CN115724768A - Bisamide compound and preparation method and application thereof - Google Patents

Bisamide compound and preparation method and application thereof Download PDF

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CN115724768A
CN115724768A CN202210892248.8A CN202210892248A CN115724768A CN 115724768 A CN115724768 A CN 115724768A CN 202210892248 A CN202210892248 A CN 202210892248A CN 115724768 A CN115724768 A CN 115724768A
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compound
trifluoromethyl
formula
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hydrogen
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张立新
张静
裴鸿艳
康卓
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Guangxi Siyue Biotechnology Co ltd
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Guangxi Siyue Biotechnology Co ltd
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Abstract

The invention provides a bisamide compound and a preparation method and application thereof, wherein the compound is shown as a general formula I. The compound in the general formula I can be used for preparing m-diamide compounds shown in the general formula A, and the compound in the general formula A has the characteristics of high insecticidal activity, low dosage, wide insecticidal spectrum and the like. The bisamide compound shown as the general formula I is easy to synthesize, has mild conditions, is easy to synthesize when being used for preparing the compound shown as the general formula A, has high yield and mild conditions, and greatly reduces the content of the bisamide compound shown as the general formula IThe production and manufacturing cost is reduced.

Description

Bisamide compound and preparation method and application thereof
Cross-referencing
The present application claims priority from an invention patent application having application number 202110991587.7, entitled "a bisamide compound and a method for producing the same and use thereof", filed 26.08/2021, which is incorporated herein by reference in its entirety.
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a bisamide compound as well as a preparation method and application thereof.
Background
The isophthalamide compounds are high-efficiency novel insecticides, and are disclosed in patents CN110194726A, CN111793008A, CN112430210A, CN112430211A and CN113149900A, and show excellent insecticidal activity on pests such as diamondback moth, armyworm, chilo suppressalis and beet armyworm.
Figure BDA0003768047010000011
The compound of the general formula A can be prepared by a route 1, namely, a compound of a general formula II is subjected to acyl chlorination reaction to prepare a compound of a general formula II-1, and the compound of the general formula II-1 is subjected to condensation reaction with a compound of a general formula M-2 (prepared by halogenating the compound of the general formula M-1). A serious problem in scheme 1 is that the overall yield of the condensation reaction is low, typically not more than 50%, which leads to a low overall yield of the synthesis of the compound of formula a.
Figure BDA0003768047010000021
Note: in formula A and scheme 1, Q isQ 1 Or Q 2 ；R 1 、R 2 、R 3 、R 4 And R 5 Is hydrogen, halogen, cyano, nitro, C 1 -C 6 Alkyl radical, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy radical, C 1 -C 6 Haloalkoxy, C 1 -C 6 Alkylthio or C 1 -C 6 A haloalkylthio group; r is 6 Is fluoro, difluoromethyl, trifluoromethyl or cyano; n is 1,2, 3 or 4; w is a group of 1 Is hydrogen, C 1 -C 6 Haloalkyl or C 1 -C 6 A haloalkoxy group; w is a group of 2 Is trifluoromethyl or perfluoroethyl; x is bromine or iodine.
Figure BDA0003768047010000022
Therefore, it is desired in the art to develop more intermediate compounds capable of preparing a m-diamide compound having insecticidal activity in high yield.
Disclosure of Invention
Technical problem
In order to find a method suitable for large-scale industrial production of the m-diamide compounds (compounds of the general formula A), the inventor completely explores the traditional preparation process.
The inventors have adjusted the synthetic procedure of scheme 1 in the course of research on new preparation methods (as shown in scheme 2), and have surprisingly found that the compound of general formula II-1 is first condensed with the compound of general formula M-1 to obtain the compound of general formula I of the present invention, and then the compound of general formula I is halogenated to prepare the compound of formula A in high yield, which extremely effectively solves the problem of low yield of condensation reaction in the preparation of the compound of formula A, and is suitable for large-scale industrial production.
Figure BDA0003768047010000031
Technical scheme
The invention aims to provide a bisamide compound and a preparation method and application thereof. The compounds can be used for further preparing certain m-diamide compounds with insecticidal activity, and the m-diamide compounds with insecticidal activity have the characteristics of high insecticidal activity, low dosage, wide insecticidal spectrum and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
according to a first aspect of the present invention, there is provided a bisamide compound, as shown in formula I:
Figure BDA0003768047010000032
in the general formula I:
q is selected from Q 1 Or Q 2 In which
Figure BDA0003768047010000034
Represents the position of attachment of the group,
Figure BDA0003768047010000033
R 1 、R 2 、R 3 、R 4 and R 5 Each independently selected from hydrogen, halogen, cyano, nitro, C 1 -C 6 Alkyl radical, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy radical, C 1 -C 6 Haloalkoxy, C 1 -C 6 Alkylthio or C 1 -C 6 A haloalkylthio group;
R 6 selected from fluoro, difluoromethyl, trifluoromethyl or cyano;
n is selected from 1,2, 3 or 4;
W 1 selected from hydrogen, C 1 -C 6 Haloalkyl or C 1 -C 6 A haloalkoxy group;
W 2 is selected from threeFluoromethyl or perfluoroethyl.
Preferably, in formula I, R 1 、R 2 、R 3 、R 4 And R 5 Each independently selected from hydrogen, halogen, cyano, nitro, C 1 -C 3 Alkyl radical, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy radical, C 1 -C 3 Haloalkoxy, C 1 -C 3 Alkylthio or C 1 -C 3 A haloalkylthio group; r 6 Selected from fluoro, difluoromethyl, trifluoromethyl or cyano; n is selected from 1,2, 3 or 4; w is a group of 1 Selected from hydrogen, C 1 -C 3 Haloalkyl or C 1 -C 3 A haloalkoxy group; w 2 Selected from trifluoromethyl or perfluoroethyl.
Preferably, in formula I, R 1 、R 2 、R 3 、R 4 And R 5 Each independently selected from hydrogen, fluoro, chloro, bromo, cyano, nitro, methyl, ethyl, propyl, tert-butyl, trifluoromethyl, heptafluoroisopropyl, methoxy or trifluoromethoxy; r is 6 Selected from fluoro, difluoromethyl, trifluoromethyl or cyano; n is selected from 1,2, 3 or 4; w 1 Selected from hydrogen, trifluoromethyl, trifluoromethoxy or difluoromethoxy; w 2 Selected from trifluoromethyl or perfluoroethyl.
Preferably, in formula I, R 1 、R 2 、R 4 And R 5 Each independently selected from hydrogen; r 3 Selected from hydrogen, fluoro, chloro, bromo, cyano, nitro, methyl, ethyl, propyl, tert-butyl, trifluoromethyl, heptafluoroisopropyl, methoxy or trifluoromethoxy; r 6 Selected from fluoro, difluoromethyl, trifluoromethyl or cyano; n is selected from 1,2, 3 or 4; w 1 Selected from hydrogen, trifluoromethyl, trifluoromethoxy or difluoromethoxy; w is a group of 2 Selected from trifluoromethyl or perfluoroethyl.
Preferably, the bisamide type compounds are selected from the compounds in table 1, wherein the compounds in table 1 have the structure shown as the general formula I, and Q and R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、n、W 1 And W 2 As shown in Table 1, wherein"-" indicates no substitution;
TABLE 1
Figure BDA0003768047010000041
Figure BDA0003768047010000051
Figure BDA0003768047010000061
Figure BDA0003768047010000071
Figure BDA0003768047010000081
Figure BDA0003768047010000091
Figure BDA0003768047010000101
Figure BDA0003768047010000111
Figure BDA0003768047010000121
The invention also comprises an intermediate for preparing the bisamide compound (i.e. the compound of the general formula I) as described above, which has the following structure shown in the general formula II:
Figure BDA0003768047010000122
in formula II:
q is selected from Q 1 Or Q 2 Wherein
Figure BDA0003768047010000124
Represents the attachment position of the group,
Figure BDA0003768047010000123
R 1 、R 2 、R 3 、R 4 and R 5 Each independently selected from hydrogen, halogen, cyano, nitro, C 1 -C 6 Alkyl radical, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy radical, C 1 -C 6 Haloalkoxy, C 1 -C 6 Alkylthio or C 1 -C 6 A haloalkylthio group;
R 6 selected from fluoro, difluoromethyl, trifluoromethyl or cyano;
n is selected from 1,2, 3 or 4;
preferably, in formula II, R 1 、R 2 、R 3 、R 4 And R 5 Each independently selected from hydrogen, halogen, cyano, nitro, C 1 -C 3 Alkyl radical, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy radical, C 1 -C 3 Haloalkoxy, C 1 -C 3 Alkylthio or C 1 -C 3 A haloalkylthio group; r is 6 Selected from fluoro, difluoromethyl, trifluoromethyl or cyano; n is selected from 1,2, 3 or 4.
Preferably, in formula II, R 1 、R 2 、R 3 、R 4 And R 5 Each independently selected from hydrogen, fluoro, chloro, bromo, cyano, nitro, methyl, ethyl, propyl, tert-butyl, trifluoromethyl, heptafluoroisopropyl, methoxy or trifluoromethoxy; r is 6 Selected from fluorine, difluoromethyl, trifluoromethyl orA cyano group; n is selected from 1,2, 3 or 4.
Preferably, in formula II, R 1 、R 2 、R 4 And R 5 Each independently selected from hydrogen; r 3 Selected from hydrogen, fluoro, chloro, bromo, cyano, nitro, methyl, ethyl, propyl, tert-butyl, trifluoromethyl, heptafluoroisopropyl, methoxy or trifluoromethoxy; r 6 Selected from fluoro, difluoromethyl, trifluoromethyl or cyano; n is selected from 1,2, 3 or 4.
Preferably, the intermediate compound is selected from the compounds of table 2, said compounds of table 2 having a structure according to formula II and Q, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 And n is as shown in table 2, wherein "-" indicates no substitution;
TABLE 2
Figure BDA0003768047010000131
Figure BDA0003768047010000141
The present invention also includes an intermediate useful in the preparation of compounds of formula I and formula II as described above, having the structure shown in formula III below:
Figure BDA0003768047010000142
in formula III:
q is selected from Q 1 Or Q 2 In which
Figure BDA0003768047010000143
Represents the position of attachment of the group,
Figure BDA0003768047010000151
R 1 、R 2 、R 3 、R 4 and R 5 Each independently selected from hydrogen, halogen, cyano, nitro, C 1 -C 6 Alkyl radical, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy radical, C 1 -C 6 Haloalkoxy, C 1 -C 6 Alkylthio or C 1 -C 6 A haloalkylthio group;
R 6 selected from fluoro, difluoromethyl, trifluoromethyl or cyano;
R 7 is selected from C 1 -C 6 An alkyl group;
n is selected from 1,2, 3 or 4.
Preferably, in formula III, R 1 、R 2 、R 3 、R 4 And R 5 Each independently selected from hydrogen, halogen, cyano, nitro, C 1 -C 3 Alkyl radical, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy radical, C 1 -C 3 Haloalkoxy, C 1 -C 3 Alkylthio or C 1 -C 3 A haloalkylthio group; r 6 Selected from fluoro, difluoromethyl, trifluoromethyl or cyano; r 7 Is selected from C 1 -C 3 An alkyl group; n is selected from 1,2, 3 or 4.
Preferably, in formula III, R 1 、R 2 、R 3 、R 4 And R 5 Each independently selected from hydrogen, fluoro, chloro, bromo, cyano, nitro, methyl, ethyl, propyl, tert-butyl, trifluoromethyl, heptafluoroisopropyl, methoxy or trifluoromethoxy; r is 6 Selected from fluoro, difluoromethyl, trifluoromethyl or cyano; r 7 Selected from methyl or ethyl; n is selected from 1,2, 3 or 4.
Preferably, in formula III, R 1 、R 2 、R 4 And R 5 Each independently selected from hydrogen; r is 3 Selected from hydrogen, fluoro, chloro, bromo, cyano, nitro, methyl, ethyl, propyl, tert-butyl, trifluoromethyl, heptafluoroisopropyl, methoxy or trifluoromethoxy; r 6 Selected from fluoro, difluoromethyl, trifluoromethyl or cyano; r is 7 Selected from methyl or ethyl; n is selected from 1,2.3 or 4.
Preferably, the intermediate compound is selected from the group consisting of the compounds of Table 3, said compounds of Table 3 having a structure according to formula III and Q, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 And n is as shown in table 3, wherein "-" represents no substitution;
TABLE 3
Figure BDA0003768047010000152
Figure BDA0003768047010000161
Figure BDA0003768047010000171
The present invention also includes an intermediate useful in the preparation of compounds of formula I, formula II, and formula III, as described above, having the structure shown in formula IV below:
Figure BDA0003768047010000181
in formula IV:
n is selected from 1,2, 3 or 4;
R 7 is selected from C 1 -C 6 An alkyl group.
Preferably, in formula IV, n is selected from 1,2, 3 or 4; r 7 Is selected from C 1 -C 3 An alkyl group.
Preferably, in formula IV, n is selected from 1,2, 3 or 4; r 7 Selected from methyl or ethyl.
Preferably, the intermediate compound is selected from the group consisting of the compounds of Table 4, the compounds of Table 4 having a structure according to formula IV and n and R 7 As shown in table 4;
TABLE 4
Compound number n R 7
4.1 1 CH 3
4.2 2 CH 3
4.3 3 CH 3
4.4 4 CH 3
4.5 1 CH 2 CH 3
4.6 2 CH 2 CH 3
4.7 3 CH 2 CH 3
4.8 4 CH 2 CH 3
。
In the definitions of the radicals in the compounds of the formulae given in the present invention, the terms used are generally defined as follows:
halogen means fluorine, chlorine, bromine or iodine;
alkyl means straight-chain or branched alkyl, such as methyl, ethyl, n-propyl, isopropyl or the different butyl isomers;
haloalkyl means straight-chain or branched alkyl groups in which the hydrogen atoms may be partially or fully substituted by halogen, for example chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 2-trifluoroethyl, and the like;
alkoxy means a straight or branched chain alkyl group attached to the structure via an oxygen atom, such as methoxy, ethoxy, t-butoxy, and the like;
haloalkoxy means that the hydrogen atoms on the alkoxy group may be partially or fully substituted with halogen, for example, chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, trifluoroethoxy, and the like.
Alkylthio group: straight or branched chain alkyl groups attached to the structure via a sulfur atom, such as methylthio, ethylthio, and the like.
Haloalkylthio: straight-chain or branched alkylthio groups in which hydrogen atoms may be partially or fully substituted by halogen, such as difluoromethylthio, trifluoroethylthio, and the like.
And (3) perfluoroethyl: -CF 2 CF 3 。
The compounds of the general formula I according to the invention can be prepared by the following processes, in which the radicals are as defined above, unless otherwise indicated.
Figure BDA0003768047010000191
(1) Preparation of Compounds of formula IV from Compounds of formula M-4
The compound of formula IV is prepared by reacting a compound of formula M-4 with a cyanoalkylating agent in a suitable solvent at a temperature of from-10 ℃ to the boiling point of the solvent for 0.5 to 48 hours.
Preferably, the cyanoalkylating agent is selected from chloroacetonitrile (CAS number: 107-14-2), bromoacetonitrile (CAS number: 590-17-0), iodoacetonitrile (CAS number: 624-75-9), 3-chloropropionitrile (CAS number: 542-76-7), 3-bromopropionitrile (CAS number: 2417-90-5), acrylonitrile (CAS number: 107-13-1), 4-chlorobutyronitrile (CAS number: 628-20-6), 4-bromobutyronitrile acrylate (CAS number: 5332-06-9), 5-chlorovaleronitrile (CAS number: 6280-87-1) or 5-bromovaleronitrile (CAS number: 5414-21-1).
Preferably, the suitable solvent is selected from any one or a combination of at least two of aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, halogenated hydrocarbons such as chloroform and methylene chloride, esters such as methyl acetate and ethyl acetate, ethers such as tetrahydrofuran, dioxane, diethyl ether and 1, 2-dimethoxyethane, and polar solvents such as water, acetonitrile, N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide.
Preferably, the reaction in this step is carried out in the presence of a basic substance selected from any one or a combination of at least two of organic bases such as trimethylamine, triethylamine, pyridine, N-diisopropylmethylamine, N-diisopropylethylamine, DBU, and 4-dimethylaminopyridine, alkali metal hydrides such as sodium hydride and potassium hydride, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali earth metal hydroxides such as calcium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal bicarbonates such as sodium bicarbonate, and metal alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide, and sodium tert-butoxide.
Preferably, the molar ratio of the compound of the reaction formula M-4 to the cyanoalkylating agent fed in this step is from 0.1 to 1, 1 to 30, such as 0.1.
Preferably, the molar ratio of the compound of the reaction formula M-4 to the basic substance in the feed is from 0.1 to 1, to 1 to 30, such as from 0.1.
(2) Carrying out condensation reaction on the compound in the general formula IV and the compound in the general formula M-3 to obtain the compound in the general formula III
Preferably, the reaction temperature of the reaction described in this step is from-10 ℃ to the boiling point of the solvent.
Preferably, the reaction time of the reaction described in this step is 0.5 to 48 hours.
Preferably, the solvent for the reaction in this step is any one or a combination of at least two selected from aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, halogenated hydrocarbons such as chloroform and dichloromethane, esters such as methyl acetate and ethyl acetate, ethers such as tetrahydrofuran, dioxane, diethyl ether and 1, 2-dimethoxyethane, and polar solvents such as water, acetonitrile, N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide.
Preferably, the reaction in this step is carried out in the presence of a basic substance selected from any one or a combination of at least two of organic bases such as trimethylamine, triethylamine, pyridine, N-diisopropylmethylamine, N-diisopropylethylamine, DBU, and 4-dimethylaminopyridine, alkali metal hydrides such as sodium hydride and potassium hydride, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali earth metal hydroxides such as calcium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal hydrogen carbonates such as sodium bicarbonate, and metal alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide, and sodium tert-butoxide.
Preferably, the reaction of this step is carried out in the presence of a catalyst selected from any one of lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, sodium fluoride, potassium fluoride, cesium fluoride or 4-dimethylaminopyridine or a combination of at least two thereof.
Preferably, this step involves reacting the compound of formula IV with the compound of formula M-3 in a molar ratio of 0.1-1.
Preferably, the molar ratio of the compound of the reaction formula IV to the basic substance added in this step is 0.1-1, such as 0.1.
Preferably, the molar ratio of the compound of the reaction formula IV to the catalyst charge in this step is 0.1-1, such as 0.1.
(3) The compound of the general formula III is hydrolyzed to obtain a compound of a general formula II
Preferably, the reaction in this step is carried out in the presence of a basic substance selected from any one or a combination of at least two of alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal bicarbonates such as sodium bicarbonate, and metal alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide and sodium tert-butoxide.
Preferably, the molar ratio of the compound of the reaction formula III to the basic substance added in this step is 0.1-1, such as 0.1.
Preferably, the reaction in this step is carried out in the presence of a mixture of lithium bromide and triethylamine or ammonia water, and the molar ratio of lithium bromide to triethylamine or lithium bromide to ammonia water is 1.
Preferably, the molar ratio of the compound of the reaction formula III to lithium bromide added in this step is 0.1-1, such as 0.1.
Preferably, the reaction temperature of the reaction described in this step is from-10 ℃ to the boiling point of the solvent.
Preferably, the reaction time of the reaction described in this step is 0.5 to 48 hours.
The solvent for the reaction in this step is preferably any one or a combination of at least two selected from aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, halogenated hydrocarbons such as chloroform and methylene chloride, esters such as methyl acetate and ethyl acetate, ethers such as tetrahydrofuran, dioxane, diethyl ether and 1, 2-dimethoxyethane, and polar solvents such as water, acetonitrile, methanol, ethanol, N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide.
(4) The compound of the general formula II is subjected to acyl chlorination reaction to prepare a compound of a general formula II-1
The compound of the general formula II can be prepared into the compound of the general formula II-1 by reacting the compound of the general formula II with thionyl chloride, oxalyl chloride, carbonyl chloride, phosphorus oxychloride, phosphorus pentachloride, phosphorus trichloride or triphosgene and other acyl chloride reagents by conventional means.
(5) The compound of the general formula I is prepared by the condensation reaction of the compound of the general formula II-1 and the compound of the general formula M-1
Preferably, the reaction temperature of the reaction described in this step is from-10 ℃ to the boiling point of the solvent.
Preferably, the reaction time of the reaction described in this step is 0.5 to 48 hours.
Preferably, the solvent for the reaction in this step is any one or a combination of at least two selected from aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, halogenated hydrocarbons such as chloroform and dichloromethane, esters such as methyl acetate and ethyl acetate, ethers such as tetrahydrofuran, dioxane, diethyl ether and 1, 2-dimethoxyethane, and polar solvents such as water, acetonitrile, N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide.
Preferably, the reaction in this step is carried out in the presence of a basic substance selected from any one or a combination of at least two of organic bases such as trimethylamine, triethylamine, pyridine, N-diisopropylmethylamine, N-diisopropylethylamine, DBU, and 4-dimethylaminopyridine, alkali metal hydrides such as sodium hydride and potassium hydride, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali earth metal hydroxides such as calcium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal bicarbonates such as sodium bicarbonate, and metal alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide, and sodium tert-butoxide.
Preferably, the reaction of this step is carried out in the presence of a catalyst selected from any one or a combination of at least two of lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, sodium fluoride, potassium fluoride, cesium fluoride or 4-dimethylaminopyridine.
Preferably, this step involves reacting a compound of general formula II-1 with a compound of general formula M-1 in a molar ratio of 0.1 to 1 to 30, such as 0.1, 0.2.
Preferably, the molar ratio of the compound of the reaction formula II-1 to the basic substance added in this step is 0.1-1, 1-30, such as 0.1.
Preferably, the molar ratio of the compound of the reaction formula II-1 to the catalyst is from 0.1 to 1, to 1 to 30, such as from 0.1.
According to a second aspect of the invention, the invention provides the application of the bisamide-based compound shown in the general formula I in preparing the m-bisamide-based compound shown in the general formula A.
Figure BDA0003768047010000221
In the general formula A:
q is selected from Q 1 Or Q 2 In which
Figure BDA0003768047010000223
Represents the position of attachment of the group,
Figure BDA0003768047010000222
R 1 、R 2 、R 3 、R 4 and R 5 Each independently selected from hydrogen, halogen, cyano, nitro, C 1 -C 6 Alkyl radical, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy radical, C 1 -C 6 Haloalkoxy, C 1 -C 6 Alkylthio or C 1 -C 6 A haloalkylthio group;
R 6 selected from fluoro, difluoromethyl, trifluoromethyl or cyano;
n is selected from 1,2, 3 or 4;
W 1 selected from hydrogen, C 1 -C 6 Haloalkyl or C 1 -C 6 A haloalkoxy group;
W 2 selected from trifluoromethyl or perfluoroethyl;
x is selected from bromine or iodine.
Preferably, in formula A, R 1 、R 2 、R 3 、R 4 And R 5 Each independently selected from hydrogen, halogen, cyano, nitro, C 1 -C 3 Alkyl radical, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy radical, C 1 -C 3 Haloalkoxy, C 1 -C 3 Alkylthio or C 1 -C 3 A haloalkylthio group; r is 6 Selected from fluoro, difluoromethyl, trifluoromethyl or cyano; n is selected from 1,2, 3 or 4; w 1 Selected from hydrogen, C 1 -C 3 Haloalkyl or C 1 -C 3 A haloalkoxy group; w 2 Selected from trifluoromethyl or perfluoroethyl; x is selected from bromine or iodine.
Preferably, in formula A, R 1 、R 2 、R 3 、R 4 And R 5 Each independently selected from hydrogen, fluorine, chlorine,Bromo, cyano, nitro, methyl, ethyl, propyl, tert-butyl, trifluoromethyl, heptafluoroisopropyl, methoxy, or trifluoromethoxy; r 6 Selected from fluoro, difluoromethyl, trifluoromethyl or cyano; n is selected from 1,2, 3 or 4; w 1 Selected from hydrogen, trifluoromethyl, trifluoromethoxy or difluoromethoxy; w 2 Selected from trifluoromethyl or perfluoroethyl; x is selected from bromine or iodine.
Preferably, in formula A, R 1 、R 2 、R 4 And R 5 Each independently selected from hydrogen; r 3 Selected from hydrogen, fluoro, chloro, bromo, cyano, nitro, methyl, ethyl, propyl, tert-butyl, trifluoromethyl, heptafluoroisopropyl, methoxy or trifluoromethoxy; r 6 Selected from fluoro, difluoromethyl, trifluoromethyl or cyano; n is selected from 1,2, 3 or 4; w 1 Selected from hydrogen, trifluoromethyl, trifluoromethoxy or difluoromethoxy; w 2 Selected from trifluoromethyl or perfluoroethyl; x is selected from bromine or iodine.
Preferably, the compounds of formula A are selected from the compounds of Table A having a structure as in formula A and Q, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、n、W 1 、W 2 X is as shown in Table A, wherein "-" represents no substitution;
TABLE A
Figure BDA0003768047010000231
Figure BDA0003768047010000241
Figure BDA0003768047010000251
Figure BDA0003768047010000261
Figure BDA0003768047010000271
Figure BDA0003768047010000281
Figure BDA0003768047010000291
Figure BDA0003768047010000301
Figure BDA0003768047010000311
Continuing from Table A: in formula A, when X = I, the substituents Q, R of compounds A.225-A.448 of Table A 1 、R 2 、R 3 、R 4 、R 5 、R 6 、n、W 1 、W 2 Corresponding in turn to compounds A.1 to A.224 of Table A.
Preferably, the application comprises the steps of:
reacting the compound shown in the general formula I with a halogenating agent to obtain a m-diamide compound shown in the general formula A, wherein the reaction formula is as follows:
Figure BDA0003768047010000312
wherein, Q and R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、n、W 1 、W 2 And X is the same as defined above, and is not described in detail herein.
Preferably, the halogenating agent for the reaction is any one of chlorine, liquid bromine, N-bromosuccinimide, 1, 3-dibromo-5, 5-dimethylhydantoin, pyridine tribromide, carbon tetrabromide, 5-dibromo-2, 2-dimethyl-4, 6-dione-1, 3-dioxane, 2-dibromo-3-nitrilopropionamide, tetrabromoobenzoquinone, 1, 3-dibromo-1, 3, 5-triazine-2, 4, 6-trione, 1,3, 5-tribromo-1, 3, 5-thiazinan-2, 4, 6-trione, N-bromoacetamide, N-bromoo-sulfonylbenzimide, phenyltrimethylammonium tribromide, dibromobarbituric acid, hydrobromic acid, sodium bromide, potassium bromide, iodine, N-iodosuccinimide, hydroiodic acid, sodium iodide, or potassium iodide, or a combination of at least two thereof.
Preferably, the halogenating agent for the reaction is a mixture of hydrogen peroxide and hydrobromic acid in any proportion, a mixture of sodium hypochlorite and hydrobromic acid in any proportion, a mixture of sodium chlorate and hydrobromic acid in any proportion, a mixture of sodium hypochlorite and sodium bromide in any proportion, a mixture of sodium hypochlorite and potassium bromide in any proportion, a mixture of sodium chlorate and sodium bromide in any proportion, a mixture of sodium chlorate and potassium bromide in any proportion, a mixture of hydrogen peroxide and hydroiodic acid in any proportion, a mixture of sodium hypochlorite and hydroiodic acid in any proportion, a mixture of sodium chlorate and hydroiodic acid in any proportion, a mixture of sodium hypochlorite and sodium iodide in any proportion, a mixture of sodium hypochlorite and potassium iodide in any proportion, a mixture of sodium chlorate and sodium iodide in any proportion or a mixture of sodium chlorate and potassium iodide in any proportion.
Preferably, the reaction is carried out in the presence of a basic substance selected from any one or a combination of at least two of organic bases such as trimethylamine, triethylamine, pyridine, N-diisopropylmethylamine, N-diisopropylethylamine, DBU, and 4-dimethylaminopyridine, alkali metal hydrides such as sodium hydride and potassium hydride, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali earth metal hydroxides such as calcium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal bicarbonates such as sodium bicarbonate, and metal alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide, and sodium tert-butoxide.
The solvent for the reaction is preferably one or a combination of at least two selected from ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, halogenated hydrocarbons such as chloroform and methylene chloride, esters such as methyl acetate and ethyl acetate, ethers such as tetrahydrofuran, dioxane, diethyl ether and 1, 2-dimethoxyethane, and polar solvents such as water, acetonitrile, N-dimethylformamide, N-methylpyrrolidone and dimethylsulfoxide.
Preferably, the reaction temperature of the reaction described in this step is from-10 ℃ to the boiling point of the solvent.
Preferably, the reaction time of the reaction described in this step is 0.5 to 48 hours.
Advantageous effects
The invention has the following advantages: in the preparation process of the m-diamide compounds (compounds in a general formula A), the condensation reaction yield of the route 1 is low (generally not more than 50%), while the condensation reaction yield of the invention is more than 80%, so that the m-diamide compounds are prepared with high yield, and the method is suitable for large-scale industrial production.
Detailed Description
The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
Synthesis example 1: synthesis of 3- [ N- (cyanomethyl) benzamido ] -2-fluoro-N- [4- (perfluoropropan-2-yl) phenyl ] benzamide (Compound No. 1.1 of the present invention)
(1) Synthesis of methyl 3- [ (cyanomethyl) amino ] -2-fluorobenzoate (Compound No. 4.1 of the present invention)
Figure BDA0003768047010000331
To a 200mL reaction flask were added methyl 2-fluoro-3-aminobenzoate (5 g, 29.56mmol) and 50mL tetrahydrofuran to dissolve, and N, N-diisopropylethylamine (11.46g, 88.67mmol) and bromoacetonitrile (7.09g, 59.11mmol) were added to conduct a reaction under reflux for 3 hours. Cooling to room temperature, extracting and washing the reaction solution with 10% dilute hydrochloric acid solution and saturated sodium bicarbonate solution in sequence, drying the organic phase with anhydrous magnesium sulfate, filtering, concentrating under reduced pressure, and purifying the residue by column chromatography to obtain 5.53g of white solid with the yield of 90%.
1 H NMR(600MHz,Chloroform-d)δ7.41–7.35(m,1H),7.15(td,1H),6.97(td,1H),4.50–4.42(m,1H),4.19(d,2H),3.93(s,3H).LC-MS(m/z,ESI):231.07(M+Na) + .
(2) Synthesis of methyl 3- [ N- (cyanomethyl) benzamido ] -2-fluorobenzoate (Compound No. 3.1 of the present invention)
Figure BDA0003768047010000332
To a 100mL reaction flask was added methyl 3- [ (cyanomethyl) amino ] -2-fluorobenzoate (3g, 14.42mmol), 30mL of toluene was dissolved, and benzoyl chloride (2.83g, 20.21mmol) was added and the reaction was refluxed for 2.5 hours. And cooling to room temperature until no black solid is separated out from the reaction solution. And (4) carrying out suction filtration on the reaction solution, and separating to obtain a black solid. The black solid was transferred to a 250mL beaker and 100mL of water and 3mL of ethyl acetate were added, stirred for 3 hours, and filtered with suction to give 4.04g of a pale yellow solid, 89.84% yield.
1 H NMR(600MHz,Chloroform-d)δ7.91–7.86(m,1H),7.39–7.27(m,4H),7.23(t,2H),7.14–7.08(m,1H),5.14(s,1H),4.35(s,1H),3.94(s,3H).LC-MS(m/z,ESI):313.15(M+H) + .
(3) Synthesis of 3- [ N- (cyanomethyl) benzamido ] -2-fluorobenzoic acid (Compound No. 2.1 of the present invention)
Figure BDA0003768047010000333
To a 100mL reaction flask, methyl 3- [ N- (cyanomethyl) benzamido ] -2-fluorobenzoate (2g, 6.41mmol) and 40mL of acetonitrile were added and dissolved, followed by addition of lithium bromide (5.57g, 64.13mmol), water (0.58g, 32.20mmol) and triethylamine (3.24g, 32.02mmol) in this order under stirring, followed by reaction at 50 ℃ for 3.5 hours, and the progress of the reaction was monitored by TLC. After the reaction was completed, the reaction mixture was cooled to room temperature, 100mL of water was added, the solution PH =2 to 3 was adjusted with hydrochloric acid solution under stirring, and then the reaction mixture was extracted with ethyl acetate and water, and the organic layers were combined, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain 1.87g of a white solid with a yield of 97.73%.
1 H NMR(600MHz,DMSO-d 6 )δ13.47(s,1H),7.78(td,1H),7.71(td,1H),7.40–7.32(m,3H),7.31–7.25(m,3H),4.91(s,2H).
(4) Synthesis of 3- [ N- (cyanomethyl) benzamido ] -2-fluorobenzoyl chloride
Figure BDA0003768047010000341
3- [ N- (cyanomethyl) benzamido ] -2-fluorobenzoic acid (4.29g, 14.39mmol) is added into a 100mL single-neck flask, then 30mL of toluene is added to dissolve and dilute, thionyl chloride (8.56g, 71.95mmol) is added, reaction is carried out for 3 hours under reflux, and the toluene and the thionyl chloride are removed by distillation under reduced pressure to obtain 4.36g of oil with the yield of 95.57%.
(5) Synthesis of 3- [ N- (cyanomethyl) benzamido ] -2-fluoro-N- [4- (perfluoropropan-2-yl) phenyl ] benzamide (Compound No. 1.1 of the present invention)
Figure BDA0003768047010000342
To a 50mL reaction flask was added 3- [ N- (cyanomethyl) benzoylamino ] -2-fluorobenzoyl chloride (2g, 6.31mmol) and 20mL acetonitrile to dissolve, and 4- (perfluoropropan-2-yl) aniline (1.48g, 5.67mmol) was added and the reaction was refluxed for 3 hours. The reaction mixture was extracted with 100mL of ethyl acetate and 100mL of a saturated aqueous sodium bicarbonate solution, and the organic phase was dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and purified by column chromatography to give 2.86g of an oil with a yield of 93.16%.
1 H NMR(600MHz,Chloroform-d)δ8.23(d,1H),8.06(td,1H),7.77(d,2H),7.62(d,2H),7.46–7.21(m,7H),4.78(d,2H).LC-MS(m/z,ESI):564.29(M+Na) + .
Synthesis example 2: preparation of insecticidal Compound 3- [ N- (cyanomethyl) benzamido ] -N- [2, 6-dibromo-4- (perfluoropropan-2-yl) phenyl ] -2-fluorobenzamide (Compound No. 2.321 disclosed in CN 110194726A)
Figure BDA0003768047010000351
3- [ N- (cyanomethyl) benzamido ] -2-fluoro-N- [4- (perfluoropropan-2-yl) phenyl ] benzamide (3g, 5.54mmol) and 30mL of N, N-dimethylformamide were added to a 100mL reaction flask to dissolve the same, followed by addition of sodium hydroxide (0.33g, 8.25mmol), stirring in ice bath for 10 minutes, addition of N-bromosuccinimide (2.02g, 11.35mmol) to the reaction mixture in portions, and reaction at room temperature. After the completion of the TLC detection reaction, the reaction mixture was extracted with 100mL of ethyl acetate and 100mL of water, and the organic phase was dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and purified by column chromatography to obtain 3.08g of a white solid with a yield of 79.92%.
1 H NMR(600MHz,Chloroform-d)δ8.10(t,1H),7.98(d,1H),7.86(s,2H),7.54–7.48(m,1H),7.41–7.29(m,4H),7.28–7.21(m,2H),4.80(d,2H).LC-MS(m/z,ESI):722.0(M+Na) + .
Comparative example 1: preparation of the insecticidal Compound 3- [ N- (cyanomethyl) benzamido ] -N- [2, 6-dibromo-4- (perfluoropropan-2-yl) phenyl ] -2-fluorobenzamide (Compound No. 2.321 disclosed in CN 110194726A)
Figure BDA0003768047010000352
To a 100mL reaction flask was added 3- [ N- (cyanomethyl) benzamido ] -2-fluorobenzoyl chloride (4.29g, 13.57mmol), 30mL of acetonitrile was dissolved, and sodium bromide (1.48g, 14.38mmol) and 2, 6-dibromo-4- (perfluoropropan-2-yl) aniline (6.00g, 14.39mmol) were added and reacted for 5 hours under reflux. The reaction mixture was extracted with 100mL of ethyl acetate and 100mL of a saturated aqueous sodium bicarbonate solution, and the organic phase was dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and purified by column chromatography to give 3.99g of a white solid with a yield of 42.13%.
1 H NMR(600MHz,Chloroform-d)δ8.10(t,1H),7.98(d,1H),7.86(s,2H),7.54–7.48(m,1H),7.41–7.29(m,4H),7.28–7.21(m,2H),4.80(d,2H).LC-MS(m/z,ESI):722.0(M+Na) + .
Synthetic example 3: synthesis of 3- [ N- (cyanomethyl) -4-fluorobenzamide ] -2-fluoro-N- [4- (perfluoropropan-2-yl) phenyl ] benzamide (Compound No. 1.2 of the present invention)
(1) Synthesis of methyl 3- [ N- (cyanomethyl) -4-fluorobenzamide ] -2-fluorobenzoate (Compound No. 3.2 of the present invention)
Figure BDA0003768047010000361
To a 50mL reaction flask was added methyl 3- ((cyanomethyl) amino) -2-fluorobenzoate (1g, 4.81mmol), 10mL toluene was dissolved, and p-fluorobenzoyl chloride (1.14g, 7.22mmol) was added and the reaction was refluxed for 2.5h. The reaction mixture was extracted with 50mL of ethyl acetate and 50mL of saturated aqueous sodium bicarbonate solution, and the organic phase was dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain 1.42g of a pale yellow solid with a yield of 89.31%.
1 H NMR(600MHz,Chloroform-d)δ7.88(td,1H),7.40–7.33(m,2H),7.30(t,1H),7.13(t,1H),6.89(t,2H),5.02(s,1H),4.37(s,1H).LC-MS(m/z,ESI):331.17(M+H) + .
(2) Synthesis of 3- [ N- (cyanomethyl) -4-fluorobenzamide ] -2-fluorobenzoic acid (Compound No. 2.2 of the present invention)
Figure BDA0003768047010000362
To a 100mL reaction flask was added methyl 3- [ N- (cyanomethyl) -4-fluorobenzamide ] -2-fluorobenzoate (1.5g, 4.54mmol) and 30mL acetonitrile to dissolve them, and lithium bromide (3.95g, 45.48mmol), water (0.41g, 22.77mmol) and triethylamine (2.30g, 22.73mmol) were added successively under stirring to react at room temperature for 6 hours, and the progress of the reaction was monitored by TLC. After the reaction was completed, the reaction solution was cooled to room temperature, 50mL of water was added, the PH =2 to 3 of the reaction solution was adjusted with a hydrochloric acid solution under stirring, then the reaction solution was extracted with ethyl acetate and water, and the organic layers were combined, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain 1.32g of a white solid with a yield of 91.67%.
1 H NMR(600MHz,DMSO-d 6 )δ7.83–7.78(m,1H),7.75–7.70(m,1H),7.44–7.39(m,2H),7.30(t,1H),7.16–7.10(m,2H),4.90(s,2H).LC-MS(m/z,ESI):315.11(M-H) - .
(3) Synthesis of 3- [ N- (cyanomethyl) -4-fluorobenzamide ] -2-fluorobenzoyl chloride
Figure BDA0003768047010000363
3- [ N- (cyanomethyl) -4-fluorobenzamide ] -2-fluorobenzoic acid (1g, 3.16mmol) was added to a 50mL single-neck flask, followed by addition of 10mL of toluene for dissolution and dilution, addition of thionyl chloride (0.38g, 15.8mmol), reaction under reflux for 3 hours, and removal of toluene and thionyl chloride by distillation under reduced pressure gave 0.98g of an oil in 92.63% yield.
(4) Synthesis of 3- [ N- (cyanomethyl) -4-fluorobenzamide ] -2-fluoro-N- [4- (perfluoropropan-2-yl) phenyl ] benzamide (Compound No. 1.2 of the present invention)
Figure BDA0003768047010000371
To a 200mL reaction flask was added 3- [ N- (cyanomethyl) -4-fluorobenzamide ] -2-fluorobenzoyl chloride (5 g, 14.97mmol), 50mL of acetonitrile was dissolved, and 4- (perfluoropropan-2-yl) aniline (3.91g, 14.98mmol) was added and the reaction was refluxed for 5 hours. The reaction mixture was extracted with 100mL of ethyl acetate and 100mL of a saturated aqueous sodium bicarbonate solution, and the organic phase was dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and purified by column chromatography to give 7.68g of an oil with a yield of 91.76%.
1 H NMR(600MHz,Chloroform-d)δ8.23(d,1H),8.10(td,1H),7.78(d,2H),7.63(d,2H),7.46–7.38(m,3H),7.32(t,1H),6.94(t,2H),4.76(d,2H).LC-MS(m/z,ESI):560.06(M+H) + .
Synthetic example 4: preparation of insecticidal Compound 3- [ N- (cyanomethyl) -4-fluorobenzamide ] -N- [2, 6-dibromo-4- (perfluoropropan-2-yl) phenyl ] -2-fluorobenzamide (Compound No. 2.7 disclosed in CN 110194726A)
Figure BDA0003768047010000372
To a 100mL reaction flask was added 3- [ N- (cyanomethyl) -4-fluorobenzamide ] -2-fluoro-N- [4- (perfluoropropan-2-yl) phenyl ] benzamide (3g, 5.37mmol) and 30mL of N, N-dimethylformamide to dissolve, followed by addition of sodium hydroxide (0.32g, 8.00mmol), stirring in ice bath for 10 minutes, and then N-bromosuccinimide (1.96g, 11.01mmol) was added to the reaction mixture in portions and reacted at room temperature. After the completion of the TLC detection reaction, the reaction mixture was extracted with 100mL of ethyl acetate and 100mL of water, and the organic phase was dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and purified by column chromatography to give 3.25g of a white solid with a yield of 84.64%.
1 H NMR(600MHz,Chloroform-d)δ8.13(t,1H),7.95(d,1H),7.87(s,2H),7.54–7.49(m,1H),7.44–7.39(m,2H),7.35(t,1H),6.95(t,2H),4.79(d,2H).LC-MS(m/z,ESI):718.1(M+H) + .
Comparative example 2: preparation of insecticidal Compound 3- [ N- (cyanomethyl) -4-fluorobenzamide ] -N- [2, 6-dibromo-4- (perfluoropropan-2-yl) phenyl ] -2-fluorobenzamide (Compound No. 2.7 disclosed in CN 110194726A)
Figure BDA0003768047010000381
To a 100mL reaction flask was added 3- [ N- (cyanomethyl) -4-fluorobenzamide ] -2-fluorobenzoyl chloride (4 g, 11.97mmol), 40mL of acetonitrile was dissolved, and sodium bromide (1.23g, 11.95mmol), 2, 6-dibromo-4- (perfluoropropan-2-yl) aniline (4.99g, 11.97mmol) were added and the reaction was refluxed for 5 hours. The reaction mixture was extracted with 150mL of ethyl acetate and 150mL of a saturated aqueous sodium bicarbonate solution, and the organic phase was dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and purified by column chromatography to give 3.20g of a white solid with a yield of 37.42%.
1 H NMR(600MHz,Chloroform-d)δ8.13(t,1H),7.95(d,1H),7.87(s,2H),7.54–7.49(m,1H),7.44–7.39(m,2H),7.35(t,1H),6.95(t,2H),4.79(d,2H).LC-MS(m/z,ESI):718.1(M+H) + .
Synthetic example 5: synthesis of 3- [ N- (cyanomethyl) benzamido ] -2-fluoro-N- [4- (perfluoropropan-2-yl) -2- (trifluoromethyl) phenyl ] benzamide (Compound No. 1.4 of the present invention)
Figure BDA0003768047010000382
To a 50mL reaction flask was added 3- [ N- (cyanomethyl) benzoylamino ] -2-fluorobenzoyl chloride (1.92g, 6.08mmol), 20mL acetonitrile was dissolved, and sodium bromide (0.63g, 6.12mmol), 4- (perfluoropropan-2-yl) -2- (trifluoromethyl) aniline (2g, 6.08mmol) were added and the reaction was refluxed for 5 hours. The reaction mixture was extracted with 100mL of ethyl acetate and 100mL of a saturated aqueous sodium bicarbonate solution, and the organic phase was dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and purified by column chromatography to give 3.04g of a yellow solid with a yield of 82.17%.
1 H NMR(600MHz,Chloroform-d)δ8.75(d,1H),8.66(d,1H),8.11(t,1H),7.89(s,1H),7.84(d,1H),7.52(t,1H),7.42–7.30(m,4H),7.29–7.21(m,2H),4.80(d,2H).LC-MS(m/z,ESI):610.06(M+H) + .
Synthetic example 6: preparation of insecticidal Compound N- [ 2-bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) phenyl ] -3- [ N- (cyanomethyl) benzamido ] -2-fluorobenzamide (Compound No. 9.321 disclosed in CN 110194726A)
Figure BDA0003768047010000383
3- [ N- (cyanomethyl) benzamido ] -2-fluoro-N- [4- (perfluoropropane-2-yl) -2- (trifluoromethyl) phenyl ] benzamide (2g, 3.28mmol) and 30mL of N, N-dimethylformamide are added into a 100mL reaction bottle to be dissolved, then sodium hydroxide (0.2g, 5 mmol) is added, the mixture is stirred for 10 minutes in ice bath, and N-bromosuccinimide (0.61g, 3.43mmol) is added into the reaction liquid in batches to react at room temperature. After the completion of the TLC detection reaction, the reaction mixture was extracted with 80mL of ethyl acetate and 80mL of water, and the organic phase was dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and purified by column chromatography to obtain 1.94g of a white solid with a yield of 85.68%.
1 H NMR(600MHz,Chloroform-d)δ8.13(s,1H),8.08(t,1H),8.03(d,1H),7.91(s,1H),7.53(t,1H),7.40–7.30(m,4H),7.28–7.22(m,2H),4.80(d,2H).LC-MS(m/z,ESI):687.9(M+H) + .
Comparative example 3: preparation of insecticidal Compound N- [ 2-bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) phenyl ] -3- [ N- (cyanomethyl) benzamido ] -2-fluorobenzamide (Compound No. 9.321 disclosed in CN 110194726A)
Figure BDA0003768047010000391
To a 200mL reaction flask was added 3- [ N- (cyanomethyl) benzoylamino ] -2-fluorobenzoyl chloride (4.00g, 12.66mmol), 50mL acetonitrile was dissolved, and sodium bromide (1.30g, 12.63mmol), 2-bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) aniline (5.15g, 12.66mmol) and the reaction was refluxed for 5 hours. The reaction mixture was extracted with 200mL of ethyl acetate and 200mL of a saturated aqueous sodium bicarbonate solution, and the organic phase was dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and purified by column chromatography to give 1.33g of a white solid with a yield of 15.26%.
1 H NMR(600MHz,Chloroform-d)δ8.13(s,1H),8.08(t,1H),8.03(d,1H),7.91(s,1H),7.53(t,1H),7.40–7.30(m,4H),7.28–7.22(m,2H),4.80(d,2H).LC-MS(m/z,ESI):687.9(M+H) + .
Synthetic example 7: synthesis of 3- [ N- (cyanomethyl) -4-fluorobenzamide ] -2-fluoro-N- [4- (perfluoropropan-2-yl) -2- (trifluoromethyl) phenyl ] benzamide (Compound No. 1.5 of the present invention)
Figure BDA0003768047010000392
To a 100mL reaction flask was added 3- [ N- (cyanomethyl) -4-fluorobenzamide ] -2-fluorobenzoyl chloride (3g, 8.98mmol), 30mL of acetonitrile was dissolved, and sodium bromide (0.92g, 8.94mmol), 4- (perfluoropropan-2-yl) -2- (trifluoromethyl) aniline (2.96g, 9.00mmol) were added and the reaction was refluxed for 5 hours. The reaction mixture was extracted with 100mL of ethyl acetate and 100mL of a saturated aqueous sodium bicarbonate solution, and the organic phase was dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and purified by column chromatography to give 4.68g of a yellow solid with a yield of 83.13%.
1 H NMR(600MHz,Chloroform-d)δ8.73(d,1H),8.67(d,1H),8.18–8.11(m,1H),7.89(d,1H),7.85(d,1H),7.53(td,1H),7.45–7.34(m,3H),6.94(t,2H),4.78(d,2H).LC-MS(m/z,ESI):626.21[M-H] - .
Synthetic example 8: preparation of insecticidal Compound N- [ 2-bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) phenyl ] -3- [ N- (cyanomethyl) -4-fluorobenzamide ] -2-fluorobenzamide (Compound No. 9.7 disclosed in CN 110194726A)
Figure BDA0003768047010000401
To a 100mL reaction flask was added 3- [ N- (cyanomethyl) -4-fluorobenzamide ] -2-fluoro-N- [4- (perfluoropropan-2-yl) -2- (trifluoromethyl) phenyl ] benzamide (3g, 4.78mmol) and 30mL of N, N-dimethylformamide to dissolve, followed by addition of sodium hydroxide (0.29g, 7.25mmol), stirring for 10 minutes in ice bath, and N-bromosuccinimide (0.89g, 5 mmol) in portions to the reaction mixture and reaction at room temperature. After the completion of the TLC detection reaction, the reaction mixture was extracted with 100mL of ethyl acetate and 100mL of water, and the organic phase was dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and purified by column chromatography to obtain 2.81g of a white solid with a yield of 83.37%.
1 H NMR(600MHz,Chloroform-d)δ8.14(d,1H),8.13–8.08(m,1H),8.03(d,1H),7.91(d,1H),7.53(td,1H),7.44–7.38(m,2H),7.35(t,1H),6.95(t,2H),4.78(d,2H).LC-MS(m/z,ESI):706.13[M+H] + .
Comparative example 4: preparation of insecticidal Compound N- [ 2-bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) phenyl ] -3- [ N- (cyanomethyl) -4-fluorobenzamide ] -2-fluorobenzamide (Compound No. 9.7 disclosed in CN 110194726A)
Figure BDA0003768047010000402
To a 100mL reaction flask was added 3- [ N- (cyanomethyl) -4-fluorobenzamido ] -2-fluorobenzoyl chloride (3g, 8.98mmol), 30mL acetonitrile and dissolved, and sodium bromide (0.92g, 8.94mmol), 2-bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) aniline (3.65g, 8.97mmol) were added and the reaction refluxed for 5 hours. The reaction mixture was extracted with 100mL of ethyl acetate and 100mL of a saturated aqueous sodium bicarbonate solution, and the organic phase was dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and purified by column chromatography to obtain 0.87g of a white solid with a yield of 13.75%.
1 H NMR(600MHz,Chloroform-d)δ8.14(d,1H),8.13–8.08(m,1H),8.03(d,1H),7.91(d,1H),7.53(td,1H),7.44–7.38(m,2H),7.35(t,1H),6.95(t,2H),4.78(d,2H).LC-MS(m/z,ESI):706.13[M+H] + .
Synthetic example 9: synthesis of N- (cyanomethyl) -6-fluoro-N- { 2-fluoro-3- { [4- (perfluoropropan-2-yl) -2- (trifluoromethyl) phenyl ] carbamoyl } phenyl } nicotinamide (Compound No. 1.25 of the present invention)
(1) Synthesis of methyl 3- [ N- (cyanomethyl) -6-fluoronicotinamide ] -2-fluorobenzoate (Compound No. 3.4 of the present invention)
Figure BDA0003768047010000411
To a 50mL reaction flask was added methyl 3- [ (cyanomethyl) amino ] -2-fluorobenzoate (1g, 4.81mmol), 10mL toluene was dissolved, and 6-fluoronicotinoyl chloride (1.07g, 6.73mmol) was added and the reaction was refluxed for 2.5 hours. After cooling to room temperature, the reaction mixture was extracted three times with 50mL of ethyl acetate and 50mL of saturated aqueous sodium bicarbonate solution, and the organic phase was dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to give 1.4g of oil in 88.34% yield.
1 H NMR(600MHz,Chloroform-d)δ8.19(d,1H),7.99–7.93(m,1H),7.89–7.84(m,1H),7.44–7.37(m,1H),7.22(td,1H),6.85(dd,1H),5.07(d,1H),4.40(d,1H),3.93(s,3H).LC-MS(m/z,ESI):332.02[M+H] + .
(2) Synthesis of 3- [ N- (cyanomethyl) -6-fluoronicotinamide ] -2-fluorobenzoic acid (Compound No. 2.4 of the present invention)
Figure BDA0003768047010000412
To a 250mL reaction flask, methyl 3- [ N- (cyanomethyl) -6-fluoronicotinamide ] -2-fluorobenzoate (8g, 24.24mmol) and 80mL of acetonitrile were added and dissolved, followed by addition of lithium bromide (21.05g, 242.37mmol), water (2.18g, 121.04mmol) and triethylamine (12.26g, 121.16mmol) while stirring, followed by reaction at room temperature for 6 hours and TLC for monitoring the progress of the reaction. After the reaction was completed, the reaction solution was cooled to room temperature, 80mL of water was added, the PH of the reaction solution was adjusted to 2 to 3 with hydrochloric acid solution under stirring, and then the reaction solution was extracted with ethyl acetate and water, and the organic layers were combined, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain 7.48g of a white solid with a yield of 97.40%.
1 H NMR(600MHz,DMSO-d 6 )δ13.50(s,1H),8.23(d,1H),7.97(td,1H),7.85–7.79(m,2H),7.34(t,1H),7.15(dd,1H),4.95(d,2H).LC-MS(m/z,ESI):316.06(M-H) - .
(3) Synthesis of 3- [ N- (cyanomethyl) -6-fluoronicotinamide ] -2-fluorobenzoyl chloride
Figure BDA0003768047010000413
3- [ N- (cyanomethyl) -6-fluoronicotinamide ] -2-fluorobenzoic acid (2g, 6.31mmol) is added into a 50mL single-neck flask, then 20mL toluene is added for dissolving and diluting, thionyl chloride (3.75g, 31.52mmol) is added, reaction is carried out for 3h under reflux, and toluene and thionyl chloride are removed by reduced pressure distillation, thus obtaining 1.97g of oily matter with the yield of 93.27%.
(4) Synthesis of N- (cyanomethyl) -6-fluoro-N- { 2-fluoro-3- { [4- (perfluoropropan-2-yl) -2- (trifluoromethyl) phenyl ] carbamoyl } phenyl } nicotinamide (Compound No. 1.25 of the present invention)
Figure BDA0003768047010000421
To a 50mL reaction flask was added 3- [ N- (cyanomethyl) -6-fluoronicotinamide ] -2-fluorobenzoyl chloride (2g, 5.97mmol) and 20mL acetonitrile to dissolve, followed by addition of sodium bromide (0.61g, 5.93mmol) and 4- (perfluoropropan-2-yl) -2- (trifluoromethyl) aniline (1.96g, 5.96mmol), and the reaction was refluxed for 5 hours. The reaction mixture was extracted with 60mL of ethyl acetate and 60mL of a saturated aqueous sodium bicarbonate solution, and the organic phase was dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and purified by column chromatography to give 3.27g of an oil, yield 87.33%.
1 H NMR(600MHz,Chloroform-d)δ8.70(d,1H),8.66(d,1H),8.23–8.16(m,2H),7.96–7.91(m,1H),7.89(d,1H),7.85(d,1H),7.59(td,1H),7.43(t,1H),6.90(dd,1H),5.01(s,1H),4.58(s,1H).LC-MS(m/z,ESI):629.25[M+H] + .
Synthesis example 10: preparation of insecticidal Compound N- {3- ([ 2-bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) phenyl ] carbamoyl) -2-fluorophenyl } -N- (cyanomethyl) -6-fluoronicotinamide (Compound No. 9 disclosed in CN 112430211A)
Figure BDA0003768047010000422
To a 25mL reaction flask was added N- (cyanomethyl) -6-fluoro-N- { 2-fluoro-3- { [4- (perfluoropropan-2-yl) -2- (trifluoromethyl) phenyl ] carbamoyl } phenyl } nicotinamide (1g, 1.59mmol), and 10mL of N, N-dimethylformamide was dissolved, followed by addition of sodium hydroxide (0.1g, 2.39mmol), stirring for 10 minutes under ice bath, and N-bromosuccinimide (0.3g, 1.67mmol) was further added to the reaction mixture in divided portions, and the reaction was carried out at room temperature. After the completion of the TLC detection reaction, the reaction mixture was extracted three times with 50mL of ethyl acetate and 50mL of water, and the organic phase was dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and purified by column chromatography to obtain 0.98g of a white solid with a yield of 87.50%.
1 H NMR(600MHz,Chloroform-d)δ8.21(d,1H),8.17–8.12(m,2H),8.01(d,1H),7.92–7.85(m,2H),7.57(td,1H),7.41(t,1H),6.88(dd,1H),4.95(br s,1H),4.63(br s,1H).LC-MS(m/z,ESI):707.08(M+H) + .
Although specific embodiments of the present invention have been described above, it will be appreciated by those skilled in the art that these are merely illustrative and that various changes or modifications may be made without departing from the principles and spirit of the invention. The scope of the invention is therefore defined by the appended claims.

Claims (20)

1. A bisamide compound, which is characterized by having a structure shown in the following general formula I:
Figure FDA0003768046000000011
in formula I:
q is selected from Q 1 Or Q 2 In which
Figure FDA0003768046000000012
Represents the attachment position of the group,
Figure FDA0003768046000000013
R 1 、R 2 、R 3 、R 4 and R 5 Each independently selected from hydrogen, halogen, cyano, nitro, C 1 -C 6 Alkyl radical, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy radical, C 1 -C 6 Haloalkoxy, C 1 -C 6 Alkylthio or C 1 -C 6 A haloalkylthio group;
R 6 selected from fluoro, difluoromethyl, trifluoromethyl or cyano;
n is selected from 1,2, 3 or 4;
W 1 selected from hydrogen, C 1 -C 6 Haloalkyl or C 1 -C 6 A haloalkoxy group;
W 2 selected from trifluoromethyl or perfluoroethyl.
2. The bisamide-based compound according to claim 1, wherein:
in the general formula I, R 1 、R 2 、R 3 、R 4 And R 5 Each independently selected from hydrogen, halogen, cyano, nitro, C 1 -C 3 Alkyl radical, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy radical, C 1 -C 3 Haloalkoxy, C 1 -C 3 Alkylthio or C 1 -C 3 A haloalkylthio group; r 6 Selected from fluoro, difluoromethyl, trifluoromethyl or cyano; n is selected from 1,2, 3 or 4; w is a group of 1 Selected from hydrogen, C 1 -C 3 Haloalkyl or C 1 -C 3 A haloalkoxy group; w is a group of 2 Selected from trifluoromethyl or perfluoroethyl;
preferably, in formula I, R 1 、R 2 、R 3 、R 4 And R 5 Each independently selected from hydrogen, fluoro, chloro, bromo, cyano, nitro, methyl, ethyl, propyl, tert-butyl, trifluoromethyl, heptafluoroisopropyl, methoxy or trifluoromethoxy; r 6 Selected from fluoro, difluoromethyl, trifluoromethyl or cyano; n is selected from 1,2, 3 or 4; w 1 Selected from hydrogen, trifluoromethyl, trifluoromethoxy or difluoromethoxy; w is a group of 2 Selected from trifluoromethyl or perfluoroethyl;
preferably, in formula I, R 1 、R 2 、R 4 And R 5 Each independently selected from hydrogen; r is 3 Selected from hydrogen, fluoro, chloro, bromo, cyano, nitro, methyl, ethyl, propyl, tert-butyl, trifluoromethyl, heptafluoroisopropyl, methoxy or trifluoromethoxy; r is 6 Selected from fluoro, difluoromethyl, trifluoromethyl or cyano; n is selected from 1,2, 3 or 4; w 1 Selected from hydrogen, trifluoromethyl, trifluoromethoxy or difluoromethylAn oxy group; w 2 Selected from trifluoromethyl or perfluoroethyl.
3. The bisamide-based compound according to any one of claims 1 to 2, wherein the bisamide-based compound is selected from the group consisting of:
the compounds of Table 1, the compounds of Table 1 have the structure shown in the general formula I, and Q and R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、n、W 1 And W 2 As shown in table 1, wherein "-" indicates no substitution;
TABLE 1
Figure FDA0003768046000000021
Figure FDA0003768046000000031
Figure FDA0003768046000000041
Figure FDA0003768046000000051
Figure FDA0003768046000000061
Figure FDA0003768046000000071
Figure FDA0003768046000000081
Figure FDA0003768046000000091
Figure FDA0003768046000000101
4. Use of bisamide-based compounds according to any of claims 1 to 3 for the preparation of isophthalamide-based compounds of general formula a;
Figure FDA0003768046000000102
wherein X is bromine or iodine; q, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、n、W 1 And W 2 Is as defined in any one of claims 1 to 3.
5. The application according to claim 4, characterized in that it comprises the following steps:
reacting the compound shown in the general formula I with a halogenating agent to obtain a m-diamide compound shown in the general formula A, wherein the reaction formula is as follows:
Figure FDA0003768046000000103
wherein, X is bromine or iodine; q, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、n、W 1 And W 2 Is as defined in any one of claims 1 to 3.
6. A compound which is an intermediate for producing the bisamide-based compound according to any one of claims 1 to 3, wherein the compound has a structure represented by the following general formula II:
Figure FDA0003768046000000111
in formula II:
q is selected from Q 1 Or Q 2 In which
Figure FDA0003768046000000112
Represents the attachment position of the group,
Figure FDA0003768046000000113
R 1 、R 2 、R 3 、R 4 and R 5 Each independently selected from hydrogen, halogen, cyano, nitro, C 1 -C 6 Alkyl radical, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy radical, C 1 -C 6 Haloalkoxy, C 1 -C 6 Alkylthio or C 1 -C 6 A haloalkylthio group;
R 6 selected from fluoro, difluoromethyl, trifluoromethyl or cyano;
n is selected from 1,2, 3 or 4;
preferably, in formula II, R 1 、R 2 、R 3 、R 4 And R 5 Each independently selected from hydrogen, halogen, cyano, nitro, C 1 -C 3 Alkyl radical, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy radical, C 1 -C 3 Haloalkoxy, C 1 -C 3 Alkylthio or C 1 -C 3 A haloalkylthio group; r is 6 Selected from fluoro, difluoromethyl, trifluoromethyl or cyano; n is selected from 1,2, 3 or 4;
preferably, in formula II, R 1 、R 2 、R 3 、R 4 And R 5 Each independently selected from hydrogen, fluorine, chlorine, bromine,Cyano, nitro, methyl, ethyl, propyl, tert-butyl, trifluoromethyl, heptafluoroisopropyl, methoxy or trifluoromethoxy; r is 6 Selected from fluoro, difluoromethyl, trifluoromethyl or cyano; n is selected from 1,2, 3 or 4;
preferably, in formula II, R 1 、R 2 、R 4 And R 5 Each independently selected from hydrogen; r is 3 Selected from hydrogen, fluoro, chloro, bromo, cyano, nitro, methyl, ethyl, propyl, tert-butyl, trifluoromethyl, heptafluoroisopropyl, methoxy or trifluoromethoxy; r 6 Selected from fluoro, difluoromethyl, trifluoromethyl or cyano; n is selected from 1,2, 3 or 4.
7. The compound of claim 6, wherein the compound is selected from the group consisting of:
the compounds of Table 2, the compounds of Table 2 having the structure of formula II and Q, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 And n is as shown in table 2, wherein "-" indicates no substitution;
TABLE 2
Figure FDA0003768046000000121
Figure FDA0003768046000000131
8. A compound which is an intermediate in the preparation of a compound according to any one of claims 6 to 7, wherein the compound has the following general formula III:
Figure FDA0003768046000000132
in formula III:
q is selected from Q 1 Or Q 2 Wherein
Figure FDA0003768046000000133
Represents the attachment position of the group,
Figure FDA0003768046000000134
R 1 、R 2 、R 3 、R 4 and R 5 Each independently selected from hydrogen, halogen, cyano, nitro, C 1 -C 6 Alkyl radical, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy radical, C 1 -C 6 Haloalkoxy, C 1 -C 6 Alkylthio or C 1 -C 6 A haloalkylthio group;
R 6 selected from fluoro, difluoromethyl, trifluoromethyl or cyano;
R 7 is selected from C 1 -C 6 An alkyl group;
n is selected from 1,2, 3 or 4;
preferably, in formula III, R 1 、R 2 、R 3 、R 4 And R 5 Each independently selected from hydrogen, halogen, cyano, nitro, C 1 -C 3 Alkyl radical, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy radical, C 1 -C 3 Haloalkoxy, C 1 -C 3 Alkylthio or C 1 -C 3 A haloalkylthio group; r 6 Selected from fluoro, difluoromethyl, trifluoromethyl or cyano; r is 7 Is selected from C 1 -C 3 An alkyl group; n is selected from 1,2, 3 or 4;
preferably, in formula III, R 1 、R 2 、R 3 、R 4 And R 5 Each independently selected from hydrogen, fluoro, chloro, bromo, cyano, nitro, methyl, ethyl, propyl, tert-butyl, trifluoromethyl, heptafluoroisopropyl, methoxy or trifluoromethoxy; r is 6 Selected from fluoro, difluoromethyl, trifluoromethyl or cyano; r 7 Selected from methyl or ethyl; n is selected from1.2, 3 or 4;
preferably, in formula III, R 1 、R 2 、R 4 And R 5 Each independently selected from hydrogen; r 3 Selected from hydrogen, fluoro, chloro, bromo, cyano, nitro, methyl, ethyl, propyl, tert-butyl, trifluoromethyl, heptafluoroisopropyl, methoxy or trifluoromethoxy; r 6 Selected from fluoro, difluoromethyl, trifluoromethyl or cyano; r 7 Selected from methyl or ethyl; n is selected from 1,2, 3 or 4.
9. The compound of claim 8, wherein the compound is selected from the group consisting of:
the compounds of Table 3, the compounds of Table 3 have the structure of formula III and Q, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 And n is as shown in table 3, wherein "-" indicates no substitution;
TABLE 3
Figure FDA0003768046000000141
Figure FDA0003768046000000151
Figure FDA0003768046000000161
10. A compound which is an intermediate in the preparation of a compound according to any one of claims 8 to 9, wherein the compound has the following general formula IV:
Figure FDA0003768046000000162
in formula IV:
n is selected from 1,2, 3 or 4;
R 7 is selected from C 1 -C 6 An alkyl group;
preferably, in formula IV, n is selected from 1,2, 3 or 4; r 7 Is selected from C 1 -C 3 An alkyl group;
preferably, in formula IV, n is selected from 1,2, 3 or 4; r 7 Selected from methyl or ethyl.
11. The compound of claim 10, wherein the compound is selected from the group consisting of:
table 4 Compounds, table 4 Compounds having the structure of formula IV and n and R 7 As shown in table 4;
TABLE 4
Figure FDA0003768046000000163
Figure FDA0003768046000000171
12. A compound which is an intermediate for producing the bisamide-based compound according to any one of claims 1 to 3, wherein the compound has a structure represented by the following general formula V:
Figure FDA0003768046000000172
in formula V:
n is selected from 1,2, 3 or 4;
W 1 selected from hydrogen, C 1 -C 6 Haloalkyl or C 1 -C 6 A haloalkoxy group;
W 2 selected from trifluoromethyl or perfluoroethyl;
preferably, in formula V, n is selected from 1,2.3 or 4; w 1 Selected from hydrogen, C 1 -C 3 Haloalkyl or C 1 -C 3 A haloalkoxy group; w 2 Selected from trifluoromethyl or perfluoroethyl;
preferably, in formula V, n is selected from 1,2, 3 or 4; w 1 Selected from hydrogen, trifluoromethyl, trifluoromethoxy or difluoromethoxy; w is a group of 2 Selected from trifluoromethyl or perfluoroethyl.
13. The compound of claim 12, wherein the compound is selected from the group consisting of:
the compounds of Table 5, the compounds of Table 5 have a structure as shown in formula V and n, W 1 And W 2 As shown in table 5;
TABLE 5
Figure FDA0003768046000000173
Figure FDA0003768046000000181
14. A compound which is an intermediate in the preparation of a compound according to any one of claims 12 to 13, wherein the compound has the structure of formula VI:
Figure FDA0003768046000000191
in formula VI:
W 1 selected from hydrogen, C 1 -C 6 Haloalkyl or C 1 -C 6 A haloalkoxy group;
W 2 selected from trifluoromethyl or perfluoroethyl;
preferably, in formula VI, W 1 Selected from hydrogen, C 1 -C 3 Haloalkyl or C 1 -C 3 A haloalkoxy group; w 2 Selected from trifluoromethyl or perfluoroethyl;
preferably, in formula VI, W 1 Selected from hydrogen, trifluoromethyl, trifluoromethoxy or difluoromethoxy; w is a group of 2 Selected from trifluoromethyl or perfluoroethyl.
15. The compound of claim 14, wherein the compound is selected from the group consisting of:
the compounds of Table 6, the compounds of Table 6 have the structure of formula VI and W 1 And W 2 As shown in table 6;
TABLE 6
Compound number W 1 W 2 6.1 H CF 3 6.2 CF 3 CF 3 6.3 OCF 3 CF 3 6.4 OCHF 2 CF 3 6.5 H CF 2 CF 3 6.6 CF 3 CF 2 CF 3 6.7 OCF 3 CF 2 CF 3 6.8 OCHF 2 CF 2 CF 3
。
16. A compound which is an intermediate in the preparation of a compound according to any one of claims 14 to 15, wherein the compound has the structure shown in formula VII:
Figure FDA0003768046000000201
in formula VII:
W 1 selected from hydrogen, C 1 -C 6 Haloalkyl or C 1 -C 6 A haloalkoxy group;
W 2 selected from trifluoromethyl or perfluoroethyl;
preferably, in formula VII, W 1 Is selected from hydrogen、C 1 -C 3 Haloalkyl or C 1 -C 3 A haloalkoxy group; w 2 Selected from trifluoromethyl or perfluoroethyl;
preferably, in formula VII, W 1 Selected from hydrogen, trifluoromethyl, trifluoromethoxy or difluoromethoxy; w is a group of 2 Selected from trifluoromethyl or perfluoroethyl.
17. The compound of claim 16, wherein the compound is selected from the group consisting of:
the compounds of Table 7, the compounds of Table 7 having the structure of formula VII and W 1 And W 2 As shown in table 7;
TABLE 7
Compound number W 1 W 2 7.1 H CF 3 7.2 CF 3 CF 3 7.3 OCF 3 CF 3 7.4 OCHF 2 CF 3 7.5 H CF 2 CF 3 7.6 CF 3 CF 2 CF 3 7.7 OCF 3 CF 2 CF 3 7.8 OCHF 2 CF 2 CF 3
。
18. A compound having the structure of formula VIII:
Figure FDA0003768046000000202
general formula VIII
In formula VIII:
n is selected from 1,2, 3 or 4;
x is selected from bromine or iodine;
y is selected from bromine, iodine, C 1 -C 6 Haloalkyl or C 1 -C 6 A haloalkoxy group;
W 2 selected from trifluoromethyl or perfluoroethyl;
preferably, in formula VIII, n is selected from 1,2, 3 or 4; x is selected from bromine or iodine; y is selected from bromine, iodine, C 1 -C 3 Haloalkyl or C 1 -C 3 A haloalkoxy group; w is a group of 2 Selected from trifluoromethyl or perfluoroethyl;
preferably, in formula VIII, n is selected from 1,2, 3 or 4; x is selected from bromine or iodine; y is selected from bromine, iodine, trifluoromethyl, trifluoromethoxy or difluoromethoxy; w 2 Selected from bromine, iodine, trifluoromethyl or perfluoroethyl.
19. The compound of claim 18, wherein the compound is selected from the group consisting of:
the compounds of Table 8, the compounds of Table 8 having the structure of formula VIII and n, X, Y and W 2 As shown in table 8;
TABLE 8
Figure FDA0003768046000000211
Figure FDA0003768046000000221
Figure FDA0003768046000000231
20. The use of a compound according to claim 18 for the preparation of a compound of the meta-diamide type represented by general formula B;
Figure FDA0003768046000000232
and, the application comprises the steps of:
(1) Reacting a compound of formula IX with a compound of formula X to provide a compound of formula VIII:
Figure FDA0003768046000000241
(2) Reacting a compound of formula VIII with a compound of formula XI to provide a compound of formula B, wherein:
Figure FDA0003768046000000242
wherein:
LG is selected from chlorine, bromine or iodine;
q is selected from Q 1 Or Q 2 Wherein
Figure FDA0003768046000000243
Represents the attachment position of the group,
Figure FDA0003768046000000244
R 1 、R 2 、R 3 、R 4 and R 5 Each independently selected from hydrogen, halogen, cyano, nitro, C 1 -C 6 Alkyl radical, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy radical, C 1 -C 6 Haloalkoxy, C 1 -C 6 Alkylthio or C 1 -C 6 A haloalkylthio group;
R 6 selected from fluoro, difluoromethyl, trifluoromethyl or cyano;
n is selected from 1,2, 3 or 4;
x is selected from bromine or iodine;
y is selected from bromine, iodine, C 1 -C 6 Haloalkyl or C 1 -C 6 A haloalkoxy group;
W 2 selected from trifluoromethyl or perfluoroethyl.
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