代苯基)-3-氰基-4-甲硫基吡唑(20mg)在甲醇中的溶液中加入硫酸/异丙醇催化剂溶液(0.02ml),然后加入30%过氧化氢(0.02ml)。将混合物在20℃搅拌2日。再加入H2SO4/异丙醇溶液和过氧化氢,将混合物搅拌过夜并将其在二氯甲烷与水之间分配。用亚硫酸氢钠、碳酸氢钠溶液和水洗涤有机层。将有机层干燥(硫酸钠),蒸干,并以70%乙酸乙酯/己烷为洗脱液,将残余物用制备性TLC纯化,得到5-氨基-1-(2,6-二氯-4-五氟硫代苯基)-3-氰基-4-甲亚硫酰基吡唑。1H-NMR(CDCl3):7.8ppm(2H,d),3.0ppm(3H,s)。参考例4I)甲硫基氯的制备
将磺酰氯(1.48g)加入到二甲基二硫醚(3.16g)在甲基·叔丁基醚中的溶液中。在20℃搅拌混合液5小时。将所得溶液0.6ml用于下面的反应中。II)甲硫基化
将5-氨基-1-(2,6-二氯-4-五氟硫代苯基)-3-氰基吡唑(40mg)在惰性气氛下在甲基·叔丁基醚中加热回流。加入甲硫基氯(在甲基·叔丁基醚中的溶液0.6ml)并将该混合液加热回流(4小时)。将冷却的混合液在饱和的碳酸氢钠溶液与二氯甲烷之间分配。将有机层洗涤(水),干燥(硫酸钠),蒸干,以40%乙酸乙酯/己烷为洗脱液,用制备性TLC纯化残余物,得到5-氨基-1-(2,6-二氯-4-五氟硫代苯基)-3-氰基-4-甲硫基吡唑。1H-NMR(CDCl3):7.8ppm(2H,d),2.3ppm(3H,s)。参考例5
在4℃,用10分钟将5-氨基-1-(2,6-二氯-4-三氟甲基苯基)-3-氰基-4-甲亚硫酰基吡唑(10g)在干DMF中的溶液加入到在干DMF中的氢化钾(在油中的35%悬浮液0.7g)中,搅拌20分钟。在4℃,用5小时加入在干DMF中的乙烯基·乙基砜(3.13g),并在氮气氛下将混合液温热至20℃的同时搅拌过夜。然后将混合液重新冷却,加入氯化铵溶液,并将有机层洗涤(水),干燥(硫酸钠)和蒸干。将残余物重结晶(乙酸乙酯/己烷),得到1-(2,6-二氯-4-三氟甲基苯基)-3-氰基-5-(2-乙基磺酰基乙氨基)-4-甲亚硫酰基吡唑(4.08g),熔点131-132℃。
实施例1中所用的进一步的中间体即通式(II)的3-氰基吡唑是已知的或通过选择合适的反应物而制得的。所述合适的反应物具有合适的结构式,例如,如欧洲专利EP 0295117和美国专利No.5,232,940中所述的和下面的表中所示的。在下面的表中,Et表示乙基。
R1 | R2 | R3 | R4 | X | m.p.℃ |
SOCH3 | NHCH3 | Cl | CF3 | C-Cl | 147-150 |
SOCH3 | NHCH2CONH2 | Cl | CF3 | C-Cl | 155-157 |
SOCH3 | NH(CH2)2CONH2 | Cl | CF3 | C-Cl | 159-160 |
SOCH3 | NH2 | Br | CF3 | C-Cl | 150-151 |
下面是代表性的哺乳动物毒性的试验方法。用家蝇头代替大鼠大脑进行的类似试验是代表性的昆虫毒性试验方法。GABA受体试验
用生理盐水(其pH与大鼠血浆的相同)将大鼠大脑制成匀浆。将该悬浮液0.1ml与放射性配位体〔双环原苯甲酸4’-乙炔基-4-正丙酯(EBOB)〕混合。将含该混合物和受试化合物的试管与参照物(含该混合物但不含受试化合物的试管)进行比较。
将所有试管恒温培养(90分钟,20℃)。将试管内的物质过滤,测定滤器上残留的放射活性。将50%的控制结合抑制的受试化合物的浓度定为该化合物的IC50。
放射性配位体与已知的GABA受体通道内的位点结合。如果没有受试化合物,放射性配位体就结合;而如果有毒性化合物作用于同一位点,则放射性配位体的量就减少,因为该放射性配位体被受试的毒性化合物取代了。
在上面的对GABA受体通道的体内试验中,本发明的化合物在非常高的浓度是活性的(IC50高),这表明,即使在对昆虫有毒时,本发明的化合物对哺乳动物仍是安全的。用下面的试验方法对前面制得的本发明的代表性的化合物进行了试验。所用的试虫种类如下:
种类
常用名
缩写
Aphis gossypii 棉叶蚜 APHIGO
Schizaphis graminum 绿蚜 TOXOGR
Musca domestica 家蝇 MUSCDO
Meloidogyne incognita 黄麻根疣线虫 MELGIN土壤湿透法
在土罐中植入棉花和高粱作物。在处理的前1天,在各土罐中放入约25条混合种群的蚜虫。在棉花作物上寄生的是棉叶蚜,而在高粱作物上寄生的是绿蚜。将受试化合物的溶液喷洒在土壤表面上,使喷洒浓度达到相当于土壤重量的百万分之20、5和1.25(即20、5和1.25ppm)。在处理后第5日对蚜虫计数。将处理过的作物上的蚜虫数目与未处理过的对照作物上的蚜虫数目进行比较。
化合物1-12在2.5ppm或更小的剂量有效地防治了棉叶蚜。化合物1-7和9-12在2.5ppm或更小的剂量有效地防治了绿蚜。线虫土壤湿透法
用受试化合物处理土壤,处理浓度为土壤的10.0ppm。将从寄生的西红柿根上收集和分离到的幼虫放入到处理过的土壤中。在处理过的和线虫寄生的土壤中植入西红柿秧苗或棉籽(两者均易受线虫侵害)。待作物生长和根节形成一段合适的时间之后,将作物从土壤中移出,检查根部根节的形成情况。未处理过的、没有线虫寄生的作物的根上没有结节,受试化合物显示较高活性的作物的根上也没有结节。家蝇诱饵/接触试验
将约25只4至6日龄的家蝇麻醉并放入装有含受试化合物的糖水诱饵溶液的笼中。诱饵溶液中的受试化合物的浓度为100ppm。24小时之后,对刺激无反应的家蝇被认定为已死亡。
使用本发明的代表性化合物的结果是,家蝇的死亡率为100%。
本发明提供一种系统防治节足害虫(尤其是寄生在作物地面部分的某些昆虫或螨)的方法。对这些叶面害虫的防治的方法可以是,直接向叶面施药或向土壤施药,或者向作物根部或作物种子施用药剂颗粒,然后药剂被内吸转移,到达作物的地上部分。这样的系统活性不仅包括防治在施药位置上的昆虫,而且包括例如通过从叶子一端向另一端的转移或从处理过的叶子向未处理过的叶子的转移而防治在作物远处的昆虫。可用本发明的化合物系统防治的害虫的种类的例子包括同翅目(穿透/吸吮)、半翅目(穿透/吸吮)和缨翅目。本发明尤其适用于蚜虫和牧草虫。
前述杀虫应用表明,本发明提供杀虫活性化合物和使用该化合物防治许多害虫的方法,这些害虫包括:节足害虫,尤其是昆虫或螨:植物线虫;或蠕虫或原虫。由此,式(I)化合物或其可用于杀虫的盐可方便地在实践中应用,例如,可用于农业或园艺作物、林地、兽医或家畜管理、或公共卫生。从这点出发,无论“式(I)化合物”一词何时被使用,该术语包括式(I)化合物及其可用于杀虫的盐。“式(I)化合物”一词包括式(I)化合物及其可用于杀虫的盐。
由此,本发明提供一种防治害虫的方法,它包括用有效量的式(I)化合物或其可用于杀虫的盐对需处理的场所进行处理(例如通过施用或投药),式(I)化合物的取代基的定义如前所述。需处理的场所包括害虫自身或害虫停留或寄生的位置(作物、动物、田地、构造物、房屋、林地、果园、水道、土壤、植物或动物产品等)。
此外,本发明的化合物可用来防治土壤昆虫,如长角叶甲、白蚁(尤其是用于保护构造物)、根蛆、切根虫、根象鼻虫、普通蛀茎夜蛾、夜蛾、根蚜虫或幼虫。它们还可用来防治植物病原性线虫,如根结、胚囊、达格尔叶、侵蚀斑,或者茎或球茎上的线虫,也可用于防治螨。为防治土壤害虫(如长角叶甲),本发明化合物可方便地以有效比率施用于或掺入作物植入的或待植入的土壤中,或者施用于或掺入种子或生长着的植物根部。
在公共卫生区域,本发明的化合物尤其对防治许多昆虫(特别是家蝇或其他双翅目害虫,如家蝇、螯蝇、水虻、骚扰角蝇、斑虻、马蝇、蚋、蠓、墨蚊或蚊子)有用。
本发明的化合物可用于下述施用和防治包括节足害虫(尤其是昆虫或螨、线虫、或蠕虫或原虫)在内的下述害虫:
在保护贮存物品(如谷物,包括谷粒或面粉、落花生、动物饲料、木材,或地毯和纺织品等家用物品)方面,本发明的化合物可用于防止节足害虫〔尤其是甲虫,包括象鼻虫、蛀虫或螨,例如,Ephestia(地中海粉螟)属、Anthrenus(皮蠹)属、Tribolium(谷盗)属、Sitophilus(谷象)属或Acarus(螨)属〕的侵害;
防治民居或工业用建筑物中滋生的蟑螂、蚂蚁或白蚁或类似的节足害虫或水道、井、水库或其他流水或静水中的幼蚊;
处理地基、构造物或土壤以防止建筑物被白蚁(如Reticulitermes目、Heterotermes目、Coptotermes目)侵害;
在农业上,防治鳞翅目(蝴蝶和蛾)的成虫、幼虫和虫卵,鳞翅目包括Heliothisvirescens(烟芽夜蛾)等Heliothis属;防治鞘翅目(甲虫)的成虫和幼虫,鞘翅目包括grandis(棉铃象甲)等花象甲属、Leptinotarsa decemlineata(马铃薯甲虫)、Diabrotica spp.(长角叶甲);防治异翅目(半翅目和同翅目)如Psylla(木虱)属、Bemisia(粉虱)属、Trialeurodes(粉虱)属、Aphis(蚜)属、Myzus(瘤额蚜)属、Megoura viciae(巢菜修尾蚜)、Phylloxera(根瘤蚜)属、Nephotettix(叶蝉)属、Nilaparvata属。
防治Musca(家蝇)属等双翅目害虫;防治Thrips tabaci(葱蓟马)等缨翅目害虫;防治直翅目害虫,如Locusta(飞蝗)属、Schistocerca(蚱蜢)属、Gryllus(蟋蟀)属和Acheta(蟋蟀)属害虫,其例子有东方蜚蠊、美洲大蠊、德国小蠊、亚洲飞蝗和荒地蚱蜢;防治Periplaneta(大蠊)属和Blattela(小蠊)属等弹尾目害虫;防治Coptotermes(白蚁)属等等翅目害虫;
防治在农业上具有重要意义的Acari(螨)等节足害虫,如Tetranychus(叶螨)属和Panonychus(爪螨)属害虫;
防治或侵害农业上重要的植物或树木、林地或园艺作物的线虫,其方法是直接喷洒在线虫上或喷洒在患细菌、病毒、支原体或真菌疾病的植物上。这样的线虫的例子有根疣线虫属(如黄麻根疣线虫)等根节线虫。
在兽医或家畜管理领域,或在保持公共卫生方面,防治寄生于脊椎动物,特别是温血脊椎动物例如牛、绵羊、山羊、马、猪、家禽、狗或锚等家畜体内或体外的节足害虫、蠕虫或原虫,如蜱螨目,包括蜱〔如硬蜱属、方头蜱属(如微小牛蜱)、扇头蜱属(如Rhipicephalus appendiculatus)、钝缘蜱属(如Ornithodorusmoubata)和螨(如疥螨属);双翅目(如伊蚊属、按纹属、家蝇属、皮蝇属);半翅目;蠊螳亚目(如大蠊属和小蠊属);膜翅目;例如,防治寄生的线虫(例如毛圆线虫科成员)引起的胃肠道感染;防治和处理由下述原虫引起的原虫性疾病:如艾美耳球虫属(如克鲁氏锥虫)、利什曼原虫属、疟原虫属、巴贝虫属、毛滴虫属、弓浆虫属和泰勒虫属。
在实际应用中,防治植物上的节足害虫尤其是昆虫、螨或线虫的方法例如包括向节足害虫生长的植物或介质施用有效量的本发明化合物。在该方法中,活性化合物通常以约在每公顷5-1000g活性化合物之间的有效比率施用于需防治节足害虫或线虫滋生的场所。在理想的情况下,根据需防治的害虫,较低的施用比率也能产生合适的保护效果。另一方面,不利的气候条件、害虫的耐药性或其他因素可能要求以较高的比率使用活性成分。最佳比率通常取决于许多因素,例如,需防治的害虫的类型、受侵害的植物的类型或生长期、作物种植密度以及活性化合物的施用方法。更好的是,活性化合物的有效比率范围在约50-400g/公顷之间。
当害虫是土壤传播的时,在配制的组合物中的活性化合物通常以任何方便的方式(例如,撒播或扩散处理)均匀地施用于需处理的区域,施用比率约为5-1000g活性成分/公顷,更好的约为50-250g活性成分/公顷。当以将秧苗的根浸渍或滴灌植物的方式施用时,液体溶液或悬浮液含约0.075-1000mg活性成分/升,更好的含约25-200mg活性成分/升。视需要,可施用于通常需加保护的或非常靠近需加保护的种子或植物的田地或作物生长区域。可通过在区域上用水喷洒的方法将活性成分洗入土壤中,或者可将活性成分置于土壤上,依靠降雨的自然作用。在施用的过程中或之后,视需要,可用机械的方式(如耕犁、圆盘耙耕作或使用牵引链)将配制的化合物施用于土壤中。施用可以在种植之前、种植过程中、种植之后发芽之前,或者在发芽之后进行。
本发明的化合物和使用该化合物防治害虫的方法在对下述对象进行保护方面具有特殊价值:田地、饲料、耕地、暖房、果园,或葡萄园作物、观赏植物、人造林、林木,谷物(如小麦或稻谷)、棉花、蔬菜(如胡椒)、田间作物(如甜菜、大豆或油菜)、草地或饲料作物(如玉米或高粱)、果园或小树林(如核果或仁果或柑橘类果园或小树林),温室、花园或公园中的观赏植物、花卉或蔬菜或灌木,森林、人造林或苗圃中的林木(每年落叶的和常青的)。
它们对保护木料(挺立的、伐倒的、已加工的、贮存的或作为构造物的一部分的)免受例如锯蝇、甲虫或白蚁的侵害也是有价值的。
它们可用于保护贮存物品(如谷物、果物、坚果、香料或烟草,不论是完整的、磨成粉的还是掺入产品中的)免受蛀虫、甲虫、螨或谷象的侵害。还可用于保护贮藏的动物制品(如皮、毛、毛制品或皮革,包括天然的或已过加工的,如地毯或纺织品)免受蛀虫或甲虫的侵害或保护贮藏的肉、鱼或谷物免受甲虫、螨或蝇的侵害。
此外,本发明的化合物及其使用方法在防治对家畜有害的、或传播疾病的或作为疾病载体的节足害虫、蠕虫或原虫(例如前面所述的,更具体地说,如虱、螨、白虱、跳蚤、蚋或刺螯蝇、骚扰蝇或蛆蝇)方面具有特殊价值。本发明的化合物对防治存在于家庭宿主动物内脏的或在动物皮肤中或皮肤上寄生的或吸吮动物血液的节足害虫、蠕虫或原虫特别有用,为此,可通过经口、胃肠外、经皮给药或局部给药的方式施用本发明的化合物。
而且本发明的化合物对防治由艾美耳属原虫寄生虫的滋生引起的球虫病有用。这是可能造成家畜和鸟类(尤其是那些在强化条件下饲养的)的经济损失的一个重要原因。例如,牛、羊、猪或兔可能受到感染,但球虫病对家禽尤其是鸡特别重要。施用小量的本发明化合物(较好的是通过与饲料的组合)可有效地防止或大大减小球虫病的发生率。本发明化合物对防治盲肠型和大小肠型均有效。而且,本发明的化合物还可大大减少卵母细胞的数目和由卵母细胞产生的孢子,从而抑制卵母细胞。家禽疾病通常通过拾食在被污染的垃圾、地面、食物或饮用水中或粪便中受传染的细小动植物的鸟而传播的。该疾病的症状是出血、血在盲肠中积聚、便血、虚弱和消化紊乱。该疾病往往会导致动物死亡,但在重度感染中幸存的家禽的市场价值则由于受到过感染而大大下降。
下面所述的施用于生长的作物或作物生长的场所或作为种子的敷料的组合物通常也可用来局部施用于动物或保护贮存物品、家用物品、财产或综合环境的区域。施用本发明的化合物的合适方式包括:
通过叶面喷洒、撒粉、撒颗粒、喷雾、喷泡沫的形式施用于生长的作物,或者以细碎的或制成胶囊的组合物的悬浮液的形式通过液体湿透、撒粉、撒颗粒、烟熏或喷泡沫对土壤或植物根进行处理;以液体料浆或粉尘的形式敷裹在作物种子上;
例如通过掺入在饲料或合适的口服药剂、可食用的饵料、盐渍地、食物增补剂、灌浇用制剂、喷雾剂、浴剂、浸渍液、淋液、射流、粉尘、油脂、香波、乳液、蜡涂料或家畜自我处理系统中的形式将组合物胃肠外、经口或局部给药于有节足害虫、蠕虫或原虫滋生或与这些害虫接触的动物,其中,活性成分在一定时期对节足害虫、蠕虫或原虫具有迅即的和/或长期的作用;
以喷雾剂、气雾、粉尘、烟尘、蜡-涂料、漆、颗粒或诱饵的形式一般地施用于环境或施用于害虫可能潜藏的特定场所,包括贮存物品、木料、家用物品或民用建筑物或工业用建筑物,或者掺入在滴流饲料中施用于水道、井、水库或其他流水或静水中;
掺入在饲料中施用于家畜以防治以其粪屎为食的幼蝇。
在实际中,本发明的化合物最通常的是以组合物的形式施用。这些组合物可用来防治:节足害虫,尤其是昆虫或螨;或蠕虫或原虫。组合物可以是本领域已知的任何类型的,只要适合施用于建筑物中的或室内、室外区域中的目标害虫,或者适合内用或外用于脊椎动物即可。这些组合物含至少一种式(I)化合物或其可用于杀虫的盐,如前面所描述的,在这些组合物中,除了活性成分之外,还有一种或多种其他可相容的成分,这些成分例如是固体或液体载体或稀释剂、辅剂、表面活性剂或其他适合于拟定用途并合乎农艺学或医学要求的物质。可用任何本领域已知的方式制得的这些组合物同样地构成本发明的一部分。
这些组合物还可含其他种类的成分,如保护胶体、粘合剂、增稠剂、流变剂、渗透剂、杀虫油(尤其是用于杀螨的)、稳定剂、防腐剂(尤其是防霉剂)、螯合剂等以及其他已知的具有杀虫性能(尤其是杀昆虫、杀螨、杀线虫、或杀真菌性能)或调节植物生长性能的活性成分。更通常地,可将本发明所用的化合物与所有对应于常用制剂技术的固体或液体添加剂混合。
适合在农业、园艺等方面施用的组合物包括适合以例如喷雾剂、粉尘、颗粒、气雾、泡沫、乳液等形式使用的制剂。
本发明化合物的有效使用剂量可在大的范围内变化,具体地根据需消灭的害虫的种类或对作物的侵害程度而定。一般地,本发明的组合物通常含约0.05-95%(重量)的一种或多种本发明的活性成分及1-95%一种或多种固体或液体载体,并可任选地含约0.1-50%的一种或多种其他相容的成分,如表面活性剂等。
在本文中,“载体”一词是指天然的或合成的有机或无机成分,与活性成分混合能有利于活性成分施用于例如植物、种子或土壤。由此,该载体通常是惰性的,且必须合乎要求(例如合乎农艺上的要求,尤其是适合施用于被处理的植物)。
载体可以是固体,例如粘土、天然的或合成的硅酸盐、硅石、树脂、蜡、固体肥料(如铵盐)、磨细的天然矿石,如高岭土、粘土、滑石粉、白垩、石英、硅酸铝铁载体、蒙脱石、膨润土或硅藻土,或磨细的合成矿石,如硅石、氧化铝或硅酸盐,尤其是硅酸铝或硅酸镁。下列物质适合用作粒剂的载体:碾碎的或分级过的天然岩石,如方解石、大理石、浮石、海泡石和白云石;合成的无机或有机粉的颗粒;锯屑、椰子壳、玉米棒子、玉米壳或烟草茎等有机物质的颗粒;硅藻土、磷酸三钙、栓皮粉、吸收性炭黑;水溶性聚合物、树脂、蜡;或固体肥料。视需要,这些固体组合物可含一种或多种可相容的湿润剂、分散剂、乳化剂或着色剂,当这些成分是固体时,还可用作稀释剂。
载体还可以是液体,例如水;醇,尤其是丁醇或乙二醇以及它们的醚或酯,尤其是methylglycol acetate;酮类,尤其是丙酮、环己酮、甲基·乙基酮、甲基·异丁基酮或异佛尔酮;石油馏分,如链烷烃或芳香烃,尤其是二甲苯或烷基萘;矿物油或植物油;脂族氯化烃,尤其是三氯乙烷或二氯甲烷;芳香族氯化烃,尤其是氯代苯;水溶性或强极性溶剂,如二甲基甲酰胺、二甲亚砜或N-甲基吡咯烷酮;液化气;或其他类似物或它们的混合物。
表面活性剂可以是离子型的或非离子型的乳化剂、分散剂或湿润剂或这些表面活性剂的混合物。这些表面活性剂的例子有聚丙烯酸盐、木素磺酸盐、苯酚磺酸或萘磺酸的盐、环氧乙烷与脂肪族醇或脂肪酸、脂肪族酯或脂肪族胺的缩聚物取代的苯酚(尤其是烷基苯酚或芳基苯酚)、磺基琥珀酸酯的盐、牛磺酸衍生物(尤其是牛磺酸烷基酯)、醇的磷酸酯或环氧乙烷与苯酚的缩聚物的磷酸酯、脂肪酸与多醇的酯,或上述化合物的硫酸酯、磺酸酯或磷酸酯官能衍生物。当活性成分和/或惰性载体仅微溶于水或不溶于水时和当施用的组合物的载体是水时,通常必须至少有一种表面活性剂。
本发明的组合物还可含其他添加剂,如粘合剂或着色剂。可在本发明的组合物中使用的粘合剂的例子有羧甲基纤维素,天然的或合成的聚合物,这些聚合物可以是粉状的、颗粒状的或格子状的,如阿拉伯树胶、聚乙烯醇或聚乙酸乙烯酯,天然的磷脂,如脑磷脂或卵磷脂,或合成的磷脂。可使用着色剂,如无机色素,其例子有氧化铁、氧化钛或普鲁士蓝;有机染料,如茜素染料、偶氮染料或金属酞菁染料;或微量营养素,如铁、镁、硼、铜、钴、钼或锌的盐。
可用于防治节足害虫、植物线虫、蠕虫或原虫的含式(I)化合物或其可用于杀虫的盐的组合物还可含增效剂(如胡椒基丁醚或增效菊)、稳定物质、其他杀虫剂、杀螨剂、杀植物线虫剂、杀蠕虫剂或杀介壳虫剂、杀真菌剂(适合农业或兽医要求的,如苯菌灵和异菌脲)、杀菌剂、节足害虫或脊椎动物引诱剂或驱避剂或信息素、除臭剂、芳香剂、染料或辅助治疗剂,如微量元素。这些成分可用来改善组合物的效力、持续时间、安全性、被目标害虫吸收的程度、所防治的害虫谱,或用来使组合物能在所处理的同一动物或区域起到其他有用的功能。
其他可包含于本发明组合物中或与本发明组合物合用的具有杀虫活性的化合物有:乙酰甲胺磷、毒死蜱、甲基内吸磷、乙拌磷、灭线磷、杀螟硫磷、虫胺磷、地虫硫磷、氯唑磷、异丙胺磷、马拉硫磷、久效磷、对硫磷、甲拌磷、伏杀硫磷、甲基嘧啶磷、特丁磷、三唑磷、氟氯氰菊酯、涕灭威、丁硫克百威、灭多威、杀线威、抗蚜威、噁虫威、伏虫隆、三氯杀螨醇、硫丹、林丹、苯螨特、杀螟丹、三环锡、三氯杀螨砜、阿威定(avermectins)、埃威定(ivermectins)、灭尔霉素(milbemycins)、硫菌灵、敌百虫、敌敌畏、代伏定(diaveridine)或代特唑(dimetridazole)。
在农业应用中,式(I)化合物或其可用于杀虫的盐一般以组合物的形式(各种固体或液体形式)使用。
可以使用的组合物的固体形式是尘化粉末式(I)化合物或其可用于杀虫的盐的含量≤80%)、可湿性粉末或颗粒(包括水可分散性颗粒),特别是通过颗粒载体的挤压、压紧、浸渍或从粉末开始颗粒化而得到的颗粒(这些可湿性粉末或颗粒中式(I)化合物或其可用于杀虫的盐的含量约为0.5-80%)。所述含有一种或几种式(I)化合物或其可用于杀虫的盐的均匀或不均匀组合物,例如颗粒、丸、团块或胶囊,可用来对死水或流水处理一段时间。本文所描述的水可分散性浓缩物的细流或间歇馈入可得到类似的效果。
液体组合物,例如包括水或非水溶液或悬浮液(如可乳化的浓缩物、乳剂、流体、分散体或溶液)或气溶胶。液体组合物还包括,特别是,可乳化的浓缩物、分散体、乳剂、流体、气溶胶、可湿性粉末(或喷雾用粉末)、干流体或组合物形式的糊剂,它们是液体或打算在使用时形成液体组合物,例如用作水性喷雾剂(包括低或超低容量)或用作雾剂或气溶胶。
液体组合物,例如以可乳化或可溶性浓缩物形式存在,最常包含约5-80重量%活性成分,而可以即用的乳剂或溶液,在各自情况下包含约0.01-20%活性成分。除了溶剂外,可乳化或可溶性浓缩物需要时可包含约2-50%适当的添加剂,如稳定剂、表面活性剂、渗透剂、腐蚀抑制剂、着色剂或粘合剂。用水稀释,可从这些浓缩物得到任何需要浓度的乳剂,例如特别适用于植物的乳剂。这些组合物包括在可应用于本发明的组合物范围内。乳剂可以是油包水或水包油型的,可有稠的粘度。
本发明的液体组合物除了正常的农业应用外,还可用于例如处理已被或易被节足害虫(或用本发明的化合物防治的其它害虫)感染的基质或地点,包括房屋、室外或室内储藏或加工区、容器或设备或死水或流水。
所有这些水性分散体或乳剂或喷雾混合物可用任何合适的方法(主要是喷雾),一般以约100-1,200升喷雾混合物/公顷的量施用于作物,但根据需要或施用技术,用量可较高或较低(如低或超低体积)。按照本发明的化合物或组合物方便地施用于植物,特别是有拟消灭的害虫的根部或叶子。按照本发明的化合物或组合物的另一个施用方法是化学灌溉(chemigation),即在灌溉水加入含活性成分的制剂。对于用于叶子的农药,此灌溉可以是喷淋灌溉,对于土壤或内吸性农药,可地面灌溉或地下灌溉。
制备可喷雾施用的浓悬浮液,以便产生不沉降的稳定的液体产品(研得很细),它通常包含约10-75重量%活性成分、约0.5-30%表面活性剂、约0.1-10%触变剂和约0-30%合适的添加剂,如防泡剂、腐蚀抑制剂、稳定剂、渗透剂、粘合剂以及活性成分难溶或不溶于其中的作为载体的水或有机液体。一些有机固体或无机盐可溶于载体中,帮助预防沉降,或作为水的防冻剂。
可湿性粉末(或喷雾用粉末)常制成含约10-80重量%活性成分、约20-90%固体载体、约0-5%湿润剂、约3-10%分散剂,及需要时含约0-80%一种或几种稳定剂和/或其它添加剂,如渗透剂、粘合剂、防结块剂、着色剂等。为了获得这些可湿性粉末,在合适的混合器中将活性成分与可浸渗在多孔填料上的添加物质混合,并用磨机或磨床研磨。这样就产生了可湿性粉末,其可湿性和可悬浮性均佳。它们可悬浮于水中,得到任何所需要的浓度,此悬浮液可非常有益地使用,特别是施用于植物的叶子。
“水可分散的颗粒(WG)(容易分散于式中的颗粒)具有基本上接近可湿性粉末的组成。其制备可以是通过湿法途径(将细分的活性成分与惰性填充剂和少量水(如1-20重量%)或与分散剂或粘合剂的水溶液接触,接着干燥和过筛)或通过干法途径(压紧,接着研磨和过筛)将关于可湿性粉末所描述的配方进行颗粒化。
配制的组合物的比率和浓度可根据施用方法或组合物的性质或其用途加以改变。一般来说,用于防治节足害虫、植物线虫、蠕虫或原虫的组合物通常包含约0.00001-95重量%(特别是约0.0005-50%)的一种或几种式(I)化合物或其可用于杀虫的盐,或总活性成分(即式(I)化合物或其可用于杀虫的盐,以及对节足害虫或植物线虫有毒的其它物质、驱虫剂、抗球虫剂、增效剂、痕量元素或稳定剂)。由农民、家畜生产者、医学或兽医开业者、防治害虫的操作者或其它本领域技术人员选择实际采用的组合物及其用量以得到所需要的效应。
局部施用于动物、树木、储藏品或家用品的固体或液体组合物通常包含约0.00005-90重量%(更特别是约0.001-10%)的一种或几种式(I)化合物或其可用于杀虫的盐。口服或胃肠外给动物施用(包括经皮施用)的固体或液体组合物通常包含约0.1-90重量%一种或几种式(I)化合物或其可用于杀虫的盐。医用饲料通常包含约0.001-3重量%一种或几种式(I)化合物或其可用于杀虫的盐。用于与饲料混合的浓缩物或补充剂通常包含约5-90重量%(较佳为约5-50%)一种或几种式(I)化合物或其可用于杀虫的盐。动物常去舔盐的矿盐盐渍地(mineral salt licks)通常包含约0.1-10重量%一种或几种式(I)化合物或其可用于杀虫的盐。
施用于家畜、货物、房屋或户外区域的尘化粉末或液体组合物包含约0.0001-15重量%(更特别是约0.005-2.0重量%)的一种或几种式(I)化合物或其可用于杀虫的盐。受处理的水中的合适浓度为约0.0001-20ppm(更特别是约0.001-5.0ppm)的一种或几种式(I)化合物或其可用于杀虫的盐,可以适当的暴露时间在鱼场中作治疗用。食饵可包含约0.01-5重量%(较佳为约0.01-1.0%)的一种或几种式(I)化合物或其可用于杀虫的盐。
当胃肠外、口服或经皮或其它途径施用于脊椎动物时,一种或几种式(I)化合物或其可用于杀虫的盐的剂量根据脊椎动物的种类、年龄或健康状况,并根据其实际或潜在的受节足害虫、蠕虫或原虫感染的情况而定。通常适合于口服或胃肠外施用的单剂为约0.1-100mg/kg动物体重(较佳为约2.0-20.0mg/kg体重),或约0.01-20.0mg/kg动物体重/天(较佳为约0.1-5.0mg/体重/天)的剂量持续给药。用缓释制剂或给药装置时,历时数月所需的每日剂量可一次合并给予动物。
下面的组合物实施例2A-2M阐述了用于抗节足害虫(特别是螨或昆虫、植物线虫或蠕虫或原虫)的组合物,包括如制备实施例中描述的那些式(I)化合物或其可用于杀虫的盐作为活性成分。实施例2A-2M中描述的组合物每个都可稀释成适合于田地中使用浓度的可喷雾组合物。下面例举的组合物实施例2A-2M中所用成分(其如下百分率均为重量百分率)的一般化学描述如下:
商品名
化学描述
Ethylan BCP 聚氧乙烯化壬基苯酚
Soprophor BSU 聚氧乙烯化三苯乙烯基苯酚
Arylan CA 十二烷基苯磺酸钙的70%w/v溶液
Solvesso 150 轻质C10芳烃溶剂
Arylan S 十二烷基苯磺酸钠
Darvan No2 木素磺酸钠
Celite PF 合成硅酸镁载体
Sopropon T36 多元羧酸钠盐
Rhodigel 23 多糖黄原胶
Bentone 38 蒙脱石镁的有机衍生物
Aerosil 微细二氧化硅实施例2A
制备具有如下组分的水溶性浓缩物:
活性成分 7%
Ethylan BCP 10%
N-甲基吡咯烷酮 83%
在加热和搅拌下,向溶于部分N-甲基吡咯烷酮的Ethylan BCP溶液中加入活性成分,直至溶解。用剩余量的溶剂使所得溶液达到一定体积。
实施例2B
制备具有如下组分的可乳化浓缩物(EC):
活性成分 25%(最大)
Soprophor BSU 10%
Arylan CA 5%
N-甲基吡咯烷酮 50%
Solvesso 150 10%
将前面三种组份溶于N-甲基吡咯烷酮,然后向其中加入solvesso 150,得到最终体积。
实施例2C
制备具有如下组分的可湿性粉末(WP):
活性成分 40%
Arylan S 2%
Darvan No2 5%
Celite PF 53%
将各成分混合,在锤磨机中磨成颗粒大小小于50微米的粉末。实施例2D
制备具有如下组分的水性可流动制剂:
活性成分 40.00%
Ethylan BCP 1.00%
Sopropon T360 0.20%
乙二醇 5.00%
Rhodigel 230 0.15%
水 53.65%
将各成分充分混合,在球磨机中压磨直至达到平均颗粒大小小于3微米。
实施例2E
制备具有如下组分的可乳化浓缩物(EC):
活性成分 30.0%
Ethylan BCP 10.0%
Bentone 38 0.5%
Solvesso 150 59.5%
将各成分充分混合,在球磨机中压磨直至达到平均颗粒大小小于3微米。
实施例2F
制备具有如下组分的水可分散颗粒:
活性成分 30%
Darvan No 2 15%
Arylan S 8%
Celite PF 47%
将各成分混合,在流体动力磨机中微粉化,然后在旋转式制粒机中喷水(≤10%)制粒。所得的颗粒在流化床中干燥,除去过量水分。实施例2G
制备具有如下组分的尘化粉末:
活性成分 1-10%
滑石粉(超细) 99-90%
将各成分充分混合,如果需要再进一步研磨,达到细粉。此粉可施用于节足害虫感染的场所,例如,垃圾堆、储藏品或家用品,或受节足害虫感染或处于其感染危险中的动物通过经口摄入以防治害虫。将尘化粉末分散到节足害虫感染场所的合适方法包括机械鼓风机、手摇摇动器或家畜自处理装置。
实施例2H
制备如下组合物食饵:
活性成分 0.1-1.0%
小麦粉 80%
糖浆 19.9-19%
将各成分充分混合。需要时形成饵状。此食饵可分散于感染了节足害虫(如蚂蚁、蝗虫、蟑螂或苍蝇)的场所,如家庭居室或工业用房(如厨房、医院或商店)或室外空地,通过经口摄入以防治害虫。
实施例2I
制备具有如下组分的溶液制剂:
活性成分 15%
二甲亚砜 85%
根据需要,在混合和/或加热下,将活性成分溶于二甲亚砜。该溶液可通过经口施用而倾注于受节足害虫感染的家庭动物,或通过聚四氟乙烯膜(0.22微米孔径)过滤灭菌后,以1.2-12ml溶液/100kg动物体重的用量经胃肠外注射给药。实施例2J
制备具有如下组分的可湿性粉末:
活性成分 50%
Ethylan BCP 5%
Aerosil 5%
Celite PF 40%
将Ethylan BCP吸附在Aerosil上,然后将其与其它成分混合,在锤磨机中研磨,得到可湿性粉末,将其用水稀释成活性化合物浓度为0.001%-2重量%,喷雾施用于受节足害虫(如双翅目幼虫或植物线虫)感染的场所,或通过喷雾或浸蘸或加在饮用水中口服,施用于受节足害虫、蠕虫或原虫感染或处于其感染危险中的家庭动物,用来防治节足害虫、蠕虫或原虫。
实施例2K
根据需要,从含不同百分率的如下组分(类似于对前面的组合物所作的描述)的颗粒形成缓释大丸剂组合物:
活性成分
密度剂
缓释剂
粘合剂
将充分混合的成分形成颗粒,再压成比重为2或更大的大丸剂。它可给家庭反刍动物口服给药,保留在蜂窝胃中,经长时间持续缓慢释放活性化合物,用来防治节足害虫、蠕虫或原虫对家庭反刍动物的感染。
实施例2L
用如下组合物可制备颗粒、丸剂、brickettes等形式的缓释组合物:
活性成分 0.5-25%
聚氯乙烯 75-99.5%
邻苯二甲酸二辛酯(增塑剂)
将各组分混合,然后熔融挤压或模压成合适的形状。这些组合物可用于例如添加到死水中或加工成圈环或耳标,附着在家庭动物身上,通过缓慢释放来防治虫害。实施例2M
用如下组分制成水可分散的颗粒:
活性成分 85%(最大)
聚乙烯吡咯烷酮 5%
美国活性白陶土 6%
十二烷基硫酸钠 2%
甘油 2%
将各成分用水混合成45%的浆料,湿磨成4微米颗粒大小,然后喷雾干燥除去水分。
上面已借助各种优选的实施例对本发明进行了描述,但熟练技术人员会懂得,可作各种修改、替代、省略和改变而不背离其精神。因此,本发明的范围仅仅受下面的权利要求书(包括其等同物)范围的限制。
Claims (29)
1.一种防治昆虫的方法,它包括向有昆虫或预计会有昆虫的位置施用具有1-芳基吡唑基团的杀虫活性成分,所述施用在哺乳动物类可能接触到杀虫活性成分的条件下进行,所述活性成分的吡唑环上具有3-乙酰取代基,但为了预防或治疗哺乳动物的疾病的目的而将活性成分直接施用于哺乳动物本身的除外。
2.如权利要求1所述的方法,其中,上述可能与活性成分接触的哺乳动物是工作人员。
3.如权利要求2所述的方法,其中,工作人员与活性成分的接触为大量接触。
4.如权利要求1所述的方法,其中,有或预计会有选自蚜虫、盲蝽和刺益蝽的吸吮的昆虫。
5.如权利要求4所述的方法,其中,系统防治所述的吸吮性昆虫。
6.如权利要求1所述的方法,其中,1-芳基吡唑是式(I)化合物或其可用于杀虫的盐:式中,
R1是S(O)mR5;
R2选自氢原子、卤原子、-NR6R7、-S(O)nR8、C(O)R8、C(O)OR9、烷基、卤代烷基、-OR9或-N=C(R10)(R11);
R3选自卤原子或氢原子;
R4选自卤原子、卤代烷基、卤代烷氧基、-S(O)pCF3或-SF5;
R5是烷基或卤代烷基;
R6和R7独立地选自氢原子、烷基、卤代烷基、-C(O)R8、C(O)OR8、-S(O)qCF3;其烷基部分可任选地被一个或多个R12取代;或R6与R7结合在一起,形成一个具有4至6个链原子的二价基团,该二价基团是亚烷基、亚烷基氧基亚烷基或亚烷基氨基亚烷基;
R8是烷基或卤代烷基;
R9选自烷基、卤代烷基或氢原子;
R10选自R9或烷氧基;
R11是烷基或卤代烷基;或选自苯基或杂芳基,该苯基或杂芳基可任选地被一个或多个选自羟基、卤素、烷氧基、-S(O)rR8、氰基、R8或它们的组合的基团取代;
R12选自氰基、硝基、烷氧基、卤代烷氧基、-S(O)s-烷基、-S(O)s-卤代烷基、C(O)-烷基、C(O)-卤代烷基、C(O)O-烷基、C(O)O-卤代烷基、氨基羰基、烷氨基羰基、二烷基氨基羰基、羟基、氨基磺酰基、烷氨基磺酰基或二烷基氨基磺酰基;
X选自氮原子或C-R13基团;
R13是卤原子;
m、n、p、q、r和s彼此独立地表示数值0、1或2。
7.如权利要求6所述的方法,其中,R6与R7结合在一起,形成吗啉环、吡咯烷环、哌啶环或哌嗪环。
8.如权利要求6所述的方法,其中,1-芳基吡唑是式(I)化合物,式中,
R2是NR6R7;
R3是卤素;
R4是CF3-、CF3O-和-SF5;
R5是烷基;
X是CR13;
R13是卤素;
m是0或1。
9.如权利要求6所述的方法,其中,1-芳基吡唑是式(I)化合物,式中,
R2是NR6R7;
R3是氯;
R4是CF3-、CF3O-和-SF5;
R5是烷基;
R6是氢;
R7是氢、-S(O)qCF3或可被-S(O)sR8或氨基羰基任意取代的烷基;
X是CR13;
R13是氯或溴;
m是0或1。
10.如权利要求6所述的方法,其中,1-芳基吡唑是式(I)化合物,式中,
R2是NR6R7;
R3是氯;
R4是CF3-和-SF5;
R5是甲基和乙基;
R6是氢;
R7是氢、或可被-S(O)sR8或氨基羰基任意取代的甲基和乙基;
R8是甲基和乙基;
R9是甲基和乙基;
X是CR13;
R13是氯或溴;
m是0或1。
11.如权利要求1-10中任一项所述的方法,其中,施用的位置是用来或拟用来种植作物的区域,式(I)化合物的施用比率为5-1000g/公顷。
12.一种杀虫组合物,它含杀虫有效量的权利要求1-9中任一项所述的式(I)化合物及可用于杀虫剂的稀释剂或载体。
13.一种杀蚜虫组合物,它含杀蚜虫有效量的权利要求1-9中任一项所述的式(I)化合物及可用于杀蚜虫剂的稀释剂或载体。
14.如权利要求12所述的杀虫组合物,它含0.00005-90重量%的式(I)化合物。
15.如权利要求13所述的杀蚜虫组合物,它含0.00005-90重量%的式(I)化合物。
16.如权利要求12所述的杀虫组合物,其中,所述式(I)化合物选自
3-乙酰-5-氨基-1-(2,6-二氯-4-三氟甲基苯基)-4-甲基亚硫酰基吡唑、
3-乙酰-5-氨基-1-(2,6-二氯-4-三氟甲基苯基)-4-甲基硫基吡唑、
3-乙酰-5-氨基-1-(2,6-二氯-4-三氟甲基苯基)-4-乙基亚硫酰基吡唑、
3-乙酰-1-(2,6-二氯-4-三氟甲基苯基)-5-乙氨基-4-甲基亚硫酰基吡唑、
3-乙酰-1-(2,6-二氯-4-三氟甲基苯基)-5-甲氨基-4-甲基亚硫酰基吡唑、
3-乙酰-5-(2-氨基甲酰基甲基氨基)-1-(2,6-二氯-4-三氟甲基苯基)-4-甲基亚硫酰基吡唑、
3-乙酰-1-(2,6-二氯-4-三氟甲基苯基)-5-(2-乙基磺酰基乙氨基)-4-甲基亚硫酰基吡唑、
3-乙酰-1-(2,6-二氯-4-三氟甲基苯基)-5-(2-氨基甲酰基乙氨基)-4-甲基亚硫酰基吡唑、
3-乙酰-5-氨基-1-(2-溴-6-氯-4-三氟甲基苯基)-4-甲基亚硫酰基吡唑、
3-乙酰-1-(2,6-二氯-4-三氟甲基苯基)-4-甲基亚硫酰基-5-三氟甲硫基氨基吡唑、
3-乙酰-5-氨基-1-(2,6-二氯-4-五氟硫代苯基)-4-甲基亚硫酰基吡唑和
3-乙酰-5-氨基-1-(2,6-二氯-4-五氟硫代苯基)-4-甲基硫基吡唑
的化合物。
17.式(I)化合物,其定义如权利要求6中所述,但当R2为氨基、R3为氯、R4为CF3和X为C-Cl时,R1不是SCF3或SO2CH3。
18.如权利要求17所述的化合物,其中,R2是氨基,它是未取代的或具有一个或二个选自烷基、-C(O)R8和-C(O)OR8的取代基;其烷基部分可任选地被一个或多个R12取代。
19.如权利要求17所述的化合物,其中R3是卤原子。
20.如权利要求19所述的化合物,其中R3是氯原子。
21.如权利要求17所述的化合物,其中R4选自卤原子、卤代烷基、卤代烷氧基或-SF5。
22.如权利要求21所述的化合物,其中,R4选自CF3-、CF3O-和-SF5。
23.如权利要求17所述的化合物,其中,R5是甲基、乙基或丙基。
24.式(I)化合物或其农业用盐,其定义如权利要求6中所述,式中,
R2是NR6R7;
R3是卤素;
R4是CF3-、CF3O-和-SF5;
R5是烷基;
X是CR13;
R13是卤素;
m是0或1。
25.如权利要求24所述的式(I)化合物或其农业用盐,其定义如权利要求6中所述,式中,
R2是NR6R7;
R3是氯;
R4是CF3-、CF3O-和-SF5;
R5是烷基;
R6是氢;
R7是氢、-S(O)qCF3或可被-S(O)sR8或氨基羰基任意取代的烷基;
X是CR13;
R13是氯或溴;
m是0或1。
26.如权利要求24所述的式(I)化合物或其农业用盐,其定义如权利要求6中所述,式中,
R2是NR6R7;
R3是氯;
R4是CF3-和-SF5;
R5是甲基和乙基;
R6是氢;
R7是氢、可被-S(O)sR8或氨基羰基任意取代的甲基和乙基;
R8是甲基和乙基;
R9是甲基和乙基;
X是CR13;
R13是氯或溴;
m是0或1。
27.如权利要求24所述的式(I)化合物或其农业用盐,其中,所述式(I)化合物是
3-乙酰-5-氨基-1-(2,6-二氯-4-三氟甲基苯基)-4-甲基亚硫酰基吡唑、
3-乙酰-5-氨基-1-(2,6-二氯-4-三氟甲基苯基)-4-甲基硫基吡唑、
3-乙酰-5-氨基-1-(2,6-二氯-4-三氟甲基苯基)-4-乙基亚硫酰基吡唑、
3-乙酰-1-(2,6-二氯-4-三氟甲基苯基)-5-乙氨基-4-甲基亚硫酰基吡唑、
3-乙酰-1-(2,6-二氯-4-三氟甲基苯基)-5-甲氨基-4-甲基亚硫酰基吡唑、
3-乙酰-5-(2-氨基甲酰基甲基氨基)-1-(2,6-二氯-4-三氟甲基苯基)-4-甲基亚硫酰基吡唑、
3-乙酰-1-(2,6-二氯-4-三氟甲基苯基)-5-(2-乙基磺酰基乙氨基)-4-甲基亚硫酰基吡唑、
3-乙酰-1-(2,6-二氯-4-三氟甲基苯基)-5-(2-氨基甲酰基乙氨基)-4-甲基亚硫酰基吡唑、
3-乙酰-5-氨基-1-(2-溴-6-氯-4-三氟甲基苯基)-4-甲基亚硫酰基吡唑、
3-乙酰-1-(2,6-二氯-4-三氟甲基苯基)-4-甲基亚硫酰基-5-三氟甲硫基氨基吡唑、
3-乙酰-5-氨基-1-(2,6-二氯-4-五氟硫代苯基)-4-甲基亚硫酰基吡唑或
3-乙酰-5-氨基-1-(2,6-二氯-4-五氟硫代苯基)-4-甲基硫基吡唑。
28.如权利要求27所述的式(I)化合物或其农业用盐,其中,所述式(I)化合物是3-乙酰-5-氨基-1-(2,6-二氯-4-三氟甲基苯基)-4-甲基亚硫酰基吡唑或3-乙酰-5-氨基-1-(2,6-二氯-4-三氟甲基苯基)-4-甲基硫基吡唑。
29.一种制备其定义如权利要求17中所述的式(I)化合物的方法,该方法包括:
其中,R1、R2、R3、R4和X的定义如权利要求17中所述
与合适的试剂CH3M反应,其中,M表示碱金属,如锂;或碱土金属盐;
(b)用合适的试剂R5S(O)mY,其中,R5的定义如权利要求17中所述,m表示0或1,Y表示卤素
将相应的式(III)化合物硫基化或亚硫酰化,制备R1、R3、R4和X的定义如权利要求17中所述,m为0或1的式(I)化合物;
(c)将式(IV)化合物与式(V)化合物反应,然后环化,制备R1、R3、R4和X的定义如权利要求17中所述,R2表示氨基的式(I)化合物;
(d)将m为0或1的相应的式(I)化合物氧化,制备R1、R2、R3、R4和X的定义如权利要求17中所述,m为1或2的式(I)化合物;
(e)将R2为氨基的相应的式(I)化合物与式(VI)化合物
R12-CH=CH2 (VI)
式中,R12的定义同上进行迈克尔加成反应,制备具有如下定义的式(I)化合物,R1、R3、R4和X的定义如权利要求17中所述,R2表示NR6R7,其中,R6表示氢,R7表示在2位被R12取代的乙基,R12表示氰基、硝基、-S(O)sR8、C(O)R8、C(O)OR9、氨基羰基、烷氨基羰基、二烷基氨基羰基、氨基磺酰基、烷氨基磺酰基或二烷基氨基磺酰基;
(f)作为本发明的又一个方面,R1、R3、R4和X的定义如权利要求17中所述,R2表示NR6R7,其中,R6和/或R7表示可被一个或多个R12任意取代的烷基或卤代烷基的通式(I)化合物可通过用式(VII)化合物
R14-Y (VII)
式中,R14为可被一个或多个R12任意取代的烷基或卤代烷基,Y表示离去基团,优选卤素将R2为氨基的相应的式(I)化合物烷基化而制得;
(g)用式(VIII)的醇
R8OH (VIII)
将R2为羧基的相应的式(I)化合物酯化,制备R2为C(O)OR8的式(I)化合物;
(h)将R2被甲酰基取代的相应的式(I)化合物氧化,制备R2为羧基的式(I)化合物;
(i)将R2为氨基的相应的式(I)化合物与式(IX)的化合物
RaCH=CH2 (IX)反应,制备R2表示RaCH(Cl)CH2-,Ra表示烷基的式(I)化合物;
(k)将m为0或1的式(I)化合物氧化,制备m为1或2的式(I)化合物;
任选地将由此制得的式(I)化合物转换成其可用于杀虫的盐。
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