CN109265381B - Cyano-containing phthalic diamide derivative and preparation and application thereof - Google Patents
Cyano-containing phthalic diamide derivative and preparation and application thereof Download PDFInfo
- Publication number
- CN109265381B CN109265381B CN201810985655.7A CN201810985655A CN109265381B CN 109265381 B CN109265381 B CN 109265381B CN 201810985655 A CN201810985655 A CN 201810985655A CN 109265381 B CN109265381 B CN 109265381B
- Authority
- CN
- China
- Prior art keywords
- formula
- acid
- compound shown
- compound
- methyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C323/39—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton at least one of the nitrogen atoms being part of any of the groups, X being a hetero atom, Y being any atom
- C07C323/40—Y being a hydrogen or a carbon atom
- C07C323/42—Y being a carbon atom of a six-membered aromatic ring
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/34—Nitriles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
- A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
- A01N41/10—Sulfones; Sulfoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C317/28—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to acyclic carbon atoms of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
Abstract
The invention discloses a phthalic acid diamide derivative containing a cyano group, and a preparation method and application thereof. The structural formula of the compound is shown in formula I,
in the formula I, R1Is methyl, halogen, nitro; r2Is H or methyl; r3Is H or methyl; m is 0, 1 or 2; n is any integer from 1 to 6; a is any integer from 1 to 3; y is selected from halogen, nitro, C1‑C6Alkyl of (C)1‑C6At least one of alkoxy, trifluoromethyl, heptafluoroisopropyl, and methoxyhexafluoroisopropyl. The use of the compounds and/or their salts which are tried in agriculture, and/or their stereoisomers, in the preparation of agrochemical insecticides. The compound has excellent insecticidal activity, and shows good activity to lepidoptera pest diamondback moth under the dosage of 0.25 mg/L; the daphnia magna compound has lower toxicity to daphnia magna at the bottom end of a food chain of an aquatic ecosystem and low toxicity to aquatic organisms; the compound of the invention has reasonable ecological toxicity and environmental compatibility, and belongs to a high-efficiency, low-toxicity and green pesticide.
Description
Technical Field
The invention relates to a phthalic acid diamide derivative containing cyano and a preparation method and application thereof, belonging to the technical field of discovery and synthesis of agricultural chemical pesticides.
Background
The ever-expanding pesticide market and the problems of pest resistance, drug life and environmental pollution require scientists to research continuously, and further develop more efficient, less toxic, environmentally safe and different pesticide varieties with different action modes.
Phthalic acid diamide and anthranilic acid diamide (acting on an insect ryanodine receptor) derivatives are effective insecticides for controlling lepidopteran pests developed in recent years. The phthalic acid diamide derivative with insecticidal bioactivity does not have low toxicity to aquatic organisms.
Disclosure of Invention
The invention aims to provide a cyano-containing phthalic diamide derivative, and a preparation method and an application thereof.
The invention provides a compound, which has a structural formula shown in a formula I,
in the formula I, R1Is methyl, halogen, nitro;
R2is H or methyl;
R3is H or methyl;
m is 0, 1 or 2;
n is any integer from 1 to 6;
a is any integer from 1 to 3;
y is selected from halogen, nitro, C1-C6Alkyl of (C)1-C6At least one of alkoxy, trifluoromethyl, heptafluoroisopropyl, and methoxyhexafluoroisopropyl.
In the present invention, the expression of Y in formula I is a general knowledge in the art, and is an arbitrary position or an ortho-para position on the benzene ring.
In the above compound, the halogen is fluorine, chlorine, bromine or iodine;
said C is1-C6And said C1-C6The alkyl groups in the alkoxy groups of (1) are all straight-chain or branched alkyl groups.
The invention also provides a preparation method of the compound shown in the formula I, which comprises the following steps: 1) mixing a compound shown as a formula II and a compound shown as a formula III in an organic solvent for reaction to obtain a compound shown as a formula IV;
in the formula II, R1Is methyl, halogen, nitro;
in the formula III, R2Is H or methyl;
R3is H or methyl;
m is 0, 1 or 2
n is any integer of 1-6;
in the formula IV, R1Is methyl, halogen, nitro;
R2is H or methyl;
R3is H or methyl;
m is 0, 1 or 2
n is any integer of 1-6;
2) in the organic solvent, the compound shown in the formula IV is mixed with acid anhydride for reaction to obtain a compound shown in a formula V;
in formula V, R1Is methyl, halogen, nitro;
R2is H or methyl;
R3is H or methyl;
m is 0, 1 or 2;
n is any integer from 1 to 6;
3) in the organic solvent, the compound shown in the formula V and the compound shown in the formula VI are mixed and reacted to obtain the compound shown in the formula I;
in the formula VI, a is any integer of 1-3, and Y is selected fromHalogen, nitro, C1-C6Alkyl of (C)1-C6At least one of alkoxy, trifluoromethyl, heptafluoroisopropyl, and methoxyhexafluoroisopropyl.
In the present invention, the representation of Y in formula VI is common knowledge in the art, and is a substitution position at an arbitrary position or an ortho-para substitution position on the benzene ring; may be one or more substituents.
In the above preparation method, the halogen is fluorine, chlorine, bromine or iodine;
in the step 1), the molar ratio of the compound represented by the formula II to the compound represented by the formula III may be 1: 1-10, specifically 1:1, 1: 1-5 or 1: 1-8;
the reaction temperature is from-10 ℃ to the boiling point of the organic solvent, and the reaction time can be 0.5 to 48 hours, specifically 0.5 to 4 hours, 4 to 48 hours, or 2 to 40 hours.
Adding organic base into the reaction in the step 1) for reaction, wherein the molar ratio of the organic base to the compound shown in the formula III is 0.001-0.1: 1;
and 2) adding an acid for acidification after the reaction in the step 1), wherein the molar ratio of the acid to the compound shown in the formula III is 0.001-0.1: 1.
In the above preparation method, in step 2), the molar ratio of the compound represented by the formula iv to the acid anhydride may be 1: 0.5-20, specifically 1: 1;
the acid anhydride includes acetic anhydride, propionic anhydride, trifluoroacetic anhydride, trichloroacetic anhydride, etc
The reaction temperature can be-5-100 ℃, and the reaction time can be 0.5-6 hours.
In the above preparation method, in step 3), the molar ratio of the compound represented by the formula v to the compound represented by the formula vi may be 1: 1-10, specifically 1: 1;
adding organic acid in the reaction in the step 3); the organic acid is selected from trifluoroacetic acid and/or trichloroacetic acid;
the molar weight of the organic acid is 1-20% of that of the compound shown in the formula V;
the reaction temperature can be from-10 ℃ to the boiling point of the organic solvent, and the reaction time can be 0.5 to 48 hours, specifically 3 hours, 5 hours, 3 to 5 hours, 1 to 20 hours, or 2 to 40 hours.
In the present invention, the boiling point of the organic solvent is common knowledge in the art.
In the above preparation method, the organic solvent is one or more selected from dichloromethane, chloroform, carbon tetrachloride, benzene, toluene, xylene, cyclohexane, N-hexane, ethyl acetate, tetrahydrofuran, 1, 4-dioxane, N-dimethylformamide and dimethyl sulfoxide.
In the above preparation method, the organic base is selected from triethylamine, pyridine or N, N-dimethylaniline; or an inorganic base: one or a mixture of more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, sodium tert-butoxide and potassium tert-butoxide;
the acid is selected from organic acid or inorganic acid, wherein the organic acid is selected from one or a mixture of more of methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, acetic acid, trifluoroacetic acid and trichloroacetic acid, and the inorganic acid is selected from one or a mixture of more of hydrochloric acid, sulfuric acid and phosphoric acid.
The invention also discloses application of the compound shown as the formula I and/or agriculturally suitable salt thereof and/or stereoisomer thereof in preparing agricultural chemical pesticides.
In the invention, the agricultural chemical pesticide is particularly suitable for at least one of lepidoptera pests, homoptera pests and daphnia magna at the bottom end of a food chain of an aquatic ecosystem; more specifically, the lepidopteran pest is a diamondback moth, and the homopteran pest is a soybean aphid.
The invention further provides a pesticide which consists of the compound shown as the formula I as an active ingredient and agriculturally acceptable auxiliaries.
The invention has the following advantages:
according to the invention, alkyl cyanide is introduced into the phthalic acid diamide structure for the first time, and the structure of the compound is novel; the compound has excellent insecticidal activity, and shows good activity to lepidoptera pest diamondback moth under the dosage of 0.25 mg/L; compared with the commercialized phthalic diamide compound, the compound disclosed by the invention has lower toxicity to daphnia magna at the bottom end of a food chain of an aquatic ecosystem and low toxicity to aquatic organisms; the compound of the invention has reasonable ecological toxicity and environmental compatibility, and belongs to a high-efficiency, low-toxicity and green pesticide.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Examples 1,
Derivative N2- (1- (2-cyanoethylmercapto) -2-methyl-2-propyl) -3-fluoro-N1Synthesis of- (2-methyl-4-heptafluoroisopropylphenyl) phthalic acid amide:
step A: 2-methyl-1- (2-cyanoethylmercapto) -2-propylamine
A100 mL three-necked flask was charged with 2, 2-dimethylaziridine (14.2g, 0.2mol), 2-cyanoethanethiol (17.4g, 0.2mol), and 60mL of ethylene glycol dimethyl ether, heated under reflux for 4 hours, rotary-evaporated to remove the solvent, and subjected to column chromatography to give 27.8 g of 2-methyl-1- (2-cyanoethylmercapto) -2-propylamine in 88% yield.
1H NMR(300MHz,Chloroform-d)2.62(t,J＝6.9Hz,2H),2.47(t,J＝6.8Hz,2H),2.44(s,2H),1.43(s,2H),0.96(s,6H).
And B: preparation of 2- ((1- (2-cyanoethylthio) -2-methyl-2-propyl) -carbamoyl) -3-fluorobenzoic acid
A100 mL three-necked flask was charged with 3-fluorophthalic anhydride (4.98g, 30mmol) and 30mL of dichloromethane, triethylamine (3.03g, 30mmol) and 2-methyl-1- (2-cyanoethylmercapto) -2-propylamine (4.74g, 30mmol) were dissolved in 30mL of dichloromethane, slowly added dropwise to the reaction system, and the reaction was stirred for 5 hours. After the reaction, the reaction mixture was poured into 50mL of water, acidified to pH 2-3 with dilute hydrochloric acid, extracted with dichloromethane (3X 20mL), dried over anhydrous sodium sulfate, and rotary-desolventized to proceed the next reaction.
And C: preparation of N2- (1- (2-cyanoethylmercapto) -2-methyl-2-propyl) -3-fluoro-N1- (2-methyl-4-heptafluoroisopropylphenyl) phthalic acid diamides
A100 mL three-necked flask was charged, the reaction product from the previous step and trifluoroacetic anhydride (6.3g, 30mmol) were dissolved in 50mL of dry toluene, stirred at room temperature (25 ℃) for 3 hours, and rotary desolventized. 40mL of methylene chloride was added to the residue, followed by dropwise addition of 2-methyl-4-heptafluoroisopropylaniline (6.75g, 30mmol) to the reaction system, further dropwise addition of two drops of trifluoroacetic acid, and stirring at room temperature for 1 hour. After the reaction is finished, the reaction solution is washed by 20mL of dilute hydrochloric acid, 20mL of sodium carbonate aqueous solution and 20mL of water, dried by anhydrous sodium sulfate, and subjected to column chromatography after rotary desolventizing to obtain 8.89g N2- (1- (2-cyanoethylmercapto) -2-methyl-2-propyl) -3-fluoro-N1- (2-methyl-4-heptafluoroisopropylphenyl) phthalic acid amide, yield 51%.
1H NMR(300MHz,DMSO-d6)9.88(s,1H),8.29(s,1H),7.85(d,J＝8.9Hz,1H), 7.54(m,4H),7.40(m,1H),3.06(s,2H),2.76–2.69(m,4H),2.39(s,3H),1.31(s,6H).
Examples 2,
Preparation of N2- (1- (2-cyanoethylsulfinyl) -2-methyl-2-propyl) -3-fluoro-N1- (2-methyl-4-heptafluoroisopropylphenyl) phthalic acid diamides
100mL three-necked flask, adding N2- (1- (2-cyanoethylmercapto) -2-methyl-2-propyl) -3-fluoro-N1- (2-methyl-4-heptafluoroisopropylphenyl) o-benzeneDimethylamide (2.9g, 5mmol) and 20mL of dichloromethane were dissolved in 30mL of dichloromethane at 0 ℃ and then added dropwise to the reaction system after m-chloroperoxybenzoic acid (0.86g, 5mmol) was added. After the completion of the dropwise addition, the reaction mixture was transferred to room temperature to react for 3 hours. After the reaction is finished, the reaction solution is washed by 30mL of sodium bisulfite aqueous solution and 30mL of sodium carbonate aqueous solution in sequence, dried by anhydrous sodium sulfate, and subjected to column chromatography after rotary desolventizing to obtain 2.68g N2- (1- (2-cyanoethylsulfinyl) -2-methyl-2-propyl) -3-fluoro-N1- (2-methyl-4-heptafluoroisopropylphenyl) phthalic acid amide, yield 90%.
1H NMR(300MHz,DMSO-d6)9.99(s,1H),8.60(s,1H),7.79(d,J＝9.0Hz,1H),7.61–7.52(m,4H),7.43(m,1H),3.63(d,J＝13.4Hz,1H),3.05–2.69(m,5H),2.39(s, 3H),1.45(s,6H).
Examples 3,
Preparation of N2- (1- (2-cyanoethylsulfonyl) -2-methyl-2-propyl) -3-fluoro-N1- (2-methyl-4-heptafluoroisopropylphenyl) phthalic acid diamides
100mL three-necked flask, adding N2- ((1- (2-cyanoethylmercapto) -2-methyl-2-propyl) -3-fluoro-N1- (2-methyl-4-heptafluoroisopropylphenyl) phthalic acid amide (2.9g, 5mmol) and 20mL of methylene chloride, m-chloroperoxybenzoic acid (1.81g, 10.5mmol) was dissolved in 30mL of methylene chloride at 0 ℃ and then added dropwise to the reaction system. After the completion of the dropwise addition, the reaction mixture was transferred to room temperature to react for 3 hours. After the reaction is finished, the reaction solution is washed by 30mL of sodium bisulfite aqueous solution and 30mL of sodium carbonate aqueous solution in sequence, dried by anhydrous sodium sulfate, and subjected to column chromatography after rotary desolventizing to obtain 2.82g N2- (1- (2-cyanoethylsulfonyl) -2-methyl-2-propyl) -3-fluoro-N1- (2-methyl-4-heptafluoroisopropylphenyl) phthalic acid amide, yield 92%.
1H NMR(300MHz,DMSO-d6)10.01(s,1H),8.60(s,1H),7.81(d,J＝8.2Hz,1H),7.63–7.51(m,4H),7.48–7.40(m,1H),3.80(s,2H),3.52(t,J＝7.1Hz,2H),2.91(t,J＝7.1Hz,2H),2.39(s,3H),1.51(s,6H).
Representative compounds of formula (I) of the present invention prepared according to the above preparation process of example 1 using different starting materials are now listed in table 1, but they by no means limit the scope of the present invention.
TABLE 1 Structure of cyano-modified phthalic acid diamide derivatives and their melting points
The following table 2 shows the nuclear magnetic data of some of the compounds shown in table 1.
Note: the compound numbers in table 2 correspond to the compound numbers in table 1. Where s is singlet, d is doublet, dd is doublet, t is triplet, q is quartet, and m is multiplet.
TABLE 2 partially cyano-modified phthalimide derivatives1H NMR data
Examples 4,
The novel cyano-containing phthalic acid diamide derivative provided by the invention is used for testing the biological activity of the derivative on pests:
examples of biological activity assays using the compounds of the present invention are given below, it being noted that the present invention is not limited solely to the scope of the following examples.
The insecticidal activity evaluation test was carried out according to the following method:
weighing a certain mass of the compound of the invention, dissolving the compound in a solvent, water and a surfactant, mixing to form a uniform water phase, diluting with water when in use to prepare the concentration required by determination, and screening the concentration to be 100, 10, 1, 0.5 and 0.25 mg/L. The test object and test method were as follows:
(1) evaluation of biological Activity of Plutella xylostella: the tested insects were plutella xylostella 2-instar larvae (L.) which were normal populations normally raised indoors; dipping the cabbage leaves in the prepared solution for 5 seconds by using a leaf dipping method and using tweezers to throw off residual liquid; one at a time, 3 pieces per sample; after the liquid medicine is dried, putting the liquid medicine into a watch glass with the diameter of 9cm, inoculating 2-year-old plutella xylostella larvae, and covering the surface with a cover; placing the test treatment in a standard treatment chamber, and observing the test result after 72 hours;
(2) evaluation of biological Activity of Aphis Dolichi: the tested insects are wingless adult aphids with the same size and are normal groups which are normally raised indoors; dipping the bean sprout leaves in the prepared solution for 5 seconds by using a leaf dipping method, and throwing off residual liquid; one at a time, 3 pieces per sample; after the liquid medicine is dried, transferring the liquid medicine into a clean culture dish, inoculating wingless adult aphids with the same size, covering the culture dish with a cover, and culturing at the constant temperature of 23 ℃; the test results were observed after 48 hours of treatment.
And (3) test statistics: counting the number of dead insects and the number of live insects of each treatment, and calculating the death rate
The mortality rate of the blank control group is less than 15%, the test result is credible, the test result is corrected, the mortality rate of the blank control group is less than 5%, and the test result can not be corrected.
The results of the bioassay experiments show that: the compound has good insecticidal activity, and particularly has certain insecticidal activity on lepidoptera pests (diamondback moths) and homoptera pests (soybean aphids). "mg/L" means per mg of active compound per liter.
At the concentration of 100mg/L, the mortality rate of the compounds 07 and 10 to soybean aphid is 100 percent
The mortality rate of the compounds 07, 11 and 31 to diamondback moth is 60 percent under the concentration of 0.25mg/L
The insecticidal activity of the compounds of the present invention was compared with that of the control compound flubendiamide (diamond back moth), and the results are shown in Table 3.
TABLE 3 comparison of pesticidal Activity
Examples 5,
The toxicity to aquatic organisms is tested by using the novel cyano-containing phthalic diamide derivative provided by the invention.
Examples of toxicity tests for aquatic organisms using the compounds of the present invention are given below.
The evaluation test of the acute toxicity of the daphnia magna of the aquatic organism is carried out according to the following method:
weighing a certain mass of the compounds 10 and 11 of the invention, respectively dissolving the compounds in a solvent, water and triton X-100 (triton X-100 is used as a surfactant), mixing the compounds to form a uniform water phase, diluting the uniform water phase by using aeration water to prepare the concentration required by the test, setting the concentration to be 2, 1, 0.5, 0.25 and 0.125mg/L, pouring the uniform water phase into a 50mL beaker, setting a blank control (clear water) and a maximum concentration auxiliary agent control, repeating the concentration three times, adding 10 young daphnia natans for 6-24 h in each repetition, keeping the water temperature at 20 +/-2 ℃, setting the ratio of the illumination period to the darkness period to be 16h:8h, not feeding the compound during the test, not replacing the test solution, respectively observing the survival conditions of the daphnia magna after 24h and 48h, and recording the test results.
The acute toxicity of the compounds 10 and 11 of the present invention to daphnia magna, a control compound, flubendiamide and chlorantraniliprole, was compared and the results are listed in table 4.
TABLE 4 comparison of acute toxicity of daphnia magna
Table 4 shows that compared with flubendiamide and chlorantraniliprole, the compounds 10 and 11 of the present invention have significantly lower acute toxicity to daphnia magna, which is a marine organism, and are safer.
Claims (9)
1. A compound has a structural formula shown in formula I,
in the formula I, R1-R3Ya, m and n are selected from any one of the following:
(1)R1is F, R2Is H, R3Is methyl, m is 0, n is 2, Ya is 2-CH3-4-CF(CF3)2；
(2)R1Is I, R2Is H, R3Is methyl, m is 0, n is 2, Ya is 2-CH3-4-CF(CF3)2；
(3)R1Is I, R2Is methyl, R3Is methyl, m is 0, 1 or 2, n is 2, Ya is 2-CH3-4-CF(CF3)2；
(4)R1Is Br, R2Is H, R3Is methyl, m is 0 or 2, n is 2, Ya is 2-CH3-4-CF(CF3)2。
2. A process for the preparation of a compound of formula i as claimed in claim 1, comprising the steps of: 1) mixing a compound shown as a formula II and a compound shown as a formula III in an organic solvent for reaction to obtain a compound shown as a formula IV;
in the formulae II, III and IV, R1-R3M and n are as defined in claim 1;
2) in the organic solvent, the compound shown in the formula IV is mixed with acid anhydride for reaction to obtain a compound shown in a formula V;
in formula V, R1-R3M and n are as defined in claim 1;
3) in the organic solvent, the compound shown in the formula V and the compound shown in the formula VI are mixed and reacted to obtain the compound shown in the formula I;
in formula VI, Ya is as defined in claim 1.
3. The method of claim 2, wherein: in the step 1), the molar ratio of the compound shown in the formula II to the compound shown in the formula III is 1: 1-10;
the reaction temperature is-10 ℃ to the boiling point of the organic solvent, and the reaction time is 0.5-48 hours.
Adding organic base into the reaction in the step 1) for reaction, wherein the molar ratio of the organic base to the compound shown in the formula III is 0.001-0.1: 1;
and adding an acid for acidification after the reaction in the step 1), wherein the molar ratio of the acid to the compound shown in the formula III is 0.001-0.1: 1.
4. The production method according to claim 2 or 3, characterized in that: in the step 2), the molar ratio of the compound shown in the formula IV to the acid anhydride is 1: 0.5 to 20;
the acid anhydride includes acetic anhydride, propionic anhydride, trifluoroacetic anhydride, trichloroacetic anhydride, etc
The reaction temperature is-5-100 ℃, and the reaction time is 0.5-6 hours.
5. The production method according to claim 2 or 3, characterized in that: in the step 3), the molar ratio of the compound shown in the formula V to the compound shown in the formula VI is 1: 1-10;
adding organic acid in the reaction in the step 3); the organic acid is selected from trifluoroacetic acid and/or trichloroacetic acid;
the molar weight of the organic acid is 1-20% of that of the compound shown in the formula V;
the reaction temperature is-10 ℃ to the boiling point of the organic solvent, and the reaction time is 0.5-48 hours.
6. The production method according to claim 2 or 3, characterized in that: the organic solvent is one or a mixture of more of dichloromethane, chloroform, carbon tetrachloride, benzene, toluene, xylene, cyclohexane, N-hexane, ethyl acetate, tetrahydrofuran, 1, 4-dioxane, N-dimethylformamide and dimethyl sulfoxide.
7. The production method according to claim 3, characterized in that: the organic base is selected from triethylamine, pyridine or N, N-dimethylaniline; or an inorganic base: one or a mixture of more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, sodium tert-butoxide and potassium tert-butoxide;
the acid is selected from organic acid or inorganic acid, wherein the organic acid is selected from one or a mixture of more of methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, acetic acid, trifluoroacetic acid and trichloroacetic acid, and the inorganic acid is selected from one or a mixture of more of hydrochloric acid, sulfuric acid and phosphoric acid.
8. Use of a compound of formula i as defined in claim 1 and/or an agriculturally suitable salt thereof, and/or a stereoisomer thereof, for the preparation of an agrochemical insecticide.
9. An insecticide, characterized by: which comprises as active ingredient a compound of formula I as defined in claim 1 and agriculturally acceptable adjuvants.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810985655.7A CN109265381B (en) | 2018-08-28 | 2018-08-28 | Cyano-containing phthalic diamide derivative and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810985655.7A CN109265381B (en) | 2018-08-28 | 2018-08-28 | Cyano-containing phthalic diamide derivative and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109265381A CN109265381A (en) | 2019-01-25 |
| CN109265381B true CN109265381B (en) | 2020-10-27 |
Family
ID=65154673
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810985655.7A Active CN109265381B (en) | 2018-08-28 | 2018-08-28 | Cyano-containing phthalic diamide derivative and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109265381B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110606828A (en) * | 2019-07-23 | 2019-12-24 | 贵州大学 | Trifluoromethyl pyridine amide derivative containing chiral thioether structure and application thereof |
| CN115583916A (en) * | 2022-10-21 | 2023-01-10 | 中国农业大学 | Substituted heterocycle-containing bisamide compound and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101935291A (en) * | 2010-09-13 | 2011-01-05 | 中化蓝天集团有限公司 | Cyano phthalic diamide compounds, preparation method thereof and use thereof as agricultural chemical pesticide |
| CN102171190A (en) * | 2008-07-31 | 2011-08-31 | 拜尔农作物科学股份公司 | Insecticidal benzenedicarboxamide derivative |
-
2018
- 2018-08-28 CN CN201810985655.7A patent/CN109265381B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102171190A (en) * | 2008-07-31 | 2011-08-31 | 拜尔农作物科学股份公司 | Insecticidal benzenedicarboxamide derivative |
| CN101935291A (en) * | 2010-09-13 | 2011-01-05 | 中化蓝天集团有限公司 | Cyano phthalic diamide compounds, preparation method thereof and use thereof as agricultural chemical pesticide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109265381A (en) | 2019-01-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2861104B2 (en) | Pyrazolamides and insecticides and acaricides containing the same as an active ingredient | |
| KR101319063B1 (en) | 1,2-benzisothiazole derivative, and agricultural or horticultural plant disease-controlling agent | |
| WO2008145052A1 (en) | Substituted pyrimidine ether compounds and their use | |
| CN110330455B (en) | Amide derivative, preparation method and application thereof | |
| CN109169668B (en) | Application of 2-aryl substituted pyrrole compound in drug for killing vesicular snails | |
| CN109265381B (en) | Cyano-containing phthalic diamide derivative and preparation and application thereof | |
| CN109232429B (en) | Bisamide compound containing 1, 3-dialkyl substituted pyrazole, and preparation method and application thereof | |
| JPH03128355A (en) | 4-acyloxyquinoline derivative and insecticide and acaricide containing the same derivative as active ingredient | |
| CN111362931A (en) | Isoxazoline pyrazole amide compound, and preparation method and application thereof | |
| JP4052942B2 (en) | 2-Pyrimidinyloxy-N-arylbenzylamine derivatives, their production and use | |
| JP2640664B2 (en) | Pyrimidine derivatives and herbicides | |
| RO104617B1 (en) | Solid insecticide composition | |
| JPH072738B2 (en) | Benzothiazolone derivative and herbicide containing the same as active ingredient | |
| CN104072455B (en) | 6-aroyl acetyl oxygen base Aurone compound and the application on pesticide thereof | |
| CN105622534B (en) | Heterocyclic imines derivative containing biamide structure and its preparation method and application | |
| CN105777733A (en) | Isoxazoline-containing tetrahydrophthalimide compound and use thereof | |
| JPH04128275A (en) | N-benzylamides and insecticidal miticide containing the compound as active component | |
| CN114763331B (en) | Trifluoroethyl thioether (sulfoxide) substituted benzene compound and application thereof | |
| CN115925576A (en) | Heptafluoroisopropyl-containing bisamide compound and preparation method and application thereof | |
| CN113045561B (en) | Diarylamine derivatives as fungicides | |
| CN107216291A (en) | Fragrant phenoxy group propionic acid compounds containing bishydrazide and preparation method and application | |
| JPH09301973A (en) | Chromene derivative and herbicide containing the same as active ingredient | |
| JPH0356447A (en) | New herbicide composition | |
| CN114605399B (en) | Isoxazoline compound containing trifluoromethyl, preparation method and application thereof | |
| WO1995025730A1 (en) | Nicotinic acid derivative and herbicide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |