CN1077709A - 取代(杂)-芳基-烷基-酮肟-o-醚类的杀螨剂、杀虫剂和杀线虫剂 - Google Patents
取代(杂)-芳基-烷基-酮肟-o-醚类的杀螨剂、杀虫剂和杀线虫剂 Download PDFInfo
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Abstract
具杀螨、杀虫和杀线虫作用的取代的(杂)-芳基
-烷基-酮肟-O-醚,它们的制备方法,含此类化合物
的药剂以及它们作为农药的应用。
本发明是有关式I所示的化合物,它们的制备方
法,含此类化合物的药剂和它们在防治有害生物中的
应用。(在式中Ar1和Ar2是芳基或杂芳基,有时可被
取代的,R代表取代的脂族或脂环族基团。)
Description
本发明是有关新的取代(杂)-芳基-烷基-酮肟-O-醚,它们的制备方法,以及含有此有效成分的药剂和它们在防治有害生物,特别是防治害虫,螨类以及线虫方面的应用。
肟醚和将它们作为农药使用在部分程度上是已知的。
[G.Holan et al.,Recent Advances in the Chemistry of Insect Control Ⅱ,p.114 et seq.Cambridge 1990;T.G.Cullen et al.,ACS Symp.Ser.335(1987)173;M.J.Bull et al.,Pestic.Sci.11(1980)349;WO-A-84/01772]。
带有杀虫剂特性的杂芳香烃肟醚在EP-A-4754和EP-A-24888中是已知的。然而它们的作用效果並不完全令人满意。
已发现了一些具有很好的农药性质的,特别是具有杀虫、杀螨和/或杀线虫性能的新的肟-O-醚化合物。
本发明是有关式(1)所示的化合物和它们的盐
式中
Ⅰ.Ar1和Ar2是相同的或不同的,并代表
a)(C6-C12)-芳基或是带多至10个碳原子的杂芳基,或
b)如在1.a)中所确定的含义,必要时被选自下列中5个相同或不同的取代基取代:
1.(C1-C6)-烷基,
2.(C2-C6)-链烯基,
3.(C2-C6)-炔基,
4.(C3-C8)-环烷基,有时被多至6个相同的或不同的选自卤素和(C1-C4)-烷基基团取代,
5.卤素,
6.(C1-C6)-卤代烷基,
7.(C2-C6)-卤代链烯基,
8.(C2-C6)-卤代炔基,
9.(C1-C6)-烷氧基-(C1-C6)-烷基,
10.(C6-C12)-芳基,有时被选自(C1-C6)-烷基,(C1-C6)-烷氧基,卤素,(C1-C6)-卤代烷基和(C1-C6)-卤代烷氧基的相同或不同的基团取代三次,
11.带多至10个碳原子的杂芳基,有时如1.b)10发生取代,
12.(C6-C12)-芳基-(C1-C4)-烷基,在芳基部分有时如1.b)10.发生取代,
13.在芳基部分带有多至10个碳原子的杂芳基-(C1-C4)-烷基,它有时也如1.b)10.发生取代,
14.(C1-C6)-烷氧基,
15.(C2-C6)-链烯基氧基,
16.(C2-C6)-炔基氧基,
17.(C3-C8)-环烷基氧基,有时如1.b)4.发生取代,
18.(C1-C6)-烷氧基-(C1-C4)-烷氧基,
19.(C6-C12)-芳基氧基,有时如1.b)10.发生取代,
20.带多至10个碳原子的杂芳基氧基,有时如1.b)10.发生取代,
21.(C1-C6)-卤代烷氧基,
22.(C2-C6)-卤代链烯基氧基,
23.(C2-C6)-卤代炔基氧基,
24.-O-N=CR′2,式中R′代表相同的或不同的选自氢,(C1-C6)-烷基,(C3-C8)-环烷基和(C6-C12)-芳基的基团,
25.(C1-C6)-烷基氨基,
26.二-(C1-C6)-烷基氨基,
27.(C3-C8)-环烷基氨基,有时如1.b)4.发生取代,
28.(C6-C12)-芳基氨基,有时如1.b)10.发生取代,
29.带多至10个碳原子的杂芳基氨基,有时如1.b)10.发生取代,
30.(C1-C6)-烷基氢硫基,
31.(C6-C12)-芳基氢硫基,
32.带多至10个碳原子的杂芳基氢硫基,
33.(C1-C6)-烷基亚磺酰基,
34.(C6-C12)-芳基亚磺酰基,
35.带多至10个碳原子的杂芳基亚磺酰基,
36.(C1-C6)-烷基磺酰基,
37.(C6-C12)-芳基磺酰基,
38.带多至10个碳原子的杂芳基磺酰基,
39.硝基,
40.氰基,
41.氰基-(C1-C6)-烷基,
42.(C1-C6)-烷氧基羰基,
43.(C6-C12)-芳基氧基羰基和
44.在杂芳基部分带多至10个碳原子的杂芳基氧基羰基,或
45.a)取代基中的2个代表甲二氧基,
b)甲二氧基有时带1个或2个相同或不同的选自卤素和(C1-C4)-烷基的取代基;
Ⅱ.R代表a)(C1-C6)-烷基,
b)(C2-C6)-链烯基,
c)(C2-C6)-炔基或
d)(C3-C8)-环烷基,或
e)如在11.a)-d)中所确定的含义,带有多至3个相同或不同的选自下面的取代基
1.卤素,
2.羟基,
3.(C1-C6)-烷氧基,
4.(C1-C6)-烷基氢硫基,
5.(C1-C6)-烷基亚磺酰基,
6.(C1-C6)-烷基磺酰基,
7.氰基,
8.硝基和
9.(C1-C6)-烷氧基羰基,或
f)如在11.a)-d)中所确定的含义,如果氢原子数≥5,它们是部分地或完全被卤素取代,卤原子数是≥4;
在1.a)和b)中确定了含义的芳基和杂芳基也可以部分氢化,其中1个或2个CH2-基团能被CO取代;
Ⅲ.条件是:
a)如果R是甲基或取代甲基,它带有1,2或3个相同或不同的如在Ⅱ.e)1.或3-9中所定义的基团,其中至少有一个基团是卤素,和如果Ar1是如在1.b)2-4.,7.,8.,11.,13.,15.-44.或45.b)中的基团取代的芳基,或有时是取代的杂芳基,那么Ar2是如在1.a)或b)中所确定的含义,
b)如果R是甲基或取代的甲基。它带有1,2或3个相同或不同的如在11.e)1.或3.-9.中定义的基团,其中至少有一个基团是卤素,和如果Ar′是如在Ⅰ.b)1.,5.,6.,9.,10.,12.,14.,或45a)中的基团取代的芳基,那么Ar2如在1.a)或b)中所确定的含义,但不是4-氟-3-苯氧基苯基,3-苯氧基苯基,五氟代苯基或2,6-二卤代苯基;
c)如果R是(C2-C6)-烷基或是如在Ⅱ.b)-f)中所确定的含义和如果Ar1是如在1.a)中所确定的含义,或如在1.b)中确定了含义的芳基或如在1.b)1.-20.或24.-45.)中确定了含义的杂芳基,那么Ar2是如在1.a)和b)中所确定的含义,但不是
2,6-二卤代苯基,五氟代苯基,
式中
Z 是卤素或氢,
Q 是O,S,NH或CH2,
R4是卤素,
X 是O或S,
R10,R11和R12相同或不同,代表氢或如在1.b)1.-45.中所确定的含义,
R13是氢,氟或甲基,
O 是0,1或2,
R6是氢,氟或烷基,
R7是卤代苯氧基,卤代苄基,O-CH2-CH=CH2,0-CH2-C≡CH;CH2-CH=CH2或CH2-C≡CH和
R8是链烯基或卤代链烯基;
d)如果R是(C2-C6)-烷基或如在Ⅱ.b)-f)中所确定的含义和如果Ar1是如在Ⅰ.b)21.-23.所确定含义的杂芳基,那么Ar2此外还能有在Ⅰ.a)和b)中已确定的含义;
e)如果R是(C2-C6)-烷基或如在Ⅱ.b)-f)中所确定的含义和如果Ar1是如在1.a)或b)中确定含义的杂芳基,那么Ar2此外还可有五氟代苯基的含义或
式中R13和O有上面所给定的含义;
f)如果R是如在Ⅱ.e)中确定含义的取代的(C2-C6)-烷基,(C2-C6)-链烯基或(C2-C6)-炔基和如果Ar1是如在1.a)或b)中确定含义的芳基,那么Ar2此外还有下式的含义
式中R13和O具有上面所确定的含义;和
g)如果R是(C2-C6)-烷基或如在Ⅱ.b)-f)中所确定的含义和如果Ar1是如在Ⅰ.b)21.中所定义的取代的(C6-C12)-芳基,那么Ar2此外还可以是五氟代苯基。
烷基,链烯基和炔基可以是直链的或支链的。它也适用于由它们派生出的基团如烷氧基,烷基氢硫基,卤代烷基和芳基烷基。
卤代烷基,卤代链烯基和卤代炔基可理解为式中1个,多个或所有的氢原子被卤素取代的烷基,链烯基或炔基。它也适用于由它们派生出的基团,如卤代烷氧基,卤代链烯基氧基或卤代炔基氧基。
卤素指的是氟、氯、溴或碘,优选氟,氯或溴。
(C6-C12)-芳基优选苯基和由它派生出的基团如萘基,联苯基和茚满基。
带多至10个碳原子杂芳基优选为一或二环芳基,在式中至少有1个CH被N取代和/或式中至少2个相邻的CH基被NH,O和/或S取代。这一类基团例如可是噻嗯基,苯并噻嗯基,呋喃基,苯并呋喃基,吡咯基,咪唑基,吡唑基,吡啶基,吡嗪基,嘧啶基,哒嗪基,吲哚基,噁唑基,异噁唑基,噻唑基和异噻唑基。
如果式(1)化合物能形成盐,本发明还涉及它们的盐,特别是它们的酸加成盐。能形成盐的酸是无机酸如盐酸,氢溴酸,硝酸,硫酸,磷酸或有机酸如甲酸,醋酸,丙酸,丙二酸,草酸,富马酸,己二酸,硬脂酸,油酸,甲磺酸,苯磺酸或甲苯磺酸。
优选如下式(1)化合物,式中
Ar1是苯基,萘基,茚满基,苯并呋喃基,苯并噻嗯基,
如噻嗯基或呋喃基或
如噻唑基
这些基团有时如上面所定义的取代,和式中
X 是O,S或NR3和
R3是氢,
(C1-C6)-烷基,
(C2-C6)-链烯基,优选-CH2-CH2=CH2,
(C2-C6)-炔基,优选-CH2-C≡CH,
(C3-C8)-环烷基,有时被多至6个相同或不同的选自卤素和(C1-C4)-烷基的基团取代,
(C1-C6)-卤代烷基,
(C2-C6)-卤代链烯基,
(C2-C6)-卤代炔基,
(C1-C6)-烷氧基-(C1-C6)-烷基,
(C6-C12)-芳基-(C1-C4)-烷基,
杂芳基-(C1-C4)-烷基,其杂芳基部分带有多至10个碳原子,
氰基-(C1-C6)-烷基,
(C1-C6)-烷氧基羰基,
(C6-C12)-芳基氧基羰基或
带多至10个碳原子的杂芳基氧基羰基,
特别是这样的式(1)化合物,式中
Ar1是如下所示的一个基团
X 含义如上,
P 是1个0至5的整数,和
R1是相同的或不同的,并代表卤素,
(C1-C6)-烷基,
(C2-C6)-链烯基,
(C2-C6)-炔基,
(C3-C8)-环烷基,有时被多至6个相同或不同的选自卤素和(C1-C4)-烷基的基团取代,
(C1-C6)-卤代烷基,
(C2-C6)-卤代链烯基,
(C2-C6)-卤代炔基,
(C1-C6)-烷氧基-(C1-C6)-烷基,
(C6-C12)-芳基,有时被多至3个相同或不同的选自卤素,(C1-C6)-烷基,(C1-C6)-烷氧基,(C1-C6)-卤代烷基和(C1-C6)-卤代烷氧基的基团取代,
带多至10个碳原子的杂芳基,有时发生如上面所述芳基的取代,
(C6-C12)-芳基-(C1-C4)-烷基,在芳基部分有时发生如上面所述芳基的取代,
在杂芳基部分带有多至10个碳原子的杂芳基-(C1-C4)-烷基和有时发生如上面所述芳基的取代,
(C1-C6)-烷氧基,
(C2-C6)-链烯基氧基,
(C2-C6)-炔基氧基,
(C3-C8)-环烷基氧基,
(C1-C6)-烷氧基-(C1-C6)-烷氧基,
(C6-C12)-芳基氧基,有时发生如上面所述的芳基的取代,
带多至10个碳原子的杂芳基氧基,有时发生如上面所述的芳基的取代,
(C1-C6)-卤代烷氧基,
(C2-C6)-卤代链烯基氧基,
(C2-C6)-卤代炔基氧基或
-O-N=CR′2,式中R是相同的或不同的选自氢,(C1-C6)-烷基,(C3-C8)-环烷基和(C6-C12)-芳基的基团,或
对于R1有时是如在1.b)45.b)中取代的亚甲二氧基基团的2个基团,
式中R1优选的基团是
(C1-C6)-烷基,
(C2-C6)-链烯基,
(C2-C6)-炔基,
(C3-C8)-环烷基,
卤素,
(C1-C6)-卤代烷基,
(C2-C6)-卤代链烯基,
(C2-C6)-卤代炔基,
有时如上取代的(C6-C12)-芳基或带多至10个碳原子的杂芳基,
(C1-C6)-烷氧基,
(C2-C6)-链烯基氧基,
(C2-C6)-炔基氧基,
(C3-C8)-环烷基氧基,
有时如上取代的(C6-C12)-芳基氧基或带多至10个碳原子的杂芳基氧基,
(C1-C6)-烷氧基-(C1-C6)-烷基,
(C1-C6)-烷氧基-(C1-C6)-烷氧基,
(C1-C6)-卤代烷氧基,
(C2-C6)-卤代链烯基氧基或
(C2-C6)-卤代炔基氧基,
或对于R1有时是如在1.b)45.b)中取代的甲二氧基基团中的2个基团,
式中R1特别是指(C1-C6)-卤代烷氧基,如OCHF2,OCF3,OCF2CF2H,OCH2CF3,或OCH(CF3)2,(C1-C6)-烷氧基,氟,氯,溴,(C1-C6)-烷基,(C2-C6)-卤代链烯基氧基,(C2-C6)-卤代炔基氧基,(C1-C6)-卤代烷基,(C2-C6)-卤代链烯基,或(C2-C6)-卤代炔基。
上述优选的R1基团最好是在苯基的4-位,或杂芳6-元环的相应位置或杂芳5-元环的类似位置上,尤其优选下列Ar1基团:
R 优选(C1-C6)-烷基或(C3-C8)-环烷基,它可部分地或全部地被卤素取代,特别是(C1-C6)-烷基,它能用多至3个氟取代,如CF3,CF2H,或异丙基或环丙基。
Ar2优选
X=O,S或NR3X=O,S或NR3
式中
A,B和C是相同和不同的并且是N,CH或C-卤素,
Q 是O,S,NH或CH2,优选O或CH2,
R4是氢,卤素,O-CH2-CH=CH2或O-CH2-C≡CH,优选氢,4-F,3-F,4-Cl
Hal是卤素,
R9是氢或如R1的含义,
m和n是相同的或不同的和代表1,2,3或4,
m+n=5,
R5是氢或如R1的含义,
q,r和s是相同或不同的和代表1,2或3,
q+r+s=5,
R3如上面的含义,
R10,R11和R12是如上面的含义,优选CH3,CF3,CN,苯基,CH2-CH=CH2,-CH2-C≡CH或苄基,
R13是氢,氟或甲基,
O 是0,1或2,
R6是氢,氟或(C1-C6)-烷基,
R7是卤代苯氧基,卤代苄基,O-CH2-CH=CH2,O-CH2-C≡CH,CH2-CH=CH2或CH2-C≡CH和
R8是(C2-C6)-链烯基或(C2-C6)-卤代链烯基。
如果Ar2如上面A.的含义,那么优选的化合物是,式中A,B和C不能同时是N,特别是这样的化合物,式中A,B或C仅有一个是N。优选的Ar2是
在B.c)中所定义的Ar2-基团中优选
式中R9是(C1-C6)-烷基,特别是甲基,(C1-C6)-烷氧基,(C1-C6)-卤代烷氧基或(C1-C6)-卤代烷基。
上面B.d)中所定义的Ar2-基中优选
上面C.中所定义的Ar2-基团中优选
X=NR3,O或S,Q′是O或CH2和R11和R12如上面的含义。
上面在D.中所定义的基团中优选式中O=O的基团,特别优选式中R13是氢的基团。
特别优选的式1化合物是,式中Ar2是如在上面B.c),B.d),C.b),C.c),或C.d)的定义,以及这样一些在式中Ar1有时是取代的杂环芳基和R是三氟甲基或式中Ar1有时是取代的芳基或杂芳基,Ar2是如在上面D.或E.中的含义和R是三氟甲基。
式(Ⅰ)所示的肟醚可以两种异构体形式出现:“顺式”和“反式”形式。与取代基R无关,“顺式”应是标记肟醚,即肟-氧对芳基或杂芳基Ar1呈顺式关系。
本发明不仅涉及顺式-也涉及反式形式以及两者的混合物。
此外,式Ⅰ化合物可具有1个或多个不对称碳原子。它可是外消旋体和非对映体。本发明不仅包括纯的异构体,也包括它们的混合物。非对映体的混合物可以采用一些常规方法如用合适的溶剂进行选择性重结晶或用色析的方法使混合组分得以分离。用常用的方法可以从对映体中拆分出外消旋体,比如通过与一个光活性酸形成盐的方法,借助于碱分离非对映体的盐和游离纯对映体的方法。
本发明还涉及式Ⅰ化合物的制备方法,其特征在于,
a)式Ⅱ化合物
式中Ar1和R如式Ⅰ中定义,M是氢或一碱金属原子,如果M是氢,在合适的碱的存在下,与式Ⅲ所示的化合物反应
式Ⅲ中Ar2是如在式Ⅰ中定义,X代表一个离去基团,或b)式Ⅳ化合物
必要时在一合适的碱的存在下与式Ⅴ化合物或它们的盐如与氢卤化物的盐反应,
必要时将得到的式Ⅰ化合物转化为它们的盐。(参考文献:
Houben-Weyl,Methoden der organischen Chemie[Methods in Organic Chemistry],Volume 10/4,P.55et seq.,p.217 et seq.,p.352 et seq.)Volume E 14b Part 1,p.287 et seq.,p.307 et seq.,p.367 et seq.).
如果按方法a)从肟醚(M=氢)开始,反应可在一个合适的碱存在下如叔胺,碱金属,碱金属氢化物,碱金属酰胺,碱金属醇盐,有机锂-和有机镁化合物,碱金属氢氧化物,碱金属碳酸氢盐,碱金属碳酸盐于一个合适的有机溶剂中,优选醚类(乙醚,四氢呋喃,二甲氧基乙烷,二噁烷等),芳香烃和非芳香烃的,还有卤代烃类(甲苯,庚烷,氯代苯等)以及对质子呈惰性的,偶极溶剂如二甲基甲酰胺,二甲基亚砜,乙腈,丙酮,N-甲基吡咯烷酮,温度在-20°和150℃之间的条件下进行。烷基化反应也能在相转移催化下进行。
合适的离去基团X是卤素(氟除外),OSO2CH3,OSO2CF3,P-甲苯磺酰基氧基或季铵盐等。
分离的碱金属肟盐(M=碱金属原子)的烷基化反应在同一条件下进行。不需要有碱的存在。
肟(盐)烷基化反应时通常肟的立体结构不会失去,即从“顺式”-肟(盐)可得到“顺式”-肟醚。“反式”化合物也同样如此。
本发明的肟醚还可以通过一个羟胺-O-烷基-芳基2-醚(盐)与酮,或许需要有一个合适的碱和一个合适的溶剂存在之下,于-20℃和+150℃之间通过缩合反应合成(方法b)。
特别适合的碱是碱金属羧酸盐,叔胺,碱金属氢氧化物,碱金属碳酸盐和一碳酸氢盐,溶剂(也可是混合溶剂)优选醇类,烃类,卤代或非卤代(芳香烃)烃类,醚类。羟胺-O-醚也可按文献记载的方法制备(Kaztreiner et al.,Acta Chem.Hung.80(1975)167)。
式Ⅱ所示的酮肟(M=氢)可按通常的制备方法由酮与羟基铵盐如盐酸羟胺在温度-20和+150℃之间于一合适的溶剂中,优选水,醇类,(卤代)芳香烃和非芳香烃类,醚(四氢呋喃,二噁烷,乙醚,二甲氧基乙烷),有时还需加入一个如在(b)中定义的合适的碱进行合成。
Methoden der organischen Chemie[Methods in Organic Chemistry],Volume10/4 p.55 et seq.,352 et seq.;Volume E 14b Part 1,p.287 et seq.,307 et seq.,367 et seq.and R.L.Salvador et al.,J.Med.Chem.15(1972)646).
肟或异构肟的混合物可借助于(路易士)酸如三氟化硼-醚盐,四氯化钛,HCl按文献记载的方法(US4158015)被转化为热力学稳定的形式。
本发明肟醚的结构按类似于下列文献获得:
G.J.Karabatsos,N.H.Si,Tetrahedron 23(1967)1079 and A.Boder,A.Barabs,Tetrahedron 35(1979)233.
式Ⅳ所示的三氟甲基或五氟烷基酮。
三氟甲基酮可用不同的方法合成,如在文献(J.-P.Begue et al.,Tetrahedron 47(1991)3207)中所记载的方法,优选下面的方法
a)有机锂-和/或-格利雅-反应
Ar1=芳基,杂芳基
(Houben-Weyl,Band7/2a,S.548ff,X.Creary,J.Org.Chem.52(1987)5026)
b)或通过三氟甲硼烷/锌与相应的醛的加成,继之发生氧化反应(HOE92/F011)
c)活化的,富电子的芳香化合物按照Friedel Crafts(弗瑞德-克来福特)方法乙酰化或按Houben-Hoesch(与三氟乙腈)方法〔Houben-Weyl,Methoden der Organischen Chemie,Band 7/2a,S.39,83〕。
烷基-芳基酮。
烷基(环烷基)-Ar1-酮的制备(文献:Houben-Weyl,Methoden der Organischen Chemie,Band 7/2a)可通过下面的反应制备。
a)芳基1-格利雅-或-锂化合物与相应的羧酸衍生物(X=Li,MgHal)反应
式Ⅲ所示的烷基化试剂的合成:
烷基化试剂,特定的磺酸盐和苄基卤,可按标准方法,或由醇与氯磺酸(-酐),与亚硫酰氯(X=Cl),与氢溴酸或三溴化磷(X=Br)反应,或者通过有关的甲基芳香化合物CH3-Ar2CX=Br,Cl)合成制备(见K.Naumann,Synthetic Pyrethroid Insecticides(合成拟除虫菊酯类杀虫剂),Chemistry and Patent(化学与专利),Band5,Berlin 1990和由这里引证的一些文献)。
本发明的有效成分适合于防治有害生物而植物对其有很好的耐受性且对温血动物安全。其防治对象特别是指昆虫,螨类,蠕虫,线虫和软体动物,尤其适合于防治在农业、畜牧、森林、贮藏和物资保护以及卫生等领域里出现的害虫和螨类。它们对普通的敏感和抗性品种以及防治对象整个或单个生长发育阶段都有防治效果。上面所论及的有害生物都属于防治对象。
蜱螨目:例如粗脚粉螨,锐缘蜱属数种,印缘蜱属数种,鸡皮刺蜱,茶藨瘿螨,柑桔锈螨,牛蜱属数种,扇头蜱,花蜱属数种,璃眼蜱属数种,硬蜱属数种,瘙螨属数种,疥螨属数种,疥螨属数种,线螨属数种,苜蓿苔螨,全爪螨属数种,叶螨属数种,始叶螨属数种,小爪螨属数种,真叶螨属数种。
等足目:例如鼠妇,Porcellio Scaber。
马陆目:例如Blaniulus guttulatus。
蜈蚣目:例如Geophilus Carpophagus,家蚰蜓属数种。
综合纲:例如庭园么蚰。
Tysanurap例如西洋衣鱼。
弹尾目:例如棘。
直翅目:例如东方蜚蠊,美洲大蠊,马德拉蜚蠊,德国小蠊,家蟋蟀,蝼蛄属数种,热带飞蝗,殊种蚱蜢,沙漠蝗。
革翅目:例如欧洲球螋。
等翅目:例如散白蚁属数种。
虱目:例如葡萄根瘤蚜,瘿绵蚜属数种,体虱,血虱属数种,颚虱属数种。
食毛目:例如嚼虱属数种,畜虱属数种。
缨翅目:例如温室条蓟马,棉蓟马。
异翅亚目:例如扁盾蝽属数种,棉红蝽,甜菜拟网蝽,温带臭虫,长红猎蝽,猎蝽属数种。
同翅目:例如甘蓝粉虱,甘薯粉虱,温室粉虱,棉蚜,甘蓝蚜,茶藨隐瘤蚜,Doralis fabae,Doralis Pomi,苹果绵蚜,桃大尾蚜,麦长管蚜,瘤蚜属数种,忽布疣额蚜,禾谷缢管蚜,微叶蝉属数种,Euscelus bilobatus,黑尾叶蝉,褐盔蜡蚧,乌盔蚧,灰稻虱,稻褐飞虱,红圆蚧,夹竹桃圆蚧,粉蚧属数种,木虱属数种。
鳞翅目:例如红铃麦蛾,松天蛾,冬尺蛾,苹细蛾,苹果巢蛾,菜蛾,天幕毛虫,黄毒蛾,毒蛾属数种,棉潜蛾,桔叶潜蛾,地老鼠属数种,切根虫属数种,叶
属数种,棉斑实蛾,夜蛾属数种,甜菜夜蛾,甘蓝夜蛾,小眼夜蛾,斜纹夜蛾,粘虫属数种,粉纹夜蛾,苹蠹蛾,菜粉蝶属数种,稻暝属数种,玉米暝,地中海斑暝,蜡暝,亚麻黄卷蛾,烟卷蛾,枞色卷蛾,葡萄果蠹蛾,茶长卷蛾,栎绿卷蛾。
鞘翅目:例如具斑窃蠹,家具窃蠹,谷蠹,豆象,大豆象,北美家天牛,赤扬紫跳甲、马铃薯甲虫,辣根猿叶虫,叶甲属数种,油菜蓝跳甲,墨西哥豆
,隐食甲属数种,锯谷盗,象属数种,米象属数种,葡萄黑耳喙象,香蕉根象甲,甘蓝荚象甲,苜蓿叶象甲,皮蠹属数种,皮蠹,皮蠹属数种,毛蠹属数种,粉蠹属数种,油菜花露尾甲,蛛甲属数种,黄蛛甲,麦蛛甲,拟谷盗属数种,黄粉虫,叩甲属数种,金针虫属数种,西方五月鳃角金龟,六月金龟,褐新西兰肋翅鳃角金龟。
膜翅目:例如松叶蜂属数种,叶蜂属数种,蚁属数种,法老蚁,胡蜂属数种。
双翅目:例如伊蚊属数种,按蚊属数种,库蚊属数种,黄腥腥果蝇,蝇属数种,夜蝉属数种,红头丽蝇,绿蝇属数种,果蝇属数种,疽蝇属数种,胃蝇属数种,Hypobosca spp,螫蝇属数种,狂蝇属数种,皮蝇属数种,虻蝇属数种,蝇属数种,Bibio hortulanus,瑞典麦杆蝇,花蝇属数种,菠菜潜叶花蝇,地中海实蝇,油榄实蝇,沼泽大蚊。
蚤目:例如印度客蚤、叶蚤属数种。
蜘蛛目:例如蝎子,黑寡妇。
蠕虫目:例如血矛线虫属,Trichostrongulus,奥斯脱牛肠线虫属,Cooperia,夏柏线虫属,粪圆线虫属,结节线虫属,红猪圆虫属,钩口线虫属,蛔虫属和Heterakis以及Fasciola和植物和动物线虫例如Gattungen Meloidogyne,胞囊线虫属,茎线虫属,滑刃线虫属,穿孔线虫属,Globodera,根腐线虫属,长针线虫属和剑线虫属。
腹足纲:例如蛞蝓属数种,阿勇蛞蝓属数种,沼泽蜗牛属数种,Galba spp.,琥珀螺属数种,Biomphalaria spp.,豆田螺属数种,钉螺属数种。
牡蛎纲:例如贝属数种。
本发明的对象是除含有合适的剂型助剂外还含有式Ⅰ所示的化合物的药剂。
本发明的药剂通常含式Ⅰ有效成分1~95%(重量)。
根据所给定的生物学和/或化学/物理参数,可加工成不同的剂型。可加工的剂型是:可湿性粉剂(WP),乳油(Ec),水溶液(SC),乳液,可喷洒的溶液,以油或水为基质的分散液(SC),悬浮乳液(SC),粉剂(DP),浸渍剂,微颗粒剂,喷洒颗粒剂,包衣颗粒剂和吸附颗粒剂,水中可分散的颗粒剂(WG),超低量剂型,蜡剂和诱饵。
这些剂型基本上是已知的,在下面的文献中有记载:
Winnacker-Küchler,“Chemische Technologie”[Chemical Technology],Volume 7,C.Hauser Verlag Munich,4th Ed.1986;van Falkenberg,“Pesticides Formulations”,Marcel Dekker N.Y.,2nd Ed.1972-73;K.Martens,“Spray Drying Handbook”,3rd Ed.1979,G.Goodwin Ltd.London.
必要的剂型助剂物质如惰性材料,表面活性剂,溶剂和其它的添加剂同样也是已知的,在下面的文献中有记载:Watkins,“Handbook of Insecticide Dust Diluents and Carriers”,2nd Ed.,Darland Books,Caldwell N.J.;H.v.Olphen,“Introduction to Clay Colloid Chemistry”,2nd Ed.,J.Wiley & Sons,N.Y.;Marschen,“Solvents Guide”,2nd Ed.,Interscience,N.Y.1950;McCutcheon′s,“Detergents and Emulsifiers Annual”,MC Pubabl.I.Corp.,Ridgewood N.J.;Sisley and Wood.“Encyclopedia of Surface Active Agents”,Chem.Publ.Co.Inc.,N.Y.1964;Sch
nfeldt,“Grenzfl
chenaktive
thylenoxidaddukte”[Surface-active Ethylene Oxide Adducts],Wiss,Verlagsgesell.,Stuttgart 1976;Winnacker-Küchler,“Chemische Technologie”[Chemical Technology],Volume 7,C.Hauser Verlag Munich,4th Ed.1986.
在这些剂型的基础上也可与其它的农药有效成分物质,肥料和/或生长调节剂制备成组合物,例如以成品制剂或罐装混合物的形式。可湿性粉剂是在水中能均匀分散的制剂,它除了有效成分,一个稀释或惰性物质外,还含有润湿剂,如聚氧乙基烷基酚类,聚氧乙基脂肪醇类,烷基-或烷基酚磺酸盐和分散剂如木质素磺酸钠,2,2′-二萘基甲-6,6′-二磺酸钠,二丁基萘磺酸钠或油酰甲基牛磺酸钠。乳油是将有效成分溶解在如丁醇,环己酮,二甲基甲酰胺,甲苯或也可是高沸点的芳香烃或烃类中的某一种有机溶剂中,再添加1个或多个乳化剂制备而成。可作为乳化剂使用的有例如:烷基芳基磺酰钙盐类如十二烷基磺酸钙或非离子化乳化剂如脂肪酸聚乙二醇酯,烷基芳基聚乙二醇醚,脂肪醇聚乙二醇醚,环氧丙烷-环氧乙烷-缩合产物,烷基聚醚,山梨烷脂肪酸酯,聚氧乙烯山梨烷脂肪酸酯或聚氧乙烯山梨酯。
粉剂是将有效成分与细颗粒的,呈分散状固体物质如滑石,天然粘土如高岭土,皂土,叶蜡石土或硅藻土经磨碎加工而制得。颗粒剂的制备是将有效成分喷洒在具有吸附性能的颗粒状惰性物质表面或是将有效成分用聚乙烯醇,聚丙烯酸钠这些粘合剂或矿物油粘附到砂子,高岭土等载体物质表面或颗粒状惰性物质的表面。也可以用通常制备颗粒肥料的方法将某些合适的有效成分加工成颗粒剂。需要时也可以与肥料混在一起加工。
可湿性粉剂含有效成分浓度例如大约在10至90%(重量),其余部分由常用的一些剂型助剂物质组成。乳油含有效成分浓度大约为5-80%(重量)。粉剂含有效成分浓度至少5~20%(重量),可喷洒的溶液含有效成分浓度大约2~20%(重量)。颗粒剂有效成分含量部分取决于有效成分是呈液态或固态和使用什么样的颗粒助剂,填料等。
除此之外,所列举的有效成分剂型有时还含有常用的粘合剂,润湿剂,分散剂,乳化剂,渗透剂,溶剂,填料或载体。
通常以商品形式提供的剂型在使用时有时需用常规的方法稀释,例如可湿性粉剂,乳油,分散剂及部分微颗粒剂可用水稀释,粉状和颗粒状制剂以及可喷洒的溶液在使用前通常不再用惰性物质稀释。
药剂的用量因温度、湿度等而变化。它可以在一个很大的范围内变动,例如在0.005和10.0公斤/公顷之间或更多的有效成分,优选用量在0.01和5公斤/公顷之间。
本发明的有效成分可以以其商品剂型以及由这些剂型与其它有效成分相混合的应用剂型,可与其混合的有效成分,如杀虫剂,引诱剂,不孕剂,杀螨剂,杀线虫剂,杀菌剂,生长调节剂或除草剂。
农药包括例如有机磷酸酯类,氨基甲酸酯类,羧酸酯类,甲脒类,锌化合物,微生物制剂等,优选作为混配配对的农药是:
1.有机磷类化合物
乙酰甲胺磷,Azamethiphos,乙基谷硫磷,谷硫磷,溴硫磷,乙基溴硫磷,毒虫畏,氯甲硫硫磷,氯蜱硫磷,甲基氯蜱硫磷,内吸磷,甲基内吸磷,磺吸硫磷,氯甲亚胺硫磷,敌敌畏,百治磷,0.0-1,2,2,2-四氯乙基硫代磷酸酯(SD208304),乐果,乙拌磷,苯硫磷,乙硫磷,丙线磷,乙嘧硫磷,伐灭硫磷,克线磷,杀暝松,砜线灵,倍硫磷,地虫硫磷,安果,Heptenophos Isozophos,甲丙乙拌磷,异噁唑硫磷,马拉硫磷,丁烯硫磷,甲胺磷,甲噻硫磷,水杨硫磷,速灭磷,久效磷,二溴磷,氧化乐果,砜吸硫磷,对硫磷,甲基对硫磷,稻丰散,3911,伏杀硫磷,氧环胺磷,亚胺硫磷,磷胺,辛硫磷,嘧啶硫磷,甲基嘧啶硫磷,Profenofos,丙虫磷,Proetamphos,甲基乙拌磷,三唑硫磷,敌百虫,完灭硫磷;
2.氨基甲酸酯类
涕灭威,2-仲-丁基苯基甲基氨基甲酸酯(BPMC),西维因,呋喃丹,丁硫克百亩,Cloethocarb,Benfuracarb,乙硫甲威,Furathiocarb,异丙威,乙肟威,5-甲基-m-cu-甲基丁酰基(甲基)氨基甲酸酯,草肟威,灭定畏,残杀威,Thiodicarb,乙酮肟,乙基-4,6,9-三氮-4-苄基-6-10-二甲基-8-噁-7-氧代-5,11-二硫杂-9-十二碳烯酸酯(OK135),1-甲基硫代(乙基叉氨基)-N-甲基-N-(硫代吗啉)-氨基甲酸酯(UC51717);
3.羧酸酯类
Allethrin,顺式氯氰菊酯,5-苄基-3-呋喃基甲基-(E)-(1R)-顺式-2,2-二甲基-3-(2-氧四氢噻吩-3-基-叉甲基)环丙烷羧酸酯,生物丙烯菊酯,S-生物丙烯菊酯((S)-环戊基异构体),苄呋菊酯,Biphenate,(RS)-1-氰基-1-(6-苯氧基-2-吡啶基)甲基-(1RS)-反式-3-(4-叔丁基苯基)-2,2-二甲基环丙烷羧酸酯(NCI85193),Cycloprothrin,氟氯氰菊酯,三氟氯氰菊酯,氯氰菊酯,Cyphenothrin,溴氰菊酯,Empenthrin顺式氰戊菊酯,Fenfluthrin,灭扫利,氰戊菊酯,氟氰戊菊酯,氟氯苯菊酯,氟胺氰菊酯(D-异构体),氯菊酯,苯醚菊酯((R)-异构体),d-Pralethrin,除虫菊酯Ⅰ(天然产物),苄呋菊酯,Tefluthrin,胺菊酯,Tralomethrin;
4.醚类
双甲脒,杀虫脒;
5.锌化合物
三环锡,螨完锡;
6.其它
爱力克螨,苏云金杆菌,Bensutap,乐杀螨,溴杀螨,优乐得,毒杀芬,巴丹,乙酯杀螨醇,定虫隆,2-(4-(氯代苯基)-4,5-二-苯基噻吩(UBI-T930),Chlofentezine环丙烷羧酸-(2-萘基甲基)酯(Ro12-0470),Cyromazin,N-(3,5-二氯-4-(1,1,2,3,3,3-六氟-1-丙基氧基)苯基)氨基甲酰基)-2-羧亚胺酸乙酯,DDT,伏虫脲,N-(2,3-二氢-3-甲基-1,3-噻唑-2-基叉)-2,4-二甲代苯胺,消螨通,消螨普,硫丹,多来宝,(4-乙氧基苯基)-(二甲基)-(3-(3-苯氧基苯基)丙基硅烷,Fenoxycarb,Flubenzimine,Flucycloxuron,卡死克,r-六六六,尼索朗,Hydramechylnon(AC217300),Ivermectin,2-硝基甲基-4,5-二氢-6H-噻嗪(SD52618),2-硝基甲基-3,4-二氢噻唑(SD35651),2-硝基甲撑-1,2-噻嗪烷-3-基氨基甲醛(WL108477),Propargite,农梦特,三氯杀螨砜,四氯杀螨砜,杀虫环,Triflumuron。
由商品剂型得到的应用形式的药剂中有效成分含量可从0.00000001高至99%(重量),优选在0.00001和1%(重量)之间。使用时用一适合于药剂应用形式的常规方法施药。
本发明的化合物适合于防治体内外寄生虫如在兽医领域或畜牧领域中的线虫。
本发明的有效成分可采用已知的方法加以应用如口服、药浴、喷洒、泼浇和撒粉以及非肠道应用的形式如注射。
本发明的式Ⅰ所示的新化合物特别适合于在畜牧业(例如牛、羊、猪和家禽如鸡、鹅等)上使用。本发明优选的施用方式是将新化合物有时以一个合适的剂型(见上面所述)和有时以饮水或饲料方式通过口服提供给动物。由于药剂有效成分可随粪便排泄,所以用此简单的方式可以阻止粪便中害虫的生长发育。使用的剂量和剂型特别与有用动物的种类和发育阶段有关,也与被侵染的情况有关,它可通过常规的方法很容易地调查和确定。新化合物对于牛的使用剂量为0.01~1毫克/公斤体重。
下面的例子用以解释本发明,但不限于此。
剂型制备例
a)粉剂:10份重有效成分和90份重用作惰性材料的滑石相混合在锤式破碎机中磨碎。
b)可湿性粉剂:25份重的有效成分,65份重充作惰性材料的含高岭土的石英粉,10份重木质素磺酸钾和1份重的作为润湿剂,分散剂的油酰甲基牛磺酸钠相混合于一棒式磨碎机中加工磨碎。
c)水中易分散的分散浓缩剂:将40份重有效成分与7份重磺基琥珀酸半酯,2份重木质素磺酸钠盐和51份重水混合,于一个球磨机中将颗粒磨细至5微米以下。
d)乳油:它由15份重有效成分,75份重用作为溶剂的环己酮和10份重作为乳化剂的乙氧基化壬基酚(10Eo)组成。
e)颗粒剂:由2-15份重的有效成分和作为惰性颗粒载体的物质如活性白土,浮石颗粒和/或石英砂组成。
人们还可以将由例b)制备的含固体组分30%的可湿性粉剂悬浮液喷洒于活性白土颗粒的表面,干燥,混匀。如此可以得到含可湿性粉剂大约5%和惰性载体大约95%的成品颗粒剂。
化学制备例:
肟醚合成的一般方法
方法A(表例65)
将1.44克(5.0mmol)〔6-(2,2,2-三氟乙氧基)-吡啶-3-基〕-三氟甲基-酮肟(熔点57-58℃)与含0.69克(5.0mmol)碳酸钾和0.13克(0.05mmol)18-冠醚-6的7毫升甲苯一起搅拌。再滴加入含1.53克(5.1mmol)4-氟-3-(4-氟代苯氧基)-苄基溴的5毫升甲苯。3小时后(薄层监测)滤去不溶物,用水洗涤有机相3次,经无水硫酸镁干燥后得到2.45克(97%)无色,粘稠的分析纯油状物。
方法B(表例27)
将含有5.46克(20.0mmol)〔6-(2,2,2-三氟乙氧基)-吡啶-3-基〕-三氟甲基酮和5.53克(20.5mmol)羟胺-O-(4-氟-3-苯氧基苯基)-甲基醚盐酸化物的20毫升无水乙醇加热至沸腾(薄层监测)。15小时后(薄层监测)冷却,滤去不溶物。用醋酸/水溶解吸收,有机相用水洗涤3次。经无水硫酸镁干燥后得到9.32克(95%)轻的不纯的油状物,此油状物经硅胶层析纯化,流动相为乙酸乙酯∶庚烷=1∶20
收率:8.75克(90%)分析纯油状物
沸点:367℃(气谱)
纯度(气谱)=98%
肟合成的通常方法
方法C:
将11.76克(50.04mmol)(6-丙基氧基吡啶-3-基)-三氟甲基酮与3.85克(55.7mmol)羟基胺盐酸盐和含3.48克(25.2mmol)碳酸钾的40ml乙醇加热回流8小时(薄层监测)。冷却至室温后在真空条件下(12Torr/40℃)蒸去乙醇。残渣用水溶解后再用乙酸乙酯多次萃取。经无水硫酸镁干燥后得到12.03克(96%)黄色蜡状物,它无须纯化即可使用。
所有的肟和肟醚可以用类似的方法合成。
在下表中基团Ar2简化用Ex(x=1-61)缩写表示
其它的含义给在下表中
M is 甲基
Et is 乙基
Bu is 丁基
t-Bu is 叔丁基
Ph is 苯基
物理数据和核磁共振谱数据
例号 熔点 沸点19F NMR
(℃) (℃;GC) (94.2MHz,CDCl3,CFCl3)
2 oil - syn:
-131.3(m,1F)
-66.6(s,3F)
6 oil - syn:
-131.8(m,1F)
-66.3(s,3F)
27 oil 367 syn:
-131.7(m,1F)
-74.1(t,3F)
-66.3(s,3F)
32 103 - syn:anti=96:4
syn: anti:
-131.9(m,1F)
-65.6(s,3F) -63.0
35 oil - syn:
-66.0(s)
48 oil - syn:anti=85:15
syn: anti:
-73.9(t,3F)
-66.3(s,3F) -63.0
58 oil - syn:
-74.1(t,3F)
-66.4(s,3F)
例号 熔点 沸点19F NMR
(℃) (℃;GC) (94.2MHz,CDCl3,CFCl3)
59 oil - syn:
-74.3(t,3F)
-66.8(s,3F)
62 oil - syn:
-74.3(t,3F)
-66.4(s,3F)
63 oil 373 syn:anti=57:43
syn: anti:
-130.6(m,1F)
-111.3(m,1F)
-66.4(s,3F) -62.8
64 oil - syn:
-130.6(m,1F)
-111.0(m,1F)
-74.3(t,3F)
-66.3(s,3F)
65 oil - syn:
-131.9(m,1F)
-120.3(m,1F)
-74.3(t,3F)
-66.3(s,3F)
66 oil - syn:anti=70:30
syn: anti:
-131.5(m,1F)
-120.0(m,1F)
-66.5(s,3F) -62.9
例号 熔点 沸点19F NMR
(℃) (℃;GC) (94.2MHz,CDCl3,CFCl3)
67 oil - syn:
-161.4(m,2F)
-151.8(m,1F)
-142.0(m,2F)
-66.8(s,3F)
70 oil - syn:anti=91:9
syn: anti:
-161.9(m,2F)
-152.4(m,1F)
-142.0(m,2F) -142.6
-66.3(s,3F) -62.8
72 oil - syn:anti=94:6
syn: anti:
-161.9(m,2F) -163.0
-152.5(m,1F) -154.9
-142.3(m,2F) -142.8
-66.3(s,3F) -62.9
73 oil - syn:
-161.8(m,2F)
-152.3(m,1F)
-142.2(m,2F)
-74.3(t,3F)
-66.4(s,3F)
91 oil - syn:anti=63:37
syn: anti:
-144.3(m,4F)
-66.5(s,3F) -62.8
例号 熔点 沸点19F NMR
(℃) (℃;GC) (94.2MHz,CDCl3,CFCl3)
syn:anti=66:34-
92 oil - syn:anti=66:34
syn: anti:
-144.3(m,4F)
-66.5(s,3F) -62.8
syn-
92 oil - syn:
-144.0(m,4F)
-66.4(s,3F)
96 oil - syn:
-144.3(m,4F)
-66.4(s,3F)
97 oil - syn:
-144.2(m,4F)
-66.3(s,3F)
99 oil 361 syn:anti=94:6
syn: anti:
-145.0(m,2F)
-143.8(m,2F)
-66.3(s,3F) -62.8
104 oil 306 syn:
-144.3(m,4F)
-74.0(t,3F)
-66.0(s,3F)
108 103 - syn:anti=93.7
syn: anti:
-144.5(m,4F)
-65.8(s,3F) -62.9
例号 熔点 沸点19F NMR
(℃) (℃;GC) (94.2MHz,CDCl3,CFCl3)
121 oil 328 syn:
-158.0(m,2F)
-144.3(m,2F)
-66.5(s,3F)
125 oil - syn:
-158.5(m,2F)
-144.1(m,2F)
-66.5(s,3F)
127 oil - syn:anti=90:10
syn: anti:
-158.9(m,2F)
-144.3(m,2F)
-66.1(s,3F) -62.8
130 oil - syn:
-158.3(m,2F)
-144.4(m,2F)
-66.4(s,3F)
131 oil - syn:anti=93:7
syn: anti:
-158.0(m,2F)
-144.1(m,2F)
-66.5(s,3F) -62.7
141 oil - syn:anti=61:39
syn: anti:
-142.8(m,2F)
-134.3(m,2F)
-66.6(s,3F) -62.7
例号 熔点 沸点19F NMR
(℃) (℃;GC) (94.2MHz,CDCl3,CFCl3)
145 oil - syn:
-142.8(m,2F)
-134.8(m,2F)
-66.3(s,3F)
148 oil - syn:
-143.0(m,2F)
-134.5(m,2F)
-74.5(m,2F)
-66.5(s,3F)
153 semi-solid - syn:
-138.8(m,2F)
-136.5(m,2F)
-74.3(t,3F)
-66.5(s,3F)
201 semi-solid - syn:anti=64:36
syn: anti:
-142.5(m,4F)
-66.5(s,3F) -62.7
208 oil - syn:
-142.3(m,4F)
-74.5(t,3F)
-66.4(s,3F)
244 oil syn:anti=64:36
syn: anti:
-142.1(m,4F)
-66.6(s,3F) -62.8
例号 熔点 沸点19F NMR
(℃) (℃;GC) (94.2MHz,CDCl3,CFCl3)
247 oil - syn:
-142.3(s,3F)
-74.3(t,6F)
-66.5(s,6F)
250 oil - syn:
-109.3(m,2F)
-74.3(t,3F)
-66.5(s,3F)
252 oil syn:
-113.5(m,1F)
-108.8(m,1F)
-74.2(t,3F)
-66.3(s,3F)
254 oil - syn:
-114.5(m,2F)
-74.1(t,3F)
-66.3(s,3F)
258 oil - syn:
-113.3(m,1F)
-74.3(t,3F)
-66.3(s,3F)
261 oil - syn:
-137.8(m,2F)
-74.1(t,3F)
-66.5(s,3F)
例号 熔点 沸点19F NMR
(℃) (℃;GC) (94.2MHz,CDCl3,CFCl3)
264 oil - syn:
-142.9(m,1F)
-138.2(m,1F)
-74.3(t,3F)
-66.4(s,3F)
267 oil - syn:
-124.1(m,1F)
-118.8(m,1F)
-74.3(t,3F)
-66.4(s,3F)
270 oil - syn:
-113.4(m,2F)
-105.8(m,1F)
-74.3(t,3F)
-66.4(s,3F)
274 oil - syn:anti=59:41
syn: anti:
-137.3(m,2F)
-88.6(m,2F)
-66.5(s,3F) -63.0
275 oil - syn:
-137.3(m,2F)
-87.8(m,2F)
-66.3(s,3F)
276 oil - syn:
-137.1(m,2F)
-88.5(m,2F)
-74.4(t,3F)
-66.5(s,3F)
例号 熔点 沸点19F NMR
(℃) (℃;GC) (94.2MHz,CDCl3,CFCl3)
285 oil - syn:
-74.3(t,3F)
-66.3(s,3F)
288 oil - syn:
-74.1(t,3F)
-66.3(s,3F)
361 oil - syn:
-131.6(m,1F)
-65.6(s,3F)
363 oil - syn:
-144.4(m,4F)
-65.6(s,3F)
378 oil - syn:
-131.5(m,1F)
-65.5(s,3F)
380 108-110 - syn:
-144.3(m,4F)
-65.5(s,3F)
384 oil - syn:
-131.6(m,1F)
-65.6(s,3F)
386 oil - syn:anti=84:16
syn: anti:
-144.2(m,4F)
-65.8(s,3F) -60.5
397 72 - syn:
-162.5(m,2F)
-154.0(m,1F)
例号 熔点 沸点19F NMR
(℃) (℃;GC) (94.2MHz,CDCl3,CFCl3)
-142.5(m,2F)
-74.3(t,3F)
398 71 - syn:
-144.7(m,4F)
-74.3(t,3F)
402 oil - syn:
-131.6(m,1F)
-74.0(t,3F)
403 oil - syn:
-74.3(t)
404 oil - syn:
-74.2(t)
405 oil - syn:
-162.8(m,2F)
-154.1(m,1F)
-146.3(m,2F)
-74.3(t,3F)
406 oil - syn:
-145.0(m,4F)
-74.0(t,3F)
407 oil - syn:
-157.4(m,2F)
-143.6(m,2F)
-74.3(t,3F)
-66.5(s,3F)
例号 熔点 沸点19F NMR
(℃) (℃;GC) (94.2MHz,CDCl3,CFCl3)
429 oil - syn:
-162.9(m,2F)
-154.3(m,1F)
-142.5(m,2F)
430 oil - syn:
-144.9(m)
432 oil - syn:
-143.0(m,2F)
-135.4(m,2F)
454 oil - syn:
-74.3(t,3F)
-66.4(s,3F)
458 oil - syn:
-74.1(t,3F)
-66.3(s,3F)
460 oil - syn:
-74.4(t,3F)
-66.5(s,3F)
462 oil - syn:
-66.5(s,3F)
-60.0(s,3F)
464 oil - syn:
-66.0(s,3F)
-60.3(s,3F)
465 oil - syn:
-74.3(t,3F)
-66.5(s,3F)
-60.3(s,3F)
例号 熔点 沸点19F NMR
(℃) (℃;GC) (94.2MHz,CDCl3,CFCl3)
syn:anti=57:43-
466 oil - syn:anti=57:43
syn: anti:
-66.6(s,3F)
-63.5(s,3F) -63.5
468 oil - syn:
-66.3(s,3F)
-63.3(s,3F)
469 oil - syn:
-74.2(t,3F)
-66.5(s,3F)
-63.2(s,3F)
470 oil - syn:
-66.5(s,3F)
-63.1(s,3F)
471 oil - syn:
-65.8(s,3F)
-63.1(s,3F)
472 oil - syn:
-66.5(s,3F)
-63.0(s,3F)
473 oil 301 syn:
-74.3(s,3F)
-66.4(s,3F)
-63.0(s,3F)
例号 熔点 沸点19F NMR
(℃) (℃;GC) (94.2MHz,CDCl3,CFCl3)
474 98 - syn:
-74.3(t,3F)
-66.4(s,3F)
475 oil - syn:anti=87:13
syn: anti:
-66.0(s) -62.9
477 oil - syn:
-66.3(s)
478 oil - syn:
-74.2(t,3F)
-66.3(s,3F)
480 oil - syn:
-73.9(t,3F)
-66.4(s,3F)
481 oil - syn:
-74.1(t,3F)
-66.3(s,3F)
485 oil - syn:
-74.3(t,3F)
-66.5(s,3F)
-58.3(s,3F)
489 oil - syn:
-74.3(t,3F)
-66.4(s,3F)
-58.1(s,3F)
493 oil - syn:
-74.5(t,3F)
-66.5(s,3F)
例号 熔点 沸点19F NMR
(℃) (℃;GC) (94.2MHz,CDCl3,CFCl3)
496 oil - syn:
-66.0(s,3F)
497 oil - syn:
-74.3(t,3F)
-66.3(s,3F)
502 oil - syn:
-66.5(s,3F)
506 oil - syn:
-66.0(s,3F)
507 51 368 syn:
-74.3(t,3F)
-66.3(s,3F)
513 oil - syn:
-66.3(s,3F)
514 68 - syn:
-74.3(t,3F)
-66.3(s,3F)
517 oil - syn:
-66.5(s,3F)
518 104 - syn:
-74.5(t,3F)
-66.5(s,3F)
764 oil - syn:
-144.3(m,4F)
-66.8(s,3F)
例号 熔点 沸点19F NMR
(℃) (℃;GC) (94.2MHz,CDCl3,CFCl3)
765 oil - syn:
-158.6(m,2F)
-144.3(m,2F)
-66.6(s,3F)
766 oil - syn:
-143.0(m,2F)
-134.5(m,2F)
-67.0(s,3F)
778 oil - syn:
-144.3(m,4F)
-66.8(s,3F)
779 56 - syn:
-158.5(m,2F)
-144.3(m,2F)
-66.5(s,3F)
785 oil - syn:
-66.4(s,3F)
791 53 - syn:
-74.4(m,4F)
-66.8(s,3F)
804 oil - syn:anti=90:10
syn: anti:
-144.5(m,4F)
-103.0(m,1F)
-66.1(s,3F) -62.5
805 oil - syn:
-158.3(m,2F)
例号 熔点 沸点19F NMR
(℃) (℃;GC) (94.2MHz,CDCl3,CFCl3)
-142.5(m,2F)
-103.0(m,1F)
-66.5(s,3F)
817 oil 328 syn:
-143.4(m,4F)
-66.5(s,3F)
818 oil 335 syn:
-158.5(m,2F)
-144.3(m,2F)
-66.3(s,3F)
syn-
819 oil - syn:
-142.9(m,2F)
-137.8(m,2F)
-66.4(s,3F)
syn:anti=87:13-
819 oil - syn:anti=87:13
syn: anti:
-142.9(m,2F)
-137.8(m,2F)
-66.4(s,3F) -62.5
824 oil - syn:
-66.2(s,3F)
-62.9(s,3F)
825 oil - syn:
-65.8(s,3F)
例号 熔点 沸点19F NMR
(℃) (℃;GC) (94.2MHz,CDCl3,CFCl3)
826 oil - syn:
-66.5(s,3F)
-56.0(s,3F)
831 oil - syn:anti=59:41
syn: anti:
-144.4(m,4F)
-66.3(s,3F) -62.5
832 oil - syn:anti=59.41
syn: anti:
-158.5(m,2F)
-144.4(m,2F)
-66.4(s,3F) -62.3
838 oil - syn:anti=66:34
syn: anti:
-66.4(s,3F) -62.0
845 oil - syn:anti=89:11
syn: anti:
-144.5(m,4F)
-81.6(md,2F)
-66.5(s,3F) -62.5
846 oil - syn:
-158.5(m,2F)
-144.3(m,2F)
-81.8(md,2F)
-66.5(s,3F)
852 oil - syn:
-81.9(md,2F)
-66.5(s,3F)
例号 熔点 沸点19F NMR
(℃) (℃;GC) (94.2MHz,CDCl3,CFCl3)
859 oil - syn:
-144.3(m,4F)
-66.6(s,3F)
-58.3(s,3F)
860 oil 295 syn:
-158.5(m,2F)
-144.4(m,2F)
-66.9(s,3F)
-58.5(s,3F)
866 oil - syn:
-66.4(s,3F)
-58.0(s,3F)
872 oil - syn:
-161.9(m,2F)
-152.1(m,1F)
-142.0(m,2F)
-74.3(t,3F)
-66.5(s,3F)
873 oil - syn:
-144.4(m,4F)
-74.3(t,3F)
-66.4(s,3F)
874 oil - syn:
-74.3(t,3F)
-66.8(s,3F)
879 oil - syn:
-74.3(t,3F)
-66.5(s,3F)
例号 熔点 沸点19F NMR
(℃) (℃;GC) (94.2MHz,CDCl3,CFCl3)
886 oil - syn:
-144.4(m,4F)
-66.5(s,3F)
892 oil - syn:
-66.5(s,3F)
898 oil - syn:anti=80:20
syn: anti:
-144.5(m,4F)
-66.6(s,3F) -62.8
911 oil - syn:
-145.0(m,4F)
-62.0(s,3F)
anti- oil - anti:
917 -144.8(m,4F)
-113.0(m,1F)
syn:anti-
917 oil - syn:anti=50:50
syn: anti:
-144.8(m,4F)
-112.3(m,1F) -113.0
syn:anti=12:88-
918 63 syn:anti=12:88(1H)
-159.0(m,2F)
-144.5(m,2F)
-113.0(m,1F)
924 oil - syn:
-144.6(m,4F)
例号 熔点 沸点19F NMR
(℃) (℃;GC) (94.2MHz,CDCl3,CFCl3)
932 oil - syn:
-144.7(m,4F)
938 oil - syn:
-132.3(m,1F)
-120.0(m,1F)
-66.6(s,3F)
-63.5(s,3F)
939 oil - syn:
-130.8(m,1F)
-111.5(m,1F)
-66.8(s,3F)
-63.8(s,3F)
942 oil - syn:
-144.3(m,4F)
-67.0(s,3F)
-63.8(s,3F)
943 oil - syn:
-158.5(m,2F)
-144.3(m,2F)
-66.9(s,3F)
-63.8(s,3F)
944 oil - syn:
-143.0(m,2F)
-134.5(m,2F)
-66.8(s,3F)
-63.8(s,3F)
例号 熔点 沸点19F NMR
(℃) (℃;GC) (94.2MHz,CDCl3,CFCl3)
945 oil - syn:
-144.2(m,4F)
-65.9(s,3F)
949 oil - syn:
-66.5(s,3F)
-63.5(s,3F)
950 oil - syn:
-74.3(t,3F)
-66.7(s,3F)
-63.3(s,3F)
954 oil - syn:
-66.1(s,3F)
955 oil - syn:
-66.4(s,3F)
-63.5(s,3F)
958 oil - syn:
-65.7(s,3F)
959 66 - syn:
-66.0(s,3F)
syn-
987 oil - syn:
-66.5(s,3F)
syn:anti=88:12-
987 oil - syn:anti=88:12
syn: anti:
-66.5 -63.0
例号 熔点 沸点19F NMR
(℃) (℃;GC) (94.2MHz,CDCl3,CFCl3)
988 oil - syn:
-74.4(t,3F)
-66.3(s,3F)
989 oil - syn:
-142.3(m,1F)
-137.3(m,1F)
-119.5(s,3F)
-74.3(t,3F)
-66.5(s,3F)
993 oil - syn:
-74.2(t,3F)
-66.3(s,3F)
994 93 - syn:
-74.0(t,3F)
-66.1(s,3F)
995 oil - syn:
-74.0(t,3F)
-66.4(s,3F)
996 oil - syn:
-74.0(t,3F)
-66.6(s,3F)
997 oil - syn:
-74.3(t,3F)
-66.4(s,3F)
998 oil - syn:
-74.3(m,6F)
-66.3(s,3F)
例号 熔点 沸点19F NMR
(℃) (℃;GC) (94.2MHz,CDCl3,CFCl3)
1028 oil - syn:anti=75:25
syn: anti:
-161.6(m,2F)
-151.8(m,1F)
-138.1(m,2F) -137.0
-114.0(m,2F) -115.5
-74.3(t,3F)
1029 oil - syn:anti=75:25
syn: anti:
-144.5(m,4F)
-138.5(m,2F) -137.0
-114.1(m,2F) -115.8
-73.3(t,3F)
1030 oil - syn:anti=70:30
syn: anti:
-158.0(m,2F)
-143.3(m,2F)
-138.5(m,2F) -137.0
-114.0(m,2F) -115.8
-74.3(t,3F)
1036 oil - syn:anti=54:46
syn: anti:
-138.0(m,2F) -137.0
-113.9(m,2F) -116.0
-74.3(t,3F)
-63.3(s,3F)
例号 熔点 沸点19F NMR
(℃) (℃;GC) (94.2MHz,CDCl3,CFCl3)
1093 oil - syn:
-144.1(m,4F)
1094 oil - syn:anti=75:25(1H)
-158.3(m,2F)
-144.5(m,2F)
1095 oil - syn:
-103.0(m,1F)
-66.8(s,3F)
-63.0(s,3F)
1096 oil - syn:anti=80:20(1H)
-63.0(s,3F)
1098 86-88 - syn:
-66.0(s,3F)
1099 oil - syn:
-66.4(s,3F)
1100 oil - syn:
-66.0(s,3F)
1101 oil - syn:
-142.6(m,1F)
-137.3(m,1F)
-119.3(m,3F)
-66.3(s,3F)
1105 oil - syn:
-111.5(m,2F)
-106.3(m,1F)
-66.2(s,3F)
例号 熔点 沸点19F NMR
(℃) (℃;GC) (94.2MHz,CDCl3,CFCl3)
syn:anti=14:86-
1137 oil - syn:anti=14:86(1H)
-144.7(m,4F)
syn:anti=49:51-
1137 oil - syn:anti=49:51(1H)
-145.0(m,4F)
1201 oil - syn:
-144.3(m,4F)
-112.9(m,1F)
-66.5(s,3F)
1207 oil - syn:
-113.0(m,1F)
-66.3(s,3F)
1210 oil - syn:
-144.4(m,4F)
-127.5(m,1F)
-66.6(s,3F)
1216 oil - syn:
-127.3(m,1F)
-66.5(s,3F)
1219 oil - syn:anti=92:8
syn: anti:
-144.4(m,4F)
-66.2(s,3F) -62.5
1228 oil - syn:
-144.3(m,4F)
-66.8(s,3F)
-63.5(s,3F)
例号 熔点 沸点19F NMR
(℃) (℃;GC) (94.2MHz,CDCl3,CFCl3)
1234 oil - syn:
-66.4(s,3F)
-63.3(s,3F)
1291 oil - syn:
-145.3(m,4F)
-65.3(s,3F)
1318 oil - syn:anti=33:67(1H)
-145.5(m,4F)
1324 oil - syn:anti=35:65(1H)
1390 75-80 - -144.3(m,4F)
1396 121-123 - ┄
1426 oil - syn:
-131.8(m,1F)
-65.1(s,3F)
1427 oil - syn:
-65.3(s,3F)
1433 oil - syn:
-65.3(s,3F)
1437 oil - -145.0(s,4F)
1438 oil - -158.8(m,2F)
-144.3(m,2F)
生物实施例
例1
在培养皿盖子的内侧和培养皿底部均匀涂抹1ml供试制剂的水乳液,待药液干后放入10只家蝇成虫,培养皿盖好之后于室温下保存,3小时后确定供试家蝇的死亡率。在250ppm(以有效成分含量计)时编号为 6,27,32,35,48,58,62至67,72,73,91,顺式-92,(顺式∶反式=63∶37)-92,96,97,104,108,127,141,145,148,153,169,208,244,250,252,254,258,261,264,267,275,276,285,288,361,397,398,402至407,429,430,432,454,458,464,465,466,468,469,470,471,472,473,474,477,480,481,485,493,496,497,506,507,513,517,764至766,804,805,817,818,顺式-819,824,831,832,838,845,852,859,860,866,872,873,874,879,892,898,911,924,932,938,939,942,943,944,949,958,959,987,988,989,993,994,995,996,997,998,1029,1030,1094,1098,1099,1101,1105,(顺式∶反式=14∶86)-1137,(顺式∶反式=49∶51)-1137,1318,1426,1427,1433,1437和1438。的制剂对家蝇显示了优良的效果(死亡率100%)。
例2
将水稻种子置于培养玻璃器皿内湿润的脱脂棉上让其发芽,当秧苗长至连叶片计算茎高大约8厘米高时将其转放入供试药液中。待药液滴落之后将处理的秧苗分离出,按照试验浓度放入到培养容器中,每个容器内放入10只稻褐飞虱的幼虫。将封闭的容器置于21℃下保持4天后检查蝉幼虫的死亡率。
在上述试验条件下编号为 27,48,58,64,65,顺式-92,96,97,104,125,127,145,148,208,402,403,406,407,478,507,791,804,817,818,顺式-819,(顺式∶反式=87∶13)-819,825,826,831,832,845,852,859,860,866,873,874,879,892,(顺式∶反式=50∶50)-917,924,932,938,942,949,959,987,996,1029,1101,1105,(顺式∶反式=14∶86)-1137和1201的供试化合物在有效成分浓度为250ppm时药效100%。
例3
小麦种子于水中预发芽6小时,然后转入10ml试管中,每个用2ml土复盖。加入1ml水,在室温下待幼苗长至大约3Cm高时,向每只试管的土层上引入10只瓜十一星叶甲幼虫,2小时后向每只试管的土层表滴入1ml一定浓度的供试化合物溶液。在实验室条件下(21℃)放置5天后在试管内的土中寻找存活的叶甲幼虫並确定死亡率。
试验证实在所给的试验条件下编号为
2,27,48,58,59,63 to 65,67,72,73,顺式-92,(顺式∶反式=63∶27)-92,96,97,104,121,125,127,148,169,208,250,254,258,261,267,274,363,380,402至407,429,430,469,474,481,817,831,845,852,859,860,866,873,924,942,943,987,1101,(顺式∶反式=14∶86)-1137和(顺式∶反式=49∶51)-1137的化合物当供试药液有效成分浓度为250ppm时药效为100%。
例4
用有效成分浓度为250ppm的可湿性粉剂水稀释液喷洒处理被黑豆蚜严重侵染的蚕豆直至有液滴开始往下滴落。3天后确定蚜虫死亡率。使用编号为 27,48,58,96,97,148,402至404,406,407,470,506,791,817,818,顺式-819,825,826,838,852,859,860,866,873,874,879,898,924,938,939,942,944,949,987,1101,(顺式∶反式=14∶86)-1137和(顺式∶反式=49∶50)-1137.的化合物可取得100%的致死率。
例5
用有效成分浓度为250ppm的可湿性粉剂的水稀释液喷洒被豆螨严重侵染的豆株,7天后调查死亡率,用编号为35,58,402至404,454,506,818,866,879和949的化合物可取得100%的致死率。
例6
用0.5ml供试剂型的水稀释液处理载有棉花马利筋长蝽卵的滤纸片,待药液干后,封住培养皿,其内部维持最大空气湿度。在室温下保存7天后调查药剂的杀卵和杀幼虫作用。用有效成分浓度为500ppm的编号为27,58,64,67,70,73,92,96,127,145,148,208,250,402至407,429,496,497和817的化合物可取得100%的死亡率。
Claims (16)
1、顺式,反式或顺反混合形式的式1化合物或它们的盐,
式中
Ⅰ.Ar1和Ar2是相同的或不同的,并代表
a)(C8-C12)-芳基或是带多至10个碳原子的杂芳基,或
b)如在1.a)中所确定的含义,必要时被选自下列中5个相同或不同的取代基取代:
1.(C1-C8)-烷基,
2.(C2-C6)-链烯基,
3.(C2-C6)-炔基,
4.(C3-C8)-环烷基,有时被多至6个相同的或不同的选自卤素和(C1-C4)-烷基基团取代,
5.卤素,
6.(C1-C6)-卤代烷基,
7.(C2-C6)-卤代链烯基,
8.(C2-C6)-卤代炔基,
9.(C1-C6)-烷氧基-(C1-C6)-烷基,
10.(C6-C12)-芳基,有时被选自(C1-C6)-烷基,(C1-C6)-烷氧基,卤素,(C1-C6)-卤代烷基和(C1-C8)-卤代烷氧基的相同或不同的基团取代三次,
11.带多至10个碳原子的杂芳基,有时如1.b)10发生取代,
12.(C6-C12)-芳基-(C1-C4)-烷基,在芳基部分有时如1.b)10.发生取代,
13.在芳基部分带有多至10个碳原子的杂芳基-(C1-C4)-烷基,它有时也如1.b)10.发生取代,
14.(C1-C6)-烷氧基,
15.(C2-C6)-链烯基氧基,
16.(C2-C6)-炔基氧基,
17.(C3-C8)-环烷基氧基,有时如1.b)4.发生取代,
18.(C1-C6)-烷氧基-(C1-C4)-烷氧基,
19.(C6-C12)-芳基氧基,有时如1.b)10.发生取代,
20.带多至10个碳原子的杂芳基氧基,有时如1.b)10.发生取代,
21.(C1-C6)-卤代烷氧基,
22.(C2-C6)-卤代链烯基氧基,
23.(C2-C6)-卤代炔基氧基,
24.-O-N=CR′2,式中R′代表相同的或不同的选自氢,(C1-C6)-烷基,(C3-C8)-环烷基和(C6-C12)-芳基的基团,
25.(C1-C6)-烷基氨基,
26.二-(C1-C6)-烷基氨基,
27.(C3-C8)-环烷基氨基,有时如1.b)4.发生取代,
28.(C6-C12)-芳基氨基,有时如1.b)10.发生取代,
29.带多至10个碳原子的杂芳基氨基,有时如1.b)10.发生取代,
30.(C1-C6)-烷基氢硫基,
31.(C6-C12)-芳基氢硫基,
32.带多至10个碳原子的杂芳基氢硫基,
33.(C1-C6)-烷基亚磺酰基,
34.(C6-C12)-芳基亚磺酰基,
35.带多至10个碳原子的杂芳基亚磺酰基,
36.(C1-C6)-烷基磺酰基,
37.(C6-C12)-芳基磺酰基,
38.带多至10个碳原子的杂芳基磺酰基,
39.硝基,
40.氰基,
41.氰基-(C1-C6)-烷基,
42.(C1-C6)-烷氧基羰基,
43.(C6-C12)-芳基氧基羰基和
44.在杂芳基部分带多至10个碳原子的杂芳基氧基羰基,或
45.a)取代基中的2个代表甲二氧基,
b)甲氧基有时带1个或2个相同或不同的选自卤素和(C1-C4)-烷基的取代基;
Ⅱ.R代表a)(C1-C6)-烷基,
b)(C2-C6)-链烯基
c)(C2-C6)-炔基或
d)(C3-C8)-环烷基,或
e)如在11.a)-d)中所确定的含义,带有多至2个相同或不同的选自下面的取代基
1.卤素,
2.羟基,
3.(C1-C6)-烷氧基,
4.(C1-C6)-烷基氢硫基,
5.(C1-C6)-烷基亚磺酰基,
6.(C1-C6)-烷基磺酰基,
7.氰基,
8.硝基和
9.(C1-C6)-烷氧基羰基,或
f)如在11.a)-d)中所确定的含义,如果氢原子数≥
5,它们是部分地或完全被卤素取代,卤原子数是≥4;在1.a)和b)中确定了含义的芳基和杂芳基也可以部分氢化,其中1个或2个CH2-基团能被CO取代;
Ⅲ.条件是:
a)如果R是甲基或取代甲基,它带有1,2或3个相同或不同的如在Ⅱ.e)1.或3-9中所定义的基团,其中至少有一个基团是卤素,和如果Ar1是如在1.b)2-4.,7.,8.,11.,13.,15.-44或45.b)中的基团取代的芳基,或有时是取代的杂芳基,那么Ar2是如在1.a)或b)中所确定的含义,
b)如果R是甲基或取代的甲基,它带有1,2或3个相同或不同的如在11.e)1.或3.-9.中所定义的基团,其中至少有一个基团是卤素,和如果Ar1是如在Ⅰ.b)1.,5.,6.,9.,10.,12.,14.,或45a)中的基团取代的芳基,那么Ar2如在1.a)或b)中所确定的含义,但不是4-氟-3-苯氧基苯基,3-苯氧基苯基,五氟代苯基或2,6-二卤代苯基;
c)如果R是(C2-C6)-烷基或是如在Ⅱ.b)-f)中所确定的含义和如果Ar1是如在1.a)中所确定的含义,或如在1.b)中确定了含义的芳基或如在1.b)1.-20.或24.-45.)中确定了含义的杂芳基,那么Ar2是如在1.a)和b)中所确定的含义,但不是
2,6-二卤代苯基,五氟代苯基,
式中
Z是卤素或氢,
Q是O,S,NH或CH2,
R4是卤素,
X是O或S,
R10,R11和R12相同或不同,代表氢或如在1.b)1.-45.中所确定的含义,
R13是氢,氟或甲基,
O是0,1或2,
R6是氢,氟或烷基,
R7是卤代苯氧基,卤代苄基,O-CH2-CH=CH2,O-CH2-C≡CH;CH2-CH=CH2或CH2-C≡CH和
R8是链烯基或卤代链烯基;
d)如果R是(C2-C6)-烷基或如在Ⅱ.b)-f)中所确定的含义和如果Ar1是如在Ⅰ.b)21.-23.所确定含义的杂芳基,那么Ar2此外还能有在Ⅰ.a)和b)中已确定的含义;
e)如果R是(C2-C6)-烷基或如在Ⅱ.b)-f)中所确定的含义和如果Ar1是如在1.a)或b)中确定含义的杂芳基,那么Ar2此外还可有五氟代苯基的含义或
式中R13和O有上面所给定的含义;
f)如果R是如在Ⅱ.e)中确定含义的取代的(C2-C6)-烷基,(C2-C6)-链烯基或(C2-C6)-炔基和如果Ar1是如在1.a)或b)中确定含义的芳基,那么Ar2此外还有下式的含义
式中R13和O具有上面所确定的含义;和
g)如果R是(C2-C6)-烷基或如在Ⅱ.b)-f)中所确定的含义和如果Ar1是如在Ⅰ.b)21.中所定义的取代的(C6-C12)-芳基,那么Ar2此外还可以是五氟代苯基。
2、根据权利要求1的化合物或它们的盐,式中
Ar1是苯基,萘基,茚满基,苯并呋喃基,苯并噻嗯基,
这些基团有时发生如在权利要求1中所定义的取代,和式中X是O,S或NR3和
R3是氢,
(C1-C6)-烷基,
(C2-C6)-链烯基,优选-CH2-CH2=CH2,
(C2-C6)-炔基,优选-CH2-C=CH,
(C3-C8)-环烷基,有时被多至6个相同或不同的选自卤素和(C1-C4)-烷基的基团取代,
(C1-C6)-卤代烷基,
(C2-C6)-卤代链烯基,
(C2-C6)-卤代炔基,
(C1-C6)-烷氧基-(C1-C6)-烷基,
(C6-C12)-芳基-(C1-C4)-烷基,
杂芳基-(C1-C4)-烷基,其杂芳基部分带有多至10个碳原子,
氰基-(C1-C6)-烷基,
(C1-C6)-烷氧基羰基,
(C6-C12)-芳基氧基羰基或
带多至10个碳原子的杂芳基氧基羰基,
3、根据权利要求1或2的化合物或它们的盐,式中
Ar1是下式所示的一个基团
X 是如在权利要求2中定义,
P 是一个0至5的整数,和
R1是相同的或不同的,并代表
卤素,
(C1-C6)-烷基,
(C2-C6)-链烯基,
(C2-C6)-炔基,
(C3-C8)-环烷基,有时被多至6个相同或不同的选自卤素和(C1-C4)-烷基的基团取代,
(C1-C6)-卤代烷基,
(C2-C6)-卤代链烯基,
(C2-C6)-卤代炔基,
(C1-C6)-烷氧基-(C1-C6)-烷基,
(C6-C12)-芳基,有时被多至3个相同或不同的选自卤素,(C1-C6)-烷基,(C1-C6)-烷氧基,(C1-C6)-卤代烷基和(C1-C6)-卤代烷氧基的基团取代,
带多至10个碳原子的杂芳基,有时发生如上面所述芳基的取代,
(C6-C12)-芳基-(C1-C4)-烷基,在芳基部分有时发生如上面所述芳基的取代,
在杂芳基部分带有多至10个碳原子的杂芳基-(C1-C4)-烷基和有时发生如上面所述芳基的取代,
(C1-C6)-烷氧基,
(C2-C6)-链烯基氧基,
(C2-C6)-炔基氧基,
(C3-C8)-环烷基氧基,
(C1-C6)-烷氧基-(C1-C6)-烷氧基,
(C6-C12)-芳基氧基,有时发生如上面所述的芳基的取代,
带多至10个碳原子的杂芳基氧基,有时发生如上面所述的芳基的取代,
(C1-C6)-卤代烷氧基,
(C2-C6)-卤代链烯基氧基,
(C2-C6)-卤代炔基氧基或
-O-N=CR′2,式中R是相同的或不同的选自氢,(C1-C6)-烷基,(C3-C8)-环烷基和(C6-C12)-芳基的基团,或
对于R1有时是如在1.b)45.b)中取代的亚甲二氧基基团的2个基团,
4、根据权利要求3的化合物或它们的盐,式中R1是(C1-C6)-烷基,(C2-C6)-链烯基,(C2-C6)-炔基,(C3-C8)-环烷基,卤素,(C1-C6)-卤代烷基,(C2-C6)-卤代链烯基,(C2-C6)-卤代炔基,有时如在权利要求3中取代的(C6-C12)-芳基或带多至10个碳原子的杂芳基,(C1-C6)-烷氧基,(C2-C6)-链烯基氧基,(C2-C6)-炔基氧基,(C3-C8)-环烷基氧基,有时如在权利要求3中取代的(C6-C12)-芳基氧基或带多至10个碳原子的杂芳基氧基,(C1-C6)-烷氧基-(C1-C6)-烷基,(C1-C6)-烷氧基-(C1-C6)-烷氧基,(C1-C6)-卤代烷氧基,(C2-C6)-卤代链烯氧基或(C2-C6)-卤代炔基氧基,或对于R1有时是如在1.b)45.a和b中取代的亚甲二氧基基团中的2个基团。
5、根据权利要求3或4的化合物或它们的盐,在式中R1是(C1-C6)-卤代烷氧基,如OCHF2,OCF3CF2H,OCH2CF3或OCH(CF3)2,(C1-C6)-烷氧基,氟,氯,溴,(C1-C6)-烷基,(C1-C6)-卤代链烯基氧基,(C2-C6)-卤代炔基氧基,(C1-C6)-卤代烷基,(C2-C6)-卤代链烯基,(C2-C6)-卤代炔基。
7、根据权利要求1至6的一项所述的化合物或它们的盐,式中R是(C1-C6)-烷基或(C3-C8)-环烷基,它们可以部分地或全部地用卤素取代。优选(C1-C6)-烷基,它们可以被多至3个氟取代。
8、根据权利要求2至7的一项中的化合物或它们的盐,式中Ar2特别具有下面含义:
和式中
A,B和C是相同和不同并且是N、CH或C-卤素,
Q是O,S,NH或CH2,优选O或CH2,
R4是氢,卤素,O-CH2-CH=CH2或O-CH2-C≡CH,
优选氢,4-F,3-F,4-Cl
Hal 代表卤素,
R9是氢或如在权利要求3中R1的含义,
m和n是相同的或不同的,代表1,2,3或4m+n=5
R5是氢或如在权利要求2中的R1的含义,
q,r,s是相同或不同的,是1,2或3,
q+r+s=5
R3如上面的含义,
R10,R11和R12如上面的含义,优选CH3,CF3,CN,苯基,CH2CH=CH2,-CH2-C≡CH或苄基,
R13是氢,氟或甲基,
O 是1或2,
R6是氢,氟或(C1-C6)-烷基,
R7是卤代苯氧基,卤代苄基,O-CH2-CH=CH2,O-CH2-C≡CH,CH2-CH=CH2或CH2-C≡CH和
R8是(C2-C6)-链烯基或(C2-C6)-卤代链烯基。
9、根据权利要求1至8的一项中的化合物或它们的盐,式中Ar1有时是取代的杂芳基和R是三氟甲基。
10、根据权利要求1至9的一项中的化合物或它们的盐,式中Ar2是如在权利要求8中B.c),B.d),C.b),C.c)或C.d)中的含义。
11、根据权利要求1至10的一项中的化合物或它们的盐,式中Ar1有时是取代的芳基或杂芳基,Ar2是如在权利要求8中D.或E.中的含义和R是三氟甲基。
13、含有至少一个按照权利要求1至11的一项中的化合物及常规的添加剂和助剂物质的杀虫剂,杀螨剂或杀线虫剂。
14、防治害虫,螨类和线虫的方法,其中对这些有害生物或被它们侵染的植物,表面或基质上施用一有效量的按照权利要求1至11的一项中的一个化合物。
15、按照权利要求1至11的一项中的化合物在防治害虫,螨类和线虫中的用途。
16、按照权利要求1至11的一项中的化合物在防治体内外寄生虫和线虫中的用途。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEP4213149.9 | 1992-04-22 | ||
DE4213149A DE4213149A1 (de) | 1992-04-22 | 1992-04-22 | Akarizide, insektizide und nematizide substituierte (Hetero)-Aryl-Alkyl-ketonoxim-O-ether, Verfahren zu ihrer Herstellung, sie enthaltende Mittel und ihre Verwendung als Schädlingsbekämpfungsmittel |
Publications (1)
Publication Number | Publication Date |
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CN1077709A true CN1077709A (zh) | 1993-10-27 |
Family
ID=6457192
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CN93104615A Pending CN1077709A (zh) | 1992-04-22 | 1993-04-21 | 取代(杂)-芳基-烷基-酮肟-o-醚类的杀螨剂、杀虫剂和杀线虫剂 |
Country Status (17)
Country | Link |
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US (2) | US5646147A (zh) |
EP (1) | EP0638069A1 (zh) |
JP (1) | JP2931407B2 (zh) |
KR (1) | KR0173146B1 (zh) |
CN (1) | CN1077709A (zh) |
AU (1) | AU3953593A (zh) |
BR (1) | BR9306285A (zh) |
CA (1) | CA2134099A1 (zh) |
DE (1) | DE4213149A1 (zh) |
HU (1) | HUT69308A (zh) |
IL (1) | IL105462A0 (zh) |
MA (1) | MA22877A1 (zh) |
OA (1) | OA10106A (zh) |
PL (1) | PL171344B1 (zh) |
RU (1) | RU94046033A (zh) |
WO (1) | WO1993021157A2 (zh) |
ZA (1) | ZA932788B (zh) |
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CN111978268A (zh) * | 2019-05-24 | 2020-11-24 | 湖南大学 | 1-(4-氯苯基)-2-环丙基丙酮肟噁唑甲基醚及其应用 |
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US6358883B1 (en) * | 1998-11-16 | 2002-03-19 | American Cyanamid Company | Pesticidal and parasiticidal use of 1-aryl-1-(substituted thio, sulfinyl and sulfonyl)-2-nitroethane compounds |
EA004574B1 (ru) | 1999-11-05 | 2004-06-24 | Ниппон Сода Ко., Лтд. | Оксимные о-эфирные соединения и фунгициды для применения в земледелии и садоводстве |
EP1125931A1 (en) * | 2000-02-17 | 2001-08-22 | Hunan Research Institute of Chemical Industry | Biocidal alkyl-substituted-(hetero)aryl-ketoxime-O-ethers and the production method thereof |
CA2411418C (en) * | 2000-06-15 | 2010-01-12 | Taisho Pharmaceutical Co., Ltd. | Hydroxyformamidine derivatives and medicines containing the same |
WO2002064566A1 (fr) * | 2001-02-14 | 2002-08-22 | Nippon Soda Co.,Ltd. | Composes d'oxime o-ether et fongicides a usage agricole et horticole |
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WO2006125637A1 (en) * | 2005-05-25 | 2006-11-30 | Basf Aktiengesellschaft | O-(phenyl/heterocyclyl)methyl oxime ether compounds for combating animal pests |
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TW201605800A (zh) * | 2014-06-24 | 2016-02-16 | 日本曹達股份有限公司 | 吡啶化合物及其用途 |
RU2617413C1 (ru) * | 2015-12-10 | 2017-04-25 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Российский химико-технологический университет имени Д.И. Менделеева (РХТУ им. Д.И. Менделеева)" | О-замещенные 3-пиридилкетоксимы, обладающие фунгицидной активностью |
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-
1992
- 1992-04-22 DE DE4213149A patent/DE4213149A1/de not_active Withdrawn
-
1993
- 1993-04-16 EP EP93908947A patent/EP0638069A1/de not_active Withdrawn
- 1993-04-16 BR BR9306285A patent/BR9306285A/pt not_active Application Discontinuation
- 1993-04-16 JP JP5517988A patent/JP2931407B2/ja not_active Expired - Lifetime
- 1993-04-16 KR KR1019940703734A patent/KR0173146B1/ko not_active IP Right Cessation
- 1993-04-16 PL PL93305523A patent/PL171344B1/pl unknown
- 1993-04-16 CA CA002134099A patent/CA2134099A1/en not_active Abandoned
- 1993-04-16 HU HU9403050A patent/HUT69308A/hu unknown
- 1993-04-16 WO PCT/EP1993/000916 patent/WO1993021157A2/de not_active Application Discontinuation
- 1993-04-16 AU AU39535/93A patent/AU3953593A/en not_active Abandoned
- 1993-04-16 RU RU94046033/04A patent/RU94046033A/ru unknown
- 1993-04-20 MA MA23170A patent/MA22877A1/fr unknown
- 1993-04-20 IL IL105462A patent/IL105462A0/xx unknown
- 1993-04-21 CN CN93104615A patent/CN1077709A/zh active Pending
- 1993-04-21 ZA ZA932788A patent/ZA932788B/xx unknown
-
1994
- 1994-04-20 US US08/230,134 patent/US5646147A/en not_active Expired - Fee Related
- 1994-10-21 OA OA60574A patent/OA10106A/fr unknown
-
1995
- 1995-06-05 US US08/460,977 patent/US5728696A/en not_active Expired - Fee Related
Cited By (1)
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CN111978268A (zh) * | 2019-05-24 | 2020-11-24 | 湖南大学 | 1-(4-氯苯基)-2-环丙基丙酮肟噁唑甲基醚及其应用 |
Also Published As
Publication number | Publication date |
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JPH07506097A (ja) | 1995-07-06 |
JP2931407B2 (ja) | 1999-08-09 |
IL105462A0 (en) | 1993-08-18 |
ZA932788B (en) | 1993-11-16 |
HU9403050D0 (en) | 1995-01-30 |
HUT69308A (en) | 1995-09-28 |
US5728696A (en) | 1998-03-17 |
WO1993021157A3 (de) | 1994-02-03 |
AU3953593A (en) | 1993-11-18 |
RU94046033A (ru) | 1996-09-27 |
US5646147A (en) | 1997-07-08 |
BR9306285A (pt) | 1998-06-30 |
EP0638069A1 (de) | 1995-02-15 |
OA10106A (fr) | 1996-12-18 |
PL171344B1 (pl) | 1997-04-30 |
MA22877A1 (fr) | 1993-12-31 |
DE4213149A1 (de) | 1993-10-28 |
KR0173146B1 (ko) | 1999-02-01 |
WO1993021157A2 (de) | 1993-10-28 |
KR950701318A (ko) | 1995-03-23 |
CA2134099A1 (en) | 1993-10-28 |
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