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CN101497602B - Anthranilic acid compound and use thereof - Google Patents

Anthranilic acid compound and use thereof Download PDF

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CN101497602B
CN101497602B CN2008100571021A CN200810057102A CN101497602B CN 101497602 B CN101497602 B CN 101497602B CN 2008100571021 A CN2008100571021 A CN 2008100571021A CN 200810057102 A CN200810057102 A CN 200810057102A CN 101497602 B CN101497602 B CN 101497602B
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CN101497602A (en
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刘长令
柴宝山
袁静
彭永武
张弘
杨吉春
李慧超
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Shenyang Sinochem Agrochemicals R&D Co Ltd
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Shenyang Research Institute of Chemical Industry Co Ltd
Sinochem Corp
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Abstract

本发明公开了一种邻氨基苯甲酸类化合物，结构如通式I所示：式中各取代基的定义见说明书。本发明的邻氨基苯甲酸类化合物具有广谱杀虫活性，特别是对甜菜夜蛾、小菜蛾的活性更好，在较低的剂量下就可以获得很好的防治效果。The invention discloses an anthranilic acid compound, the structure of which is shown in the general formula I: For the definition of each substituent in the formula, see the description. The anthranilic acid compound of the present invention has broad-spectrum insecticidal activity, especially better activity on beet armyworm and diamondback moth, and can obtain good control effect at a lower dose.

Description

邻氨基苯甲酸类化合物及其应用Anthranilic acid compounds and their applications

技术领域technical field

本发明属于杀虫剂领域，具体地涉及一种邻氨基苯甲酸类化合物、及N-氧化物、盐和组合物，以及使用它们在农业或其他领域中作为杀虫剂的应用。The invention belongs to the field of insecticides, and in particular relates to an anthranilic acid compound, N-oxide, salt and composition, and their application as insecticides in agriculture or other fields.

背景技术Background technique

无脊椎动物害虫的防治在实现高种植效率中极为重要。无脊椎动物害虫对生长和贮存的农作物的损害会引起生产率的显著降低，并因此导致消费者的花费增加。用于这些目的的许多产品是可购买的，但是仍然需要更有效、低成本、低毒型、对环境安全或具有不同作用方式的新化合物。邻氨基苯甲酸类化合物(鱼尼丁受体类)是近几年开发的防治无脊椎动物害虫的有效杀虫剂。Control of invertebrate pests is extremely important in achieving high planting efficiency. Damage to growing and stored crops by invertebrate pests can cause significant reductions in productivity and, consequently, increased costs to consumers. Many products are commercially available for these purposes, but there is still a need for new compounds that are more effective, low cost, less toxic, environmentally safe or have a different mode of action. Anthranilic acid compounds (ryanodine receptors) are effective insecticides developed in recent years to control invertebrate pests.

专利WO03015519中公开了如下具有杀虫活性的化合物：Patent WO03015519 discloses the following compounds with insecticidal activity:

专利WO2004033468中公开了如下具有杀虫活性的化合物：Patent WO2004033468 discloses the following compounds with insecticidal activity:

Figure S2008100571021D00012
Figure S2008100571021D00012

专利WO2004067528中公开了如下具有杀虫活性的化合物：Patent WO2004067528 discloses the following compounds with insecticidal activity:

Figure S2008100571021D00013
Figure S2008100571021D00013

以上专利(申请)中所有公开的化合物虽与本发明化合物有相似之处，但结构仍存在显著的不同。Although all the compounds disclosed in the above patents (applications) have similarities with the compounds of the present invention, there are still significant differences in their structures.

发明内容Contents of the invention

本发明的目的在于提供一种在很小的剂量下就可以控制多种病虫害的邻氨基苯甲酸类化合物，其N-氧化物或其盐，它可应用于在农学和非农学环境中防治无脊椎动物害虫。The object of the present invention is to provide a kind of anthranilic acid compound that just can control various diseases and insect pests under very small dosage, its N-oxide compound or its salt, it can be applied in the prevention and treatment of pest in agronomy and non-agronomy environment. Vertebrate pests.

本发明的技术方案如下：Technical scheme of the present invention is as follows:

本发明提供一种邻氨基苯甲酸类化合物，如通式I所示：The present invention provides a kind of anthranilic acid compound, as shown in general formula I:

Figure S2008100571021D00021
Figure S2008100571021D00021

式中：In the formula:

R1选自氢、卤素、氰基、硝基、甲硫基、甲磺酰基、甲氧基羰基、甲胺基羰基、未取代的或被以下基团取代的氨基：甲基、二甲基、乙酰基或甲磺酰基； R is selected from hydrogen, halogen, cyano, nitro, methylthio, methylsulfonyl, methoxycarbonyl, methylaminocarbonyl, Amino group which is unsubstituted or substituted by: methyl, dimethyl, acetyl or methylsulfonyl;

R2选自卤素；R 2 is selected from halogen;

R3选自氢、卤素、氰基、硝基或氨基； R is selected from hydrogen, halogen, cyano, nitro or amino;

R4选自氰基、-CONHCH2CH2Cl、-CO2R、-CO2CH2CH2N(R)2、

Figure S2008100571021D00023
Figure S2008100571021D00024
-CONHCH(OR)2、-CONHCH(CH3)CH2CO2Et、-CONHCH(CH3)CH2CN、-COCH2COR、
Figure S2008100571021D00025
Figure S2008100571021D00026
或者Q1-Q5基团之一；R4 is selected from cyano, -CONHCH 2 CH 2 Cl, -CO 2 R, -CO 2 CH 2 CH 2 N(R) 2 ,
Figure S2008100571021D00023
Figure S2008100571021D00024
-CONHCH(OR) 2 , -CONHCH(CH 3 )CH 2 CO 2 Et, -CONHCH(CH 3 )CH 2 CN, -COCH 2 COR,
Figure S2008100571021D00025
Figure S2008100571021D00026
Or one of the Q1-Q5 groups;

其中：in:

R选自氢、C1-C6烷基、卤代C1-C6烷基或苯基；R is selected from hydrogen, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl or phenyl;

Figure S2008100571021D00027
Figure S2008100571021D00027

R5和R6可相同或不同，分别选自氢、卤素、氰基、C1-C6烷基、C2-C6烯基、C2-C6炔基、卤代C1-C6烷基、苯基、苄基、噻吩基、呋喃基或吡啶基。R 5 and R 6 may be the same or different, and are selected from hydrogen, halogen, cyano, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, halogenated C 1 -C 6 Alkyl, phenyl, benzyl, thienyl, furyl or pyridyl.

本发明中较为优选的化合物为：通式I中More preferred compounds in the present invention are: in general formula I

R1选自氢、Cl、Br、I、氰基、硝基、甲硫基、甲磺酰基、甲氧基羰基、甲胺基羰基、未取代的或被以下基团取代的氨基：甲基、二甲基、乙酰基或甲磺酰基； R1 is selected from hydrogen, Cl, Br, I, cyano, nitro, methylthio, methylsulfonyl, methoxycarbonyl, methylaminocarbonyl, amino unsubstituted or substituted by: methyl , dimethyl, acetyl or methylsulfonyl;

R2选自Cl或Br；R 2 is selected from Cl or Br;

R3选自氢、Cl、Br、氰基、硝基或氨基； R is selected from hydrogen, Cl, Br, cyano, nitro or amino;

R4选自氰基、-CONHCH2CH2Cl、-CO2CH3、

Figure S2008100571021D00031
Figure S2008100571021D00032
-CONHCH(OCH3)2、-COCH2COCH3、-CONHCH(CH3)CH2CO2Et、-CONHCH(CH3)CH2CN、-COCH2CN、
Figure S2008100571021D00033
或者Q1-Q5基团之一；R4 is selected from cyano, -CONHCH 2 CH 2 Cl, -CO 2 CH 3 ,
Figure S2008100571021D00031
Figure S2008100571021D00032
-CONHCH(OCH 3 ) 2 , -COCH 2 COCH 3 , -CONHCH(CH 3 )CH 2 CO 2 Et, -CONHCH(CH 3 )CH 2 CN, -COCH 2 CN,
Figure S2008100571021D00033
Or one of the Q1-Q5 groups;

其中：in:

Figure S2008100571021D00036
Figure S2008100571021D00036

R5和R6可相同或不同，分别选自氢、卤素、氰基、C1-C6烷基、C2-C6烯基、C2-C6炔基、卤代C1-C6烷基、苯基、苄基、噻吩基、呋喃基或吡啶基。R 5 and R 6 may be the same or different, and are selected from hydrogen, halogen, cyano, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, halogenated C 1 -C 6 Alkyl, phenyl, benzyl, thienyl, furyl or pyridyl.

本发明进一步优选的化合物为：通式I中Further preferred compounds of the present invention are: in general formula I

R1选自氢、Cl或氰基； R is selected from hydrogen, Cl or cyano;

R2选自Cl或Br；R 2 is selected from Cl or Br;

R3选自氢、Cl、硝基或氨基； R is selected from hydrogen, Cl, nitro or amino;

R4选自氰基、-CONHCH2CH2Cl、-CO2CH3、

Figure S2008100571021D00037
-COCH2COCH3、-CONHCH(CH3)CH2CO2Et、-CONHCH(CH3)CH2CN、-COCH2CN、
Figure S2008100571021D00039
Figure S2008100571021D00042
或者Q1-Q5基团之一；R4 is selected from cyano, -CONHCH 2 CH 2 Cl, -CO 2 CH 3 ,
Figure S2008100571021D00037
-COCH 2 COCH 3 , -CONHCH(CH 3 )CH 2 CO 2 Et, -CONHCH(CH 3 )CH 2 CN, -COCH 2 CN,
Figure S2008100571021D00039
Figure S2008100571021D00042
Or one of the Q1-Q5 groups;

其中：in:

Figure S2008100571021D00043
Figure S2008100571021D00043

R5和R6可相同或不同，分别选自氢、C1-C6烷基、苯基或苄基。R 5 and R 6 may be the same or different, and are respectively selected from hydrogen, C 1 -C 6 alkyl, phenyl or benzyl.

本发明更进一步优选的化合物为：通式I中The further preferred compound of the present invention is: in general formula I

R1选自氢、Cl或氰基； R is selected from hydrogen, Cl or cyano;

R2选自Cl或Br；R 2 is selected from Cl or Br;

R3选自氢、Cl、硝基或氨基； R is selected from hydrogen, Cl, nitro or amino;

R4选自氰基、-CONHCH2CH2Cl、-CO2CH3、

Figure S2008100571021D00044
-CONHCH(OCH3)2或Q1；R4 is selected from cyano, -CONHCH 2 CH 2 Cl, -CO 2 CH 3 ,
Figure S2008100571021D00044
- CONHCH (OCH 3 ) 2 or Q1;

其中：R5和R6可相同或不同，分别选自C1-C3烷基。Wherein: R 5 and R 6 may be the same or different, and are respectively selected from C 1 -C 3 alkyl groups.

上面给出的通式I化合物的定义中，汇集所用术语一般定义如下：In the definitions of the compounds of general formula I given above, the collectively used terms are generally defined as follows:

未取代表示所有取代基都为氢。Unsubstituted means that all substituents are hydrogen.

取代的胺基中取代基的数目可为1～2。The number of substituents in the substituted amino group may be 1-2.

卤：指氟、氯、溴或碘。Halogen: refers to fluorine, chlorine, bromine or iodine.

烷基：直链或支链烷基，例如甲基、乙基、丙基、异丙基或叔丁基。Alkyl: straight-chain or branched-chain alkyl such as methyl, ethyl, propyl, isopropyl or tert-butyl.

卤代烷基：直链或支链烷基，在这些烷基上的氢原子可部分或全部被卤原子所取代，例如，卤代烷基诸如氯甲基、二氯甲基、三氯甲基、氟甲基、二氟甲基或三氟甲基。Haloalkyl: Straight chain or branched chain alkyl in which hydrogen atoms may be partially or completely replaced by halogen atoms, for example, haloalkyl such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl group, difluoromethyl or trifluoromethyl.

烯基：直链或支链并可在任何位置上存在有双键，例如乙烯基或烯丙基。Alkenyl: Straight or branched chain with double bonds at any position, such as vinyl or allyl.

炔基：直链或支链并可在任何位置上存在有三键，例如乙炔基或炔丙基。Alkynyl: Straight or branched chain with a triple bond at any position, eg ethynyl or propargyl.

本发明的化合物可以作为一种或多种立体异构体存在。本领域技术人员会理解，当一种立体异构体相对于其它立体异构体而言浓度大时，或者当其与其它立体异构体分离时，可能更有活性和/或可能表现出有利的作用。另外，本领域技术人员知道如何分离、富集和/或选择性地制备所述立体异构体。因此，本发明包括选自通式I、其N-氧化物或其盐的化合物。本发明的化合物可以作为立体异构体的混合物、单个立体异构体或者作为旋光形式存在。The compounds of the invention may exist as one or more stereoisomers. Those skilled in the art will appreciate that one stereoisomer may be more active and/or may appear advantageous when present in greater concentrations relative to the other stereoisomers, or when isolated from the other stereoisomers. role. In addition, those skilled in the art know how to separate, enrich and/or selectively prepare said stereoisomers. Accordingly, the present invention includes compounds selected from the group consisting of general formula I, N-oxides or salts thereof. The compounds of the present invention may exist as mixtures of stereoisomers, individual stereoisomers or as optically active forms.

本发明的化合物的盐包括与无机或有机酸，如氢溴酸、盐酸、硝酸、磷酸、硫酸、乙酸、丁酸、富马酸、乳酸、马来酸、丙二酸、草酸、丙酸、水杨酸、酒石酸、4-甲苯磺酸或戊酸加成盐。在本发明的组合物和方法中，本发明的化合物的盐优选适于本文描述的农学和/或非农学用途。Salts of the compounds of the present invention include those with inorganic or organic acids such as hydrobromic acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid, butyric acid, fumaric acid, lactic acid, maleic acid, malonic acid, oxalic acid, propionic acid, Salicylic acid, tartaric acid, 4-toluenesulfonic acid or valeric acid addition salts. In the compositions and methods of the invention, the salts of the compounds of the invention are preferably suitable for the agronomic and/or non-agronomic uses described herein.

可以用下面表1-表2列出的化合物来说明本发明，但并不限定本发明。The compounds listed in Table 1-Table 2 below can be used to illustrate the present invention, but not to limit the present invention.

Figure S2008100571021D00051
当R4不为Q1-Q5时，
Figure S2008100571021D00051
When R4 is not Q1-Q5,

表1Table 1

  编号 serial number   R1 R 1   R2 R 2   R3 R 3   R4 R 4   1-11-1   Hh   ClCl   Hh   CNCN   1-21-2   Hh   BrBr   Hh   CNCN   1-31-3   ClCl   ClCl   Hh   CNCN   1-41-4   ClCl   BrBr   Hh   CNCN   1-51-5   BrBr   ClCl   Hh   CNCN   1-61-6   BrBr   BrBr   Hh   CNCN   1-71-7   II   ClCl   Hh   CNCN   1-81-8   II   BrBr   Hh   CNCN   1-91-9   CNCN   ClCl   Hh   CNCN   1-101-10   CNCN   BrBr   Hh   CNCN   1-111-11   NH2 NH 2   ClCl   Hh   CNCN   1-121-12   NH2 NH 2   BrBr   Hh   CNCN   1-131-13   NHCH3 NHCH 3   ClCl   Hh   CNCN   1-141-14   NHCH3 NHCH 3   BrBr   Hh   CNCN   1-151-15   N(CH3)2 N(CH 3 ) 2   ClCl   Hh   CNCN   1-161-16   N(CH3)2 N(CH 3 ) 2   BrBr   Hh   CNCN   1-171-17   NHSO2CH3 NHSO 2 CH 3   C1C1   Hh   CNCN   1-181-18   NHSO2CH3 NHSO 2 CH 3   BrBr   Hh   CNCN   1-191-19   NHCOCH3 NHCOCH 3   ClCl   Hh   CNCN   1-201-20   NHCOCH3 NHCOCH 3   BrBr   Hh   CNCN   1-211-21   Hh   ClCl   BrBr   CNCN   1-221-22   Hh   BrBr   BrBr   CNCN   1-231-23   ClCl   ClCl   BrBr   CNCN   1-241-24   ClCl   BrBr   BrBr   CNCN   1-251-25   BrBr   ClCl   BrBr   CNCN   1-261-26   BrBr   BrBr   BrBr   CNCN   1-271-27   II   ClCl   BrBr   CNCN   1-281-28   II   BrBr   BrBr   CNCN

  1-291-29   CNCN   ClCl   BrBr   CNCN   1-301-30   CNCN   BrBr   BrBr   CNCN   1-311-31   NH2 NH 2   ClCl   BrBr   CNCN   1-321-32   NH2 NH 2   BrBr   BrBr   CNCN   1-331-33   NHCH3 NHCH 3   ClCl   BrBr   CNCN   1-341-34   NHCH3 NHCH 3   BrBr   BrBr   CNCN   1-351-35   N(CH3)2 N(CH 3 ) 2   ClCl   BrBr   CNCN   1-361-36   N(CH3)2 N(CH 3 ) 2   BrBr   BrBr   CNCN   1-371-37   NHSO2CH3 NHSO 2 CH 3   ClCl   BrBr   CNCN   1-381-38   NHSO2CH3 NHSO 2 CH 3   BrBr   BrBr   CNCN   1-391-39   NHCOCH3 NHCOCH 3   ClCl   BrBr   CNCN   1-401-40   NHCOCH3 NHCOCH 3   BrBr   BrBr   CNCN   1-411-41   Hh   ClCl   ClCl   CNCN   1-421-42   Hh   BrBr   ClCl   CNCN   1-431-43   ClCl   ClCl   ClCl   CNCN   1-441-44   ClCl   BrBr   ClCl   CNCN   1-451-45   BrBr   ClCl   ClCl   CNCN   1-461-46   BrBr   BrBr   ClCl   CNCN   1-471-47   II   ClCl   ClCl   CNCN   1-481-48   II   BrBr   ClCl   CNCN   1-491-49   CNCN   ClCl   ClCl   CNCN   1-501-50   CNCN   BrBr   ClCl   CNCN   1-511-51   NH2 NH 2   ClCl   ClCl   CNCN   1-521-52   COOCH3 COOCH 3   BrBr   Hh   CNCN   1-531-53   COOCH3 COOCH 3   ClCl   ClCl   CNCN   1-541-54   COOCH3 COOCH 3   BrBr   ClCl   CNCN   1-551-55   N(CH3)2 N(CH 3 ) 2   ClCl   ClCl   CNCN   1-561-56   N(CH3)2 N(CH 3 ) 2   BrBr   ClCl   CNCN   1-571-57   NHSO2CH3 NHSO 2 CH 3   ClCl   ClCl   CNCN   1-581-58   NHSO2CH3 NHSO 2 CH 3   BrBr   ClCl   CNCN   1-591-59   CONHCH3 CONHCH 3   ClCl   Hh   CNCN   1-601-60   CONHCH3 CONHCH 3   BrBr   Hh   CNCN   1-611-61   Hh   ClCl   NO2 NO 2   CNCN   1-621-62   Hh   BrBr   NO2 NO 2   CNCN   1-631-63   ClCl   ClCl   NO2 NO 2   CNCN   1-641-64   ClCl   BrBr   NO2 NO 2   CNCN   1-651-65   BrBr   ClCl   NO2 NO 2   CNCN   1-661-66   BrBr   BrBr   NO2 NO 2   CNCN   1-671-67   II   ClCl   NO2 NO 2   CNCN   1-681-68   II   BrBr   NO2 NO 2   CNCN   1-691-69   CNCN   ClCl   NO2 NO 2   CNCN   1-701-70   CNCN   BrBr   NO2 NO 2   CNCN   1-711-71   NH2 NH 2   ClCl   NO2 NO 2   CNCN

  1-721-72   NH2 NH 2   BrBr   NO2 NO 2   CNCN   1-731-73   NHCH3 NHCH 3   ClCl   NO2 NO 2   CNCN   1-741-74   NHCH3 NHCH 3   BrBr   NO2 NO 2   CNCN   1-751-75   N(CH3)2 N(CH 3 ) 2   ClCl   NO2 NO 2   CNCN   1-761-76   N(CH3)2 N(CH 3 ) 2   BrBr   NO2 NO 2   CNCN   1-771-77   NHSO2CH3 NHSO 2 CH 3   ClCl   NO2 NO 2   CNCN   1-781-78   NHSO2CH3 NHSO 2 CH 3   BrBr   NO2 NO 2   CNCN   1-791-79   NHCOCH3 NHCOCH 3   ClCl   NO2 NO 2   CNCN   1-801-80   NHCOCH3 NHCOCH 3   BrBr   NO2 NO 2   CNCN   1-811-81   Hh   ClCl   NH2 NH 2   CNCN   1-821-82   Hh   BrBr   NH2 NH 2   CNCN   1-831-83   ClCl   ClCl   NH2 NH 2   CNCN   1-841-84   ClCl   BrBr   NH2 NH 2   CNCN   1-851-85   BrBr   ClCl   NH2 NH 2   CNCN   1-861-86   BrBr   BrBr   NH2 NH 2   CNCN   1-871-87   II   ClCl   NH2 NH 2   CNCN   1-881-88   II   BrBr   NH2 NH 2   CNCN   1-891-89   CNCN   ClCl   NH2 NH 2   CNCN   1-901-90   CNCN   BrBr   NH2 NH 2   CNCN   1-911-91   NH2 NH 2   ClCl   NH2 NH 2   CNCN   1-921-92   NH2 NH 2   BrBr   NH2 NH 2   CNCN   1-931-93   NHCH3 NHCH 3   ClCl   NH2 NH 2   CNCN   1-941-94   NHCH3 NHCH 3   BrBr   NH2 NH 2   CNCN   1-951-95   N(CH3)2 N(CH 3 ) 2   ClCl   NH2 NH 2   CNCN   1-961-96   N(CH3)2 N(CH 3 ) 2   BrBr   NH2 NH 2   CNCN   1-971-97   NHSO2CH3 NHSO 2 CH 3   ClCl   NH2 NH 2   CNCN   1-981-98   NHSO2CH3 NHSO 2 CH 3   BrBr   NH2 NH 2   CNCN   1-991-99   NHCOCH3 NHCOCH 3   ClCl   NH2 NH 2   CNCN   1-1001-100   NHCOCH3 NHCOCH 3   BrBr   NH2 NH 2   CNCN   1-1011-101   Hh   ClCl   Hh   CO2CH3 CO 2 CH 3   1-1021-102   Hh   BrBr   Hh   CO2CH3 CO 2 CH 3   1-1031-103   ClCl   ClCl   Hh   CO2CH3 CO 2 CH 3   1-1041-104   ClCl   BrBr   Hh   CO2CH3 CO 2 CH 3   1-1051-105   CNCN   ClCl   Hh   CO2CH3 CO 2 CH 3   1-1061-106   CNCN   BrBr   Hh   CO2CH3 CO 2 CH 3   1-1071-107   NH2 NH 2   ClCl   Hh   CO2CH3 CO 2 CH 3   1-1081-108   NH2 NH 2   BrBr   Hh   CO2CH3 CO 2 CH 3   1-1091-109   NHCH3 NHCH 3   ClCl   Hh   CO2CH3 CO 2 CH 3   1-1101-110   NHCH3 NHCH 3   BrBr   Hh   CO2CH3 CO 2 CH 3   1-1111-111   N(CH3)2 N(CH 3 ) 2   ClCl   Hh   CO2CH3 CO 2 CH 3   1-1121-112   N(CH3)2 N(CH 3 ) 2   BrBr   Hh   CO2CH3 CO 2 CH 3   1-1131-113   NHSO2CH3 NHSO 2 CH 3   ClCl   Hh   CO2CH3 CO 2 CH 3   1-1141-114   NHSO2CH3 NHSO 2 CH 3   BrBr   Hh   CO2CH3 CO 2 CH 3

  1-1151-115   NHCOCH3 NHCOCH 3   ClCl   Hh   CO2CH3 CO 2 CH 3   1-1161-116   NHCOCH3 NHCOCH 3   BrBr   Hh   CO2CH3 CO 2 CH 3   1-1171-117   Hh   ClCl   ClCl   CO2CH3 CO 2 CH 3   1-1181-118   Hh   BrBr   ClCl   CO2CH3 CO 2 CH 3   1-1191-119   ClCl   ClCl   ClCl   CO2CH3 CO 2 CH 3   1-1201-120   ClCl   BrBr   ClCl   CO2CH3 CO 2 CH 3   1-1211-121   CNCN   ClCl   ClCl   CO2CH3 CO 2 CH 3   1-1221-122   CNCN   BrBr   ClCl   CO2CH3 CO 2 CH 3   1-1231-123   Hh   ClCl   NO2 NO 2   CO2CH3 CO 2 CH 3   1-1241-124   Hh   BrBr   NO2 NO 2   CO2CH3 CO 2 CH 3   1-1251-125   ClCl   ClCl   NO2 NO 2   CO2CH3 CO 2 CH 3   1-1261-126   ClCl   BrBr   NO2 NO 2   CO2CH3 CO 2 CH 3   1-1271-127   CNCN   ClCl   NO2 NO 2   CO2CH3 CO 2 CH 3   1-1281-128   CNCN   BrBr   NO2 NO 2   CO2CH3 CO 2 CH 3   1-1291-129   Hh   ClCl   NH2 NH 2   CO2CH3 CO 2 CH 3   1-1301-130   Hh   BrBr   NH2 NH 2   CO2CH3 CO 2 CH 3   1-1311-131   ClCl   ClCl   NH2 NH 2   CO2CH3 CO 2 CH 3   1-1321-132   ClCl   BrBr   NH2 NH 2   CO2CH3 CO 2 CH 3   1-1331-133   BrBr   ClCl   NH2 NH 2   CO2CH3 CO 2 CH 3   1-1341-134   BrBr   BrBr   NH2 NH 2   CO2CH3 CO 2 CH 3   1-1351-135   II   ClCl   NH2 NH 2   CO2CH3 CO 2 CH 3   1-1361-136   II   BrBr   NH2 NH 2   CO2CH3 CO 2 CH 3   1-1371-137   CNCN   ClCl   NH2 NH 2   CO2CH3 CO 2 CH 3   1-1381-138   CNCN   BrBr   NH2 NH 2   CO2CH3 CO 2 CH 3   1-1391-139   NH2 NH 2   ClCl   NH2 NH 2   CO2CH3 CO 2 CH 3   1-1401-140   NH2 NH 2   BrBr   NH2 NH 2   CO2CH3 CO 2 CH 3   1-1411-141   NHCH3 NHCH 3   ClCl   NH2 NH 2   CO2CH3 CO 2 CH 3   1-1421-142   NHCH3 NHCH 3   BrBr   NH2 NH 2   CO2CH3 CO 2 CH 3   1-1431-143   N(CH3)2 N(CH 3 ) 2   ClCl   NH2 NH 2   CO2CH3 CO 2 CH 3   1-1441-144   N(CH3)2 N(CH 3 ) 2   BrBr   NH2 NH 2   CO2CH3 CO 2 CH 3   1-1451-145   NHSO2CH3 NHSO 2 CH 3   ClCl   NH2 NH 2   CO2CH3 CO 2 CH 3   1-1461-146   NHSO2CH3 NHSO 2 CH 3   BrBr   NH2 NH 2   CO2CH3 CO 2 CH 3   1-1471-147   NHCOCH3 NHCOCH 3   ClCl   NH2 NH 2   CO2CH3 CO 2 CH 3   1-1481-148   NHCOCH3 NHCOCH 3   BrBr   NH2 NH 2   CO2CH3 CO 2 CH 3   1-1491-149   Hh   ClCl   Hh   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1501-150   Hh   BrBr   Hh   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1511-151   ClCl   ClCl   Hh   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1521-152   ClCl   BrBr   Hh   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1531-153   CNCN   ClCl   Hh   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1541-154   CNCN   BrBr   Hh   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1551-155   NH2 NH 2   ClCl   Hh   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1561-156   NH2 NH 2   BrBr   Hh   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1571-157   NHCH3 NHCH 3   ClCl   Hh   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2

  1-1581-158   NHCH3 NHCH 3   BrBr   Hh   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1591-159   N(CH3)2 N(CH 3 ) 2   BrBr   Hh   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1601-160   NHSO2CH3 NHSO 2 CH 3   ClCl   Hh   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1611-161   NHSO2CH3 NHSO 2 CH 3   BrBr   Hh   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1621-162   NHCOCH3 NHCOCH 3   ClCl   Hh   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1631-163   NHCOCH3 NHCOCH 3   BrBr   Hh   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1641-164   ClCl   ClCl   BrBr   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1651-165   ClCl   BrBr   BrBr   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1661-166   CNCN   ClCl   BrBr   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1671-167   CNCN   BrBr   BrBr   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1681-168   NH2 NH 2   BrBr   BrBr   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1691-169   NHCH3 NHCH 3   ClCl   BrBr   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1701-170   NHCH3 NHCH 3   BrBr   BrBr   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1711-171   N(CH3)2 N(CH 3 ) 2   ClCl   BrBr   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1721-172   N(CH3)2 N(CH 3 ) 2   BrBr   BrBr   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1731-173   NHSO2CH3 NHSO 2 CH 3   ClCl   BrBr   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1741-174   NHSO2CH3 NHSO 2 CH 3   BrBr   BrBr   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1751-175   NHCOCH3 NHCOCH 3   ClCl   BrBr   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1761-176   NHCOCH3 NHCOCH 3   BrBr   BrBr   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1771-177   ClCl   ClCl   ClCl   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1781-178   ClCl   BrBr   ClCl   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1791-179   CNCN   ClCl   ClCl   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1801-180   CNCN   BrBr   ClCl   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1811-181   NHCH3 NHCH 3   ClCl   ClCl   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1821-182   NHCH3 NHCH 3   BrBr   ClCl   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1831-183   N(CH3)2 N(CH 3 ) 2   ClCl   ClCl   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1841-184   N(CH3)2 N(CH 3 ) 2   BrBr   ClCl   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1851-185   NHSO2CH3 NHSO 2 CH 3   ClCl   ClCl   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1861-186   NHSO2CH3 NHSO 2 CH 3   BrBr   ClCl   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1871-187   Hh   ClCl   NO2 NO 2   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1881-188   Hh   BrBr   NO2 NO 2   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1891-189   ClCl   ClCl   NO2 NO 2   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1901-190   ClCl   BrBr   NO2 NO 2   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1911-191   CNCN   ClCl   NO2 NO 2   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1921-192   CNCN   BrBr   NO2 NO 2   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1931-193   NH2 NH 2   BrBr   NO2 NO 2   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1941-194   NHCH3 NHCH 3   ClCl   NO2 NO 2   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1951-195   NHCH3 NHCH 3   BrBr   NO2 NO 2   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1961-196   NHSO2CH3 NHSO 2 CH 3   ClCl   NO2 NO 2   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1971-197   NHSO2CH3 NHSO 2 CH 3   BrBr   NO2 NO 2   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1981-198   Hh   ClCl   NH2 NH 2   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-1991-199   Hh   BrBr   NH2 NH 2   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-2001-200   ClCl   ClCl   NH2 NH 2   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2

  1-2011-201   ClCl   BrBr   NH2 NH 2   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-2021-202   CNCN   ClCl   NH2 NH 2   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-2031-203   CNCN   BrBr   NH2 NH 2   CO2CH2CH2N(CH3)2 CO 2 CH 2 CH 2 N(CH 3 ) 2   1-2041-204   ClCl   ClCl   Hh   CO2CH2CH2N(C2H5)2 CO 2 CH 2 CH 2 N(C 2 H 5 ) 2   1-2051-205   ClCl   BrBr   Hh   CO2CH2CH2N(C2H5)2 CO 2 CH 2 CH 2 N(C 2 H 5 ) 2   1-2061-206   CNCN   ClCl   Hh   CO2CH2CH2N(C2H5)2 CO 2 CH 2 CH 2 N(C 2 H 5 ) 2   1-2071-207   CNCN   BrBr   Hh   CO2CH2CH2N(C2H5)2 CO 2 CH 2 CH 2 N(C 2 H 5 ) 2   1-2081-208   NHSO2CH3 NHSO 2 CH 3   ClCl   Hh   CO2CH2CH2N(C2H5)2 CO 2 CH 2 CH 2 N(C 2 H 5 ) 2   1-2091-209   NHSO2CH3 NHSO 2 CH 3   BrBr   Hh   CO2CH2CH2N(C2H5)2 CO 2 CH 2 CH 2 N(C 2 H 5 ) 2   1-2101-210   ClCl   BrBr   ClCl   CO2CH2CH2N(C2H5)2 CO 2 CH 2 CH 2 N(C 2 H 5 ) 2   1-2111-211   CNCN   ClCl   ClCl   CO2CH2CH2N(C2H5)2 CO 2 CH 2 CH 2 N(C 2 H 5 ) 2   1-2121-212   CNCN   BrBr   ClCl   CO2CH2CH2N(C2H5)2 CO 2 CH 2 CH 2 N(C 2 H 5 ) 2   1-2131-213   ClCl   BrBr   NO2 NO 2   CO2CH2CH2N(C2H5)2 CO 2 CH 2 CH 2 N(C 2 H 5 ) 2   1-2141-214   CNCN   BrBr   NO2 NO 2   CO2CH2CH2N(C2H5)2 CO 2 CH 2 CH 2 N(C 2 H 5 ) 2   1-2151-215   ClCl   ClCl   NH2 NH 2   CO2CH2CH2N(C2H5)2 CO 2 CH 2 CH 2 N(C 2 H 5 ) 2   1-2161-216   CNCN   ClCl   NH2 NH 2   CO2CH2CH2N(C2H5)2 CO 2 CH 2 CH 2 N(C 2 H 5 ) 2   1-2171-217   CNCN   BrBr   NH2 NH 2   CO2CH2CH2N(C2H5)2 CO 2 CH 2 CH 2 N(C 2 H 5 ) 2   1-2181-218   ClCl   BrBr   Hh   CONHCH2CH2Cl CONHCH2CH2Cl _   1-2191-219   CNCN   ClCl   Hh   CONHCH2CH2Cl CONHCH2CH2Cl _   1-2201-220   CNCN   BrBr   Hh   CONHCH2CH2Cl CONHCH2CH2Cl _   1-2211-221   ClCl   ClCl   BrBr   CONHCH2CH2Cl CONHCH2CH2Cl _   1-2221-222   ClCl   BrBr   BrBr   CONHCH2CH2Cl CONHCH2CH2Cl _   1-2231-223   CNCN   ClCl   BrBr   CONHCH2CH2Cl CONHCH2CH2Cl _   1-2241-224   CNCN   BrBr   BrBr   CONHCH2CH2Cl CONHCH2CH2Cl _   1-2251-225   CNCN   ClCl   ClCl   CONHCH2CH2Cl CONHCH2CH2Cl _   1-2261-226   CNCN   BrBr   ClCl   CONHCH2CH2Cl CONHCH2CH2Cl _   1-2271-227   ClCl   ClCl   NO2 NO 2   CONHCH2CH2Cl CONHCH2CH2Cl _   1-2281-228   ClCl   BrBr   NO2 NO 2   CONHCH2CH2Cl CONHCH2CH2Cl _   1-2291-229   CNCN   ClCl   NO2 NO 2   CONHCH2CH2Cl CONHCH2CH2Cl _   1-2301-230   CNCN   BrBr   NO2 NO 2   CONHCH2CH2Cl CONHCH2CH2Cl _   1-2311-231   CNCN   BrBr   NH2 NH 2   CONHCH2CH2Cl CONHCH2CH2Cl _   1-2321-232   ClCl   BrBr   Hh   CON＝CHOCH3 CON = CHOCH 3   1-2331-233   CNCN   ClCl   Hh   CON＝CHOCH3 CON = CHOCH 3   1-2341-234   CNCN   BrBr   Hh   CON＝CHOCH3 CON = CHOCH 3   1-2351-235   ClCl   ClCl   BrBr   CON＝CHOCH3 CON = CHOCH 3   1-2361-236   ClCl   BrBr   BrBr   CON＝CHOCH3 CON = CHOCH 3   1-2371-237   CNCN   ClCl   BrBr   CON＝CHOCH3 CON = CHOCH 3   1-2381-238   CNCN   BrBr   BrBr   CON＝CHOCH3 CON = CHOCH 3   1-2391-239   CNCN   ClCl   ClCl   CON＝CHOCH3 CON = CHOCH 3   1-2401-240   CNCN   BrBr   ClCl   CON＝CHOCH3 CON = CHOCH 3   1-2411-241   ClCl   BrBr   NO2 NO 2   CON＝CHOCH3 CON = CHOCH 3   1-2421-242   CNCN   ClCl   NO2 NO 2   CON＝CHOCH3 CON = CHOCH 3   1-2431-243   CNCN   BrBr   NO2 NO 2   CON＝CHOCH3 CON = CHOCH 3

  1-2441-244   CNCN   BrBr   NH2 NH 2   CON＝CHOCH3 CON = CHOCH 3   1-2451-245   ClCl   BrBr   Hh   CON＝CHN(CH3)2 CON=CHN(CH 3 ) 2   1-2461-246   CNCN   ClCl   Hh   CON＝CHN(CH3)2 CON=CHN(CH 3 ) 2   1-2471-247   CNCN   BrBr   Hh   CON＝CHN(CH3)2 CON=CHN(CH 3 ) 2   1-2481-248   CNCN   ClCl   ClCl   CON＝CHN(CH3)2 CON=CHN(CH 3 ) 2   1-2491-249   CNCN   BrBr   ClCl   CON＝CHN(CH3)2 CON=CHN(CH 3 ) 2   1-2501-250   ClCl   ClCl   NO2 NO 2   CON＝CHN(CH3)2 CON=CHN(CH 3 ) 2   1-2511-251   ClCl   BrBr   NO2 NO 2   CON＝CHN(CH3)2 CON=CHN(CH 3 ) 2   1-2521-252   CNCN   ClCl   NO2 NO 2   CON＝CHN(CH3)2 CON=CHN(CH 3 ) 2   1-2531-253   CNCN   BrBr   NO2 NO 2   CON＝CHN(CH3)2 CON=CHN(CH 3 ) 2   1-2541-254   CNCN   BrBr   NH2 NH 2   CON＝CHN(CH3)2 CON=CHN(CH 3 ) 2   1-2551-255   CNCN   ClCl   Hh   CON＝CCH3N(CH3)2 CON＝CCH 3 N(CH 3 ) 2   1-2561-256   CNCN   BrBr   Hh   CON＝CCH3N(CH3)2 CON＝CCH 3 N(CH 3 ) 2   1-2571-257   CNCN   ClCl   ClCl   CON＝CCH3N(CH3)2 CON＝CCH 3 N(CH 3 ) 2   1-2581-258   CNCN   BrBr   ClCl   CON＝CCH3N(CH3)2 CON＝CCH 3 N(CH 3 ) 2   1-2591-259   ClCl   ClCl   NO2 NO 2   CON＝CCH3N(CH3)2 CON＝CCH 3 N(CH 3 ) 2   1-2601-260   ClCl   BrBr   NO2 NO 2   CON＝CCH3N(CH3)2 CON＝CCH 3 N(CH 3 ) 2   1-2611-261   CNCN   ClCl   NO2 NO 2   CON＝CCH3N(CH3)2 CON＝CCH 3 N(CH 3 ) 2   1-2621-262   CNCN   BrBr   NO2 NO 2   CON＝CCH3N(CH3)2 CON＝CCH 3 N(CH 3 ) 2   1-2631-263   CNCN   BrBr   NH2 NH 2   CON＝CCH3N(CH3)2 CON＝CCH 3 N(CH 3 ) 2   1-2641-264   ClCl   BrBr   Hh   CONHCH(OCH3)2 CONHCH(OCH 3 ) 2   1-2651-265   CNCN   ClCl   Hh   CONHCH(OCH3)2 CONHCH(OCH 3 ) 2   1-2661-266   CNCN   BrBr   Hh   CONHCH(OCH3)2 CONHCH(OCH 3 ) 2   1-2671-267   CNCN   BrBr   ClCl   CONHCH(OCH3)2 CONHCH(OCH 3 ) 2   1-2681-268   ClCl   BrBr   NO2 NO 2   CONHCH(OCH3)2 CONHCH(OCH 3 ) 2   1-2691-269   CNCN   BrBr   NO2 NO 2   CONHCH(OCH3)2 CONHCH(OCH 3 ) 2   1-2701-270   CNCN   BrBr   NH2 NH 2   CONHCH(OCH3)2 CONHCH(OCH 3 ) 2   1-2711-271   CNCN   ClCl   Hh   COCH2COCH3 COCH 2 COCH 3   1-2721-272   CNCN   BrBr   Hh   COCH2COCH3 COCH 2 COCH 3   1-2731-273   CNCN   ClCl   ClCl   COCH2COCH3 COCH 2 COCH 3   1-2741-274   CNCN   BrBr   ClCl   COCH2COCH3 COCH 2 COCH 3   1-2751-275   ClCl   ClCl   NO2 NO 2   COCH2COCH3 COCH 2 COCH 3   1-2761-276   ClCl   BrBr   NO2 NO 2   COCH2COCH3 COCH 2 COCH 3   1-2771-277   CNCN   ClCl   NO2 NO 2   COCH2COCH3 COCH 2 COCH 3   1-2781-278   CNCN   BrBr   NO2 NO 2   COCH2COCH3 COCH 2 COCH 3   1-2791-279   CNCN   BrBr   NH2 NH 2   COCH2COCH3 COCH 2 COCH 3   1-2801-280   ClCl   BrBr   Hh   CONHCH(CH3)CH2CO2EtCONHCH(CH3)CH2CO2Et   1-2811-281   CNCN   ClCl   Hh   CONHCH(CH3)CH2CO2EtCONHCH(CH3)CH2CO2Et   1-2821-282   CNCN   BrBr   Hh   CONHCH(CH3)CH2CO2EtCONHCH(CH3)CH2CO2Et   1-2831-283   CNCN   BrBr   ClCl   CONHCH(CH3)CH2CO2EtCONHCH(CH3)CH2CO2Et   1-2841-284   ClCl   BrBr   NO2 NO 2   CONHCH(CH3)CH2CO2EtCONHCH(CH3)CH2CO2Et   1-2851-285   CNCN   BrBr   NO2 NO 2   CONHCH(CH3)CH2CO2EtCONHCH(CH3)CH2CO2Et   1-2861-286   CNCN   BrBr   NH2 NH 2   CONHCH(CH3)CH2CO2EtCONHCH(CH3)CH2CO2Et

Figure S2008100571021D00121
Figure S2008100571021D00121

Figure S2008100571021D00131
Figure S2008100571021D00131

Figure S2008100571021D00141
Figure S2008100571021D00141

Figure S2008100571021D00151
Figure S2008100571021D00151

Figure S2008100571021D00161
Figure S2008100571021D00161

Figure S2008100571021D00162
当R4为Q1-Q5之一时，
Figure S2008100571021D00162
When R 4 is one of Q 1 -Q 5 ,

表2Table 2

  编号 serial number   R1 R 1   R2 R 2   R3 R 3   R4 R 4   R5 R 5   R6 R 6   2-12-1   Hh   ClCl   Hh   Q1Q1   CH3 CH3   CH3 CH3   2-22-2   Hh   BrBr   Hh   Q1Q1   CH3 CH3   CH3 CH3   2-32-3   ClCl   ClCl   Hh   Q1Q1   CH3 CH3   CH3 CH3   2-42-4   ClCl   BrBr   Hh   Q1Q1   CH3 CH3   CH3 CH3   2-52-5   CNCN   ClCl   Hh   Q1Q1   CH3 CH3   CH3 CH3   2-62-6   CNCN   BrBr   Hh   Q1Q1   CH3 CH3   CH3 CH3   2-72-7   ClCl   ClCl   NO2 NO 2   Q1Q1   CH3 CH3   CH3 CH3   2-82-8   ClCl   BrBr   NO2 NO 2   Q1Q1   CH3 CH3   CH3 CH3   2-92-9   CNCN   ClCl   NO2 NO 2   Q1Q1   CH3 CH3   CH3 CH3   2-102-10   CNCN   BrBr   NO2 NO 2   Q1Q1   CH3 CH3   CH3 CH3   2-112-11   ClCl   BrBr   Hh   Q1Q1   CH3 CH3   CH(CH3)2 CH(CH 3 ) 2   2-122-12   CNCN   ClCl   Hh   Q1Q1   CH3 CH3   CH(CH3)2 CH(CH 3 ) 2   2-132-13   CNCN   BrBr   Hh   Q1Q1   CH3 CH3   CH(CH3)2 CH(CH 3 ) 2   2-142-14   ClCl   ClCl   NO2 NO 2   Q1Q1   CH3 CH3   CH(CH3)2 CH(CH 3 ) 2   2-152-15   ClCl   BrBr   NO2 NO 2   Q1Q1   CH3 CH3   CH(CH3)2 CH(CH 3 ) 2   2-162-16   CNCN   ClCl   NO2 NO 2   Q1Q1   CH3 CH3   CH(CH3)2 CH(CH 3 ) 2   2-172-17   CNCN   BrBr   NO2 NO 2   Q1Q1   CH3 CH3   CH(CH3)2 CH(CH 3 ) 2   2-182-18   ClCl   ClCl   Hh   Q1Q1   CH2CH3 CH 2 CH 3   CH2CH3 CH 2 CH 3   2-192-19   ClCl   BrBr   Hh   Q1Q1   CH2CH3 CH 2 CH 3   CH2CH3 CH 2 CH 3   2-202-20   CNCN   ClCl   Hh   Q1Q1   CH2CH3 CH 2 CH 3   CH2CH3 CH 2 CH 3   2-212-21   CNCN   BrBr   Hh   Q1Q1   CH2CH3 CH 2 CH 3   CH2CH3 CH 2 CH 3   2-222-22   ClCl   ClCl   Hh   Q1Q1   CH3 CH3   CH2CH3 CH 2 CH 3   2-232-23   ClCl   BrBr   Hh   Q1Q1   CH3 CH3   CH2CH3 CH 2 CH 3   2-242-24   CNCN   ClCl   Hh   Q1Q1   CH3 CH3   CH2CH3 CH 2 CH 3

Figure S2008100571021D00171
Figure S2008100571021D00171

  2-602-60   ClCl   BrBr   NO2 NO 2   Q2Q2   CH3 CH3   CH(CH3)2 CH(CH 3 ) 2   2-612-61   CNCN   ClCl   NO2 NO 2   Q2Q2   CH3 CH3   CH(CH3)2 CH(CH 3 ) 2   2-622-62   CNCN   BrBr   NO2 NO 2   Q2Q2   CH3 CH3   CH(CH3)2 CH(CH 3 ) 2   2-632-63   ClCl   ClCl   Hh   Q2Q2   CH2CH3 CH 2 CH 3   CH2CH3 CH 2 CH 3   2-642-64   ClCl   BrBr   Hh   Q2Q2   CH2CH3 CH 2 CH 3   CH2CH3 CH 2 CH 3   2-652-65   CNCN   ClCl   Hh   Q2Q2   CH2CH3 CH 2 CH 3   CH2CH3 CH 2 CH 3   2-662-66   CNCN   BrBr   Hh   Q2Q2   CH2CH3 CH 2 CH 3   CH2CH3 CH 2 CH 3   2-672-67   ClCl   ClCl   Hh   Q2Q2   CH3 CH3   CH2CH3 CH 2 CH 3   2-682-68   ClCl   BrBr   Hh   Q2Q2   CH3 CH3   CH2CH3 CH 2 CH 3   2-692-69   CNCN   ClCl   Hh   Q2Q2   CH3 CH3   CH2CH3 CH 2 CH 3   2-702-70   CNCN   BrBr   Hh   Q2Q2   CH3 CH3   CH2CH3 CH 2 CH 3   2-712-71   ClCl   ClCl   Hh   Q2Q2   CH3 CH3   CH2CH2CH3 CH2CH2CH3 _ _   2-722-72   ClCl   BrBr   Hh   Q2Q2   CH3 CH3   CH2CH2CH3 CH2CH2CH3 _ _   2-732-73   CNCN   ClCl   Hh   Q2Q2   CH3 CH3   CH2CH2CH3 CH2CH2CH3 _ _   2-742-74   CNCN   BrBr   Hh   Q2Q2   CH3 CH3   CH2CH2CH3 CH2CH2CH3 _ _   2-752-75   Hh   ClCl   Hh   Q3Q3   CH3 CH3   CH3 CH3   2-762-76   Hh   BrBr   Hh   Q3Q3   CH3 CH3   CH3 CH3   2-772-77   ClCl   ClCl   Hh   Q3Q3   CH3 CH3   CH3 CH3   2-782-78   ClCl   BrBr   Hh   Q3Q3   CH3 CH3   CH3 CH3   2-792-79   CNCN   ClCl   Hh   Q3Q3   CH3 CH3   CH3 CH3   2-802-80   CNCN   BrBr   Hh   Q3Q3   CH3 CH3   CH3 CH3   2-812-81   ClCl   ClCl   NO2 NO 2   Q3Q3   CH3 CH3   CH3 CH3   2-822-82   ClCl   BrBr   NO2 NO 2   Q3Q3   CH3 CH3   CH3 CH3   2-832-83   CNCN   ClCl   NO2 NO 2   Q3Q3   CH3 CH3   CH3 CH3   2-842-84   CNCN   BrBr   NO2 NO 2   Q3Q3   CH3 CH3   CH3 CH3   2-852-85   ClCl   BrBr   Hh   Q3Q3   CH3 CH3   CH(CH3)2 CH(CH 3 ) 2   2-862-86   CNCN   ClCl   Hh   Q3Q3   CH3 CH3   CH(CH3)2 CH(CH 3 ) 2   2-872-87   CNCN   BrBr   Hh   Q3Q3   CH3 CH3   CH(CH3)2 CH(CH 3 ) 2   2-882-88   ClCl   ClCl   NO2 NO 2   Q3Q3   CH3 CH3   CH(CH3)2 CH(CH 3 ) 2   2-892-89   ClCl   BrBr   NO2 NO 2   Q3Q3   CH3 CH3   CH(CH3)2 CH(CH 3 ) 2   2-902-90   CNCN   ClCl   NO2 NO 2   Q3Q3   CH3 CH3   CH(CH3)2 CH(CH 3 ) 2   2-912-91   CNCN   BrBr   NO2 NO 2   Q3Q3   CH3 CH3   CH(CH3)2 CH(CH 3 ) 2   2-922-92   ClCl   ClCl   Hh   Q3Q3   CH2CH3 CH 2 CH 3   CH2CH3 CH 2 CH 3   2-932-93   ClCl   BrBr   Hh   Q3Q3   CH2CH3 CH 2 CH 3   CH2CH3 CH 2 CH 3   2-942-94   CNCN   ClCl   Hh   Q3Q3   CH2CH3 CH 2 CH 3   CH2CH3 CH 2 CH 3   2-952-95   CNCN   BrBr   Hh   Q3Q3   CH2CH2 CH 2 CH 2   CH2CH3 CH 2 CH 3   2-962-96   ClCl   ClCl   Hh   Q3Q3   CH3 CH3   CH2CH3 CH 2 CH 3   2-972-97   ClCl   BrBr   Hh   Q3Q3   CH3 CH3   CH2CH3 CH 2 CH 3   2-982-98   CNCN   ClCl   Hh   Q3Q3   CH3 CH3   CH2CH3 CH 2 CH 3   2-992-99   CNCN   BrBr   Hh   Q3Q3   CH3 CH3   CH2CH3 CH 2 CH 3   2-1002-100   ClCl   ClCl   Hh   Q3Q3   CH3 CH3   CH2CH2CH3 CH2CH2CH3 _ _   2-1012-101   ClCl   BrBr   Hh   Q3Q3   CH3 CH3   CH2CH2CH3 CH2CH2CH3 _ _   2-1022-102   CNCN   ClCl   Hh   Q3Q3   CH3 CH3   CH2CH2CH3 CH2CH2CH3 _ _

  2-1032-103   CNCN   BrBr   Hh   Q3Q3   CH3 CH3   CH2CH2CH3 CH2CH2CH3 _ _   2-1042-104   Hh   ClCl   Hh   Q4Q4   CH3 CH3   CH3 CH3   2-1052-105   Hh   BrBr   Hh   Q4Q4   CH3 CH3   CH3 CH3   2-1062-106   ClCl   ClCl   Hh   Q4Q4   CH3 CH3   CH3 CH3   2-1072-107   ClCl   BrBr   Hh   Q4Q4   CH3 CH3   CH3 CH3   2-1082-108   CNCN   ClCl   Hh   Q4Q4   CH3 CH3   CH3 CH3   2-1092-109   CNCN   BrBr   Hh   Q4Q4   CH3 CH3   CH3 CH3   2-1102-110   ClCl   ClCl   NO2 NO 2   Q4Q4   CH3 CH3   CH3 CH3   2-1112-111   ClCl   BrBr   NO2 NO 2   Q4Q4   CH3 CH3   CH3 CH3   2-1122-112   CNCN   ClCl   NO2 NO 2   Q4Q4   CH3 CH3   CH3 CH3   2-1132-113   CNCN   BrBr   NO2 NO 2   Q4Q4   CH3 CH3   CH3 CH3   2-1142-114   ClCl   BrBr   Hh   Q4Q4   CH3 CH3   CH(CH3)2 CH(CH 3 ) 2   2-1152-115   CNCN   ClCl   Hh   Q4Q4   CH3 CH3   CH(CH3)2 CH(CH 3 ) 2   2-1162-116   CNCN   BrBr   Hh   Q4Q4   CH3 CH3   CH(CH3)2 CH(CH 3 ) 2   2-1172-117   ClCl   ClCl   NO2 NO 2   Q4Q4   CH3 CH3   CH(CH3)2 CH(CH 3 ) 2   2-1182-118   ClCl   BrBr   NO2 NO 2   Q4Q4   CH3 CH3   CH(CH3)2 CH(CH 3 ) 2   2-1192-119   CNCN   ClCl   NO2 NO 2   Q4Q4   CH3 CH3   CH(CH3)2 CH(CH 3 ) 2   2-1202-120   CNCN   BrBr   NO2 NO 2   Q4Q4   CH3 CH3   CH(CH3)2 CH(CH 3 ) 2   2-1212-121   ClCl   ClCl   Hh   Q4Q4   CH2CH3 CH 2 CH 3   CH2CH3 CH 2 CH 3   2-1222-122   ClCl   BrBr   Hh   Q4Q4   CH2CH3 CH 2 CH 3   CH2CH3 CH 2 CH 3   2-1232-123   CNCN   ClCl   Hh   Q4Q4   CH2CH3 CH 2 CH 3   CH2CH3 CH 2 CH 3   2-1242-124   CNCN   BrBr   Hh   Q4Q4   CH2CH3 CH 2 CH 3   CH2CH3 CH 2 CH 3   2-1252-125   ClCl   ClCl   Hh   Q4Q4   CH3 CH3   CH2CH3 CH 2 CH 3   2-1262-126   ClCl   BrBr   Hh   Q4Q4   CH3 CH3   CH2CH3 CH 2 CH 3   2-1272-127   CNCN   ClCl   Hh   Q4Q4   CH3 CH3   CH2CH3 CH 2 CH 3   2-1282-128   CNCN   BrBr   Hh   Q4Q4   CH3 CH3   CH2CH3 CH 2 CH 3   2-1292-129   ClCl   ClCl   Hh   Q4Q4   CH3 CH3   CH2CH2CH3 CH2CH2CH3 _ _   2-1302-130   ClCl   BrBr   Hh   Q4Q4   CH3 CH3   CH2CH2CH3 CH2CH2CH3 _ _   2-1312-131   CNCN   ClCl   Hh   Q4Q4   CH3 CH3   CH2CH2CH3 CH2CH2CH3 _ _   2-1322-132   CNCN   BrBr   Hh   Q4Q4   CH3 CH3   CH2CH2CH3 CH2CH2CH3 _ _   2-1332-133   Hh   ClCl   Hh   Q5Q5   CH3 CH3   CH3 CH3   2-1342-134   Hh   BrBr   Hh   Q5Q5   CH3 CH3   CH3 CH3   2-1352-135   ClCl   ClCl   Hh   Q5Q5   CH3 CH3   CH3 CH3   2-1362-136   ClCl   BrBr   Hh   Q5Q5   CH3 CH3   CH3 CH3   2-1372-137   CNCN   ClCl   Hh   Q5Q5   CH3 CH3   CH3 CH3   2-1382-138   CNCN   BrBr   Hh   Q5Q5   CH3 CH3   CH3 CH3   2-1392-139   ClCl   ClCl   NO2 NO 2   Q5Q5   CH3 CH3   CH3 CH3   2-1402-140   ClCl   BrBr   NO2 NO 2   Q5Q5   CH3 CH3   CH3 CH3   2-1412-141   CNCN   ClCl   NO2 NO 2   Q5Q5   CH3 CH3   CH3 CH3   2-1422-142   CNCN   BrBr   NO2 NO 2   Q5Q5   CH3 CH3   CH3 CH3   2-1432-143   ClCl   BrBr   Hh   Q5Q5   CH3 CH3   CH(CH3)2 CH(CH 3 ) 2   2-1442-144   CNCN   ClCl   Hh   Q5Q5   CH3 CH3   CH(CH3)2 CH(CH 3 ) 2   2-1452-145   CNCN   BrBr   Hh   Q5Q5   CH3 CH3   CH(CH3)2 CH(CH 3 ) 2

  2-1462-146   ClCl   ClCl   NO2 NO 2   Q5Q5   CH3 CH3   CH(CH3)2 CH(CH 3 ) 2   2-1472-147   ClCl   BrBr   NO2 NO 2   Q5Q5   CH3 CH3   CH(CH3)2 CH(CH 3 ) 2   2-1482-148   CNCN   ClCl   NO2 NO 2   Q5Q5   CH3 CH3   CH(CH3)2 CH(CH 3 ) 2   2-1492-149   CNCN   BrBr   NO2 NO 2   Q5Q5   CH3 CH3   CH(CH3)2 CH(CH 3 ) 2   2-1502-150   ClCl   ClCl   Hh   Q5Q5   CH2CH3 CH 2 CH 3   CH2CH3 CH 2 CH 3   2-1512-151   ClCl   BrBr   Hh   Q5Q5   CH2CH3 CH 2 CH 3   CH2CH3 CH 2 CH 3   2-1522-152   CNCN   ClCl   Hh   Q5Q5   CH2CH3 CH 2 CH 3   CH2CH3 CH 2 CH 3   2-1532-153   CNCN   BrBr   Hh   Q5Q5   CH2CH3 CH 2 CH 3   CH2CH3 CH 2 CH 3   2-1542-154   ClCl   ClCl   Hh   Q5Q5   CH3 CH3   CH2CH3 CH 2 CH 3   2-1552-155   ClCl   BrBr   Hh   Q5Q5   CH3 CH3   CH2CH3 CH 2 CH 3   2-1562-156   CNCN   ClCl   Hh   Q5Q5   CH3 CH3   CH2CH3 CH 2 CH 3   2-1572-157   CNCN   BrBr   Hh   Q5Q5   CH3 CH3   CH2CH3 CH 2 CH 3   2-1582-158   ClCl   ClCl   Hh   Q5Q5   CH3 CH3   CH2CH2CH3 CH2CH2CH3 _ _   2-1592-159   ClCl   BrBr   Hh   Q5Q5   CH3 CH3   CH2CH2CH3 CH2CH2CH3 _ _   2-1602-160   CNCN   ClCl   Hh   Q5Q5   CH3 CH3   CH2CH2CH3 CH2CH2CH3 _ _   2-1612-161   CNCN   BrBr   Hh   Q5Q5   CH3 CH3   CH2CH2CH3 CH2CH2CH3 _ _

本发明的通式I化合物可以按照以下方法制备：The compound of general formula I of the present invention can be prepared according to the following methods:

方法一：method one:

通式I化合物可由通式II所示的恶嗪酮类化合物与取代的胺、醇反应制得：The compound of general formula I can be prepared by reacting oxazinone compounds shown in general formula II with substituted amines and alcohols:

Figure S2008100571021D00201
Figure S2008100571021D00201

方法二：Method Two:

通式I化合物可由通式IV所示的茚红酸酐类化合物与取代的胺、醇反应制得的苯胺中间体III，再与吡唑酰氯缩合制得，其中吡唑酰氯可由相应的羧酸(如通式VI所示)通过常规方法制得，如与氯化亚砜反应：The compound of general formula I can be prepared by the aniline intermediate III prepared by reacting indene acid anhydride compounds shown in general formula IV with substituted amines and alcohols, and then condensed with pyrazole acid chloride, wherein pyrazole acid chloride can be prepared by corresponding carboxylic acid ( As shown in general formula VI) is prepared by conventional methods, such as reacting with thionyl chloride:

Figure S2008100571021D00202
Figure S2008100571021D00202

通式IVIV中间体可由通式V所示的取代的邻氨基苯甲酸中间体与固体光气反应制得：The intermediate of general formula IVIV can be prepared by reacting the substituted anthranilic acid intermediate shown in general formula V with solid phosgene:

通式中各基团的定义同前。The definition of each group in the general formula is the same as before.

反应在溶剂中进行，适宜的选自如乙腈、四氢呋喃、乙醚、二氯甲烷、氯仿、乙酸乙酯、二氧六环、甲苯等。The reaction is carried out in a solvent, suitably selected from acetonitrile, tetrahydrofuran, diethyl ether, dichloromethane, chloroform, ethyl acetate, dioxane, toluene and the like.

反应温度在室温至溶剂沸点温度之间，通常为20～100℃。The reaction temperature is between room temperature and the boiling point of the solvent, usually 20-100°C.

反应时间为30分钟至20小时，通常1～10小时。The reaction time is 30 minutes to 20 hours, usually 1 to 10 hours.

上述制备方法中所涉及的原料中间体及来源如下：The raw material intermediate involved in the above-mentioned preparation method and source are as follows:

Figure S2008100571021D00212
Figure S2008100571021D00212

通式II为恶嗪酮类化合物，相关综述见Biorganic and Medicinal Chemistry 2000，8，2095-2103.和J.Heterocyclic Chemistry 1999，36，563-588，其制备方法参照WO03015519、WO2005118552方法。The general formula II is an oxazinone compound. For related reviews, see Biorganic and Medicinal Chemistry 2000, 8, 2095-2103. and J. Heterocyclic Chemistry 1999, 36, 563-588. The preparation method refers to the methods of WO03015519 and WO2005118552.

通式V所示的邻氨基苯甲酸类化合物可由芳胺经两步制得，参照如下文献：OrganicSyntheses，Coll.Vo1.10，p.23(2004)；Vol.79，p.196(2002)；Adv.Heterocycl.Chem.1975，18，1-58；Journal of the Brazilian Chemical Society 2001，12(3)，273-324；Angew.Chem.Int.Ed.Engl.1980，19，222-223。The anthranilic acid compound shown in general formula V can be prepared by aromatic amine through two steps, refer to following document: Organic Syntheses, Coll.Vo1.10, p.23 (2004); Vol.79, p.196 (2002) ; Adv.Heterocycl.Chem.1975, 18, 1-58; Journal of the Brazilian Chemical Society 2001, 12(3), 273-324;

通式VI所示的羧酸化合物的制备方法参照WO2006062978、WO03015519。The preparation method of the carboxylic acid compound represented by the general formula VI refers to WO2006062978 and WO03015519.

取代的胺、醇部分有市售，也可按照常规方法自制。Substituted amines and alcohols are commercially available, and can also be made by conventional methods.

本发明的通式I化合物对农业、民用和动物技术领域中有害昆虫的成虫、幼虫和卵都显示出高杀虫活性。因此，本发明还包括通式I化合物在农业或其他领域中作为杀虫剂的应用。包括使该无脊椎动物害虫或该害虫所处的农学或非农学环境与生物学有效量的通式I化合物接触。The compound of general formula I of the present invention shows high insecticidal activity against adults, larvae and eggs of harmful insects in agricultural, civil and animal technology fields. Therefore, the present invention also includes the use of the compound of general formula I as a pesticide in agriculture or other fields. It includes contacting the invertebrate pest or the agronomic or non-agronomic environment in which the pest lives with a biologically effective amount of a compound of general formula I.

尤其是，通式I化合物对下列科和目的重要品种有活性：鳞翅目(贪夜蛾属、实夜蛾属、禾草螟属、苹果皮小卷蛾等)。例如对欧洲玉米螟、甘蔗螟、苹果小卷蛾、苹果食心虫、舞毒蛾等十分有效，特别是对小菜蛾活性更好，在很低的剂量下就可以获得很好的效果。In particular, the compounds of the general formula I are active against important species of the following families and orders: Lepidoptera (Spodoptera, Helicoptera, Grass moth, Apple-skin tortilla, etc.). For example, it is very effective against European corn borer, sugarcane borer, apple tortrix, apple borer, gypsy moth, etc., especially against diamondback moth, and can obtain good results at a very low dose.

同时，通式I化合物对许多有益的昆虫和螨虫、哺乳动物、鱼、鸟具有低毒性，而且没有植物毒性。At the same time, the compound of general formula I has low toxicity to many beneficial insects and mites, mammals, fish, birds, and has no phytotoxicity.

由于其积极的特性，上述化合物可有利地用于保护农业和园艺业重要的作物、家畜和种畜，以及人类常去的环境免于有害昆虫和真菌的伤害。Due to their positive properties, the above-mentioned compounds can be advantageously used for protecting agriculturally and horticulturally important crops, livestock and breeding stock, and environments frequented by humans from harmful insects and fungi.

为获得理想效果，化合物的用量因各种因素而改变，例如所用化合物、预保护的作物、有害生物的类型、感染程度、气候条件、施药方法、采用的剂型。The amount of compound used to achieve the desired effect will vary depending on factors such as compound used, crop to be protected, type of pest, degree of infestation, climatic conditions, method of application, formulation employed.

每公顷10克-5公斤的化合物剂量能提供充分的防治。Doses of 10 g-5 kg of compound per hectare provide adequate control.

本发明的另一目的还涉及通过施用通式I化合物，防治农业和园艺业重要的作物和/或家畜和种畜和/或人类常去的环境中的昆虫和/或植物致病性真菌的方法。尤其是，化合物的用量在每公顷10克-5公斤内变化。Another object of the present invention also relates to a method for controlling insects and/or phytopathogenic fungi in agriculturally and horticulturally important crops and/or livestock and breeding stock and/or in environments frequented by humans by applying compounds of general formula I . In particular, the amount of compound used varies from 10 g to 5 kg per hectare.

为了实际应用于农业，使用含一种或多种通式I化合物的组合物通常是有益的。For practical use in agriculture it is often advantageous to use compositions comprising one or more compounds of general formula I.

本发明还涉及用于防治无脊椎动物害虫的组合物，其包含生物学有效量的通式I化合物和至少一种选自表面活性剂、固体稀释剂和液体稀释剂，以及可以含有任选的有效量的至少一种附加生物学活性化合物。The present invention also relates to a composition for controlling invertebrate pests, which comprises a biologically effective amount of a compound of general formula I and at least one selected from surfactants, solid diluents and liquid diluents, and may optionally contain An effective amount of at least one additional biologically active compound.

本发明还涉及一种组合物在农业或其他领域中作为杀虫剂的应用，包括使该无脊椎动物害虫或该害虫所处的农学或非农学环境与生物学有效量的组合物接触，所述组合物包含生物学有效量的通式I化合物和至少一种选自表面活性剂、固体稀释剂或液体稀释剂的附加组分，所述组合物还可以任选进一步包含有效量的至少一种附加生物学活性化合物。The present invention also relates to the use of a composition as a pesticide in agriculture or other fields, comprising contacting the invertebrate pest or the agronomic or non-agronomic environment in which the pest is in contact with a biologically effective amount of the composition, wherein Said composition comprises the compound of general formula I of biologically effective amount and at least one additional component selected from surfactant, solid diluent or liquid diluent, and said composition can also optionally further comprise effective amount of at least one additional biologically active compounds.

组合物的使用形式可以是干粉、可湿性粉剂、乳油、微乳剂、糊剂、颗粒剂、溶液、悬浮剂等：组合物类型的选择取决于具体的应用。The composition can be used in the form of dry powder, wettable powder, emulsifiable concentrate, microemulsion, paste, granule, solution, suspension, etc.: the choice of composition type depends on the specific application.

组合物是以已知方法制备的，例如任选在表面活性剂的存在下，通过用溶剂介质和/或固体稀释剂稀释或溶解活性物质。The compositions are prepared in known manner, for example by diluting or dissolving the active substance with a solvent medium and/or a solid diluent, optionally in the presence of surfactants.

可用的固体稀释剂或载体是例如：二氧化硅、高岭土、膨润土、滑石、硅藻土、白云石、碳酸钙、氧化镁、白垩、粘土、合成硅酸盐、硅镁土、海泡石等。Usable solid diluents or carriers are, for example: silica, kaolin, bentonite, talc, diatomaceous earth, dolomite, calcium carbonate, magnesium oxide, chalk, clay, synthetic silicates, attapulgite, sepiolite, etc. .

除水以外，可用的液体稀释剂还包括如芳族有机溶剂(二甲苯或烷基苯的混合物、氯苯等)，石蜡(石油馏分)，醇类(甲醇、丙醇、丁醇、辛醇、甘油)，酯类(乙酸乙酯、乙酸异丁酯等)，酮类(环己酮、丙酮、苯乙酮、异佛尔酮、乙基戊基酮等)，酰胺类(N，N-二甲基甲酰胺、N-甲基吡咯烷酮等)。In addition to water, usable liquid diluents include aromatic organic solvents (mixtures of xylene or alkylbenzenes, chlorobenzene, etc.), paraffins (petroleum fractions), alcohols (methanol, propanol, butanol, octanol , glycerin), esters (ethyl acetate, isobutyl acetate, etc.), ketones (cyclohexanone, acetone, acetophenone, isophorone, ethyl amyl ketone, etc.), amides (N, N -dimethylformamide, N-methylpyrrolidone, etc.).

可用的表面活性剂是烷基磺酸盐、烷基芳基磺酸盐、聚氧乙烯烷基酚、山梨醇的聚氧乙烯酯、木质素磺酸盐等的钠、钙、三乙基胺或三乙醇胺盐。Surfactants that can be used are sodium, calcium, triethylamine of alkylsulfonates, alkylarylsulfonates, polyoxyethylene alkylphenols, polyoxyethylene esters of sorbitol, lignosulfonates, etc. or triethanolamine salt.

组合物还可含特殊的添加剂用于特定的目的，例如含有粘合剂如阿拉伯胶、聚乙烯醇、聚乙烯吡咯烷酮等。The composition may also contain special additives for specific purposes, such as binders such as gum arabic, polyvinyl alcohol, polyvinylpyrrolidone and the like.

上述组合物中活性成分的浓度可根据活性成分、使用目的、环境条件和采用的制剂类型而在宽范围内改变。通常，活性成分的浓度范围是1-90％，优选5-60％。The concentration of the active ingredient in the above compositions may vary within wide limits depending on the active ingredient, purpose of use, environmental conditions and type of formulation employed. Usually, the concentration range of the active ingredient is 1-90%, preferably 5-60%.

如果需要，可以向组合物中添加能与通式I化合物兼容的其他活性成分，例如其他杀螨剂/杀虫剂、杀真菌剂、植物生长调节剂、抗生素、除草剂、肥料。If desired, other active ingredients compatible with the compounds of general formula I, such as other acaricides/insecticides, fungicides, plant growth regulators, antibiotics, herbicides, fertilizers, can be added to the composition.

几种剂型的配制方法举例如下：The preparation methods of several dosage forms are exemplified as follows:

悬浮剂的配制：常用配方中活性组分含量为5％-35％。以水为介质，将原药、分散剂、助悬剂和抗冻剂等加入砂磨机中，进行研磨，制成悬浮剂。Suspension preparation: the content of active ingredients in common formulations is 5%-35%. Using water as the medium, add the original drug, dispersant, suspending agent and antifreeze into a sand mill for grinding to make a suspension.

水乳剂的配制：将原药、溶剂和乳化剂加在一起，使溶解成均匀油相。将水、抗冻剂等混合一起，成为均一水相。在高速搅拌下，将水相加入到油相或将油相加入到水相，形成分散性良好的水乳剂。本发明的水乳剂活性组分含量一般为5％-15％。为制备浓乳剂，本发明的化合物可溶解于一种或数种混合溶剂，再加入乳化剂来增强化合物在水中的分散效果。Preparation of emulsion in water: Add the original drug, solvent and emulsifier together to dissolve into a uniform oil phase. Mix water, antifreeze, etc. together to form a homogeneous water phase. Under high-speed stirring, add the water phase to the oil phase or add the oil phase to the water phase to form a water emulsion with good dispersibility. The active component content of the aqueous emulsion of the present invention is generally 5%-15%. To prepare a concentrated emulsion, the compound of the present invention can be dissolved in one or several mixed solvents, and then an emulsifier is added to enhance the dispersion effect of the compound in water.

可湿性粉剂的配制：按配方要求，将原药、各种表面活性剂及固体稀释剂等充分混合，经超细粉碎机粉碎后，即得到预定含量(例如10％-60％)的可湿性粉剂产品。为制备适于喷洒用的可湿性粉剂，本发明的化合物可以和研细的固体粉末如粘土、无机硅酸盐、碳酸盐以及润湿剂、粘合剂和/或分散剂组成混合物。Preparation of wettable powder: according to the formula requirements, the original drug, various surfactants and solid diluents are fully mixed, and after being pulverized by a superfine pulverizer, a wettability powder with a predetermined content (such as 10%-60%) can be obtained. Powder products. To prepare wettable powders suitable for spraying, the compounds according to the invention can be mixed with finely divided solid powders such as clays, inorganic silicates, carbonates and wetting, binding and/or dispersing agents.

水分散性粒剂的配制：将原药和粉状固体稀释剂、润湿展着剂及粘合剂等进行混合粉碎，再加水捏合后，加入装有一定规格筛网的造粒机中进行造粒，然后再经干燥、筛分(按筛网范围)。也可将原药、分散剂、崩解剂和润湿剂及固体稀释剂加入砂磨机中，以水为介质研磨，制成悬浮剂，然后进行喷雾干燥造粒，通常配制含量为20％-30％颗粒状产品。Preparation of water-dispersible granules: mix and pulverize the original drug, powdery solid diluent, wetting and spreading agent, and binder, add water and knead, then add to a granulator equipped with a certain size screen. Granulate, then dry and sieve (according to the size of the sieve). The original drug, dispersant, disintegrating agent, wetting agent and solid diluent can also be added to a sand mill, ground with water as a medium to make a suspension, and then spray-dried and granulated, usually with a preparation content of 20% -30% granular product.

具体实施方式Detailed ways

以下具体实施例用来进一步说明本发明，但本发明绝非限于这些例子。The following specific examples are used to further illustrate the present invention, but the present invention is by no means limited to these examples.

合成实施例Synthetic example

实例1：化合物1-152的制备Example 1: Preparation of Compound 1-152

取0.5克II-I于50毫升反应瓶中，加入25毫升四氢呋喃，搅拌下加入1克HOCH2CH2N(CH3)2，升温回流反应1小时。TLC监测反应完毕后，减压脱溶后，向反应瓶中倒入50毫升饱和食盐水中，用60毫升乙酸乙酯分三次进行萃取，干燥，脱溶，柱层析得产品0.31克，即化合物1-152，收率51.8％。熔点80-82℃。Take 0.5 g of II-I in a 50 ml reaction flask, add 25 ml of tetrahydrofuran, add 1 g of HOCH 2 CH 2 N(CH 3 ) 2 under stirring, and raise the temperature to reflux for 1 hour. After TLC monitors the completion of the reaction, after desolvation under reduced pressure, pour 50 milliliters of saturated saline into the reaction flask, extract three times with 60 milliliters of ethyl acetate, dry, and desolventize, and column chromatography gives 0.31 grams of the product, namely the compound 1-152, yield 51.8%. The melting point is 80-82°C.

核磁数据(1HNMR，300MHz，内标TMS，溶剂CDCl3)如下：NMR data ( 1 HNMR, 300MHz, internal standard TMS, solvent CDCl 3 ) are as follows:

化合物1-152：δppm 2.18(3H，s)，2.41(6H，s)，2.79(2H，t)，4.45(2H，t)，7.19(1H，s)，7.39(2H，m)，7.80-7.88(2H，m)，8.45(1H，q)，10.14(1H，s)。Compound 1-152: δppm 2.18 (3H, s), 2.41 (6H, s), 2.79 (2H, t), 4.45 (2H, t), 7.19 (1H, s), 7.39 (2H, m), 7.80- 7.88 (2H, m), 8.45 (1H, q), 10.14 (1H, s).

实例2：化合物2-2的制备Example 2: Preparation of compound 2-2

取1克IV-1于100毫升反应瓶，加入50毫升二氧六环及中间体H2NC(CH3)2CN，回流反应3小时。TLC监测反应完毕后，减压脱溶后，向反应瓶中倒入50毫升饱和食盐水，用90毫升乙酸乙酯分三次进行萃取，干燥，脱溶，柱层析得III-1中间体0.63克。Take 1 g of IV-1 in a 100 ml reaction bottle, add 50 ml of dioxane and intermediate H 2 NC(CH 3 ) 2 CN, and react under reflux for 3 hours. After the completion of the reaction as monitored by TLC, after desolvation under reduced pressure, 50 ml of saturated saline was poured into the reaction flask, extracted three times with 90 ml of ethyl acetate, dried, and desolvated, and column chromatography gave III-1 intermediate 0.63 gram.

将制得的中间体III-1溶于60毫升四氢呋喃，加入1毫升三乙胺，搅拌下滴加1.02克酰氯，室温反应4小时，TLC监测反应完毕后，处理，柱层析得产品0.45克，即化合物2-2，收率31％。熔点170-172℃。The prepared intermediate III-1 was dissolved in 60 ml of tetrahydrofuran, 1 ml of triethylamine was added, 1.02 g of acid chloride was added dropwise under stirring, and the reaction was carried out at room temperature for 4 hours. After the reaction was monitored by TLC, 0.45 g of the product was obtained by column chromatography , namely compound 2-2, the yield is 31%. The melting point is 170-172°C.

核磁数据(1HNMR，300MHz，内标TMS，溶剂CDCl3)如下：NMR data ( 1 HNMR, 300MHz, internal standard TMS, solvent CDCl 3 ) are as follows:

化合物2-2：δppm 1.71(6H，s)，2.10(3H，s)，3.95(1H，s)，6.75(1H，t)，6.89(1H，s)，7.16-7.24(2H，m)，7.66-7.73(2H，m)，8.38(1H，q)。Compound 2-2: δppm 1.71(6H, s), 2.10(3H, s), 3.95(1H, s), 6.75(1H, t), 6.89(1H, s), 7.16-7.24(2H, m), 7.66-7.73 (2H, m), 8.38 (1H, q).

实例3：化合物2-6的制备Example 3: Preparation of Compound 2-6

Figure S2008100571021D00241
Figure S2008100571021D00241

取0.5克II-2于50毫升反应瓶中，加入25毫升乙腈，搅拌下加入0.8克H2NC(CH3)2CN，升温回流反应3小时。TLC监测反应完毕后，减压脱溶后，向反应瓶中倒入50毫升饱和食盐水，用90毫升乙酸乙酯分三次进行萃取，干燥，脱溶，柱层析得产品0.27克，即化合物2-6，收率45.3％。熔点140-142℃。Take 0.5 g of II-2 in a 50 ml reaction flask, add 25 ml of acetonitrile, add 0.8 g of H 2 NC(CH 3 ) 2 CN while stirring, and heat up to reflux for 3 hours. After TLC monitors the completion of the reaction, after desolvation under reduced pressure, pour 50 milliliters of saturated saline into the reaction flask, extract three times with 90 milliliters of ethyl acetate, dry, and desolventize, and obtain 0.27 grams of product by column chromatography, namely compound 2-6, yield 45.3%. The melting point is 140-142°C.

核磁数据(1HNMR，300MHz，内标TMS，溶剂CDCl3)如下：NMR data ( 1 HNMR, 300MHz, internal standard TMS, solvent CDCl 3 ) are as follows:

化合物2-6：δppm 1.95(6H，s)，2.65(3H，s)，6.85(1H，s)，7.28(1H，q)，7.87(1H，s)，7.92(1H，d)，8.30(1H，q)，8.48(1H，s)。Compound 2-6: δppm 1.95 (6H, s), 2.65 (3H, s), 6.85 (1H, s), 7.28 (1H, q), 7.87 (1H, s), 7.92 (1H, d), 8.30 ( 1H,q), 8.48(1H,s).

通式I的其他化合物可以用本发明提供的制备方法制得。Other compounds of general formula I can be prepared by the preparation methods provided by the present invention.

部分通式I化合物的熔点和核磁数据(1HNMR，300MHz，内标TMS，溶剂CDCl3)如下：The melting points and NMR data ( 1 HNMR, 300 MHz, internal standard TMS, solvent CDCl 3 ) of some compounds of general formula I are as follows:

化合物1-102：熔点118-120℃。δppm 2.23(3H，s)，3.92(3H，s)，7.06(1H，s)，7.19(1H，m)，7.38(2H，m)，7.84(2H，m)，8.47(1H，q)，10.19(1H，s)。Compound 1-102: melting point 118-120°C. δppm 2.23(3H, s), 3.92(3H, s), 7.06(1H, s), 7.19(1H, m), 7.38(2H, m), 7.84(2H, m), 8.47(1H, q), 10.19 (1H, s).

化合物1-104：熔点170-172℃。δppm 2.24(3H，s)，3.74(3H，s)，7.33(1H，s)，7.51-7.59(3H，m)，8.07(1H，q)，8.47(1H，q)，10.25(1H，s)。Compound 1-104: melting point 170-172°C. δppm 2.24(3H, s), 3.74(3H, s), 7.33(1H, s), 7.51-7.59(3H, m), 8.07(1H, q), 8.47(1H, q), 10.25(1H, s ).

化合物1-205：熔点60-62℃。δppm 1.12(6H，t)，2.21(3H，s)，2.68(4H，q)，2.88(2H，t)，4.41(2H，t)，7.13(1H，s)，7.39(2H，m)，7.80(1H，d)，7.86(1H，q)，8.46(1H，q)，10.17(1H，s)。Compound 1-205: melting point 60-62°C. δppm 1.12(6H, t), 2.21(3H, s), 2.68(4H, q), 2.88(2H, t), 4.41(2H, t), 7.13(1H, s), 7.39(2H, m), 7.80 (1H, d), 7.86 (1H, q), 8.46 (1H, q), 10.17 (1H, s).

化合物1-218：熔点206-207℃。δppm 2.17(3H，s)，3.67(2H，m)，3.72(2H，m)，6.55(1H，s)，7.07(1H，s)，7.34(1H，s)，7.36(1H，s)，7.37(1H，q)，7.84(1H，d)，8.45(1H，d)，9.89(1H，s)。Compound 1-218: melting point 206-207°C. δppm 2.17(3H, s), 3.67(2H, m), 3.72(2H, m), 6.55(1H, s), 7.07(1H, s), 7.34(1H, s), 7.36(1H, s), 7.37 (1H, q), 7.84 (1H, d), 8.45 (1H, d), 9.89 (1H, s).

化合物1-220：熔点240-242℃。δppm 2.26(3H，s)，3.73(2H，m)，3.79(2H，m)，6.58(1H，s)，7.02(1H，s)，7.41(1H，q)，7.36(1H，s)，7.64(2H，m)，7.86(1H，d)，8.43(1H，d)，10.41(1H，s)。Compound 1-220: melting point 240-242°C. δppm 2.26(3H, s), 3.73(2H, m), 3.79(2H, m), 6.58(1H, s), 7.02(1H, s), 7.41(1H, q), 7.36(1H, s), 7.64 (2H, m), 7.86 (1H, d), 8.43 (1H, d), 10.41 (1H, s).

化合物1-264：熔点208-209℃。δppm 2.19(3H，s)，3.41(6H，s)，3.55(2H，m)，4.43(1H，t)，6.28(1H，t)，7.07(1H，s)，7.26(2H，m)，7.38(1H，q)，7.85(1H，q)，8.46(1H，q)，10.08(1H，s)。Compound 1-264: melting point 208-209°C. δppm 2.19(3H, s), 3.41(6H, s), 3.55(2H, m), 4.43(1H, t), 6.28(1H, t), 7.07(1H, s), 7.26(2H, m), 7.38(1H,q), 7.85(1H,q), 8.46(1H,q), 10.08(1H,s).

化合物1-266：熔点182-183℃。δppm 2.22(3H，t)，3.42(6H，s)，3.58(2H，m)，4.43(1H，t)，6.33(1H，t)，7.07(1H，s)，7.22(2H，m)，7.36(1H，q)，7.80(1H，q)，8.46(1H，q)，10.20(1H，s)。Compound 1-266: melting point 182-183°C. δppm 2.22(3H, t), 3.42(6H, s), 3.58(2H, m), 4.43(1H, t), 6.33(1H, t), 7.07(1H, s), 7.22(2H, m), 7.36(1H,q), 7.80(1H,q), 8.46(1H,q), 10.20(1H,s).

化合物2-4：熔点190-192℃。δppm 1.70(6H，s)，2.10(3H，s)，3.95(1H，s)，6.87(1H，s)，7.21-7.25(2H，m)，7.70-7.75(2H，m)，8.39(1H，d)。Compound 2-4: melting point 190-192°C. δppm 1.70(6H, s), 2.10(3H, s), 3.95(1H, s), 6.87(1H, s), 7.21-7.25(2H, m), 7.70-7.75(2H, m), 8.39(1H , d).

制剂实施例(各组分加入量均为重量百分含量，活性化合物折百后计量加入)Formulation example (the addition amount of each component is the weight percent content, and the active compound is metered in after 100 percent)

实施例4：30％可湿性粉剂Example 4: 30% WP

化合物1-152         30％Compound 1-152 30%

十二烷基硫酸钠      2％Sodium Lauryl Sulfate 2%

木质素磺酸钠        3％Sodium lignosulfonate 3%

萘磺酸甲醛缩合物    5％Naphthalenesulfonic acid formaldehyde condensate 5%

轻质碳酸钙    补足至100％Light Calcium Carbonate Top up to 100%

将化合物1-152、各种表面活性剂及固体稀释剂等充分混合，经超细粉碎机粉碎后，即得到30％的可湿性粉剂产品。Compound 1-152, various surfactants and solid diluents are fully mixed, and pulverized by an ultrafine pulverizer to obtain a 30% wettable powder product.

实施例5：20％悬浮剂Embodiment 5: 20% suspending agent

化合物1-218             20％Compound 1-218 20%

甲基萘磺酸甲醛缩合物    3％Methylnaphthalenesulfonic acid formaldehyde condensate 3%

农乳0201B               2％Agricultural Milk 0201B 2%

农乳700#                1％Farm milk 700# 1%

黄原胶                  0.2％Xanthan Gum 0.2%

乙二醇                  5％Ethylene Glycol 5%

水                补足至100％Water up to 100%

以水为介质，将化合物1-218、分散剂、助悬剂和抗冻剂等加入砂磨机中，进行研磨，制成悬浮剂。Using water as the medium, add compound 1-218, dispersant, suspending agent and antifreeze into a sand mill and grind to prepare a suspension.

实施例6：60％水分散性粒剂Example 6: 60% water dispersible granules

化合物1-220               60％Compound 1-220 60%

萘磺酸钠甲醛缩合物        12％Sodium naphthalenesulfonate formaldehyde condensate 12%

N-甲基-油酰基-牛磺酸钠    8％Sodium N-methyl-oleoyl-taurate 8%

聚乙烯吡咯烷酮            2％Polyvinylpyrrolidone 2%

羧甲基纤维素              2％Carboxymethylcellulose 2%

高岭土              补足至100％Kaolin topped up to 100%

将化合物1-220和粉状固体稀释剂、润湿展着剂及粘合剂等进行混合粉碎，再加水捏合后，加入10-100目筛网的造粒机中进行造粒，然后再经干燥、筛分(按筛网范围)。Compound 1-220 is mixed with powdery solid diluent, wetting and spreading agent, binder, etc., mixed and pulverized, added water and kneaded, then added to a granulator with a 10-100 mesh screen for granulation, and then passed through Dry and sieve (according to the sieve range).

实施例7：10％水乳剂Example 7: 10% water emulsion

化合物1-264           10％Compound 1-264 10%

聚氧乙烯(n20)苯乙基Polyoxyethylene (n 20 ) phenylethyl

酚基醚油酸酯          8％Phenyl ether oleate 8%

十二烷基苯磺酸钙      16％Calcium dodecylbenzenesulfonate 16%

胡椒基丁醚            15％Piperonyl butoxide 15%

环己酮                10％Cyclohexanone 10%

山梨醇                5％Sorbitol 5%

水              补足至100％Water up to 100%

将化合物1-264、溶剂和乳化剂加在一起，使溶解成均匀油相。将水、抗冻剂等混合一起，成为均一水相。在高速搅拌下，将水相与油相混合，形成分散性良好的水乳剂。Compound 1-264, solvent and emulsifier were added together and allowed to dissolve into a homogeneous oil phase. Mix water, antifreeze, etc. together to form a homogeneous water phase. Under high-speed stirring, mix the water phase and the oil phase to form a water emulsion with good dispersibility.

实施例8：25％悬浮剂Example 8: 25% suspending agent

化合物2-6           25％Compound 2-6 25%

农乳0201B           2.5％Agricultural Milk 0201B 2.5%

农乳1601            1％Farm Milk 1601 1%

萘磺酸甲醛缩合物    2％Naphthalenesulfonic acid formaldehyde condensate 2%

白碳黑              0.1％White carbon black 0.1%

乙二醇              5％Ethylene Glycol 5%

水            补足至100％Water to make up to 100%

以水为介质，将化合物2-6、分散剂、助悬剂和抗冻剂等加入砂磨机中，进行研磨，制成悬浮剂。Using water as the medium, add compound 2-6, dispersant, suspending agent and antifreeze into a sand mill and grind to prepare a suspension.

实施例9：20％可湿性粉剂Example 9: 20% WP

化合物2-4         20％Compound 2-4 20%

亚甲基萘磺酸钠    6％Sodium Methylene Naphthalene Sulfonate 6%

萘磺酸甲醛缩合物    3％Naphthalenesulfonic acid formaldehyde condensate 3%

十二烷基硫酸钠      2％Sodium Lauryl Sulfate 2%

白碳黑              5％White carbon black 5%

农乳600#            0.5％Farm Milk 600 # 0.5%

轻质碳酸钙    补足至100％Light Calcium Carbonate Top up to 100%

将化合物2-4、各种表面活性剂及固体稀释剂等充分混合，经超细粉碎机粉碎后，即得到20％的可湿性粉剂产品。Compounds 2-4, various surfactants and solid diluents are fully mixed, and pulverized by an ultra-fine pulverizer to obtain a 20% wettable powder product.

生物活性测定实施例Examples of biological activity assays

实例10杀虫杀螨活性测定Example 10 Determination of insecticidal and acaricidal activity

用本发明化合物对几种昆虫和螨类进行了杀虫活性测定试验。测定的方法如下：Insecticidal activity tests were carried out on several insects and acarids using the compounds of the present invention. The method of determination is as follows:

待测化合物用丙酮/甲醇(1∶1)的混合溶剂溶解后，用含有0.1％吐温80的水稀释至所需的浓度。The compound to be tested was dissolved in a mixed solvent of acetone/methanol (1:1), and then diluted to the desired concentration with water containing 0.1% Tween 80.

以小菜蛾、甜菜夜蛾为靶标，采用airbrush喷雾法和浸液法(淡色库蚊幼虫)进行杀虫活性测定，airbrush喷雾处理的压力为10psi(约合0.7kg/cm2)，喷液量为0.5毫升。处理后2-3日调查靶标的死亡率。With Plutella xylostella and beet armyworm as targets, the airbrush spray method and liquid immersion method (Culex larvae) were used to measure the insecticidal activity. for 0.5 ml. Mortality of the target was investigated 2-3 days after treatment.

部分测试结果如下：Some test results are as follows:

药液浓度为600ppm时，化合物1-102、1-104、1-152、1-205对小菜蛾和甜菜夜蛾死亡率达100％；When the liquid concentration is 600ppm, the mortality rate of compounds 1-102, 1-104, 1-152, 1-205 to diamondback moth and beet armyworm is 100%;

药液浓度为20ppm时，化合物2-2、2-4、2-6对甜菜夜蛾死亡率达100％；When the concentration of the drug solution is 20ppm, the mortality rate of compounds 2-2, 2-4, and 2-6 to beet armyworm reaches 100%;

药液浓度为1ppm时，化合物1-218、1-220、1-264、1-266对甜菜夜蛾死亡率达100％。When the concentration of the drug solution is 1 ppm, the mortality of the compounds 1-218, 1-220, 1-264 and 1-266 against the beet armyworm reaches 100%.

Claims (5)

1.一种邻氨基苯甲酸类化合物，如通式I所示：1. An anthranilic acid compound, as shown in general formula I: 式中：In the formula: R1选自氢、Cl或氰基； R is selected from hydrogen, Cl or cyano; R2选自Br；R 2 is selected from Br; R3选自氢； R is selected from hydrogen; R4选自-CO2CH3、
Figure FSB00000895670000012
或-CONHCH(OCH3)2。R4 is selected from -CO 2 CH 3 ,
Figure FSB00000895670000012
or -CONHCH(OCH 3 ) 2 . 2.根据权利要求1所述的化合物，其特征在于：如下结构的化合物2. The compound according to claim 1, characterized in that: the compound of the following structure 3.一种杀虫组合物，包含生物学有效量的如权利要求1所述的通式I化合物或权利要求2所述的化合物和至少一种选自表面活性剂、固体稀释剂或液体稀释剂。3. A pesticidal composition comprising a biologically effective amount of the compound of general formula I as claimed in claim 1 or the compound as claimed in claim 2 and at least one selected from surfactants, solid diluents or liquid diluents agent. 4.一种如权利要求1所述的通式I化合物或权利要求2所述的化合物在制备农业领域中使用的杀虫剂药物的应用。4. The application of a compound of general formula I as claimed in claim 1 or a compound as claimed in claim 2 in the preparation of pesticides used in the agricultural field. 5.一种如权利要求3所述的组合物在制备农业领域中使用的杀虫剂药物的应用。5. the application of a composition as claimed in claim 3 in the preparation of insecticide medicines used in the agricultural field.
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