CN111943931B - Preparation method of pymetrozine - Google Patents
Preparation method of pymetrozine Download PDFInfo
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- CN111943931B CN111943931B CN201910398090.7A CN201910398090A CN111943931B CN 111943931 B CN111943931 B CN 111943931B CN 201910398090 A CN201910398090 A CN 201910398090A CN 111943931 B CN111943931 B CN 111943931B
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- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
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Abstract
The invention provides a method for preparing pymetrozine, which comprises the steps of preparing carbonyl dihydrazide by using carbonic diester and hydrazine hydrate through a hydrazide reaction, preparing pyridine-3-yl methylene carbonyl dihydrazide by using the obtained carbonyl dihydrazide and 3-formylpyridine through a condensation reaction, and finally preparing pymetrozine through a cyclization reaction with monochloroacetone. The method has the advantages of cheap and easily obtained raw materials and low cost; the process flow is simple and short, and pymetrozine can be prepared only by three steps; the operation is safe and simple, and the reaction condition is easy to realize; the production amount of process wastewater is small, and the process is green and environment-friendly; the related raw materials and intermediate products have high stability, high reaction selectivity, less side reaction and high yield and purity of target products, and are beneficial to the industrial production of pymetrozine.
Description
Technical Field
The invention relates to a preparation method of pymetrozine, and belongs to the technical field of pesticide chemistry.
Background
Pymetrozine (I), known as Pymetrozine with CAS number 123312-89-0, chemical name 4, 5-dihydro-6-methyl-4- (3-pyridylmethyleneamino) -1,2, 4-triazin- (2H) -one, having the following structural formula:
pymetrozine is a novel methoximinopyridine insecticide developed by Ciba-Geigy company of Switzerland in 1988, belongs to a triazinone insecticide, is a brand-new non-biocidal insecticide, and has an excellent control effect on piercing-sucking mouthpart pests of various crops. The research shows that the pymetrozine is not only used for drop, feeding or injection test, but also used for stopping feeding and finally starving and killing as long as aphids or plant hoppers immediately generate a needle blocking effect when contacting the pymetrozine, and the process is irreversible. The pymetrozine medicament has wide insecticidal spectrum and excellent systemic osmosis effect; tests show that within 3 hours of medicament treatment, the feeding activity of aphids is reduced by about 90 percent, and after 48 hours of treatment, the death rate is close to 100 percent. The pymetrozine can be used for preventing and controlling most homopteran pests, especially pests of aphididae, aleyrodidae, leafhopper and plant hopper families, and is suitable for vegetables, rice, cotton, fruit trees and various field crops; the pymetrozine shows high insecticidal activity at a very low dosage, has low toxicity to mammals, high safety to birds, fishes and non-target arthropods, is safe to crops, people and livestock and environment, is expected to become a worldwide large-scale pesticide, and has wide development and application prospects.
At present, the preparation method of pymetrozine in the prior art is as follows:
patent documents CN103724327A, EP0433218 and TW199149 use ethyl acetate and hydrazine hydrate to react to prepare acethydrazide, acethydrazide and phosgene are subjected to cyclization reaction to prepare 2-methyl-1, 3, 4-oxadiazol-5 (4H) -one, then the 2-methyl-1, 3, 4-oxadiazol-3-yl acetone is prepared by alkylation reaction with chloropropiophenone, and then the acetamino triazone is prepared by reaction with hydrazine hydrate, hydrolysis under the action of hydrochloric acid to remove acetyl group, neutralization is performed to prepare aminotriazone, and finally the aminotriazone is condensed with 3-formyl pyridine to prepare pymetrozine; the overall yield is 80-83%, and the above procedure is depicted in scheme 1 below.
However, the synthetic route 1 has long steps and is complex to operate, a large amount of waste water and waste residues are generated in the production process, and the environmental protection property is poor; the intermediate aminotriazine ketone is easy to hydrolyze or oxidize in neutral or weak alkaline aqueous solution, and has poor stability, so that the target product pymetrozine has low purity (95%).
Chinese patent document CN104844574A describes the following synthetic scheme 2, in which acetyl-amino-triazone is used as a raw material, and undergoes an acidolysis reaction to generate amino-triazone hydrochloride, and directly undergoes a condensation reaction with 3-formyl-pyridine without neutralization to generate pymetrozine hydrochloride, and then undergoes alkali neutralization to prepare pymetrozine.
Although the synthesis route 2 adopts a mode of condensation and neutralization, which is beneficial to reducing the decomposition and oxidation of free aminotriazine, the disadvantages of long steps, complex operation, poor environmental protection and the like of the synthesis route 1 cannot be solved essentially.
In conclusion, in the prior art, the preparation method of pymetrozine has the defects of multiple steps, complex operation, large three-waste generation amount, multiple side reactions, low product purity and the like, so that the design of a synthetic route of pymetrozine with simple steps, environmental friendliness, low cost, easiness in realization, few side reactions, high selectivity, high yield and high purity has important significance.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of pymetrozine. The method has the advantages of cheap and easily obtained raw materials and low cost; the process flow is short, the reaction condition is easy to realize, the operation is safe and simple, the production amount of process wastewater is small, and the method is green and environment-friendly; the stability of raw materials and intermediate products is high, the reactivity and the selectivity are high, and the side reaction is less; the obtained pymetrozine has less impurities and high purity and yield, and is beneficial to the industrial production of pymetrozine.
Description of terms:
a compound of formula II: a carbonic acid diester;
a compound of formula III: carbodihydrazide;
a compound of formula IV: pyridin-3-ylmethylenecarbodihydrazide;
a compound of formula I: pymetrozine.
The compound numbers in the specification are completely consistent with the structural formula numbers, have the same reference relationship, and are based on the structural formula of the compound.
The technical scheme of the invention is as follows:
a preparation method of pymetrozine comprises the following steps:
(1) preparing a compound of formula III by subjecting a compound of formula II and hydrazine hydrate to a hydrazidation reaction;
wherein in the structural formula of the compound of the formula II, R is C1To C4Alkyl groups of (a);
(2) preparing a compound of formula iv by subjecting 3-formylpyridine and a compound of formula iii to a condensation reaction;
(3) pymetrozine (I) is prepared by cyclisation of a compound of formula IV with monochloroacetone.
Preferably, in step (1) according to the present invention, the hydrazidation of the compound of formula II with hydrazine hydrate is carried out in solvent A.
Preferably, the solvent A is one or a combination of more than two of water, methanol, ethanol, isopropanol, tert-butanol, acetonitrile or tetrahydrofuran; the mass ratio of the solvent A to the compound shown in the formula II is (2-20) to 1; more preferably, the solvent A is one or a combination of more than two of water, methanol or ethanol; the mass ratio of the solvent A to the compound of the formula II is (3-7) to 1.
According to the invention, in the step (1), the molar ratio of the hydrazine hydrate to the compound of the formula II is (2.0-4.0): 1; preferably, the molar ratio of the hydrazine hydrate to the compound of the formula II is (2.2-3.0): 1.
Preferably, in step (1), the reaction temperature of the hydrazidation reaction of the compound of formula II and hydrazine hydrate is 30-100 ℃; preferably, the temperature of the hydrazide reaction is 60 to 80 ℃. The hydrazide reaction time is 1-8 hours; preferably, the hydrazide reaction time is 2 to 4 hours.
Preferably, according to the invention, in step (1), the preparation of the compound of formula iii comprises the steps of: mixing the solvent A, the compound shown in the formula II and hydrazine hydrate, and performing hydrazide reaction at 30-100 ℃ to prepare the compound shown in the formula III.
According to a preferred embodiment of the invention, in step (2), the condensation of the 3-formylpyridine with the compound of the formula III is carried out in a solvent B.
Preferably, the solvent B is one or a combination of water, methanol, ethanol, isopropanol, tert-butanol, acetonitrile, chloroform, 1, 2-dichloroethane, tetrahydrofuran, 2-methyltetrahydrofuran or toluene; the mass ratio of the solvent B to the compound shown in the formula III is (3-15) to 1; further preferably, the mass ratio of the solvent B to the compound of the formula III is (5-10): 1.
According to a preferred embodiment of the invention, in step (2), the molar ratio of the compound of the formula III to the 3-formylpyridine is (0.95-1.1): 1.
Preferably, according to the invention, in step (2), the condensation reaction temperature is 50 to 130 ℃; preferably, the condensation reaction temperature is 50-90 ℃. The condensation reaction time is 1-10 hours; preferably, the condensation reaction time is 2 to 6 hours.
Preferably, in the step (2), the 3-formylpyridine is added into the system in a dropwise manner, wherein the dropwise adding temperature is 45-130 ℃, and the dropwise adding time is 2-4 hours; preferably, the dropping temperature is 45 to 90 ℃.
Preferably, in step (3), the cyclization reaction of the compound of formula IV and monochloroacetone is carried out in a solvent C under the action of an acid-binding agent.
Preferably, the solvent C is one or a combination of water, methanol, ethanol, isopropanol, tert-butanol, acetonitrile, chloroform, 1, 2-dichloroethane, tetrahydrofuran, 2-methyltetrahydrofuran or toluene; the mass ratio of the solvent C to the compound shown in the formula IV is (3-15) to 1; further preferably, the mass ratio of the solvent C to the compound of the formula IV is (4-9): 1.
Preferably, the acid-binding agent is an inorganic base or an organic base; the inorganic base is selected from potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, lithium carbonate or lithium hydroxide; the organic base is selected from triethylamine, tri-n-propylamine, diisopropylethylamine or pyridine; further preferably, the acid-binding agent is potassium carbonate or sodium carbonate.
Preferably, the mole ratio of the acid-binding agent, the monochloroacetone and the compound shown in the formula IV is (0.5-1.1): (0.95-1.1): 1.
Preferably, the cyclization reaction temperature is 20-120 ℃; further preferably, the cyclization reaction temperature is 40-70 ℃. The cyclization reaction time is 1-10 hours; further preferably, the cyclization reaction time is 2 to 6 hours.
Preferably, the monochloroacetone is added into the system in a dropping mode, the dropping temperature is 15-120 ℃, and the dropping time is 2-4 hours; preferably, the dropping temperature is 35 to 70 ℃.
The reaction process of the present invention is depicted as the following scheme 3:
wherein in the structural formula of the compound of the formula II, R is C1To C4Alkyl group of (1).
The invention has the technical characteristics and beneficial effects that:
1. the invention provides a novel method for preparing pymetrozine, which comprises the steps of preparing carbonyl dihydrazide by using carbonic diester and hydrazine hydrate through a hydrazide reaction, preparing pyridine-3-yl methylene carbonyl dihydrazide through a condensation reaction with 3-formyl pyridine, and finally preparing pymetrozine through a cyclization reaction with monochloroacetone.
2. The invention designs a proper reaction route by fully utilizing the structural characteristics of raw materials, utilizes the good nucleophilic addition activity of hydrazine hydrate to carry out the hydrazidation reaction on two molecules or a little excessive hydrazine hydrate and one molecule of carbonic acid diester, has specific reaction of the system, can carry out the hydrazidation reaction in a wide temperature range until the reaction is complete, and has high stability of the obtained carbodihydrazide and high yield and purity of the carbodihydrazide. When the carbodihydrazide and the 3-formylpyridine are subjected to condensation reaction, the mode of dripping the 3-formylpyridine is preferably utilized, the concentration effect of the carbodihydrazide is favorably reduced, the condensation side reaction of two molecules of the 3-formylpyridine and one molecule of the carbodihydrazide is favorably reduced, and the yield and the purity of the intermediate product pyridine-3-ylmethylene carbodihydrazide are ensured. In the final cyclization reaction, a mode of dripping monochloroacetone is preferably utilized, which is favorable for reducing the concentration effect of the monochloroacetone, reducing the side reaction of the monochloroacetone and two molecules of pyridine-3-yl methylene carbonyl dihydrazide (IV) and ensuring the low concentration effect of the monochloroacetone; and the concentration of the intermediate product obtained after the terminal amino group of the pyridine-3-yl methylene carbonyl dihydrazide and the carbonyl of the monochloroacetone are dehydrated is low, thereby being beneficial to the subsequent intramolecular cyclization reaction, reducing the byproducts of intermolecular reaction in the cyclization reaction, reducing the generation of polymers and being beneficial to improving the yield and the purity of the pymetrozine. In conclusion, the raw materials and the intermediate product have high stability, the high selectivity of the reaction can be ensured by controlling the concentration effect, the yield and the purity of the target product pymetrozine are high, the total yield can reach 95 percent, the purity can reach 99.5 percent, and the method is favorable for industrial production.
3. The method has the advantages of cheap and easily obtained raw materials and low cost; the process flow is short, and the target product pymetrozine can be prepared only by 3 steps; the operation is safe and simple, and the reaction condition is easy to realize; the production amount of the process wastewater is small, and the process is green and environment-friendly.
Detailed Description
The present invention is described in detail below with reference to examples, but the present invention is not limited thereto.
The raw materials and reagents used in the examples are all commercially available products. In the examples, "%" is a mass percentage unless otherwise specified.
The yields in the examples are all molar yields.
Example 1: preparation of carbodihydrazide (III)
Into a 1000 ml four-necked flask equipped with a stirrer, a thermometer and a reflux condenser were charged 200 g of methanol, 200 g of water, 90.1 g (1.0 mol) of dimethyl carbonate (II)1) 275.0 g (2.2 mol) of 40% hydrazine hydrate are heated, stirred and reacted at 70 to 75 ℃ for 3 hours, cooled to 20 to 25 ℃, filtered, and the filter cake is washed by 20 g of water and dried to obtain 88.7 g of carbodihydrazide (III), the yield is 98.5%, and the liquid phase purity is 99.9%.
Example 2: preparation of carbodihydrazide (III)
Into a 1000 ml four-necked flask equipped with a stirrer, a thermometer and a reflux condenser were charged 200 g of ethanol, 200 g of water, 118.1 g (1.0 mol) of diethyl carbonate (II)2) 275.0 g (2.2 mol) of 40% hydrazine hydrate are heated, stirred and reacted for 2 hours at the temperature of 75 to 80 ℃, cooled to 20 to 25 ℃, filtered, and a filter cake is washed by 20 g of water and dried to obtain 88.9 g of carbodihydrazide (III), the yield is 98.8%, and the liquid phase purity is 99.9%.
Example 3: preparation of pyridin-3-ylmethylenecarbodihydrazide (IV)
Into a 1000 ml four-necked flask equipped with a stirrer, a thermometer, a constant pressure dropping funnel and a reflux condenser were charged 200 g of methanol, 100 g of water, 45.0 g (0.5 mol) of carbonyldihydrazide (III) obtained in example 1, heated while maintaining the temperature between 55 and 60 ℃, and a mixed solution of 53.0 g (0.5 mol) of 3-formylpyridine and 100 g of methanol was added dropwise thereto over 3 hours, followed by stirring at 60 to 65 ℃ for 6 hours, cooling to 20 to 25 ℃, filtering, washing the filter cake with 30 g of water, and drying to obtain 88.8 g of pyridin-3-ylmethylenecarbonyldihydrazide (IV) in a yield of 99.2% and a liquid phase purity of 99.9%.
Example 4: preparation of pyridin-3-ylmethylenecarbodihydrazide (IV)
Into a 1000 ml four-necked flask equipped with a stirrer, a thermometer, a constant pressure dropping funnel and a reflux condenser were charged 200 g of ethanol, 100 g of water, 45.0 g (0.5 mol) of carbonyldihydrazide (III) obtained in example 2, heated while maintaining the temperature between 65 and 70 ℃, and a mixed solution of 53.0 g (0.5 mol) of 3-formylpyridine and 100 g of ethanol was added dropwise thereto over 3 hours, followed by stirring at 70 to 75 ℃ for 3 hours, cooling to 20 to 25 ℃, filtration, washing the filter cake with 30 g of water, and drying to obtain 89.0 g of pyridin-3-ylmethylenecarbonyldihydrazide (IV), yield 99.4%, and liquid phase purity 99.9%.
Example 5: preparation of pymetrozine (I)
Into a 1000 ml four-necked flask equipped with a stirrer, a thermometer, a constant pressure dropping funnel and a reflux condenser, 200 g of methanol, 100 g of water, 34.5 g (0.25 mol) of potassium carbonate, 71.6 g (0.4 mol) of pyridin-3-ylmethylenecarbonyldihydrazide (IV) obtained in example 3 was charged, heated, kept at 45 to 50 ℃ and added dropwise with a mixed solution of 40.7 g (0.44 mol) of monochloroacetone and 50 g of methanol, after 3 hours of dropwise addition, stirred at 50 to 55 ℃ for 5 hours of reaction, cooled to 20 to 25 ℃, filtered, and the filter cake was washed with 30 g of water and dried to obtain 83.6 g of pymetrozine (I), the yield was 96.2%, and the liquid phase purity was 99.3%.
The nuclear magnetic data of the product obtained are as follows:
1H NMR(400MHz,DMSO-d6):δ
1.96(s,3H),4.38(s,2H),7.45(m,1H),7.89(s,1H),8.09(d,1H),8.57(m,1H),8.86(d,1H),10.1(s,1H)。
example 6: preparation of pymetrozine (I)
Into a 1000 ml four-necked flask equipped with a stirrer, a thermometer, a constant pressure dropping funnel and a reflux condenser, 200 g of ethanol, 100 g of water, 34.5 g (0.25 mol) of potassium carbonate, 71.6 g (0.4 mol) of pyridin-3-ylmethylenecarbonyldihydrazide (IV) obtained in example 4 were added, heated, maintained at 50 to 55 ℃ and added dropwise with a mixed solution of 40.7 g (0.44 mol) of monochloroacetone and 50 g of ethanol, after 3 hours of dropwise addition, stirred at 55 to 60 ℃ for 3 hours of reaction, cooled to 20 to 25 ℃, filtered, and the filter cake was washed with 30 g of water and dried to obtain 83.9 g of pymetrozine (I), the yield was 96.6%, and the liquid phase purity was 99.5%.
Comparative example 1: preparation of pyridin-3-ylmethylenecarbodihydrazide (IV)
Into a 1000 ml four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 300 g of methanol, 100 g of water, 45.0 g (0.5 mol) of carbonyldihydrazide (III) obtained by the method of example 1, 53.0 g (0.5 mol) of 3-formylpyridine at 60 to 65 ℃ were added, stirred and reacted for 6 hours, cooled to 20 to 25 ℃, filtered, and the filter cake was washed with 30 g of water and dried to obtain 88.2 g of a solid, which was analyzed by the liquid phase external standard method to contain 56.8 g of pyridin-3-ylmethylenecarbonyldihydrazide (IV) at an external standard yield of 63.4% in the liquid phase, and the main impurities were carbonyldihydrazide (III) and bis (pyridin-3-ylmethylenecarbonyldihydrazide.
Comparative example 1 shows that: in the reaction process, the dropwise addition of the 3-formylpyridine is favorable for reducing the concentration effect of the 3-formylpyridine, reducing the condensation side reaction of two molecules of the 3-formylpyridine and one molecule of the carbodihydrazide, reducing the generation of a byproduct of the bis (pyridine-3-ylmethylene) carbodihydrazide and improving the conversion rate of the carbodihydrazide and the yield and the purity of a target product.
Comparative example 2: preparation of pymetrozine (I)
Into a 1000 ml four-necked flask equipped with a stirrer, a thermometer, a constant pressure dropping funnel and a reflux condenser, 250 g of methanol, 100 g of water, 34.5 g (0.25 mol) of potassium carbonate, 71.6 g (0.4 mol) of pyridin-3-ylmethylenecarbonyldihydrazide (IV) obtained by the method of example 3, 40.7 g (0.44 mol) of monochloroacetone were added, stirred at 50 to 55 ℃ for 5 hours, cooled to 20 to 25 ℃, filtered, the filter cake was washed with 30 g of water and dried to obtain 78.2 g of a white solid, which was analyzed by the liquid phase external standard method to contain 35.7 g of pymetrozine (I) and had an external standard yield of 41.1%.
Comparative example 2 shows that: in the reaction process, the dropwise addition of the monochloroacetone is favorable for reducing the concentration effect of the monochloroacetone, reducing the side reaction of the monochloroacetone and two molecules of pyridine-3-yl methylene carbonyl dihydrazide (IV), and is favorable for the intramolecular cyclization reaction of the monochloroacetone and an intermediate product obtained after dehydration of one molecule of pyridine-3-yl methylene carbonyl dihydrazide, reducing intermolecular reaction byproducts, reducing the generation of polymers and being favorable for improving the yield and the purity of the pymetrozine.
Claims (1)
1. A preparation method of pymetrozine comprises the following steps:
(1) preparing a compound of formula III by subjecting a compound of formula II and hydrazine hydrate to a hydrazidation reaction;
the preparation of the compound of formula III comprises the steps of: mixing the solvent A, the compound shown in the formula II and hydrazine hydrate, and performing hydrazide reaction for 2-3h at 70-80 ℃ to prepare a compound shown in the formula III;
the solvent A is a combination of water and methanol or a combination of water and ethanol; the mass ratio of the solvent A to the compound shown in the formula II is (2-20) to 1; the molar ratio of the hydrazine hydrate to the compound of the formula II is (2.2-3.0): 1;
wherein in the structural formula of the compound of the formula II, R is C1To C2Alkyl groups of (a);
(2) preparing a compound of formula iv by subjecting 3-formylpyridine and a compound of formula iii to a condensation reaction;
the condensation of 3-formylpyridine with the compound of the formula III is carried out in a solvent B;
the solvent B is a combination of methanol and water, or a combination of ethanol and water; the mass ratio of the solvent B to the compound shown in the formula III is (3-15) to 1; the molar ratio of the compound shown in the formula III to the 3-formylpyridine is (0.95-1.1): 1; the condensation reaction temperature is 60-70 ℃, and the condensation reaction time is 3-6 h; the 3-formyl pyridine is added into the system in a dropping mode, the dropping temperature is 55-70 ℃, and the dropping time is 3 hours;
(3) preparing pymetrozine (I) by subjecting a compound of formula IV and monochloroacetone to cyclization reaction;
the cyclization reaction of the compound shown in the formula IV and monochloroacetone is carried out in a solvent C under the action of an acid-binding agent;
the solvent C is a combination of methanol and water or a combination of ethanol and water; the mass ratio of the solvent C to the compound shown in the formula IV is (3-15) to 1; the acid-binding agent is potassium carbonate; the mole ratio of the acid-binding agent, the monochloropropione and the compound shown in the formula IV is (0.5-1.1): (0.95-1.1): 1; the cyclization reaction temperature is 50-60 ℃, and the cyclization reaction time is 3-5 hours; the monochloroacetone is added into the system in a dropping mode, the dropping temperature is 45-55 ℃, and the dropping time is 3 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012077078A (en) * | 2010-09-10 | 2012-04-19 | Ｍｅｉｊｉ Ｓｅｉｋａファルマ株式会社 | Novel triazolone derivative and pest control agent containing the same as active constituent |
| CN108707137A (en) * | 2018-05-31 | 2018-10-26 | 广东立威化工有限公司 | A kind of preparation method of pymetrozine |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012077078A (en) * | 2010-09-10 | 2012-04-19 | Ｍｅｉｊｉ Ｓｅｉｋａファルマ株式会社 | Novel triazolone derivative and pest control agent containing the same as active constituent |
| CN108707137A (en) * | 2018-05-31 | 2018-10-26 | 广东立威化工有限公司 | A kind of preparation method of pymetrozine |
Non-Patent Citations (2)
| Title |
|---|
| "An efficient protocol for the production of pymetrozine via a new synthetic strategy";Zhou Qifan等;《Journal of Chemical Research》;20180815;第42卷(第8期);第434-438页 * |
| "碳酸二甲酯合成卡巴肼的研究";石振东等;《湖北化工》;20011231(第5期);第19-20页 * |
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