CN1955162A - 邻苯二酸衍生物及其用作制备邻苯二酰胺衍生物中间体的用途 - Google Patents
邻苯二酸衍生物及其用作制备邻苯二酰胺衍生物中间体的用途 Download PDFInfo
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- CN1955162A CN1955162A CNA2006101464691A CN200610146469A CN1955162A CN 1955162 A CN1955162 A CN 1955162A CN A2006101464691 A CNA2006101464691 A CN A2006101464691A CN 200610146469 A CN200610146469 A CN 200610146469A CN 1955162 A CN1955162 A CN 1955162A
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- propyl
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- WVZPYZMQQDNINJ-UHFFFAOYSA-N tributyl(butylstannyloxy)stannane Chemical compound CCCC[SnH](CCCC)O[SnH](CCCC)CCCC WVZPYZMQQDNINJ-UHFFFAOYSA-N 0.000 description 1
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- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
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- LESVOLZBIFDZGS-UHFFFAOYSA-N vamidothion Chemical compound CNC(=O)C(C)SCCSP(=O)(OC)OC LESVOLZBIFDZGS-UHFFFAOYSA-N 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 229940100050 virazole Drugs 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000004562 water dispersible granule Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
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- WCJYTPVNMWIZCG-UHFFFAOYSA-N xylylcarb Chemical compound CNC(=O)OC1=CC=C(C)C(C)=C1 WCJYTPVNMWIZCG-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- CHNQZRKUZPNOOH-UHFFFAOYSA-J zinc;manganese(2+);n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[Zn+2].[S-]C(=S)NCCNC([S-])=S.[S-]C(=S)NCCNC([S-])=S CHNQZRKUZPNOOH-UHFFFAOYSA-J 0.000 description 1
- AMHNZOICSMBGDH-UHFFFAOYSA-L zineb Chemical compound [Zn+2].[S-]C(=S)NCCNC([S-])=S AMHNZOICSMBGDH-UHFFFAOYSA-L 0.000 description 1
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Classifications
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- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/63—Esters of sulfonic acids
- C07C309/64—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms
- C07C309/65—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms of a saturated carbon skeleton
- C07C309/66—Methanesulfonates
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- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
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- A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
- A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
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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
- A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
- A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
- A01N41/04—Sulfonic acids; Derivatives thereof
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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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/63—Esters of sulfonic acids
- C07C309/64—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms
- C07C309/65—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms of a saturated carbon skeleton
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
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- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C323/24—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/25—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
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- C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C323/39—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton at least one of the nitrogen atoms being part of any of the groups, X being a hetero atom, Y being any atom
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Abstract
本发明涉及式(VI)的邻苯二酸衍生物及其用作制备邻苯二酰胺衍生物中间体的用途,其中R1、R3、R4和R5的定义见说明书中所述。
Description
本申请为一项发明专利申请的分案申请,其母案的申请日为2003年6月11日、申请号为03818539.3(PCT/EP2003/006105)、发明名称为“新的邻苯二酰胺衍生物”。
技术领域
本发明涉及新的邻苯二酰胺衍生物、制备它们的数种方法、它们的中间体以及它们作为杀虫剂的应用。
背景技术
已知某些邻苯二酰胺衍生物具有杀虫作用(参见EP 0919542-A2,EP 1006107-A2,WO 01/00575,WO 01/00599,WO 01/21576)。
进一步地,人们还知道一些邻苯二酰胺衍生物显示出作为药物的作用(参见EP 0119428-A2)。
发明内容
现已发现新的式(I)邻苯二酰胺衍生物:
其中:
R1代表任选被卤素取代的烷基,
R2代表任选取代的烷基或任选取代的环烷基,
R3代表氢原子,卤素,或任选被卤素取代的烷基,
R4代表氢原子,卤代烷基,卤代烷氧基,卤代苯基,或卤代苯氧基,
以及
R5代表氢原子,卤素,或任选被卤素取代的烷基。
根据取代基的性质与数目,式(I)化合物可以几何和/或光学异构体、区域异构体或构型异构体或不同组成的异构体混合物的形式存在。本发明不仅要求保护纯异构体,而且也要求保护异构体混合物。
本发明式(I)化合物可以按照以下方法制备:
a)在惰性溶剂存在下,并且如果合适在碱存在下,使下面的式(II)化合物与式(III)化合物反应:
其中R1、R3、R4和R5的定义同上所述,
H2N-R2 (III)
其中R2的定义同上所述,
或者
b)在惰性溶剂存在下,并且如果合适在酸催化剂的存在下,使下面的式(IV)化合物与式(V)化合物反应:
其中R1和R2的定义同上所述,
其中R3、R4和R5的定义同上所述,
或者
c)在惰性溶剂存在下,并且如果合适在酸催化剂的存在下,使下面的式(VI)化合物与式(III)化合物反应:
其中R1、R3、R4和R5的定义同上所述,
H2N-R2 (III)
其中R2的定义同上所述,
或者
d)制备其中R2代表烷基亚磺酰基烷基或烷基磺酰基烷基的式(I)化合物:在惰性溶剂存在下,使下面的式(Id)化合物与氧化剂反应:
其中R2d代表烷硫基烷基,
R1、R3、R4和R5的定义同上所述。
本发明的式(I)邻苯二酰胺衍生物显示出强杀虫作用。
具体实施方案
本发明的式(I)邻苯二酰胺衍生物从定义上讲包括在EP0919542-A2或EP 1006107-A2中描述的通式化合物之内。但上述文献并没有具体公开本发明的式(I)邻苯二酰胺衍生物。
与上述专利文献中具体描述的化合物相比(这些化合物与本发明的式(I)化合物结构类似),令人惊奇的是,本发明的式(I)化合物显示出极强的杀虫作用,尤其是对鳞翅目害虫具有优越的杀虫活性。此外,本发明的式(I)化合物还显示出内吸性杀虫活性。
在本说明书中,“卤素”以及“任选被卤素取代的烷基”、“卤代烷基”、“卤代烷氧基”、“卤代苯基”和“卤代苯氧基”中的卤素部分代表氟、氯、溴或碘,优选代表氟、氯或溴。
“烷基”以及基团“烷氧基”、“烷硫基”、“烷基亚磺酰基”和“烷基磺酰基”中的烷基部分可以是直链或支链的,例如可以提及甲基,乙基,正-或异-丙基,正-、异-、仲-或叔-丁基,正-、异-、新-、叔-戊基,2-甲基丁基,正-、异-或仲-己基等。
“环烷基”包括例如环丙基,环丁基,环戊基,环己基、环庚基、环辛基等等。
“卤代烷基”表示其中至少一个氢被卤素取代的直链或支链烷基。例如,可以提及被1-9个氟和/或氯取代的C1-6烷基,并且作为其具体实例,可以提及二氟甲基、三氟甲基、2-氟乙基、2-氯乙基、2,2,2-三氟乙基、1,1,2,2-四氟乙基、1,1,2,2,2-五氟乙基、2-氯-1,1,2-三氟乙基、3-氟丙基、3-氯丙基、1-甲基-2,2,2-三氟乙基、2,2,3,3,3-五氟丙基、1,2,2,3,3,3-六氟丙基、全氟异丙基、全氟丁基、2,2,3,3,4,4,5,5,5-九氟戊基、3,3,4,4,5,5,6,6,6-九氟己基等。
“卤代烷氧基”中的卤代烷基部分可以与上述“卤代烷基”的定义相同,而且作为“卤代烷氧基”,例如可以具体提及二氟甲氧基、三氟甲氧基、2-氟乙氧基、2-氯乙氧基、2-溴乙氧基、2,2,2-三氟乙氧基等。
“卤代苯基”以及“卤代苯氧基”中的卤代苯基部分可以代表被1-3个、优选1-2个上述“卤素”取代的苯基,而且作为具体实例,可以提及2-、3-或4-氟苯基,2-、3-或4-氯苯基、2,3-、2,4-、2,5-、2,6-、3,4-或3,5-二氯苯基等。
在上述式(I)化合物中,优选:
R1代表任选被氟、氯或溴取代的C1-6烷基,
R2代表任选被氟、氯、溴、C1-4烷氧基、C1-4烷硫基、C1-4烷基亚磺酰基、或C1-4烷基磺酰基取代的C1-6烷基,或代表任选被卤素取代或被C1-4烷基取代的C3-6环烷基,
R3代表氢原子或卤素,或代表任选被氟、氯或溴取代的C1-6烷基,
R4代表氢原子,卤代C1-6烷基,卤代C1-6烷氧基,卤代苯基,或卤代苯氧基,以及
R5代表氢原子或卤素,或代表任选被氟、氯或溴取代的C1-6烷基。
在上述式(I)化合物中,更优选:
R1代表甲基,乙基,丙基或三氟甲基,
R2代表甲基,乙基,正丙基,异丙基,正丁基,异丁基,仲丁基,叔丁基,正戊基,异戊基,仲戊基,叔戊基,正己基,异己基,仲己基,甲硫基甲基,乙硫基甲基,甲硫基乙基,乙硫基乙基,甲硫基丙基,乙硫基丙基,甲硫基丁基,乙硫基丁基,甲硫基戊基,乙硫基戊基,甲基亚磺酰基甲基,乙基亚磺酰基甲基,甲基亚磺酰基乙基,乙基亚磺酰基乙基,甲基亚磺酰基丙基,乙基亚磺酰基丙基,甲基亚磺酰基丁基,乙基亚磺酰基丁基,甲基亚磺酰基戊基,乙基亚磺酰基戊基,甲磺酰基甲基,乙磺酰基甲基,甲磺酰基乙基,乙基磺酰基乙基,甲磺酰基丙基,乙磺酰基丙基,甲磺酰基丁基,乙磺酰基丁基,甲磺酰基戊基,乙磺酰基戊基,或代表环丙基,环丁基,环戊基或环己基,它们各自可任选被氟、氯、溴、甲基或乙基取代,
R3代表氢原子,氟,氯,溴,甲基,乙基或三氟甲基,
R4代表氟,氯或溴,或代表甲基,乙基,正丙基,异丙基,正丁基,异丁基,仲丁基,叔丁基,甲氧基,乙氧基,正丙氧基或异丙氧基,它们各自任选地是被至少一个氟部分取代的、被氟全取代的、或被至少一个氟和1或2个氯取代的,
R5代表氢原子,氟,氯或溴,或代表甲基或乙基,后两个基团各自任选被氟或氯取代。
在上述式(I)化合物中,进一步特别优选:
R1代表甲基或乙基,
R2代表异丙基,叔丁基,1-甲基-2-(甲硫基)乙基,1,1-二甲基-2-(甲硫基)乙基,1-甲基-2-(甲基亚磺酰基)乙基,1,1-二甲基-2-(甲基亚磺酰基)乙基,1-甲基-2-(甲磺酰基)乙基或1,1-二甲基-2-(甲磺酰基)乙基,
R3代表甲基,
R4代表全氟异丙基,和
R5代表氢原子。
在例如使用N-(4-七氟异丙基-2-甲基苯基)-3-甲磺酰氧基邻苯二甲酰亚胺和异丙胺作为起始原料的情况下,上述制备方法(a)可以用下述反应式举例说明。
在例如使用6-甲磺酰氧基-N-异丙基异邻苯二甲酰亚胺(phthalisoimide)和4-七氟异丙基-2-甲基苯胺作为起始原料的情况下,上述制备方法(b)可以用下面的反应式举例说明。
在例如使用N-(4-七氟异丙基-2-甲基苯基)-3-甲磺酰氧基异邻苯二甲酰亚胺(phthalisoimide)和异丙胺作为起始原料的情况下,上述制备方法(c)可以用下面的反应式举例说明。
在例如使用N2-[1,1-二甲基-2-(甲硫基)乙基]-N1-(4-七氟异丙基-2-甲基苯基)-3-甲磺酰氧基邻苯二酰胺和间-氯过苯甲酸作为起始原料的情况下,上述制备方法(d)可以用下面的反应式举例说明。
上述制备方法(a)中的起始原料式(II)化合物是文献中尚无记载的新化合物,并且可以通过例如使式(VII)化合物:
其中R3、R4和R5的定义同上,与式(VIII)化合物反应制备:
R1SO2Cl (VIII)
其中R1的定义同上所述(参见Tetrahedron Letters
1988,
29,5595-5598)。
上述式(VII)化合物中的一部分是文献中尚无记载的新化合物,并且可以通过例如由已知的3-羟基邻苯二甲酸酐与上述式(V)化合物反应制备:
其中R3、R4和R5的定义同上所述(参见JP 61-246161)。
上述式(V)化合物是已知化合物,它们可以从市场上购得或者用已知方法制备(参见J.Org.Chem.
1964,
29,1,Angew.Chem.Int.Ed.Engl.,
1985,
24,871,JP 11-302233)。
上述式(VIII)化合物是有机化学领域的公知化合物。作为具体实例,例如可以提及甲磺酰氯、乙磺酰氯、三氟甲磺酰氯、2,2,2-三氟乙磺酰氯等等。
作为制备方法(a)的起始原料使用的式(II)化合物,可以提及下列化合物:
3-甲磺酰氧基-N-(4-三氟甲基苯基)邻苯二甲酰亚胺,
3-甲磺酰氧基-N-(4-三氟甲氧基苯基)邻苯二甲酰亚胺,
3-甲磺酰氧基-N-(4-五氟乙基苯基)邻苯二甲酰亚胺,
N-(4-七氟异丙基苯基)-3-甲磺酰氧基邻苯二甲酰亚胺,
3-甲磺酰氧基-N-(2-甲基-4-三氟甲基苯基)邻苯二甲酰亚胺,
3-甲磺酰氧基-N-(2-甲基-4-三氟甲氧基苯基)邻苯二甲酰亚胺,
3-甲磺酰氧基-N-(2-甲基-4-五氟乙基苯基)邻苯二甲酰亚胺,
N-(4-七氟异丙基-2-甲基苯基)-3-甲磺酰氧基邻苯二甲酰亚胺,
3-甲磺酰氧基-N-(2,3,4-三氯苯基)邻苯二甲酰亚胺,
3-乙磺酰氧基-N-(4-三氟甲基苯基)邻苯二甲酰亚胺,
3-乙磺酰氧基-N-(4-三氟甲氧基苯基)邻苯二甲酰亚胺,
3-乙磺酰氧基-N-(4-五氟乙基苯基)邻苯二甲酰亚胺,
3-乙磺酰氧基-N-(4-七氟异丙基苯基)邻苯二甲酰亚胺,
3-乙磺酰氧基-N-(2-甲基-4-三氟甲基苯基)邻苯二甲酰亚胺,
3-乙磺酰氧基-N-(2-甲基-4-三氟甲氧基苯基)邻苯二甲酰亚胺,
3-乙磺酰氧基-N-(2-甲基-4-五氟乙基苯基)邻苯二甲酰亚胺,
3-乙磺酰氧基-N-(4-七氟异丙基-2-甲基苯基)邻苯二甲酰亚胺,
3-乙磺酰氧基-N-(2,3,4-三氯苯基)邻苯二甲酰亚胺,
3-三氟甲磺酰氧基-N-(4-三氟甲基苯基)邻苯二甲酰亚胺,
3-三氟甲磺酰氧基-N-(4-三氟甲氧基苯基)邻苯二甲酰亚胺,
N-(4-五氟乙基苯基)-3-三氟甲磺酰氧基邻苯二甲酰亚胺,
N-(4-七氟异丙基苯基)-3-三氟甲磺酰氧基邻苯二甲酰亚胺,
N-(2-甲基-4-三氟甲基苯基)-3-三氟甲磺酰氧基邻苯二甲酰亚胺,
N-(2-甲基-4-三氟甲氧基苯基)-3-三氟甲磺酰氧基邻苯二甲酰亚胺,
N-(2-甲基-4-五氟乙基苯基)-3-三氟甲磺酰氧基邻苯二甲酰亚胺,
N-(4-七氟异丙基-2-甲基苯基)-3-三氟甲磺酰氧基邻苯二甲酰亚胺,
N-(2,3,4-三氯苯基)-3-三氟甲磺酰氧基邻苯二甲酰亚胺,等等。
作为制备上述式(II)化合物用的式(VII)化合物,可以提及下列化合物:
3-羟基-N-(4-三氟甲基苯基)邻苯二甲酰亚胺,
3-羟基-N-(4-三氟甲氧基苯基)邻苯二甲酰亚胺,
3-羟基-N-(4-五氟乙基苯基)邻苯二甲酰亚胺,
N-(4-七氟异丙基苯基)-3-羟基邻苯二甲酰亚胺,
3-羟基-N-(2-甲基-4-三氟甲基苯基)邻苯二甲酰亚胺,
3-羟基-N-(2-甲基-4-三氟甲氧基苯基)邻苯二甲酰亚胺,
3-羟基-N-(2-甲基-4-五氟乙基苯基)邻苯二甲酰亚胺,
N-(4-七氟异丙基-2-甲基苯基)-3-羟基邻苯二甲酰亚胺,
3-羟基-N-(2,3,4-三氯苯基)邻苯二甲酰亚胺,等等。
作为制备上述式(VII)化合物用的式(V)化合物,可以提及下列化合物:
4-三氟甲基苯胺,
4-三氟甲氧基苯胺,
4-五氟乙基苯胺,
4-七氟异丙基苯胺,
2-甲基-4-三氟甲基苯胺,
2-甲基-4-三氟甲氧基苯胺,
2-甲基-4-五氟乙基苯胺,
4-七氟异丙基-2-甲基苯胺,
2,3,4-三氯苯胺,等等。
上述制备方法(a)中用的起始原料式(III)化合物是有机化学领域的公知化合物,并且可以按照DE-A 2045905,WO 01/23350Pamphelt等文献中记载的方法制备。
作为制备方法(a)中起始原料使用的式(III)化合物,可以提及下列化合物:
正丙胺,
异丙胺,
正丁胺,
仲丁胺,
异丁胺,
叔丁胺,
叔戊胺,
环丙胺,
环戊胺,
环己胺,
2-(甲硫基)乙胺,
2-(乙硫基)乙胺,
1-甲基-2-(甲硫基)乙胺,
1,1-二甲基-2-(甲硫基)乙胺,等等。
上述方法(b)用的起始原料式(IV)化合物是文献中尚无记载的新化合物,并且可以通过在缩合剂或酸结合剂的存在下由式(IX)化合物反应制备(例如,参见J.Med.Chem.
1967,
10,982):
其中R1和R2的定义同上。
上述式(IX)化合物也是文献中尚未记载的新化合物,并且可以通过式(X)化合物:
其中R1的定义同上所述,与式(III)化合物反应制备(例如,参见J.Org.Chem.
1981,
46,175):
H2N-R2 (III)
其中R2的定义同上所述。
上述式(X)化合物也是文献中尚未记载的新化合物,并且可以由已知的3-羟基邻苯二甲酸酐与式(VIII)化合物反应制备(例如,参见Tetrahedron Lett.
1988,
29,5595-5598):
R1SO2Cl (VIII)
其中R1的定义同上所述。
作为制备方法(b)的起始原料使用的式(IV)化合物,可以提及下列化合物:
6-甲磺酰氧基-N-正丙基异邻苯二甲酰亚胺(phthalisoimide),
N-异丙基-6-甲磺酰氧基异邻苯二甲酰亚胺,
N-正丁基-6-甲磺酰氧基异邻苯二甲酰亚胺,
N-仲丁基-6-甲磺酰氧基异邻苯二甲酰亚胺,
N-异丁基-6-甲磺酰氧基异邻苯二甲酰亚胺,
N-叔丁基-6-甲磺酰氧基异邻苯二甲酰亚胺,
6-甲磺酰氧基-N-[2-(甲硫基)乙基]异邻苯二甲酰亚胺,
N-[2-(乙硫基)乙基]-6-甲磺酰氧基异邻苯二甲酰亚胺,
6-甲磺酰氧基-N-[1-甲基-2-(甲硫基)乙基]异邻苯二甲酰亚胺,
N-[1,1-二甲基-2-(甲硫基)乙基]-6-甲磺酰氧基异邻苯二甲酰亚胺,
6-乙磺酰氧基-N-正丙基异邻苯二甲酰亚胺,
6-乙磺酰氧基-N-异丙基异邻苯二甲酰亚胺,
N-正丁基-6-乙磺酰氧基异邻苯二甲酰亚胺,
N-仲丁基-6-乙磺酰氧基异邻苯二甲酰亚胺,
6-乙磺酰氧基-N-异丁基异邻苯二甲酰亚胺,
N-叔丁基-6-乙磺酰氧基异邻苯二甲酰亚胺,
6-乙磺酰氧基-N-[2-(甲硫基)乙基]异邻苯二甲酰亚胺,
6-乙磺酰氧基-N-[2-(乙硫基)乙基]异邻苯二甲酰亚胺,
6-乙磺酰氧基-N-[1-甲基-2-(甲硫基)乙基]异邻苯二甲酰亚胺,
N-[1,1-二甲基-2-(甲硫基)乙基]-6-乙磺酰氧基异邻苯二甲酰亚胺,
N-正丙基-6-三氟甲磺酰氧基异邻苯二甲酰亚胺,
N-异丙基-6-三氟甲磺酰氧基异邻苯二甲酰亚胺,
N-正丁基-6-三氟甲磺酰氧基异邻苯二甲酰亚胺,
N-仲丁基-6-三氟甲磺酰氧基异邻苯二甲酰亚胺,
N-异丁基-6-三氟甲磺酰氧基异邻苯二甲酰亚胺,
N-叔丁基-6-三氟甲磺酰氧基异邻苯二甲酰亚胺,
N-[2-(甲硫基)乙基]-6-三氟甲磺酰氧基异邻苯二甲酰亚胺,
N-[2-(乙硫基)乙基]-6-三氟甲磺酰氧基异邻苯二甲酰亚胺,
N-[1-甲基-2-(甲硫基)乙基]-6-三氟甲磺酰氧基异邻苯二甲酰亚胺,
N-[1,1-二甲基-2-(甲硫基)乙基]-6-三氟甲磺酰氧基异邻苯二甲酰亚胺,等等。
作为制备式(IV)用的式(IX)化合物,可以提及下列化合物:
3-甲磺酰氧基-N-正丙基邻氨甲酰苯甲酸,
N-异丙基-3-甲磺酰氧基邻氨甲酰苯甲酸,
N-正丁基-3-甲磺酰氧基邻氨甲酰苯甲酸,
N-仲丁基-3-甲磺酰氧基邻氨甲酰苯甲酸,
N-异丁基-3-甲磺酰氧基邻氨甲酰苯甲酸,
N-叔丁基-3-甲磺酰氧基邻氨甲酰苯甲酸,
3-甲磺酰氧基-N-[2-(甲硫基)乙基]邻氨甲酰苯甲酸,
N-[2-(乙硫基)乙基]-3-甲磺酰氧基邻氨甲酰苯甲酸,
3-甲磺酰氧基-N-[1-甲基-2-(甲硫基)乙基]邻氨甲酰苯甲酸,
N-[1,1-二甲基-2-(甲硫基)乙基]-3-甲磺酰氧基邻氨甲酰苯甲酸,
3-乙磺酰氧基-N-正丙基邻氨甲酰苯甲酸,
3-乙磺酰氧基-N-异丙基邻氨甲酰苯甲酸,
N-正丁基-3-乙磺酰氧基邻氨甲酰苯甲酸,
N-仲丁基-3-乙磺酰氧基邻氨甲酰苯甲酸,
3-乙磺酰氧基-N-异丁基邻氨甲酰苯甲酸,
N-叔丁基-3-乙磺酰氧基邻氨甲酰苯甲酸,
3-乙磺酰氧基-N-[2-(甲硫基)乙基]邻氨甲酰苯甲酸,
3-乙磺酰氧基-N-[2-(乙硫基)乙基]邻氨甲酰苯甲酸,
3-乙磺酰氧基-N-[1-甲基-2-(甲硫基)乙基]邻氨甲酰苯甲酸,
N-[1,1-二甲基-2-(甲硫基)乙基]-3-乙磺酰氧基邻氨甲酰苯甲酸,
N-正丙基-3-三氟甲磺酰氧基邻氨甲酰苯甲酸,
N-异丙基-3-三氟甲磺酰氧基邻氨甲酰苯甲酸,
N-正丁基-3-三氟甲磺酰氧基邻氨甲酰苯甲酸,
N-仲丁基-3-三氟甲磺酰氧基邻氨甲酰苯甲酸,
N-异丁基-3-三氟甲磺酰氧基邻氨甲酰苯甲酸,
N-叔丁基-3-三氟甲磺酰氧基邻氨甲酰苯甲酸,
N-[2-(甲硫基)乙基]-3-三氟甲磺酰氧基邻氨甲酰苯甲酸,
N-[2-(乙硫基)乙基]-3-三氟甲磺酰氧基邻氨甲酰苯甲酸,
N-[2-甲基-2-(甲硫基)乙基]-3-三氟甲磺酰氧基邻氨甲酰苯甲酸,
N-[1,1-二甲基-2-(甲硫基)乙基]-3-三氟甲磺酰氧基邻氨甲酰苯甲酸,等等。
作为制备上述式(IX)化合物用的缩合剂或酸结合剂的具体实例,可以提及下列化合物:
缩合剂:例如可以提及Mukaiyama试剂(碘化2-氯-N-甲基吡啶翁),DCC(1,3-二环己基碳二亚胺),CDI(羰基二咪唑),三氟乙酸酐,氯碳酸甲酯等。
酸结合剂:例如可以提及作为有机碱的叔胺,二烷基氨基苯胺以及吡啶类,如三乙胺、1,1,4,4-四甲基乙二胺(TMEDA)、N,N-二甲基苯胺、N,N-二乙基苯胺、吡啶、4-二甲氨基吡啶(DMAP)等;作为无机碱的碱金属和碱土金属的氢氧化物、碳酸盐、碳酸氢盐等,如碳酸氢钠、碳酸氢钾、碳酸钠、碳酸钾、氢氧化锂、氢氧化钠、氢氧化钾等。
作为制备上述式(IX)用的式(X)化合物,可以提及下列化合物:
3-甲磺酰氧基邻苯二甲酸酐,
3-乙磺酰氧基邻苯二甲酸酐,
3-三氟甲磺酰氧基邻苯二甲酸酐,
3-(2,2,2-三氟乙烷)磺酰氧基邻苯二甲酸酐,等等。
上述制备方法(c)用的起始原料式(VI)化合物是文献中尚未记载的新化合物,并且可以通过在上述缩合剂或酸结合剂的存在下由式(XI)化合物反应制备(参见J.Med.Chem.
1967,
10,982):
其中R1、R3、R4和R5的定义同上所述。
上述式(XI)化合物也是文献中尚无记载的新化合物,并且可以通过使式(X)化合物:
其中R1的定义同上所述与式(III)化合物反应制备(参见J.Org.Chem.
1981,
46,175):
H2N-R2 (III)
其中R2的定义同上所述。
作为上述制备方法(c)中用的起始原料式(VI)化合物,可以提及下列化合物:
3-甲磺酰氧基-N-(4-三氟甲基苯基)异邻苯二甲酰亚胺,
3-甲磺酰氧基-N-(4-三氟甲氧基苯基)异邻苯二甲酰亚胺,
3-甲磺酰氧基-N-(4-五氟乙基苯基)异邻苯二甲酰亚胺,
N-(4-七氟异丙基苯基)-3-甲磺酰氧基异邻苯二甲酰亚胺,
N-(4-七氟异丙基-2-甲基苯基)-3-甲磺酰氧基异邻苯二甲酰亚胺,
3-甲磺酰氧基-N-(2,3,4-三氯苯基)异邻苯二甲酰亚胺,
3-乙磺酰氧基-N-(4-三氟甲基苯基)异邻苯二甲酰亚胺,
3-乙磺酰氧基-N-(4-三氟甲氧基苯基)异邻苯二甲酰亚胺,
3-乙磺酰氧基-N-(4-五氟乙基苯基)异邻苯二甲酰亚胺,
3-乙磺酰氧基-N-(4-七氟异丙基苯基)异邻苯二甲酰亚胺,
3-乙磺酰氧基-N-(4-七氟异丙基-2-甲基苯基)异邻苯二甲酰亚胺,
3-乙磺酰氧基-N-(2,3,4-三氯苯基)异邻苯二甲酰亚胺,
3-三氟甲磺酰氧基-N-(4-三氟甲基苯基)异邻苯二甲酰亚胺,
3-三氟甲磺酰氧基-N-(4-三氟甲氧基苯基)异邻苯二甲酰亚胺,
N-(4-五氟乙基苯基)-3-三氟甲磺酰氧基异邻苯二甲酰亚胺,
N-(4-七氟异丙基苯基)-3-三氟甲磺酰氧基异邻苯二甲酰亚胺,
N-(4-七氟异丙基-2-甲基苯基)-3-三氟甲磺酰氧基异邻苯二甲酰亚胺,
N-(2,3,4-三氯苯基)-3-三氟甲磺酰氧基异邻苯二甲酰亚胺,等等。
作为制备上述式(VI)化合物用的式(XI)化合物,可以提及以下化合物:
6-甲磺酰氧基-N-(4-三氟甲基苯基)邻氨甲酰苯甲酸,
6-甲磺酰氧基-N-(4-三氟甲氧基苯基)邻氨甲酰苯甲酸,
6-甲磺酰氧基-N-(4-五氟乙基苯基)邻氨甲酰苯甲酸,
N-(4-七氟异丙基苯基)-6-甲磺酰氧基邻氨甲酰苯甲酸,
N-(4-七氟异丙基-2-甲基苯基)-6-甲磺酰氧基邻氨甲酰苯甲酸,
6-甲磺酰氧基-N-(2,3,4-三氯苯基)邻氨甲酰苯甲酸,
6-乙磺酰氧基-N-(4-三氟甲基苯基)邻氨甲酰苯甲酸,
6-乙磺酰氧基-N-(4-三氟甲氧基苯基)邻氨甲酰苯甲酸,
6-乙磺酰氧基-N-(4-五氟乙基苯基)邻氨甲酰苯甲酸,
6-乙磺酰氧基-N-(4-七氟异丙基苯基)邻氨甲酰苯甲酸,
6-乙磺酰氧基-N-(4-七氟异丙基-2-甲基苯基)邻氨甲酰苯甲酸,
6-乙磺酰氧基-N-(2,3,4-三氯苯基)邻氨甲酰苯甲酸,
6-三氟甲磺酰氧基-N-(4-三氟甲基苯基)邻氨甲酰苯甲酸,
6-三氟甲磺酰氧基-N-(4-三氟甲氧基苯基)邻氨甲酰苯甲酸,
N-(4-五氟乙基苯基)-6-三氟甲磺酰氧基邻氨甲酰苯甲酸,
N-(4-七氟异丙基苯基)-6-三氟甲磺酰氧基邻氨甲酰苯甲酸,
N-(4-七氟异丙基-2-甲基苯基)-6-三氟甲磺酰氧基邻氨甲酰苯甲酸,
N-(2,3,4-三氯苯基)-6-三氟甲磺酰氧基邻氨甲酰苯甲酸,等等。
上述制备方法(d)用的起始原料式(Id)化合物是其中R2代表烷硫基烷基的本发明式(I)化合物,并且可以按照例如上述制备方法(a)-(c)加以制备。
作为上述制备方法(d)用的起始原料式(Id)化合物,可以提及下列:
N2-[1-甲基-2-(甲硫基)乙基]-N1-(4-三氟甲氧基-2-甲基苯基)-3-甲磺酰氧基邻苯二酰胺,
N1-(4-七氟异丙基苯基)-N2-[1-甲基-2-(甲硫基)乙基]-3-甲磺酰氧基邻苯二酰胺,
N1-(4-七氟异丙基-2-甲基苯基)-N2-[1-甲基-2-(甲硫基)乙基]-3-甲磺酰氧基邻苯二酰胺,
N1-(4-七氟异丙基-2-甲基苯基)-N2-[1-甲基-2-(甲硫基)乙基]-3-乙磺酰氧基邻苯二酰胺,
N1-(4-七氟异丙基-2-甲基苯基)-N2-[1-甲基-2-(甲硫基)乙基]-3-三氟甲磺酰氧基邻苯二酰胺,
N2-[1,1-二甲基-2-(甲硫基)乙基]-N1-(4-七氟异丙基-2-甲基苯基)-3-甲磺酰氧基邻苯二酰胺,
N2-[1,1-二甲基-2-(甲硫基)乙基]-N1-(4-七氟异丙基-2-甲基苯基)-3-乙磺酰氧基邻苯二酰胺,
N2-[1,1-二甲基-2-(甲硫基)乙基]-N1-(2,3,4-三氯苯基)-3-甲磺酰氧基邻苯二酰胺,等等。
作为制备方法(d)中用于式(Id)化合物的S-氧化反应的氧化剂,例如可以提及间氯过苯甲酸,过乙酸,偏高碘酸钾、过硫酸氢钾(商品名:OXONER),过氧化氢,等等。
式(II)、式(IV)、式(VI)、式(IX)、式(X)和(IX)的化合物或是上述制备本发明式(I)化合物的方法(a)-(c)用的起始原料,或者是这些方法的中间产物,并且都是文献中尚无记载的新化合物,且可以用下面的通式(XII)统一表示:
其中
R1的定义同上所述,
(a)A1和A4各自代表氧原子,
A2代表基团NH-R2且A3代表羟基,
或者
A2代表羟基而A3代表基团:
或者
A2与A3一起代表选自以下的基团:
或者
(b)A1代表基团N-R2,
A2与A3一起代表基团:
和
A4代表氧原子,
或者
(c)A1代表氧原子,
A2与A3一起代表基团
和
A4代表基团:
其中R2、R3、R4和R5的定义同上所述。
上述制备方法(a)的反应可以在适当稀释剂中进行。作为该反应用的稀释剂实例,可以提及脂族、脂环族和芳族烃类(它们可任选被氯化),例如戊烷、己烷、环己烷、石油醚、石油英、苯、甲苯、二甲苯、二氯甲烷、氯仿、四氯化碳、1,2-二氯乙烷、氯苯、二氯苯等;醚类,例如乙醚、甲乙醚、异丙醚、丁醚、二恶烷、二甲氧基乙烷(DME)、四氢呋喃(THF)、二甘醇二甲醚(DGM)等;酯类,例如乙酸乙酯、乙酸戊酯等;酰胺类,例如二甲基甲酰胺(DMF)、二甲基乙酰胺(DMA)、N-甲基吡咯烷酮、1,3-二甲基-2-咪唑烷酮、六甲基磷酰三胺(HMPA)。
制备方法(a)可以在碱存在下进行,作为这种碱的实例,例如可以提及叔胺、二烷基氨基苯胺和吡啶类,例如三乙胺、1,1,4,4-四甲基乙二胺(TMEDA)、N,N-二甲基苯胺、N,N-二乙基苯胺、吡啶、4-二甲氨基吡啶(DMAP)、1,4-二氮杂二环[2.2.2]辛烷(DABCO)、1,8-二氮杂二环[5.4.0]十一碳-7-烯(DBU)等。
制备方法(a)可以在相当宽的温度范围内进行。但一般是在大约-20到大约150℃,优选大约10℃-大约100℃的温度范围内进行。尽管所述反应适宜在常压下进行,但也可以在高压或减压的情形下进行。
在实施制备方法(a)时,式(I)目的化合物可以通过例如使1-25摩尔量的式(III)化合物与1摩尔的式(II)化合物反应获得。
上述制备方法(b)的反应可以在适当稀释剂中进行,这类稀释剂可以是单一种类或混合种类。作为该反应用的稀释剂,例如可以提及水;脂族、脂环族和芳族烃类(它们可任选被氯化),例如戊烷、己烷、环己烷、石油醚、石油英、苯、甲苯、二甲苯、二氯甲烷、氯仿、四氯化碳、1,2-二氯乙烷、氯苯、二氯苯等;醚类,例如乙醚、甲乙醚、异丙基醚、丁基醚、二恶烷、二甲氧基乙烷(DME)、四氢呋喃(THF)、乙二醇二甲醚(DGM)等;腈类如乙腈、丙腈、丙烯腈等;酯类,例如乙酸乙酯、乙酸戊酯等。
制备方法(b)可以在酸催化剂存在下进行,作为这种酸催化剂的实例,可以提到无机酸,例如盐酸、硫酸等;有机酸,例如,乙酸、三氟乙酸、丙酸、甲磺酸、苯磺酸、对-甲苯磺酸等。
制备方法(b)可以在相当宽的温度范围内进行。但一般是在大约-20到大约100℃,优选大约0℃-大约100℃的温度范围内进行。尽管所述反应适宣在常压下进行,但也可以在高压或减压的情形下进行。
在实施制备方法(b)时,式(I)目的化合物可以通过例如使1-1.5摩尔量的式(V)化合物与1摩尔的式(IV)化合物在稀释剂例如乙腈中反应获得。
在实施制备方法(b)时,式(I)化合物也可以以3-羟基邻苯二甲酸酐为起始原料,在不分离式(X)化合物、式(IX)化合物和式(IV)化合物的情形下,通过在单釜中连续反应制得。
上述制备方法(c)的反应可以在适当稀释剂中进行,这类稀释剂可以是单一种类或混合种类。作为该反应用的稀释剂,例如可以提及水;脂族、脂环族和芳族烃类(它们可任选被氯化),例如戊烷、己烷、环己烷、石油醚、石油英、苯、甲苯、二甲苯、二氯甲烷、氯仿、四氯化碳、1,2-二氯乙烷、氯苯、二氯苯等;醚类,例如乙醚、甲乙醚、异丙基醚、丁基醚、二恶烷、二甲氧基乙烷(DME)、四氢呋喃(THF)、乙二醇二甲醚(DGM)等;腈类如乙腈、丙腈、丙烯腈等;酯类,例如乙酸乙酯、乙酸戊酯等。
制备方法(c)可以在酸催化剂的存在下进行,作为这种酸催化剂的实例,可以提及无机酸,例如盐酸、硫酸等;有机酸,例如乙酸、三氟乙酸、丙酸、甲磺酸、苯磺酸、对-甲苯磺酸等。
制备方法(c)可以在相当宽的温度范围内进行。但通常是在大约-20到大约100℃,优选大约0℃-大约100℃的温度范围内进行。虽然所述反应适宜在常压下进行,但也可以在高压或减压的情形下进行。
在实施制备方法(c)时,式(I)目的化合物可以通过例如使1-2摩尔量的式(III)化合物与1摩尔的式(VI)化合物在稀释剂例如乙腈中反应获得。
在实施制备方法(c)时,式(I)化合物也可以以3-羟基邻苯二甲酸酐为起始原料,在不分离式(X)化合物、式(XI)化合物和式(VI)化合物的情形下,通过在单釜中连续反应制得。
上述制备方法(d)的反应可以在适当稀释剂中进行。作为该反应用的稀释剂,例如可以提及水;脂族、脂环族和芳族烃类(它们可任选被氯化),例如苯、甲苯、二甲苯、二氯甲烷、氯仿、四氯化碳、1,2-二氯乙烷、氯苯、二氯苯等;醇类,例如,甲醇、乙醇、异丙醇、丁醇等;酸类,例如甲酸、乙酸等。
制备方法(d)可以在相当宽的温度范围内进行。但通常是在大约-50到大约150℃,优选大约-10℃-大约100℃的温度范围内进行。虽然所述反应适宜在常压下进行,但也可以在高压或减压的情形下进行。
在实施制备方法(d)时,其中R2代表烷基亚磺酰基烷基或烷基磺酰基烷基的上述式(I)目的化合物可以通过例如使1-5摩尔量的氧化剂(例如间氯过苯甲酸)与1摩尔的式(Id)化合物在稀释剂例如二氯甲烷中反应获得。
本发明的式(I)化合物表现出强杀虫活性。因此,它们可以用作杀虫剂。同时本发明的式(I)活性化合物对害虫显示出确切的防治效果,并且对栽培植物无植物毒性。本发明化合物可以用于防治多种害虫,例如有害的刺吸式口器害虫、咀嚼口器害虫以及其它植物寄生性害虫、储藏谷物害虫、卫生害虫等,并且可以用于灭绝这些害虫。
作为这类害虫的实例,可以提及:
昆虫类:包括鞘翅目,例如
绿豆象,玉米象,赤拟谷盗,Epilachna vigintioctomaculata,细胸叩头虫,多色异丽金龟,马铃薯叶甲,diabrotica spp.,Manochamusalternatus,稻水象
欧洲介粉蠹;
鳞翅目,例如
舞毒蛾,黄褐天幕毛虫,菜粉蝶,斜纹贪夜蛾,甘蓝夜蛾,二化螟,玉米螟,干果粉斑螟,棉褐带卷蛾,苹果小卷蛾,Agrotis fucosa,蜡螟,菜蛾,烟芽夜蛾,柑桔叶潜蛾;
半翅目,例如
黑尾叶蝉,褐飞虱,康氏粉蚧,矢尖盾蚧,烟蚜,苹果蚜,棉蚜,菜缢管蚜,梨冠网蝽,Nazara spp.,温带臭虫,温室粉虱,木虱属.;
直翅目,例如
德国小蠊,美洲大蠊,非洲蝼蛄,非洲飞蝗;
同翅目,例如
栖北散白蚁,家白蚁;
双翅目,例如
家蝇,埃及伊蚊,灰地种蝇,尖音库蚊,中华按蚁,三带喙库蚊等。
而且,可提及的螨例如为:
朱砂叶螨,二斑叶螨,柑桔全爪螨,桔刺皮瘿螨,跗线螨属。等等
此外,可提及的植物线虫例如为:亲缘根癌线虫,木居伞滑刃线虫,水稻干尖线虫,大豆异皮线虫,草地垫刃线虫属等等。
另外,在兽医学方面,本发明的新化合物可以有效地用于抗各种有害的动物-寄生害虫(体内寄生虫和外寄生虫),例如,昆虫和蠕虫。作为这类动物寄生害虫的实例,可以提及以下害虫:
可提及的昆虫例如为:胃蝇属,厩蝇属,啮虱属,红猎蝽属,犬栉首蚤等
可提及的螨例如为:纯缘蜱属,硬蜱属,牛蜱属等等。
在本发明中,对害虫具有杀虫作用的物质(包括所有这些物质)在有些情形下统一称为杀虫剂。
当作为杀虫剂使用时,可以将本发明的活性化合物配制成常规制剂形式。关于这些剂型,例如可以提及溶液、乳剂、可湿性粉剂、水分散性颗粒剂、悬浮剂、粉剂、泡沫剂、糊剂、片剂、颗粒剂、气雾剂、浸渍活性化合物的天然和聚合物材料、微囊剂。与燃烧设备配套使用的制剂(作为燃烧设备,例如熏蒸和烟雾筒、罐、线圈等)、ULV[冷雾剂、热雾剂]等。
这些制剂可按照本领域已知的方法制备,例如将活性化合物与增量剂(即液体稀释剂;液化气体稀释剂;固体稀释剂或载体)混合,并任选使用表面活性剂,即乳化剂和/或分散剂和/或起泡剂。
如果所用增量剂为水,也可以使用例如有机溶剂作为助溶剂。
关于液体稀释剂或载体,例如可以提及芳烃(例如二甲苯、甲苯、烷基萘等),氯化芳烃或氯化脂族烃(例如,氯苯、氯乙烯类、二氯甲烷等),脂族烃[例如环己烷等,或石蜡(例如矿物油馏分等)],醇类(例如丁醇、乙二醇类及它们的醚和酯等),酮类(例如丙酮、甲乙酮、甲基异丁基酮、环己酮等),强极性溶剂(例如二甲基甲酰胺、二甲亚砜等),以及水。
液化的气体稀释剂或载体是指在常温常压下为气体的物质,例如可以提及气雾剂推进剂如丁烷、丙烷、氮气、二氧化碳、卤代烃类。
作为固体稀释剂,例如可以提及天然矿物粉(例如高岭土、粘土、滑石、白垩、石英、硅镁土、蒙脱土、硅藻土等),合成矿质粉(例如,高分散性硅酸、氧化铝、硅酸盐等)。
作为适用于颗粒剂的固体载体,例如可以提及分级的天然岩石粉(例如,方解石、大理石、浮石、海泡石、白云石等),合成的无机和有机粉末颗粒,有机物颗粒(例如,锯屑、椰壳、玉米棒碎块、烟草杆等),等。
作为乳化剂和/或起泡剂,例如可以提及非离子和阴离子型乳化剂[例如,聚氧乙烯脂肪酸酯,聚氧乙烯脂肪醇醚(例如烷基芳基聚乙二醇醚,烷基磺酸盐,烷基硫酸盐,芳基磺酸盐等)],蛋白水解产物等。
分散剂包括例如木质素亚硫酸盐废液和甲基纤维素。
制剂(粉剂、颗粒剂、乳油)中也可以使用粘着剂。作为这种粘着剂,例如可以提及羧甲基纤维素,天然和合成聚合物(例如阿拉伯胶、聚乙烯醇、聚乙酸乙烯酯等)。
也可以使用着色剂。例如,可以提及的这种着色剂有无机颜料(例如氧化铁、氧化钛、普鲁士蓝等),有机染料如茜素染料、偶氮染料或金属酞菁染料,并且进一步可以使用微量营养素如铁、锰、硼、铜、钼和锌的盐。
所述制剂通常含有0.1-95%重量、优选0.5-90%重量的上述活性成分。
本发明的式(I)活性化合物也可以与其它活性成分(例如,杀虫剂、毒饵、杀细菌剂、杀螨剂、杀线虫剂、杀菌剂、生长调节剂或除草剂)形成混剂的形式存在,这些其它活性成分可以是市售通用制剂形式或由这种制剂制成的施用形式。就上述杀虫剂而言,在这里可以列举有机磷类杀虫剂、氨基甲酸酯类杀虫剂、羧酸酯类化学物质、氯代烃类化学物质、微生物产生的杀虫物质等。
例如,特别有利的共混组分包括:
杀真菌剂:
邻苯基苯酚;8-羟基喹啉硫酸盐;噻二唑素;aldimorph;amidoflumet;氨丙磷酸;氨丙磷酸钾;andoprim;敌菌灵;氧环唑;嘧菌酯;苯霜灵;邻碘酰苯胺;苯菌灵;benthiavalicarb-isopropyl;苄烯酸;苄烯酸-异丁酯;双丙氨酰膦;乐杀螨;联苯;双苯三唑醇;灭瘟素;糠菌素;磺酸丁嘧啶;丁赛特;丁胺;石硫合剂;capsimycin;敌菌丹;克菌丹;多菌灵;萎锈灵;加普胺;香芹酮;灭螨猛;灭瘟唑;苯咪唑菌;地茂散;百菌清;乙菌利;clozylacon;cyazofamide;cyflufenamide;清菌脲;环唑醇;嘧菌环胺;酯菌胺;Dagger G;咪菌威;抑菌灵;二氯萘醌;双氯酚;diclocymet;哒菌清;氯硝胺;乙霉威;苯醚甲环唑;氟嘧菌胺;甲菌定;烯酰吗啉;dimoxystrobin;特普唑;烯唑醇;消螨普;二苯胺;吡菌硫;灭菌磷;二噻农;多果定;敌菌酮;克瘟散;氟环唑;ethaboxam;乙菌定;土菌灵;恶唑酮菌;fenamidone;丙烷腈;氯苯嘧啶醇;腈苯唑;甲呋酰苯胺;环酰菌胺;种衣酯;fenoxanil;拌种咯;苯锈啶;粉锈啉;福美铁;氟啶胺;噻唑螨;咯菌腈;氟联苯菌;氟氟吗啉;氟亚胺;fluoxastrobin;氟喹唑;调嘧醇;氟硅唑;磺菌胺;氟酰胺;粉唑醇;灭菌丹;乙磷铝;fosetyl-sodium;麦穗宁;呋霜灵;呋吡唑灵;二甲呋酰苯胺;拌种胺;谷种定;六氯苯;己唑醇;恶霉灵;抑霉唑;亚胺唑;双胍辛醋酸酯;双八胍盐;iodocarb;环戊唑醇;异稻瘟净;异菌脲;iprovalicarb;irumamycin;富士一号;氯苯咪菌酮;春雷霉素;醚菌酯;代森锰锌;代森锰;meferimzone;嘧菌安;灭锈胺;甲霜灵;精甲霜灵;叶菌唑;磺菌威;三甲基苯基呋喃羧酰胺;代森联;苯氧菌胺;噻菌胺;灭粉霉素;腈菌唑;甲菌利;游霉素;nicobifen;间硝酞异丙酯;noviflumuron;氟嘧醇;甲呋酰胺;orysastrobin;恶酰胺;喹菌酮;oxpoconazole;氧化萎锈灵;oxyfenthiin;多效唑;稻瘟酯;戊菌唑;纹枯脲;稻病磷;苯酞;啶氧菌酯;粉病灵;多氧菌素;polyoxorim;噻菌灵;丙氯咪;杀菌利;百维灵;propanosine-sodium;丙环唑;甲基代森锌;proquinazid;prothioconazole;pyraclostrobin;定菌磷;啶斑肟;嘧霉胺;咯喹酮;氯吡呋醚;硝吡咯菌素;唑喹菌酮;苯氧喹啉;五氯硝基苯;硅氟唑;螺茂胺;硫黄;戊唑醇;叶枯酞;四氯硝基苯;调环烯;四克利;涕必灵;噻菌清;溴氟唑菌;甲基硫菌灵;福美双;硫氰苯甲酰胺;甲基立枯磷;对甲抑菌灵;唑菌酮;三唑醇;叶锈特;咪唑嗪;tricyclamide;三环唑;克啉菌;三氟敏;氟菌唑;嗪氨灵;灭菌唑;烯效唑;有效霉素;烯菌酮;代森锌;福美锌;zoxamide;(2S)-N-[2-[4-[[3-(4-氯苯基])-2-丙炔基]氧基]-3-甲氧基苯基]乙基]-3-甲基-2-[(甲基磺酰基)氨基]-丁酰胺;1-(1-綦基)-1H-吡咯-2,5-二酮;2,3,5,6-四氯-4-(甲基磺酰基)-吡啶;2-氨基-4-甲基-N-苯基-5-噻唑甲酰胺;2-氯-N-(2,3-二氢-1,1,3-三甲基-1H-茚-4-基)-3-吡啶甲酰胺;3,4,5-三氯-2,6-吡啶甲腈;actinovate;顺式-1-(4-氯苯基)-2-(1H-1,2,4-三唑-1-基)-环庚醇;甲基-1-(2,3-二氢-2,2-二甲基-1H-茚-1-基)-1H-咪唑-5-羧酸酯;碳酸氢钾;N-(6-甲氧基-3-吡啶基)-环丙烷甲酰胺;正丁基-8-(1,1-二甲基乙基)-1-氧杂螺[4.5]癸-3-胺;三硫代碳酸钠;
以及铜盐和制剂,例如:波尔多液,氢氧化铜,环烷酸铜,王铜,硫酸铜,硫杂灵,氧化铜,锰铜混剂,喹啉酮。
杀细菌剂:
溴硝丙二醇,双氯酚,四氯草定,福美镍,春雷霉素,异噻菌铜,糠酸,氧四环素,噻菌灵,链霉素,叶枯酞,硫酸铜及其它铜制剂。
杀虫剂/杀螨剂/杀线虫剂:
齐墩螨素,ABG-9008,乙酰甲胺磷,灭螨醌,啶虫脒,acetoprole,氟酯菊酯,AKD-1022,AKD-3059,AKD-3088,棉铃威,涕灭威,氧涕灭威,丙烯除虫菊酯,丙烯除虫菊酯1R-异构体,甲体氯氰菊酯(高效氯氰菊酯),虫螨脒,除虫菌素,AZ 60541,印苦楝子素,甲基吡
磷,谷硫磷,益棉磷,三唑锡,波林杆菌芽孢,球形芽孢杆菌,枯草杆菌,苏云金杆菌,苏云金杆菌菌株EG-2348,苏云金杆菌菌株GC-91,苏云金杆菌菌株NCTC-11821,杆状病毒,白僵菌,纤细白僵菌,恶虫威,丙硫克百威,杀虫磺,苯螨特,高效氟氯氰菊酯,乙体氯氰菊酯,联苯肼酯,联苯菊酯,乐杀螨,反丙烯除虫菊,反丙烯除虫菊-S-环戊基-异构体,bioethanomethrin,右旋反二氯苯醚菊酯,右旋反灭虫菊酯,bistrifluron,丁苯威,brofenprox,乙基溴硫磷,溴螨酯,溴虫畏(-甲基),BTG-504,BTG-505,混戊威,噻嗪酮,特嘧硫磷,丁酮威,丁酮氧威,丁哒嗪酮,硫线磷,毒杀芬,西维因,克百威,三硫磷,丁硫克百威,巴丹,CGA-50439,灭螨猛,氯丹,杀虫脒,chloethocarb,氯氧磷,氟唑虫清,毒虫畏,定虫隆,氯甲磷,乙酯杀螨醇,三氯硝基甲烷,chlorproxyfen,甲基毒死蜱,毒死蜱(-乙基),chlovaporthrin,chromafenozide,顺式-氯氰菊酯,右旋反灭虫菊酯,顺式-氯菊酯,clocythrin,除线威,四螨嗪,clothianidine,clothiazoben,十二碳二烯醇,蝇毒磷,苯腈磷,杀螟腈;cycloprene,稻虫菊酯,苹果小卷蛾,氟氯氰菊酯,三氟氯氰菊酯;三环锡,苯醚氰菊酯(1R-反式异构体),灭蝇胺二氯二苯三氯乙烷,溴氰菊酯,异吸硫磷II,磺吸磷,杀螨硫隆,氯乙亚胺磷,二嗪磷,氯线磷,敌敌畏,三氯杀螨醇,百治磷,dicyclanil,除虫脲,乐果,甲基毒虫畏,消螨通,消螨普,dinetofuran,茂醚,乙拌磷,碘酰丁二辛,苯氧炔螨,DOWCQ-439,eflusilanate,emamectin,emamectin-benzonate,烯炔菊酯(1R-异构体),硫丹,,苯硫磷,亚尔发菊酯,乙硫苯威,ethiprole,乙硫磷,灭克磷,醚菊酯,特苯唑,乙氧嘧啶磷,氨磺磷,克线磷,喹螨醚,杀螨锡,五氟苯菊酯,杀螟硫磷,丁苯威,苯氧硫威,fenoxacrim,双氧威,杀螨菊酯,fenpyrad,fenpyrithrin,唑螨酯,丰索磷,倍硫磷,fentrifanil,氰戊菊酯,氟虫腈,flonicamid,fluacrypyrim,氟啶蜱脲,噻唑螨,溴氟菊酯,氟螨脲,氟氰菊酯,flufenerim,氟虫脲,氟丙苄醚;氟氯苯菊酯,flupyrazofos,flutenzin(flufenzine),氟胺氰菊酯,地虫磷,伐虫脒,安果,丁苯硫磷,噻唑酮磷,fubfenprox(fluproxyfen),呋线威,林丹,棉虫诱虫酯,诱杀烯混剂,颗粒体病毒,卤醚菊酯,特丁苯酰肼,六六六,HCN-801,庚烯磷,氟铃脲,噻螨酮,灭蝇腙,烯虫乙酯,IKA-2002,吡虫啉,咪炔菊酯,二唑虫,碘硫磷;异稻瘟净,氯唑磷,异丙胺磷,异丙威,异恶唑磷,异阿凡曼菌素,金龟诱剂,噻嗯菊酯,kempolyederviren,烯虫炔酯,氯氟氰菊酯,高丙体六六六,氟丙氧脲,马拉硫磷,灭蚜磷,甲亚砜磷,蜗牛敌,威百亩,虫螨畏,甲胺磷,metharhizium anisopliae,metharhizium flavoviride,杀扑磷,灭虫威,灭多虫,蒙五一五,甲氧滴滴涕,甲氧苯酰肼,速灭威,恶虫酮,速灭磷,米尔螨素,密比霉素,MKI-245,MON-45700,久效磷,moxidectin,MTI-800,二溴磷,NC-104,NC-170,NC-184,NC-194,NC-196,贝螺杀,烟碱,烯啶虫胺,硝虫噻嗪,NNI-0001,NNI-0101,NNI-0250,NNI-9768,双苯氟脲,noviflumuron,OK-5101,OK-5201,OK-9601,OK-9602,OK-9701,OK-9802,氧乐果,草氨酰,亚砜吸磷,玫烟色拟青霉,一六○五-甲基,一六○五(-乙基),氯菊酯(顺式-,反式-),石油醚,PH-6045,苯醚菊酯(1R-反式异构体),稻丰散,甲拌磷,伏杀磷,亚胺硫磷,磷胺,乙丙磷畏,辛硫磷,胡椒基丁醚,抗蚜威,甲基嘧啶磷,乙基虫螨磷,炔酮菊酯,丙溴磷,猛杀威,丙虫磷,克螨特,巴胺磷,残杀威,二氯丙磷,发果,protrifenbute,吡芽酮,吡唑硫磷,反灭虫菊,除虫菊,哒螨酮,pyridalyl,打杀磷,pyridathion,嘧胺苯醚,蚊蝇醚,喹恶磷,灭虫菊,RH-5849,病毒唑,RU-12457,噻嗯菊酯,S-421,S-1833,蔬果磷,硫线磷,SI-0009,灭虫硅醚,艾克利,spirodiclofen,spiromesifen,sulfluramid,硫特普,虫螨消,SZI-121,氟胺氰菊酯,虫酰肼,吡满胺,嘧丙磷,氟苯脲,七氟菊酯,双硫磷,稻丰磷,叔丁威,特丁甲拌磷,杀虫畏,三氯杀螨砜,似虫菊,似虫菊(1R-异构体),杀螨好,辛体氯氰菊酯,thiacloprid,thiamethoxam,蛾蝇腈,thiatriphos,杀虫环,硫双灭多威,己酮肟威,甲基乙拌磷,杀虫双,敌贝特,tolfenpyrad,氯溴氰菊酯,四溴菊酯,四氟菊酯,苯赛螨,唑蚜威,三唑磷,triazuron,trichiophenidine,敌百虫,杀虫隆,trimethacarb,蚜灭多,氟吡唑虫,verbutin,Verticillium lecanii,WL-108477,WL-40027,YI-5201,YI-5301,YI-5302,一氯代二甲苯,灭杀威,ZA-3274,己体氯氰菊酯,zolaprofos,ZXI-8901,化合物3-甲基-苯基-丙基氨基甲酸酯(速灭威Z),化合物3-(5-氯-3-吡啶基)-8-(2,2,2-三氟乙基)-8-氮杂二环[3.2.1]辛烷-3-甲腈(CAS登录号:185982-80-3)以及相应的3-内-异构体(CAS登录号:185984-60-5)(参照.WO 96/37494,WO 98/25923),
以及含有杀虫活性的植物提取物、植物线虫、真菌或病毒的制剂。
与其它已知活性化合物如除草剂,或与肥料、生长调节剂、安全剂或半化学品形成混合物也是可能的。
进一步地,本发明的式(I)活性化合物也可以与增效剂形成混剂的形式存在,而且这类制剂及施用形式可以是市售通用形式。增效剂是指本身不可以具有活性,但却能够增加活性化合物活性的化合物。
市售实用制剂中本发明式(I)活性化合物的含量可以在很宽的范围内变化。
本发明式(I)化合物的施用浓度例如可以是0.0000001-100%重量,优选0.00001-1%重量。
本发明式(I)化合物以适合于施用形式的常规方法使用。
在用于防治卫生害虫和储藏谷物中的害虫时,本发明的活性化合物对钙化物质表面的碱具有良好稳定性,并且进一步显示出优越的木材和土壤残留效力。
如上所述,按照本发明可以处理所有植物和它们的各个部分。在一个优选实施方案中,用于处理野生植物品种和栽培品种或用常规生物育种方法如交换或原生质体融合方法获得的那些品种,以及它们的各部分。在另一个优选实施方案中,用于处理采用基因工程方法,如果合适结合常规方法获得的转基因植物和栽培品种(基因修饰生物体),及它们的各部分。术语“部分”或“植物的部分”或“植物部分”在上文已作过解释。
特别优选的是,按照本发明可以处理在每种情况下市售可得的或已经应用的栽培品种植物。栽培品种应理解为是指具有某些特性(“性能”)并且已经通过常规育种、诱变或重组DNA技术获得的植物。它们可以是变种,生物型或基因型。
根据植物种类和栽培品种、它们的生长场所和生长条件(土壤、气候、生育期、营养情况),按照本发明进行处理也可能会产生超加合(“协同”)作用,从而能够例如减少本发明所用物质和组合物的施用量和/或拓宽它们的活性谱和/或提高它们的活性,改善植物生长,增强对高低温的耐受性,增强耐干旱或耐水灾或耐土壤盐含量的作用,增加开花习性,更易收获,加速成熟,提高收率,提高质量和/或提高收获产物的营养价值,使收获产物具有更好的贮存稳定性和/或加工性等效果,这些效果都超出实际期望的结果。
按照本发明可以优先处理的转基因植物或栽培品种(即用基因工程方法获得的植物)包括在基因修饰过程中接受了能赋予这些植物特别有利性质(“性能”)的基因材料的所有植物。这些性质例如为更好的植物生长性,对高低温的耐受性增强,耐干旱或耐水灾或土壤盐含量的能力增强,开花习性提高,易于收获,促进成熟,高收获产率,高质量和/或收获产物具有高营养价值,收获产物具有更好的贮存稳定性和/或加工性能。进一步且特别强调的这些性质例如是植物对动物和微生物害虫(如昆虫、螨虫、植物病原菌、细菌和/或病毒)具有更好的抵抗性,以及植物对某些除草活性化合物具有高耐受性。可列举的转基因植物可以是重要的农作物,如谷类(小麦、水稻),玉米、豆类、马铃薯、棉花、油芥,还有果实类植物(包括苹果树、梨树、柑橘属果树和葡萄树在内),且特别强调玉米、豆类、马铃薯、棉花和油芥。特别需强调的性能是植物体内形成的毒素,尤其是苏云金芽孢杆菌的基因材料(例如基因CryIA(a),CryIA(b),CryIA(c),CryIIA,CfyIIIA,CryIIIB2,Cry9c Cry2Ab,Cry3Bb和CryIF及其组合)在植物体内形成的毒素导致植物(以下简称“Bt植物”)对抗虫的防卫能力增强。同样需特别强调的性能是系统获得性抗性(SAR)、系统素、植物抗毒素、elicitors和抗性基因以及相应的表达蛋白和毒素诱导的植物对真菌、细菌和病毒的防卫能力增强。其它需特别强调的性能是植物对某些除草活性化合物如咪唑啉酮类、磺酰脲类、草甘膦或膦基麦黄酮(phosphinotricin)(例如“PAT”基因)的耐受性增强。能够赋予上述需要性能的基因还可以互相组合存在于转基因植物中。可提及的“Bt植物”实例有玉米品种、棉花品种、大豆品种和马铃薯品种,其上市的商品名为YIELD GARD(例如玉米、棉花、大豆),KnockOut(例如玉米),StarLink(例如玉米),Bollgard(棉花),Nucotn(棉花)和NewLeaf(马铃薯)。可举例说明的耐除草剂植物有玉米品种、棉花品种和大豆品种,其上市的商品名为RoundupReady(耐草甘膦,例如玉米、棉花、大豆),Liberty Link(耐膦酰基麦黄酮,例如油芥),IMI(耐咪唑啉酮类除草剂)和STS(耐磺酰脲除草剂,例如玉米)。可提及的抗除草剂植物(用常规方式育种得到的除草剂抗性植物)包括商品名为Clearfield的品种(例如玉米)。当然,这些描述也适用于具有这些基因特性或有待于研发的基因特性的品种,这些植物将来会进行开发和/或商品化。
按照本发明,可以按照一种特别有利的方式用通式(I)化合物或本发明活性化合物的混合物处理所列举植物。上文所述的活性化合物或混合物的优选用量范围也同样适于处理这些植物。特别强调采用本文具体提及的化合物或混合物对植物进行处理。
本发明活性化合物不仅对植物,卫生学以及储藏产物方面的害虫具有活性,而且在兽医学领域对动物寄生虫(外寄生虫)也具活性,这些寄生虫例如硬蜱,软蜱,畜痒螨,虱状蒲螨,蝇(叮咬和吸食),寄生蝇幼虫,虱,毛虱,羽虱以及跳蚤。这些寄生虫包括:
虱目,例如,血虱属,长颚虱属,人虱属,阴虱属以及管虱属。
食毛目以及长角亚目和细角亚目,例如,毛羽虱属,Menopon spp.,巨羽虱属,牛羽虱属,Werneckiella spp.,Lepikentron spp.,畜虱属,啮虱属以及猫羽虱属。
双翅目以及长角亚目和短角亚目,例如,伊蚊属,疟蚊属,库蚊属,蚋属,犹蚋属,白蛉属,Lutzomyia spp,库蠓属,斑虻属,瘤虻属,黄虻属,虻属,麻虻属,Philipomyia spp,蜂虱蝇属,家蝇属,Hydrotaea spp,厩蝇属,Haematobia spp,Morellia spp,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,lipoptena spp以及蜱蝇属。
蚤目,例如,蚤属,栉头蚤属,客蚤属和角叶蚤属。
异翅亚目,例如,臭虫属,椎蝽属,红猎蝽属和金圆蝽属。
蜚蠊目,例如,东方蠊,美洲大蠊,德国小蠊和蜚蠊属。
蜱螨亚纲以及后气门亚目和中气门亚目,例如,锐缘蜱属,钝缘蜱属,残喙蜱属,硬蜱属,钝眼蜱属,牛蜱属,矩头蝉属,Haemophysalisspp,璃眼蜱属,扇头蜱属,皮刺螨属,刺利螨属,肺刺螨属,胸孔螨属和瓦螨属。
辐螨亚目(前气门亚目)和粉螨目(无气门亚目),例如,蜂跗线螨属,攫螨属,禽螫厘螨属,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,耳癞螨属,疥螨属,痴螨属,疙螨属,胞螨属和皮膜螨属。
本发明的式(I)活性化合物也适用于防治侵染下列动物的节肢动物:农用繁殖性牲畜,例如牛、绵羊、山羊、马、猪、驴、骆驼、水牛、兔、鸡、火鸡、鸭、鹅和蜜蜂,其它宠物,例如狗、猫、笼养鸟和水族鱼,以及所谓的试验动物,例如田鼠、豚鼠、大鼠和小鼠。通过防治这些节肢动物,应当能减少动物死亡和减产(肉、奶、毛、皮、蛋、蜜等)的情形,因此,使用本发明的活性化合物能够使动物的饲养变得更经济和更容易。
本发明的活性化合物可通过已知方式用于兽医领域,即经肠给药,例如以片剂、胶囊剂、饮剂、灌药剂、颗粒剂、糊剂、大丸剂、喂食方法和栓剂等形式给药;非肠道给药,例如通过注射(肌内、皮下、静脉内、腹膜内注射等方式)给药;植入法给药;经鼻给药;经皮给药,例如通过浸泡或药浴、喷雾、泼浇和擦点、洗刷、撒粉的方式给药,也可借助于含有活性化合物的成型制品,例如项圈、耳饰物、尾饰物、肢环、笼头、标志装置等给药。
当用于家畜、家禽、宠物等动物时,本发明的式(I)活性化合物可以含1-80%重量活性化合物的制剂形式(例如粉剂、乳剂、自由流动组合物)直接或稀释100-10000倍后使用,或者它们可用作药浴。
另外,已经发现本发明的化合物还对损坏工业材料的昆虫具有强杀虫活性。
作为实例,优选列出下述昆虫,但并不局限于此:
甲虫,例如
北美家天牛,绿虎天牛,家具窃蠹,报死材窃蠹,类翼窃蠹,Dendrobiumpertinex,松芽枝窃蠹,松产品窃蠹,褐粉蠹,粉蠹(Lyctusafricanus),南方粉蠹,÷,枥粉蠹,Lyctus pubescenns,胸粉蠹,鳞毛粉蠹,材小蠹属,条木小蠹属,咖啡黑长蠹,Bostrychus capucins,褐异翅长蠹,棘长蠹属,竹蠹。
膜翅目昆虫,例如
蓝黑树蜂,云杉大树蜂,泰加大树蜂,Urocenis augur。
白蚁,例如
木白蚁,麻头堆砂白蚁,印巴结构木异白蚁,欧美散白蚁,Reticulitermes santonensis,Reticulitermes lucifligus,达尔文澳白蚁,内华达古白蚁,家白蚁。
蠹虫,例如台湾衣鱼。
在本发明中,工业材料应理解为表示无生命材料,例如,优选塑料、粘合剂、浆料、纸张和板、皮革、木材和木制品以及涂料组合物。
木材和木制品是特别需要优先保护的材料,以避免受害虫侵染。
可用本发明物质或包含这些物质的混合物保护的木材和木制品应理解为表示,例如:
建筑用木料、木梁、铁路轨枕、桥梁组件、桥型码头、木制交通工具、箱子、货架、容器、电话线杆、木外罩、木窗架和门、合板、刨花板、房屋建筑或建筑细木工行业常用的的细木工和木制品。
本发明的活性化合物可以原有形式,或以浓缩物形式或常规制剂如粉剂、颗粒剂、溶液、混悬液、乳剂或糊剂的形式使用。
上述制剂可以用本领域公知的方法制备,例如,将本发明的活性化合物与至少一种溶剂或稀释剂、乳化剂、分散剂和/或粘合剂或固定剂、抗水剂混合,必要时加入催干剂和UV稳定剂以及如果需要加入颜料、和其它加工助剂。
用于防护木材和木制品的杀虫组合物或浓缩物包括浓度为0.0001-95%重量,特别是0.001-60%重量的本发明活性化合物。
组合物或浓缩物的使用量取决于昆虫的种类和栖居地以及周围环境。最佳用量在每种使用情况下通过系列试验确定。但通常使用0.0001-20%重量,优选0.001-10%重量的活性化合物已足够(以需要保护的材料重量为基准)。
使用的溶剂和/或稀释剂是有机化学溶剂或溶剂混合物和/或低挥发性的油性或类油性有机化学溶剂或溶剂混合物和/或极性有机化学溶剂或溶剂混合物和/或水,必要时加入乳化剂和/或湿润剂。
优选使用的有机化学溶剂是蒸发值大于35且闪点高于30℃,优选高于45℃的油性或类油性溶剂。用作这种低挥发性且不溶于水的油性或类油性溶剂物质是适当的矿物油类或它们的芳烃馏分,或是含有矿物油的溶剂混合物,优选油漆溶剂油、石油和/或烷基苯。
优选使用沸程为170-220℃的矿物油、沸程为170-220℃的油漆溶剂油、沸程为250-350℃的锭子油、沸程为160-280℃的石油或芳族化物、以及松节油等。
在一个优选实施方案中,使用沸程为180-210℃的液体脂族烃或沸程为180-220℃的芳族和脂族烃的高沸点混合物和/或锭子油和/或单氯代萘,优选α-单氯代萘。
蒸发值高于35以及闪点高于30℃(优选高于45℃)的低挥发性油性或类油性有机溶剂可部分用高或中挥发性的有机化学溶剂替换,条件是溶剂混合物同样具有高于35的蒸发值和高于30℃(优选高于45℃)的闪点,并且杀虫/杀菌混合物在该溶剂混合物中是可溶的或可乳化的。
在优选实施方案中,部分有机化学溶剂或溶剂混合物可用脂族极性有机化学溶剂或溶剂混合物替换。优选使用含有羟基和/或酯基和/或醚基的脂族有机化学溶剂,例如乙二醇醚、酯等。
本发明使用的有机化学粘合剂是合成树脂和/或粘合干性油,它们本身是已知的,并可用水稀释和/或在所用的有机化学溶剂中是可溶的或可分散的或可乳化的,特别是由下列成分组成的或包含下列成分的粘合剂:丙烯酸树脂、乙烯基树脂如聚乙酸乙烯酯、聚酯树脂、缩聚或加聚树脂、聚氨基甲酸乙酯树脂、醇酸树脂或改性的醇酸树脂、酚醛树脂、烃类树脂如茚-香豆酮树脂、硅酮树脂、干性植物油和/或干性油和/或基于天然和/或合成树脂的物理干性粘合剂。
作为粘合剂使用的合成树脂可以乳剂、分散剂或溶液的形式使用。沥青或沥青状物质也可用作粘合剂,其用量至多为10%重量。另外还可以使用本领域已知的染料、颜料、抗水剂、矫味剂以及抑制剂或防腐剂等。
本发明优选的组合物或浓缩物包括至少一种醇酸树脂或改性醇酸树脂和/或干性植物油作为有机化学粘合剂。本发明优选使用油含量高于45%重量,优选50-68%重量的醇酸树脂。
上述粘合剂可全部或部分被固定剂(混合物)或增塑剂(混合物)替代。加入这些添加剂的目的是用于防止活性化合物的蒸发以及结晶或沉淀。它们优选替换0.01-30%的粘合剂(以所使用的粘合剂为100%计)。
增塑剂选自以下化学类物质:邻苯二甲酸酯,例如邻苯二甲酸的二丁酯、二辛酯或苄基·丁基酯;磷酸酯,例如磷酸三丁酯;己二酸酯,例如己二酸二(2-乙基己基酯);硬脂酸酯,例如硬脂酸丁酯或硬脂酸戊酯;油酸酯,例如油酸丁酯;甘油醚或高分子量乙二醇醚;甘油酯和对甲苯磺酸酯。
固定剂在化学上是以聚乙烯烷基醚如聚乙烯甲基醚或酮如二苯酮或亚乙基二苯酮为基础。
具体讲,可能的溶剂或稀释剂也可以是水,必要时与一种或多种上述有机化学溶剂或稀释剂、乳化剂和分散剂混合使用。
特别有效的木材防腐作用可采用大批量的浸渍方法,例如真空法、双真空法或加压法实现。
现用型组合物在必要时可以包含其它杀虫剂,并且如果合适的话,还可以含有一种或多种杀真菌剂。
可能的其它混用组分优选是WO 94/29268中提到的杀真菌剂和杀虫剂。该文献中提到的化合物明确地构成本申请的组成部分。
可提及的特别优选的混用组分是杀虫剂如毒死蜱、辛硫磷、氟硅菊酯、甲体氯氰菊酯、氟氯氰菊酯、氯氰菊酯、溴氰菊酯、氯菊酯、吡虫啉、吡虫清、氟虫脲、氟铃脲、四氟菊酯、thiacloprid、methoxyphenoxid和杀虫隆,以及杀真菌剂如氟环唑、己唑醇、戊环醇、丙环唑、戊唑醇、环唑醇、叶菌唑、抑霉唑、苯氟磺胺、甲苯氟磺胺、3-碘代-2-丙炔基-丁基氨基甲酸酯、N-辛基-异噻唑啉-3-酮和4,5-二氯-N-辛基异噻唑啉-3-酮。
同样,本发明的化合物可用于保护与海水或盐水接触的各种物体,如船体、滤器、网、船体结构、锚和信号装置免受生物附着。
定居性寡毛纲目、如龙介虫科以及甲壳类和Ledamorpha(茗荷儿)类,如各种茗荷属和铠茗荷属,或藤壶亚目(藤壶虫),如藤壶属或指茗荷属对船体的附着将会增加船体的摩擦阻力,结果因需要增加能源消耗以及另外经常滞留干船坞而显著增加运营成本。
除了藻类例如水云属和仙菜属藻类的附着之外,特别重要的是蔓足纲(蔓足类甲壳动物)中定居性软甲亚纲(昆甲类)的附着。
令人惊奇的是,现已发现本发明化合物无论是单独使用还是与活性化合物合用都具有显著的防污作用。
本发明化合物单独或与其它活性化合物合用时,可以不使用重金属物,例如硫化二(三烷基锡)、月桂酸三正丁基锡、氯化三正丁基锡、氧化亚铜、氯化三乙基锡、三正丁基(2-苯基-4-氯苯氧基)锡、氧化三丁基锡、二硫化钼、氧化锑、聚合钛酸丁酯、苯基-(联吡啶)-三氯化铋、氟化三正丁基锡、亚乙基二硫代氨基甲酸锰、二甲基二硫化氨基甲酸锌、亚乙基二硫代氨基甲酸锌、2-吡啶硫醇-1-氧化物的锌和铜盐、双二甲基二硫代氨基甲酰基亚乙基二硫代氨基甲酸锌、氧化锌、亚乙基双二硫代氨基甲酸亚铜、硫氰酸铜、环烷酸铜和三丁基卤化锡,或者能显著降低这些金属化合物的浓度。
必要时,现用型防污漆还可以包含其它活性化合物,优选杀藻剂、杀真菌剂、除草剂、杀软体动物剂或其它防污活性化合物。
与本发明防污组合物混用的适当组分优选:
杀藻剂,例如
2-叔丁基氨基-4-环丙基氨基-6-甲硫基-1,2,5-三嗪,双氯酚、敌草隆、草藻灭、薯瘟锡、异丙隆、噻唑隆、氟硝草醚、灭藻醌和克草净;
杀菌剂,例如
苯并[b]噻吩羧酸环己基酰胺S,S-二氧化物,抑菌灵、fluorfolpet、丁基氨基甲酸3-碘-2-吡啶基酯、对甲抑菌灵和唑类如戊环唑、环唑醇、氧唑菌、已唑醇、环戊唑菌、丙环唑和戊唑醇;
杀软体动物剂,例如
醋酸三苯基锡、四聚乙醛、灭虫威、贝螺杀、硫双成和混杀威;
或常用的防污活性化合物,例如
4,5-二氯-2-辛基-4-异噻唑啉-3-酮,diiodomethylparatrylsulphone,2-(N,N-二甲基硫代氨基甲酰基硫代)-5-硝基噻唑,2-吡啶硫醇-1-氧化物的钾、铜、钠和锌盐,吡啶三苯基硼烷,四丁基二锡氧烷,2,3,5,6-四氯-4-(甲磺酰基)-吡啶,2,4,5,6-四氯间苯二腈,二硫化四甲基秋兰姆和2,4,6-三氯苯基马来酰亚胺。
所用的防污组合物中包含浓度为0.001-50%重量,尤其是0.01-20%重量的本发明活性化合物。
此外,本发明的防污组合物还包括如文献Ungerer,Chem.Ind.1985,37,730-732和Williams,Antifouling Marine Coatings,Noyes,Park Ridge,1973中公开的常用组分。
除了杀藻、杀菌、杀软体动物活性化合物和本发明的杀虫活性化合物之外,防污漆还特别包括粘合剂。
公知的粘合剂的实例包括在溶剂体系中的聚氯乙稀,在溶剂体系中的氯化橡胶,在溶剂体系、特别是含水体系中的丙烯酸树脂,水分散体形式或有机溶剂体系形式的氨乙烯/乙酸乙烯酯共聚物体系,丁二烯/苯乙烯/丙烯腈橡胶,干性油如亚麻子油,树脂酯或与焦油或沥青、柏油和环氧化合物、少量氯化橡胶、氯化聚丙烯和乙烯树脂合用的改性硬树脂。
必要时,所述漆中还包含优选不溶于海水的无机颜料、有机颜料或着色剂。而且,所述漆还可以包含如松香类的物质,以便能控制活性化合物的释放。此外,所述漆也可以包含增塑剂、影响流变性的改性剂以及其它常规组分。也可以将本发明化合物或上述混合物掺入到自抛光防污体系中。
本发明的活性化合物还适合于防治封闭空间如住宅、厂房、办公室、丰厢等空间中的害虫,特别是昆虫、蛛形纲动物和螨。它们可以单独或与其它活性化合物以及辅料一起用于家用杀虫产品中用来防治这些害虫。它们对敏感和抗性种群以及所有的发育阶段都具有杀虫活性。这些害虫包括:
蝎目,例如,钳蝎(Buthus occitanus),
蜱螨目,例如波斯锐缘蜱,鸽锐缘蜱,苔螨属.,鸡皮刺螨,住家食甜恙虫,非洲钝缘蜱,血红扇头蜱,恙螨(Trombiculaalfreddugesi),Neutrombicula autumnalis,屋尘螨和粉尘螨,
蜘蛛目,例如,鸟蛤蛛科和圆蛛科,
盲蛛目,例如,Pseudoscorpiones chelifer Pseudoscorpionescheiridium和Opilionnes phalangium.,
等足目,例如,潮虫和鼠妇,
倍足亚纲,例如,具斑马陆和山蛩虫属,
唇足目,例如,地蜈蚣属,
Zygentoma目,例如,栉衣鱼属,台湾衣鱼和Lepismodesinquilinus,
蜚蠊目,例如,东方蜚蠊,德国小蠊Blattella asahinai,马得拉蜚蠊,角腹蠊属,木蠊属,澳洲大蠊,美洲大蠊,褐斑大蠊,黑胸大蠊和长须蜚蠊,
跳跃亚目,例如,家蟀,
革翅目,例如,欧洲球螋,
等翅目,例如,木白蚁属以及散白蚁属,
啮虫目,例如,Lepinatus.spp和粉啮虫属,
鞘翅目,例如,圆皮蠹属,毛皮蠹属,皮蠹属,长头谷盗,隐跗郭公虫属,蛛甲属,谷蠹,谷象,米象,玉米象和药材甲,
双翅目,例如,埃及伊蚊,白纹伊蚊,Aedes taeniorhynchus,疟蚊属,红头丽蝇,高额麻虻,致倦库蚊,尖音库蚊,跗斑库蚊,果蝇属,夏厕蝇,家蝇,白蛉属,Sarcophaga cafnaria,蚋属,厩螫蝇和大蚊,
鳞翅目,例如,小蜡螟,蜡螟印度谷螟,谷蛾,袋谷蛾和幕谷蛾,
蚤目,例如,犬栉首蚤,猫蚤,人蚤,穿皮潜蚤和印鼠客蚤,
膜翅目,例如,广布弓背蚁,亮毛蚁,黑毛蚁,Lasius umbratus,小家蚁,Paravespula spp和铺道蚁,
虱目,例如,头虱,体虱和阴虱,
异翅亚目,例如,热带臭虫,温带臭虫,长红猎蝽和侵扰锥蝽。
在家用杀虫剂领域,它们可以单独使用或与其它合适的活性化合物合用,这些化合物如磷酸酯类、氨基甲酸酯类、拟除虫菊酯类、生长调节剂或其它已知种类杀虫剂中的活性化合物。
它们可以用作气雾剂、非加压喷雾产品,例如用喷雾泵和喷雾器,烟雾自动产生系统,浓雾剂、泡沫剂、凝胶剂、附带有纤维素或聚合物制成的蒸发片的蒸发产品、液体蒸发器、凝胶和薄膜蒸发器、推进剂驱动的蒸发器、不需要能量或被动式蒸发系统、捕蛀虫纸、捕虫袋和捕虫胶、颗粒剂或粉剂、用于撒布饵剂中或饵料撒布位置。
本发明随后用实施例具体说明,但这些实施例并不以任何方式构成对本发明的限制。
合成实施例
合成实施例1
向N-(4-七氟异丙基-2-甲基苯基)-3-甲磺酰氧基邻苯二甲酰亚胺(0.71g)中加入异丙胺(1.68g),室温搅拌4小时。反应完成之后减压蒸除过量的异丙胺,并将所得残留物通过硅胶柱色谱法纯化(梯度洗脱:正己烷/乙酸乙酯=2/1-1/1),得到N1-(4-七氟异丙基-2-甲基苯基)-N2-异丙基-3-甲磺酰氧基邻苯二酰胺(0.43g),熔点168-170℃。
合成实施例2
将N-异丙基-6-N-异丙基-6-甲磺酰氧基-异邻苯二甲酰亚胺(phthalisoimide)粗产物(1.68g)和4-七氟异丙基-2-甲基苯胺(1.65g)的乙腈溶液(20mL)在50℃下搅拌5小时。反应完成之后减压蒸除溶剂,并将所得残留物通过硅胶柱色谱法纯化(梯度洗脱:正己烷/乙酸乙酯=2/1-1/1),得到与合成实施例1相同的化合物(0.89g)。
合成实施例3
室温下,向3-羟基邻苯二甲酸酐(0.82g)和三乙胺(0.76g)的1,2-二氯乙烷溶液(14mL)中加入甲磺酰氯(0.69g),之后于50℃搅拌混合物1.5小时。使反应溶液的温度降至室温,然后在冰冷却下加入1-甲基-2-(甲硫基)乙胺(0.74g)和三乙胺(0.76g),混合物进一步在室温下搅拌2小时。反应溶液用1N盐酸水溶液(20mL)、碳酸氢钠(0.84g)的水溶液(10mL)洗涤,之后向分出的有机层中加入氯碳酸甲酯(0.62g),混合物于50℃搅拌2小时。分出有机层,向其中加入4-七氟异丙基-2-甲基苯胺(1.24g)和浓盐酸(6滴),于50℃搅拌1小时。在自然冷却反应溶液到室温后,减压蒸除溶剂,将所得残留物通过硅胶柱色谱法纯化(梯度洗脱:正己烷/乙酸乙酯=2/1-1/1),得到N1-(4-七氟异丙基-2-甲基苯基)-N2-[1-甲基-2-(甲硫基)乙基]-3-甲磺酰氧基邻苯二酰胺(1.30g),熔点101-103℃。
合成实施例4
向N-(4-七氟异丙基-2-甲基苯基)-6-甲磺酰氧基-异邻苯二甲酰亚胺(0.45g)的乙腈溶液(10mL)中加入异丙胺(0.06g),室温搅拌混合物2天。反应完成后减压蒸除溶剂,将所得残留物通过硅胶柱色谱法纯化(梯度洗脱:正己烷/乙酸乙酯=2/1-1/1),得到与合成实施例1相同的化合物(0.13g)。
合成实施例5
向N2-[1,1-二甲基-2-(甲硫基)乙基]-N1-(4-七氟异丙基-2-甲基苯基)-3-甲磺酰氧基邻苯二酰胺(0.6g)的1,2-二氯乙烷(10mL)溶液中加入过氧化氢(0.54g)、甲酸(0.03g)和水(1mL),混合物于50℃搅拌4小时。自然冷却到室温后,有机层连续用硫代硫酸钠溶液、氯化钠饱和水溶液洗涤,无水硫酸钠干燥。蒸除溶剂,然后将残留物通过硅胶柱色谱法纯化(梯度洗脱:正己烷/乙酸乙酯=3/1-1/1),得到N2-[1,1-二甲基-2-(甲基亚磺酰基)乙基]-N1-(4-七氟异丙基-2-甲基苯基)-3-甲磺酰氧基邻苯二酰胺(0.59g),熔点85-88℃。
合成实施例6
向N2-[1,1-二甲基-2-(甲硫基)乙基]-N1-(4-七氟异丙基-2-甲基苯基)-3-甲磺酰氧基邻苯二酰胺(0.51g)的二氯乙烷溶液(10mL)中加入间-氨过苯甲酸(0.36g),室温搅拌混合物5小时。反应完成之后将反应溶液连续用硫代硫酸钠水溶液、碳酸氢钠饱和水溶液和氯化钠饱和水溶液洗涤,无水硫酸钠干燥。蒸除溶剂后将所得残留物通过硅胶柱色谱法纯化(梯度洗脱:正己烷/乙酸乙酯=2/1-1/1),得到N2-[1,1-二甲基-2-(甲磺酰基)乙基]-N1-(4-七氟异丙基-2-甲基苯基)-3-甲磺酰氧基邻苯二酰胺(0.41g),熔点93-97℃。
下表1列出了按照上述合成实施例1-6的相同方法制得的化合物,以及合成实施例1-6所合成的化合物。
表1
No. | R1 | R2 | R3 | R4 | R5 | MP/℃ |
1 | CH3 | CH(CH3)2 | CH3 | CF(CF3)2 | H | 168-170 |
2 | CH3 | CH(CH3)CH2CH3 | CH3 | CF(CF3)2 | H | 187-189 |
3 | CH3 | C(CH3)3 | CH3 | CF(CF3)2 | H | 119-121 |
4 | CH3 | 环丙基 | CH3 | CF(CF3)2 | H | * |
5 | CH3 | CH(CH3)CH2SCH3 | H | CF(CF3)2 | H | 181-182 |
6 | CH3 | CH(CH3)CH2SCH3 | CH3 | OCF3 | H | 129-132 |
7 | CH3 | CH(CH3)CH2SCH3 | CH3 | CF(CF3)2 | H | 101-103 |
8 | CH3 | CH(CH3)CH2SOCH3 | CH3 | CF(CF3)2 | H | 221-223 |
9 | CH3 | CH(CH3)CH2SO2CH3 | CH3 | CF(CF3)2 | H | 102-107 |
10 | CH3 | C(CH3)2CH2SCH3 | CH3 | CF(CF3)2 | H | 97-99 |
11 | CH3 | C(CH3)2CH2SOCH3 | CH3 | CF(CF3)2 | H | 85-88 |
12 | CH3 | C(CH3)2CH2SO2CH3 | CH3 | CF(CF3)2 | H | 93-97 |
13 | CH2CH3 | CH(CH3)2 | CH3 | CF(CF3)2 | H | ** |
14 | CH2CH3 | CH(CH3)CH2SCH3 | CH3 | CF(CF3)2 | H | 112-114 |
15 | CH2CH3 | CH(CH3)CH2SOCH3 | CH3 | CF(CF3)2 | H | |
16 | CH2CH3 | CH(CH3)CH2SO2CH3 | CH3 | CF(CF3)2 | H | 194-196 |
17 | CH2CH3 | C(CH3)2CH2SCH3 | CH3 | CF(CF3)2 | H | 86-91 |
18 | CH2CH3 | C(CH3)2CH2SOCH3 | CH3 | CF(F3)2 | H | *** |
19 | CH2CH3 | C(CH3)2CH2SO2CH3 | CH3 | CF(CF3)2 | H | 85-89 |
20 | CF3 | CH(CH3)2 | CH3 | CF(CF3)2 | H | |
21 | CF3 | CH(CH3)CH2SCH3 | CH3 | CF(CF3)2 | H | 209-214 |
22 | CF3 | CH(CH3)CH2SOCH3 | CH3 | CF(CF3)2 | H | |
23 | CF3 | CH(CH3)CH2SO2CH3 | CH3 | CF(CF3)2 | H | 136-138 |
24 | CH3 | C(CH3)2CH2SCH3 | Cl | Cl | 3-Cl | 193-195 |
25 | CH3 | C(CH3)2CH2SOCH3 | Cl | Cl | 3-Cl | 135-140 |
26 | CH3 | C(CH3)2CH2SO2CH3 | Cl | Cl | 3-Cl | 200-203 |
*1H-NMR(CDCl3,ppm):0.5-0.8(4H,m),2.3(3H,s),2.8(1H,m),3.2(3H,s),6.5(1H,bs),6.7(1H,d),7.3-7.7(4H,m),8.1(1H,d),8.4(1H,bs).
**1H-NMR(CDCl3,ppm):1.6(9H,m),2.1(3H,s),2.4(3H,s),3.0(2H,m),3.5(3H,q),6.9(1H,bs),7.4-7.6(4H,m),8.2(1H,d),8.4(1H,bs).
***1H-NMR(CDCl3,ppm):1.2(6H,d),1.5(3H,t),2.4(3H,s),3.4(2H,q),4.2(1H,m),6.2(1H,bd),7.4-7.7(5H,m),8.2(1H,bd),8.5(1H,bs).
参考实施例1
在冰冷却下,向N-(4-七氟异丙基-2-甲基苯基)-3-羟基邻苯二甲酰亚胺(3.60g)和三乙胺(1.73g)的四氢呋喃溶液(50mL)中逐滴加入甲磺酰氯(1.18g),然后在室温下搅拌混合物8小时。反应完成之后,减压蒸除溶剂,将所得残留物溶于乙酸乙酯(50mL),连续用2N盐酸和氯化钠饱和水溶液洗涤,无水硫酸钠干燥。减压蒸除溶剂,之后将粗产物用乙醚与正己烷的混合溶剂洗涤,得到N-(4-七氟异丙基-2-甲基苯基)-3-甲磺酰氧基邻苯二甲酰亚胺(4.04g),熔点154-155℃。
参考实施例2
将3-羟基邻苯二甲酸酐(7.29g)和4-七氟异丙基-2-甲基苯胺(12.22g)在乙酸(100mL)中回流6小时。反应完成之后减压蒸除溶剂,并将所得残留物用乙醚与正己烷的混合溶剂洗涤,从而得到N-(4-七氟异丙基-2-甲基苯基)-3-羟基邻苯二甲酰亚胺(11.23g),熔点180-182℃。
参考实施例3
向N-异丙基-3-甲磺酰氧基邻氨甲酰苯甲酸(1.80g)的甲苯溶液(20mL)中加入三氟乙酸酐(3.76g),室温搅拌混合物1小时。反应完成之后减压蒸除溶剂和过量的三氟乙酸酐,得到N-异丙基-6-甲磺酰氧基-异邻苯二甲酰亚胺(1.68g)。所得物质无需纯化直接用于下步反应。
参考实施例4
在冰冷却下,向3-甲磺酰氧基邻苯二甲酸酐(1.60g)的乙腈溶液(10mL)中加入异丙胺(0.78g)。然后进一步在室温下搅拌混合物8小时。反应完成之后减压蒸除溶剂和过量的异丙胺,并将所得粗产物用少量乙腈洗涤,从而得到N-异丙基-3-甲磺酰氧基邻氨甲酰苯甲酸(1.80g),熔点56-59℃。
参考实施例5
在冰冷却下,向3-羟基邻苯二甲酸酐(1.22g)的THF溶液(10mL)中加入三乙胺(0.83g)和甲磺酰氯(0.89g),然后室温搅拌混合物8小时。反应完成之后加入乙醚(20mL),将混合物连续用水和氯化钠饱和水溶液洗涤,无水硫酸钠干燥。减压蒸除溶剂,粗产物随后用乙醚与正己烷的混合溶剂洗涤,从而得到3-甲磺酰氧基邻苯二甲酸酐(1.75g),熔点134-140℃。
参考实施例6
向N-(4-七氟异丙基-2-甲基苯基)-6-甲磺酰氧基邻氨甲酰苯甲酸(1.01g)的1,2-二氯乙烷溶液(30mL)中连续加入碳酸氢钠(0.27g)的水溶液(5mL)和氯甲酸甲酯(0.24g),混合物于50℃搅拌3小时。反应完成之后分出有机层,用无水硫酸钠干燥。随后减压蒸除溶剂,得到N-(4-七氟异丙基-2-甲基苯基)-6-甲磺酰氧基-异邻苯二甲酰亚胺(0.49g),折射率nD 201.4430。
参考实施例7
在冰冷却下,向3-甲磺酰氧基邻苯二甲酸酐(0.51g)的乙腈溶液(10mL)中逐滴加入4-七氟异丙基-2-甲基苯胺(0.58g),然后室温搅拌混合物4小时。反应完成之后减压蒸除溶剂,并将所得粗产物用少量乙腈洗涤,从而得到N-(4-七氟异丙基-2-甲基苯基)-6-甲磺酰氧基邻氨甲酰苯甲酸(1.01g),熔点64-68℃。
应用实施例
生物试验实施例1:斜纹贪夜蛾(Spodoptera litura)幼虫试验
试验制剂的制备:
溶剂: 二甲基甲酰胺 3重量份
乳化剂:聚氧亚乙基烷基苯基醚 1重量份
为制备适当的活性化合物的制剂,将1重量份的活性化合物与上述量的溶剂混合,其中所述溶剂含有上述量的乳化剂。然后加水稀释混合物到规定浓度。
试验方法:
将甘薯叶在加水稀释到规定浓度的试验制剂中浸泡,然后风干,放到直径9cm的培养皿内。在叶面上放置10条3龄期斜纹贪夜蛾(Spodoptera litura)幼虫,置于25℃恒温的室内。在两天和四天之后进一步添加甘薯叶,7天后计数死亡幼虫的数量,计算死亡率。
在本试验中,取同一区两个培养皿的结果的平均值。
试验结果
作为具体实例,化合物序号1、2、3、4、5、6、7、8、9、10、11、12、13、14、16、17、18、19、21、23、24、25和26的化合物在20ppm有效成分浓度下显示出100%的死亡率。
生物试验实施例2:稻纵卷叶野螟(Cnaphalocrocis medinalisGuenee)幼虫试验
试验方法:
将栽培到4-5叶期水稻(品种:Tamanishiki)的根部放入到加有规定浓度活性化合物(按照上述生物试验实施例1的相同方法制备)的稀水溶液的棕色瓶内。用制剂处理后3天,收集1/3量的水稻秧苗,将它们的叶部分切成4-5cm长度,然后放入直径9cm的培养皿内,覆以用2ml水湿润的滤纸。在培养皿内放入5只2龄期稻纵卷叶野螟(Cnaphalocrocis medinalis Guenee)幼虫,然后置于25℃恒温的室内。在两天和四天之后,按照相同方式将剩余的水稻秧苗叶部分(每次1/3量)切段,并加入到培养皿内。7天后计数死亡幼虫的数量,计算死亡率。在本试验中,取同一区两个培养皿的结果的平均值。
试验结果
作为具体实例,化合物序号1、5、7、8、9、10、11和12的化合物在20ppm有效成分浓度下显示出100%的死亡率。
制剂实施例1(颗粒剂)
向10份本发明的化合物(No.1)、30份膨润土(蒙脱石)、58份滑石和2份木质素磺酸盐组成的混合物中加入25份水,充分捏合,利用挤出式造粒机制成10-40目的颗粒,在40-50℃干燥,得到所需颗粒。
制剂实施例2(颗粒剂)
将颗粒直径为0.2-2mm的粘土矿物颗粒(95份)投入旋转混合器内。在旋转的同时,一起喷雾5份本发明化合物(No.5)与液体稀释剂,均匀湿润,在40-50℃下干燥,得到所需颗粒。
制剂实施例3(乳油)
混合并搅拌30份本发明化合物(No.11)、55份二甲苯、8份聚氧亚乙基烷基苯基醚以及7份烷基苯磺酸钙,得到乳油。
制剂实施例4(可湿性粉剂)
粉碎并混合15份本发明化合物(No.17)、白碳(含水无定形氧化硅细粉)与粘土粉(1∶5)的混合物(80份)、2份烷基苯磺酸钠以及3份烷基萘磺酸钠-福尔马林-缩合物,制成可湿性溶剂。
制剂实施例5(水分散颗粒剂)
充分混合20份本发明化合物(No.8)、30份木质素磺酸钠、15份膨润土以及35份煅烧过的硅藻土,加入水,通过0.3mm筛子挤压,干燥,得到水分散颗粒剂。
Claims (8)
2.权利要求1所述的化合物,其中:
R1代表任选被氟、氯或溴取代的C1-6烷基,
R3代表氢原子或卤素,或代表任选被氟、氯或溴取代的C1-6烷基,
R4代表氢原子、卤代C1-6烷基、卤代C1-6烷氧基、卤代苯基,或卤代苯氧基,以及
R5代表氢原子或卤素,或代表任选被氟、氯或溴取代的C1-6烷基。
3.权利要求1所述的化合物,其中:
R1代表甲基、乙基、丙基或三氟甲基,
R3代表氢原子、氟、氯、溴、甲基、乙基或三氟甲基,
R4代表氟、氯或溴,或代表甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、甲氧基、乙氧基、正丙氧基或异丙氧基,它们各自任选地是被至少一个氟部分取代的、被氟全取代的、或被至少一个氟和1或2个氯取代的,和
R5代表氢原子、氟、氯或溴,或代表甲基或乙基,它们各自任选被氟取代或被氯取代。
4.权利要求1所述的化合物,其中:
R1代表甲基或乙基,
R3代表甲基,
R4代表全氟异丙基,和
R5代表氢原子。
6.权利要求5所述的用途,其中:
R1代表任选被氟、氯或溴取代的C1-6烷基,
R2代表任选被氟、氯、溴、C1-4烷氧基、C1-4烷硫基、C1-4烷基亚磺酰基或C1-4烷基磺酰基取代的C1-6烷基,或代表任选被卤素或C1-4烷基取代的C3-6环烷基,
R3代表氢原子或卤素,或代表任选被氟、氯或溴取代的C1-6烷基,
R4代表氢原子、卤代C1-6烷基、卤代C1-6烷氧基、卤代苯基,或卤代苯氧基,以及
R5代表氢原子或卤素,或代表任选被氟、氯或溴取代的C1-6烷基。
7.权利要求5所述的用途,其中:
R1代表甲基、乙基、丙基或三氟甲基,
R2代表甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、仲戊基、叔戊基、正己基、异己基、仲己基、甲硫基甲基、乙硫基甲基、甲硫基乙基、乙硫基乙基、甲硫基丙基、乙硫基丙基、甲硫基丁基、乙硫基丁基、甲硫基戊基、乙硫基戊基、甲基亚磺酰基甲基、乙基亚磺酰基甲基、甲基亚磺酰基乙基、乙基亚磺酰基乙基、甲基亚磺酰基丙基、乙基亚磺酰基丙基、甲基亚磺酰基丁基、乙基亚磺酰基丁基、甲基亚磺酰基戊基、乙基亚磺酰基戊基、甲磺酰基甲基、乙磺酰基甲基、甲磺酰基乙基、乙基磺酰基乙基、甲磺酰基丙基、乙磺酰基丙基、甲磺酰基丁基、乙磺酰基丁基、甲磺酰基戊基、乙磺酰基戊基,或代表环丙基、环丁基、环戊基或环己基,它们各自可任选被氟、氯、溴、甲基或乙基取代,
R3代表氢原子、氟、氯、溴、甲基、乙基或三氟甲基,
R4代表氟、氯或溴,或代表甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、甲氧基、乙氧基、正丙氧基或异丙氧基,它们各自任选地是被至少一个氟部分取代的、被氟全取代的、或被至少一个氟和1或2个氯取代的,和
R5代表氢原子、氟、氯或溴,或代表甲基或乙基,它们各自任选被氟取代或被氯取代。
8.权利要求5所述的用途,其中:
R1代表甲基或乙基,
R2代表异丙基、叔丁基、1-甲基-2-(甲硫基)乙基、1,1-二甲基-2-(甲硫基)乙基、1-甲基-2-(甲基亚磺酰基)乙基、1,1-二甲基-2-(甲基亚磺酰基)乙基、1-甲基-2-(甲磺酰基)乙基或1,1-二甲基-2-(甲磺酰基)乙基,
R3代表甲基,
R4代表全氟异丙基,和
R5代表氢原子。
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JP2002180028A JP2004018506A (ja) | 2002-06-20 | 2002-06-20 | 殺虫性フタラミド誘導体 |
JP180028/2002 | 2002-06-20 |
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CNB038185393A Division CN100516033C (zh) | 2002-06-20 | 2003-06-11 | 新的邻苯二酰胺衍生物 |
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CN1955162A true CN1955162A (zh) | 2007-05-02 |
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CNB038185393A Expired - Fee Related CN100516033C (zh) | 2002-06-20 | 2003-06-11 | 新的邻苯二酰胺衍生物 |
CNA2006101464691A Pending CN1955162A (zh) | 2002-06-20 | 2003-06-11 | 邻苯二酸衍生物及其用作制备邻苯二酰胺衍生物中间体的用途 |
CNB2006101464672A Expired - Fee Related CN100556903C (zh) | 2002-06-20 | 2003-06-11 | 邻苯二酸衍生物及其用作制备邻苯二酰胺衍生物中间体的用途 |
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CNB038185393A Expired - Fee Related CN100516033C (zh) | 2002-06-20 | 2003-06-11 | 新的邻苯二酰胺衍生物 |
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CNB2006101464672A Expired - Fee Related CN100556903C (zh) | 2002-06-20 | 2003-06-11 | 邻苯二酸衍生物及其用作制备邻苯二酰胺衍生物中间体的用途 |
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US (1) | US7132455B2 (zh) |
EP (1) | EP1517886B1 (zh) |
JP (2) | JP2004018506A (zh) |
KR (1) | KR101004070B1 (zh) |
CN (3) | CN100516033C (zh) |
AR (1) | AR039719A1 (zh) |
AT (1) | ATE487694T1 (zh) |
AU (1) | AU2003258495B2 (zh) |
BR (1) | BR0311955B1 (zh) |
DE (1) | DE60334907D1 (zh) |
ES (1) | ES2355138T3 (zh) |
MX (1) | MXPA04012739A (zh) |
TW (1) | TWI329101B (zh) |
WO (1) | WO2004000796A1 (zh) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2006089469A (ja) * | 2004-08-23 | 2006-04-06 | Nippon Nohyaku Co Ltd | 光学活性フタルアミド誘導体及び農園芸用殺虫剤並びにその使用方法 |
WO2006022225A1 (ja) * | 2004-08-23 | 2006-03-02 | Nihon Nohyaku Co., Ltd. | 光学活性フタルアミド誘導体及び農園芸用殺虫剤並びにその使用方法 |
CN101048370B (zh) * | 2004-08-31 | 2010-11-17 | 拜尔农作物科学股份公司 | 光学活性的邻苯二酰胺 |
GB0419420D0 (en) * | 2004-09-01 | 2004-10-06 | Syngenta Participations Ag | Novel insecticides |
TW200626532A (en) * | 2004-09-21 | 2006-08-01 | Syngenta Participations Ag | Novel insecticides |
JP2006347936A (ja) * | 2005-06-15 | 2006-12-28 | Bayer Cropscience Ag | 殺虫性ベンズアニリド類 |
BR102013021210B1 (pt) | 2013-01-25 | 2015-12-01 | Fundação Universidade Fed De São Carlos | processo de obtenção de nanopartículas biopoliméricas contendo óleo e extratos de azadirachta indica a. juss (neem), nanopartículas biopoliméricas e micropartículas em pó |
CN104007231A (zh) * | 2014-05-12 | 2014-08-27 | 青岛农业大学 | 一种用于杀虫剂对玉米螟毒力的测定方法和测定装置 |
AU2016392652B2 (en) | 2016-02-08 | 2021-01-21 | Gowan Company, L.L.C. | Fungicidal Composition |
CN118085297B (zh) * | 2024-04-23 | 2024-07-19 | 广东东溢新材料科技有限公司 | 一种用于柔性电路板的交联杂化型聚酰亚胺树脂及其制备方法、柔性电路板 |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
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GB9510459D0 (en) | 1995-05-24 | 1995-07-19 | Zeneca Ltd | Bicyclic amines |
NZ335422A (en) | 1996-11-26 | 2000-10-27 | Zeneca Ltd | 8-azabicyclo[3.2.1]octane-, 8-azabicyclo [3.2.1] oct-6-ene-, 9-azabicyclo[3.3.1]nonane-, 9-aza-3-oxabicyclo[3.3.1]nonane- and 9-aza-3-thiabicyclo[3.3.1]nonane derivatives for use in insecticides |
GB9624611D0 (en) | 1996-11-26 | 1997-01-15 | Zeneca Ltd | Bicyclic amine compounds |
US6362369B2 (en) | 1997-11-25 | 2002-03-26 | Nihon Nohyaku Co., Ltd. | Phthalic acid diamide derivatives fluorine-containing aniline compounds as starting material, agricultural and horticultural insecticides, and a method for application of the insecticides |
TW515786B (en) * | 1997-11-25 | 2003-01-01 | Nihon Nohyaku Co Ltd | Phthalic acid diamide derivatives, agricultural and horticultural insecticides, and a method for application of the insecticides |
CZ299375B6 (cs) | 1998-11-30 | 2008-07-09 | Nihon Nohyaku Co., Ltd. | Ftalamidové deriváty nebo jejich soli, zemedelsko-zahradnický insekticid je obsahující a jeho použití |
CN1358173A (zh) | 1999-06-24 | 2002-07-10 | 日本农药株式会社 | 杂环二羧酸二酰胺衍生物,农业和园艺杀虫剂以及使用它们的方法 |
AU760375B2 (en) | 1999-06-25 | 2003-05-15 | Nihon Nohyaku Co., Ltd. | Benzamide derivatives, insecticides for agricultural and horticultural use and usage thereof |
AR030154A1 (es) * | 1999-07-05 | 2003-08-13 | Nihon Nohyaku Co Ltd | Derivado de ftalamida, derivado de amina heterociclico util como intermediario para la produccion del mismo, insecticida agrohorticola y metodo para utilizar dicho insecticida |
ES2239035T3 (es) | 1999-09-24 | 2005-09-16 | Nihon Nohyaku Co., Ltd. | Derivados de diamida aromatica o sales de estos derivados, productos quimicos para la agricultura/horticultura y procedimiento de utilizacion de estos productos. |
US6639109B1 (en) | 1999-09-28 | 2003-10-28 | Nihon Nohyaku Co., Ltd. | Process for production of thioalkylamine derivatives |
HUP0204412A3 (en) * | 1999-12-22 | 2003-05-28 | Nihon Nohyaku Co Ltd | Insecticidal aromatic diamide derivatives, compositions containing them and use thereof |
DE10115406A1 (de) * | 2001-02-06 | 2002-08-08 | Bayer Ag | Phthalsäurediamide |
KR20040015151A (ko) * | 2001-04-26 | 2004-02-18 | 니혼노야쿠가부시키가이샤 | 프탈아미드 유도체, 농원예용 살충제 및 그의 사용 방법 |
AR035884A1 (es) * | 2001-05-18 | 2004-07-21 | Nihon Nohyaku Co Ltd | Derivado de amida aromatico sustituido, derivado de amina aromatico sustituido con un grupo fluoroalquilo util como intermediario para obtener el mismo, insecticida para agrohorticultura que lo contiene y metodo para usar este ultimo |
JP2004277333A (ja) * | 2003-03-14 | 2004-10-07 | Bayer Cropscience Ag | 殺虫性フタラミド誘導体 |
-
2002
- 2002-06-20 JP JP2002180028A patent/JP2004018506A/ja active Pending
-
2003
- 2003-06-11 CN CNB038185393A patent/CN100516033C/zh not_active Expired - Fee Related
- 2003-06-11 CN CNA2006101464691A patent/CN1955162A/zh active Pending
- 2003-06-11 US US10/517,859 patent/US7132455B2/en not_active Expired - Lifetime
- 2003-06-11 WO PCT/EP2003/006105 patent/WO2004000796A1/en active Application Filing
- 2003-06-11 JP JP2004514688A patent/JP4330531B2/ja not_active Expired - Fee Related
- 2003-06-11 CN CNB2006101464672A patent/CN100556903C/zh not_active Expired - Fee Related
- 2003-06-11 EP EP03760601A patent/EP1517886B1/en not_active Expired - Lifetime
- 2003-06-11 AU AU2003258495A patent/AU2003258495B2/en not_active Ceased
- 2003-06-11 KR KR1020047020417A patent/KR101004070B1/ko not_active IP Right Cessation
- 2003-06-11 DE DE60334907T patent/DE60334907D1/de not_active Expired - Lifetime
- 2003-06-11 BR BRPI0311955-6A patent/BR0311955B1/pt not_active IP Right Cessation
- 2003-06-11 ES ES03760601T patent/ES2355138T3/es not_active Expired - Lifetime
- 2003-06-11 MX MXPA04012739A patent/MXPA04012739A/es active IP Right Grant
- 2003-06-11 AT AT03760601T patent/ATE487694T1/de not_active IP Right Cessation
- 2003-06-19 TW TW092116606A patent/TWI329101B/zh not_active IP Right Cessation
- 2003-06-20 AR ARP030102204A patent/AR039719A1/es unknown
Also Published As
Publication number | Publication date |
---|---|
ATE487694T1 (de) | 2010-11-15 |
EP1517886B1 (en) | 2010-11-10 |
ES2355138T3 (es) | 2011-03-23 |
CN100556903C (zh) | 2009-11-04 |
AU2003258495B2 (en) | 2009-03-12 |
US20060035967A1 (en) | 2006-02-16 |
AU2003258495A1 (en) | 2004-01-06 |
US7132455B2 (en) | 2006-11-07 |
KR20050010057A (ko) | 2005-01-26 |
CN1671655A (zh) | 2005-09-21 |
JP4330531B2 (ja) | 2009-09-16 |
CN100516033C (zh) | 2009-07-22 |
JP2005529963A (ja) | 2005-10-06 |
KR101004070B1 (ko) | 2010-12-27 |
DE60334907D1 (de) | 2010-12-23 |
BR0311955B1 (pt) | 2014-07-29 |
WO2004000796A1 (en) | 2003-12-31 |
AR039719A1 (es) | 2005-03-09 |
JP2004018506A (ja) | 2004-01-22 |
CN1955172A (zh) | 2007-05-02 |
EP1517886A1 (en) | 2005-03-30 |
TWI329101B (en) | 2010-08-21 |
MXPA04012739A (es) | 2005-03-23 |
TW200407286A (en) | 2004-05-16 |
BR0311955A (pt) | 2005-04-26 |
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