CN1847241A - Synthesis process of 1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolyl-2-imine - Google Patents
Synthesis process of 1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolyl-2-imine Download PDFInfo
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Abstract
The synthesis process of 1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolyl-2-imine relates to farm pesticide imidacloprid synthesizing process. In dimethylforamide as solvent and with quaternary ammonium salt as catalyst, potassium carbonate, 2-chloro-5-chloro methyl pyridine and excessive imidazolyl alkane are condensed to produce 1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolyl -2-imine. The present invention has short reaction period, high product purity and high product yield.
Description
Technical field
The present invention relates to the synthesis technique of agricultural insecticide Provado.
Background technology
(6-chloro-3-picolyl)-N-nitroimidazole-2-imines is the common name of agricultural insecticide to 1-, the Provado synthetic method has a variety of, report is the synthetic 1-(6-chloro-3-picolyl) of intermediate-N-nitroimidazole-2-imines with 2-chloro-5-chloromethylpyridine at present, reaction time is long, the finished product yield can only reach about 80%, and high-content (being purity) has only 95%.This product processes is the energy consumption height not only, directly influences production cost, and the impurity that contains in the product, gives a series of defectives of use of product, as: technology discharging quantity of three wastes is big, contaminate environment, and product is easily to farm crop, and particularly cash crop produce poisoning.
Summary of the invention
The object of the invention is to invent a kind of raising reaction yield, the synthetic method of 1-(6-chloro-3-the picolyl)-N-nitroimidazole-2-imines of the content of raising reactant.
The present invention is a solvent with the dimethyl formamide, is catalyzer with the quaternary ammonium salt, salt of wormwood, 2-chloro-5-chloromethylpyridine and excessive imidazolidine condensation reaction is made 1-(6-chloro-3-picolyl)-N-nitroimidazole-2-imines go into.
Under the catalysis of quaternary ammonium salt, with DMF (dimethyl formamide) is solvent, utilize the excessive of imidazolidine to suppress to greatest extent synthesizing of the two substitution products of side reaction, obtain 1-(6-chloro-3-picolyl)-N-nitroimidazole-2-imines, the reaction process cycle is short, its content of product, promptly purity can reach 97%, and yield reaches 90%.The present invention is fit to industrialized energy-saving production, and high purity product is more suitable for being used for the control of cash crop insect pest.
Among the present invention, the weight ratio of the quaternary ammonium salt of adding and 2-chloro-5-chloromethylpyridine can be 0.1～0.6: 100.The appropriate catalyst add-on not only can not cause cost to strengthen to production, and can reach purpose of design.
The present invention can be dissolved in dimethyl formamide with salt of wormwood, imidazolidine and quaternary ammonium salt earlier and make mixed solution, mixed solution is warming up to 45～55 ℃, under the heat-retaining condition, the mixed solution that dropping is made up of 2-chloro-5-chloromethylpyridine and dimethyl formamide, treat that condensation reaction finishes, be cooled to below 30 ℃, leach solid matter, again solid matter is mixed with water and be warming up to 80～95 ℃, material is disperseed, be cooled to 60～65 ℃ again, extremely arrive 1-(6-chloro-3-picolyl)-N-nitroimidazole-2-imines crude product through suction filtration.
In order to make high purity product, in 1-(6-chloro-3-picolyl)-N-nitroimidazole-2-imines crude product, add entry, be warming up to 75 ℃, (6-chloro-3-picolyl)-N-nitroimidazole-2-imines is soluble in water fully to make 1-, to being cooled to 60～65 ℃, filter the 1-that obtains purifying (6-chloro-3-picolyl)-N-nitroimidazole-2-imines.
Quaternary ammonium salt of the present invention can be triethyl benzyl ammonia chloride or Tetrabutyl amonium bromide or tetrabutylammonium chloride.
Embodiment
Example 1
1, in the there-necked flask of 1000ml, drops into moisture DMF (dimethyl formamide) 440 grams, salt of wormwood 90 grams, imidazolidine 107 grams, catalyzer triethyl benzyl ammonia chloride 0.1 and restrain, stir, be warmed up to 45 ℃ less than 0.1%.
2, drip the mixed solution of pure 2-chloro-5-chloromethylpyridine 52 grams and 50 gram DMF, dropping temperature is controlled at 45～55 ℃, drips off in about 3 hours, is incubated 30 minutes, and sampling analysis 2-chloro-5-chloromethylpyridine (CCP) content is qualified when its content equals 0.1% for a short time.
3, reaction finishes to leach the saliniferous residue, and to divide one to three rinsing with DMF below the postcooling to 30 ℃.
4, the rinsing with the filtrate of above-mentioned steps 2 and step 3 mixes, and is 7.0～7.5 with the mixed solution pH value that neutralizes, and sloughs solvent DMF under the vacuum, takes off solvent-free.
But the DMF that deviates from control moisture is in reuse below 0.1%.
5, above-mentioned residue is added 600ml water, temperature is raised to more than 80 ℃, and material is disperseed again, cools to 60～65 ℃, and suction filtration, filter residue are 1-(6-chloro-3-picolyl)-N-nitroimidazole-2-imines, i.e. Provado crude product, and dry product is 95 grams, content 80%.
Filtrate is cooled to 3～5 ℃, filtered and recycled imidazolidine, dry back reuse.
6, in the Provado crude product, add 600ml hot water again, be warmed up to more than 75 ℃, stirred 30 minutes, cool to 60～65 ℃, filter and obtain the Provado finished product, about 77 grams of dry product, purity is 97%.
Filtrate is chilled to 3～5 ℃, filters out after the imidazolidine drying recovery set and uses.
Example 2
1, in the there-necked flask of 1000ml, drops into moisture DMF440 gram, salt of wormwood 90 grams, imidazolidine 107 grams, catalyzer Tetrabutyl amonium bromide or tetrabutylammonium chloride 0.4 and restrain, stir, be warmed up to 50 ℃ less than 0.1%.
2. drip the mixed solution of pure 2-chloro-5-chloromethylpyridine 52 grams and 50 gram DMF, dropping temperature is controlled at 45～55 ℃, drips off in about 3 hours, is incubated 30 minutes.Sampling analysis CCP content is qualified when its content equals 0.1% for a short time, and reaction finishes.
3, above-mentioned reaction is mixed life and be cooled to leach the saliniferous residue below 30 ℃, and applying mechanically below 0.1% with DMF control moisture.
4, the rinsing with the filtrate of above-mentioned steps 2 and step 3 mixes, and is 7.0～7.5 with the mixed solution pH value that neutralizes, and sloughs solvent DMF under the vacuum, takes off solvent-free.
But the DMF that deviates from control moisture is in reuse below 0.1%.
5, above-mentioned residue is added 600ml water, temperature is raised to 80 ℃～95 ℃, and material is disperseed, and cools to 60～65 ℃, and suction filtration, filter residue are the Provado crude product, and weight is 95 grams, and purity is 81%.
Filtrate is cooled to 3～5 ℃, filtered and recycled imidazolidine, dry back reuse.
6, in the Provado crude product, add 600ml hot water, be warmed up to more than 75 ℃, stirred 30 minutes, cool to 60～65 ℃, filter, obtain the Provado finished product, about 78 grams of dry product, purity is 97%.
Filtrate is chilled to 3～5 ℃, filters out after the imidazolidine drying recovery set and uses.
Simultaneous test:
1, in the there-necked flask of 1000ml, drops into moisture DMF440 gram, salt of wormwood 90 grams, imidazolidine 107 grams, stirring and be warmed up to 48 ℃ less than 0.3%.
2, drip the mixed solution of pure 2-chloro-5-chloromethylpyridine 52 grams and 30 gram DMF, dropping temperature is controlled at 45～55 ℃, drips off in about 3 hours, is incubated 30 minutes, and sampling analysis 2-chloro-5-chloromethylpyridine (CCP) content is qualified when its content equals 0.1% for a short time.
3, reaction finishes to leach the saliniferous residue, and to apply mechanically below 0.3% with DMF control moisture below the postcooling to 30 ℃.
4, the rinsing with the filtrate of above-mentioned steps 2 and step 3 mixes, and is 7.0～7.5 with the mixed solution pH value that neutralizes, and sloughs solvent DMF under the vacuum, takes off solvent-free.
5, above-mentioned residue is added 600ml water, temperature is raised to 80 ℃～95 ℃, and material is disperseed, and cools to 60～65 ℃, and suction filtration, filter residue are the Provado crude product, and weight is 85 grams, content 73%.
6, in the Provado crude product, add 600ml water, be warmed up to more than 75 ℃, stirred 30 minutes, cool to 60～65 ℃, filter and obtain the Provado finished product, about 64 grams of dry product, purity is 94%.
Example 1 by the inventive method is compared with simultaneous test with example 2, basic sample method together, difference is that example 1,2 adopts catalyzer respectively, under the effect of catalyzer, the finished product are respectively 76 grams and 77 grams, yield is respectively 91.0% and 92.0%, and simultaneous test only receive 64 the gram, yield is 73.3%; The purity of the finished product is 97%, and simultaneous test is 94%.
Claims (5)
1, the synthetic method of 1-(6-chloro-3-picolyl)-N-nitroimidazole-2-imines, with the dimethyl formamide is solvent, salt of wormwood, 2-chloro-5-chloromethylpyridine and excessive imidazolidine condensation reaction are made 1-(6-chloro-3-picolyl)-N-nitroimidazole-2-imines, it is characterized in that when condensation reaction, add the catalyzer quaternary ammonium salt.
2,, it is characterized in that the quaternary ammonium salt that adds and the weight ratio of 2-chloro-5-chloromethylpyridine are 0.1～0.6: 100 according to the synthetic method of the described 1-of claim 1 (6-chloro-3-picolyl)-N-nitroimidazole-2-imines.
3, synthetic method according to claim 1 or 2 described 1-(6-chloro-3-picolyl)-N-nitroimidazole-2-imines, it is characterized in that earlier salt of wormwood, imidazolidine and quaternary ammonium salt are dissolved in dimethyl formamide and make mixed solution, mixed solution is warming up to 45～55 ℃, under the heat-retaining condition, the mixed solution that dropping is made up of 2-chloro-5-chloromethylpyridine and dimethyl formamide, treat that condensation reaction finishes, be cooled to below 30 ℃, leach solid matter, again solid matter is mixed with water and be warming up to 80～95 ℃, material is disperseed, be cooled to 60～65 ℃ again, extremely arrive 1-(6-chloro-3-picolyl)-N-nitroimidazole-2-imines crude product through suction filtration.
4, according to the synthetic method of the described 1-of claim 3 (6-chloro-3-picolyl)-N-nitroimidazole-2-imines, it is characterized in that in 1-(6-chloro-3-picolyl)-N-nitroimidazole-2-imines crude product, adding entry, be warming up to 75 ℃, (6-chloro-3-picolyl)-N-nitroimidazole-2-imines is soluble in water fully to make 1-, to being cooled to 60～65 ℃, filter the 1-that obtains purifying (6-chloro-3-picolyl)-N-nitroimidazole-2-imines.
5,, it is characterized in that described quaternary ammonium salt is triethyl benzyl ammonia chloride or Tetrabutyl amonium bromide or tetrabutylammonium chloride according to the synthetic method of the described 1-of claim 1 (6-chloro-3-picolyl)-N-nitroimidazole-2-imines.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921261A (en) * | 2010-08-25 | 2010-12-22 | 青岛海利尔药业有限公司 | Process for separating and recovering behind a kind of imidacloprid synthesis |
| CN102276583A (en) * | 2010-06-11 | 2011-12-14 | 南通派斯第农药化工有限公司 | Process for producing imidacloprid |
| CN101747319B (en) * | 2009-12-22 | 2013-04-24 | 安徽华星化工股份有限公司 | Method for preparing imidacloprid |
| CN103073535A (en) * | 2013-01-30 | 2013-05-01 | 山东省联合农药工业有限公司 | Synthetic method of imidacloprid |
| CN104672212A (en) * | 2013-11-26 | 2015-06-03 | 嘉兴学院 | Method for synthesizing imidacloprid employing cascade reaction |
| CN111349078A (en) * | 2020-04-21 | 2020-06-30 | 江苏克胜集团股份有限公司 | Preparation method of imidacloprid |
| CN111362903A (en) * | 2020-04-21 | 2020-07-03 | 江苏克胜集团股份有限公司 | Preparation method of imidacloprid |
| CN111362904A (en) * | 2020-04-21 | 2020-07-03 | 江苏克胜集团股份有限公司 | Preparation method of imidacloprid |
| CN114573556A (en) * | 2022-03-15 | 2022-06-03 | 河北美邦膜科技有限公司 | Imidacloprid purification method |
| CN114685447A (en) * | 2022-05-07 | 2022-07-01 | 江苏常隆农化有限公司 | Method for recycling imidacloprid from concentrated mother liquor residue in imidacloprid production |
Family Cites Families (2)
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| US6307053B1 (en) * | 2000-12-29 | 2001-10-23 | Sinon Corporation | Process for preparing imidacloprid |
| CN1150184C (en) * | 2002-09-29 | 2004-05-19 | 天津大学 | Production method of imidacloprid |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747319B (en) * | 2009-12-22 | 2013-04-24 | 安徽华星化工股份有限公司 | Method for preparing imidacloprid |
| CN102276583A (en) * | 2010-06-11 | 2011-12-14 | 南通派斯第农药化工有限公司 | Process for producing imidacloprid |
| CN101921261A (en) * | 2010-08-25 | 2010-12-22 | 青岛海利尔药业有限公司 | Process for separating and recovering behind a kind of imidacloprid synthesis |
| CN101921261B (en) * | 2010-08-25 | 2013-05-01 | 山东海利尔化工有限公司 | Separation and recovery process after imidacloprid synthesis |
| CN103073535A (en) * | 2013-01-30 | 2013-05-01 | 山东省联合农药工业有限公司 | Synthetic method of imidacloprid |
| CN104672212B (en) * | 2013-11-26 | 2017-01-18 | 嘉兴学院 | Method for synthesizing imidacloprid employing cascade reaction |
| CN104672212A (en) * | 2013-11-26 | 2015-06-03 | 嘉兴学院 | Method for synthesizing imidacloprid employing cascade reaction |
| CN111349078A (en) * | 2020-04-21 | 2020-06-30 | 江苏克胜集团股份有限公司 | Preparation method of imidacloprid |
| CN111362903A (en) * | 2020-04-21 | 2020-07-03 | 江苏克胜集团股份有限公司 | Preparation method of imidacloprid |
| CN111362904A (en) * | 2020-04-21 | 2020-07-03 | 江苏克胜集团股份有限公司 | Preparation method of imidacloprid |
| CN111362903B (en) * | 2020-04-21 | 2022-06-07 | 江苏克胜集团股份有限公司 | Preparation method of imidacloprid |
| CN111362904B (en) * | 2020-04-21 | 2022-06-17 | 江苏克胜集团股份有限公司 | Preparation method of imidacloprid |
| CN111349078B (en) * | 2020-04-21 | 2022-06-17 | 江苏克胜集团股份有限公司 | Preparation method of imidacloprid |
| CN114573556A (en) * | 2022-03-15 | 2022-06-03 | 河北美邦膜科技有限公司 | Imidacloprid purification method |
| CN114685447A (en) * | 2022-05-07 | 2022-07-01 | 江苏常隆农化有限公司 | Method for recycling imidacloprid from concentrated mother liquor residue in imidacloprid production |
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| CN100441577C (en) | 2008-12-10 |
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