CN1356039A - Process for preparing insecticide 'Huanbingmazhen' - Google Patents
Process for preparing insecticide 'Huanbingmazhen' Download PDFInfo
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- CN1356039A CN1356039A CN 01132183 CN01132183A CN1356039A CN 1356039 A CN1356039 A CN 1356039A CN 01132183 CN01132183 CN 01132183 CN 01132183 A CN01132183 A CN 01132183A CN 1356039 A CN1356039 A CN 1356039A
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Abstract
本发明提供一种二步反应制备杀虫剂环丙马嗪(灭蝇胺)的方法,包括溶剂回收套用制备2,4－二胺－6－氯－1,3,5三嗪;再以水作溶剂,碱催化下直接进行环丙胺化反应;产物方便地从反应体系中过滤获得;乙醇重结晶母液中回收产物。该法工艺简便,收率高,质量好,工业生产经济效益明显。The invention provides a method for preparing the insecticide cypromazine (cyromazine) through a two-step reaction, which includes solvent recovery and mechanical preparation of 2,4-diamine-6-chloro-1,3,5 triazine; Water is used as solvent, and cyclopropylamination reaction is carried out directly under alkali catalysis; the product is conveniently obtained by filtering from the reaction system; the product is recovered from ethanol recrystallization mother liquor. The process is simple, the yield is high, the quality is good, and the economic benefit of industrial production is obvious.
Description
Technical field
The invention belongs to pharmaceutical field, be specifically related to a kind of preparation method of insecticide ' Huanbingmazhen '.
Background technology
'Huanbingmazhen ' (Cyromazine), chemistry N-cyclopropyl-1,3 by name, 5-three azines-2,4, the 6-triamine (N-Cyclopropyl-1,3,5-triazine-2,4,6-triamine), have anti-dipteral insect, particularly kill the fly effect, so have another name called fly eradication amine.
Existing bibliographical information (US 4225598 for The Merck Index.Twelfth Ed.P469, Ger2736876), get product (IV) for raw material through cyclopropylamineization, two step ammonifications and ethyl alcohol recrystallization with cyanuric trichloride (cyanuric chloride), fusing point 219-222 ℃, total recovery 48%, reaction equation is as follows:
This method synthetic route is when preparation formula II compound and product, and difference is chlorobenzene and dioxy oxane with an organic solvent, need use liquefied ammonia and autoclave especially when product prepares, and solvent recovery also must be used vacuum equipment, makes troubles to production operation, and cost is higher.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing insecticide ' Huanbingmazhen ' (fly eradication amine), the inventive method be two the step reaction methods, comprise solvent recovery apply mechanically the preparation 2,4-diamines-6-chloro-1,3,5 triazines; With water as solvent, directly carry out the cyclopropylamine reaction under the base catalysis again; Product can filter from reaction system easily and obtain; Also can from the ethyl alcohol recrystallization mother liquor, reclaim product again.The inventive method technology is easy, the yield height, and quality is good, and the industrial production economic benefit is obvious.
It is raw material that the present invention adopts cyanuric trichloride (I), is solvent with acetone, gets 2 with industrial ammonia (25%) ammonification, 4-diamines-6-chloro-1,3,5 triazines (V); Be solvent with water again, carry out the cyclopropylamine reaction with base catalysis, after the cooling, the isolated by filtration product, drying is after ethyl alcohol recrystallization, good product quality (mp 220-223 ℃, the HPLC detection level is greater than 99%), total recovery is that 59%. the inventive method reaction equations are as follows:
Wherein:
In the reaction of preparation V compound " 2,4-diamines-6-chloro-1,3,5 triazines ", ammoniacal liquor contains
Amount is 25%, and the recovery set rate of solvent acetone is 50%; The base catalysis of formula V compound,
Directly carry out the cyclopropylamine reaction, preparation 'Huanbingmazhen ' (IV), the alkali that is adopted can
Be that highly basic comprises NaOH, KOH, Ca (OH)
2With weak base Na
2CO
3, K
2CO
3Deng, it is anti-to reflux
Between seasonable is 4-14h, and PH is controlled at 6-9 during reaction, is solvent with water, and product is direct
Carry out isolated by filtration, also recyclable product in the mother liquor of ethyl alcohol recrystallization.
The inventive method process route is reasonable, possesses following advantage:
1) the inventive method is two step reaction methods, and technology is easy, the yield height, and quality is good.
2) during preparation formula V compound, the rate of applying mechanically of solvent acetone reaches 50%, has not only reduced cost, has also improved yield.
3) cyclopropylamineization react on second the step carry out, significantly reduce the expensive cyclopropylamine unit consumption of valency, it is reasonable that synthetic route more becomes.
4) the cyclopropylamine reaction is solvent with water with base catalysis, and product can be separated acquisition with filter method easily from reaction system, the method that needn't use organic solvent such as ethyl acetate, chloroform, carrene, benzene, ether etc. to extract.Product directly carries out isolated by filtration.Both eliminated the use of organic solvent, and made technology easy again, equipment requires low, so economic benefit is obvious.
5) after ethyl alcohol recrystallization mother liquor and washing lotion merged recovery ethanol, cooling crystallization reclaimed product, and total recovery reaches 59%, improves 11% than prior art, and HPLC testing product content is more than 99%.
Raw material that preparation method of the present invention adopted and solvent are the industrial goods that can buy on the domestic market.
Embodiment
The following example explanation the present invention, but the present invention is not limit by example.
Term and abbreviation used in the example have its normal meaning, except as otherwise noted.For example, " HPLC " refers to high performance liquid chromatography, " ℃ " refer to degree centigrade that " mol " refers to mole, " ml " refers to milliliter, and " g " refers to gram, and " mp " refers to fusing point (capillary tube method) etc.Embodiment one preparation 2,4-diamines-6-chloro-1,3,5 triazines (V)
In the 2000ml there-necked flask of reflux condenser, thermometer and dropping funel is housed, processing industry cyanuric trichloride (content is greater than 99%) 184.5g (1mol) and industrial acetone 800ml (wherein 400ml be last batch recovery contain the ammonia acetone solution), the industrial ammonia 500ml (6.6mol) that adds content 25%, 45 ℃ of reaction 5h.(the recyclable ammonia acetone solution 400ml that contains of filtrate, applies mechanically for following batch by cut 56-62 ℃) filtered in cooling, washing, and drying gets 128gV (chloride more than 24%), yield 88%.
Embodiment two preparation N-cyclopropyl-2,4,6-triamine-1,3,5 triazines (IV)
In the 2000ml there-necked flask of reflux condenser, thermometer and dropping funel is housed, add 2,4-diamines-6-chloro-1,3,5 triazines (V) 117g (0.8mol), water 1520ml and industrial cyclopropylamine (content＞99%) 48g (0.84mol), add 35%NaOH solution 100ml, back flow reaction 7h, control PH=6-9, cooling, filter, the ion exchange water washing dryly must be measured 96g, mp218-220 ℃, yield 72.3%.
Product 1600ml dissolve with ethanol adds active carbon 5g and decolours, and filters, and reclaims ethanol, and white crystals is separated out in cooling, filter, and washing with alcohol, drying gets IV 89g, mp220-223 ℃ (thermometer is calibrated), yield 92.7%.HPLC analyzing and testing content 99.52%, mp222.5-224.5 ℃.
After ethyl alcohol recrystallization mother liquor and washing lotion merged recovery ethanol, cooling crystallization can get the IV product, mp219-222 ℃ (thermometer is calibrated).
Claims (2)
1. a method for preparing insecticide ' Huanbingmazhen ' is characterized in that its reactions steps is the reaction of two steps, and adopting cyanuric trichloride (I) is raw material, is solvent with acetone, gets 2 with the industrial ammonia ammonification, 4-diamines-6-chloro-1,3,5 triazines (V); Be solvent with water again, carry out the cyclopropylamine reaction with base catalysis, isolated by filtration gets the product insecticide ' Huanbingmazhen '.Reaction equation is as follows:
2. by the process of claim 1 wherein preparation formula V compound 2, in the reaction of 4-diamines-6-chloro-1,3,5 triazines, ammoniacal liquor content is 25%, and the recovery set rate of solvent acetone is 50%; The cyclopropylamine reaction is directly carried out in the base catalysis of formula V compound, preparation 'Huanbingmazhen ' (IV), and the alkali that is adopted can be that highly basic comprises NaOH, KOH, Ca (OH)
2With weak base Na
2CO
3, K
2CO
3Deng, reflux time is 4-14h, and PH is controlled at 6-9 during reaction, is solvent with water, and product directly carries out isolated by filtration, recyclable product in the mother liquor of ethyl alcohol recrystallization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011321830A CN1166648C (en) | 2001-11-09 | 2001-11-09 | A kind of method for preparing insecticide cypromazine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011321830A CN1166648C (en) | 2001-11-09 | 2001-11-09 | A kind of method for preparing insecticide cypromazine |
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| Publication Number | Publication Date |
|---|---|
| CN1356039A true CN1356039A (en) | 2002-07-03 |
| CN1166648C CN1166648C (en) | 2004-09-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011321830A Expired - Fee Related CN1166648C (en) | 2001-11-09 | 2001-11-09 | A kind of method for preparing insecticide cypromazine |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101885707B (en) * | 2009-05-15 | 2012-08-29 | 中国科学院化学研究所 | Triazine derivative and preparation method thereof as well as new application as insecticide |
| CN104876884A (en) * | 2014-11-24 | 2015-09-02 | 上海化工研究院 | Synthesis method of stable isotope-labeled cyromazine and its derivative |
| CN108084102A (en) * | 2017-11-27 | 2018-05-29 | 河南后羿制药有限公司 | A kind of preparation method of cyromazine |
| CN111777567A (en) * | 2020-07-27 | 2020-10-16 | 江西禾益化工股份有限公司 | Method for refining cyromazine technical product |
| CN112500360A (en) * | 2020-12-17 | 2021-03-16 | 浙江日出药业有限公司 | Safe and environment-friendly cyromazine synthesis method |
| CN112851594A (en) * | 2021-01-27 | 2021-05-28 | 山东道可化学有限公司 | High-yield synthesis method of cyromazine technical |
-
2001
- 2001-11-09 CN CNB011321830A patent/CN1166648C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101885707B (en) * | 2009-05-15 | 2012-08-29 | 中国科学院化学研究所 | Triazine derivative and preparation method thereof as well as new application as insecticide |
| CN104876884A (en) * | 2014-11-24 | 2015-09-02 | 上海化工研究院 | Synthesis method of stable isotope-labeled cyromazine and its derivative |
| CN104876884B (en) * | 2014-11-24 | 2018-02-02 | 上海化工研究院有限公司 | A kind of synthetic method of cold labeling cyromazine and its derivative |
| CN108084102A (en) * | 2017-11-27 | 2018-05-29 | 河南后羿制药有限公司 | A kind of preparation method of cyromazine |
| CN108084102B (en) * | 2017-11-27 | 2021-03-02 | 河南后羿制药有限公司 | A kind of preparation method of cyromazine |
| CN111777567A (en) * | 2020-07-27 | 2020-10-16 | 江西禾益化工股份有限公司 | Method for refining cyromazine technical product |
| CN112500360A (en) * | 2020-12-17 | 2021-03-16 | 浙江日出药业有限公司 | Safe and environment-friendly cyromazine synthesis method |
| CN112851594A (en) * | 2021-01-27 | 2021-05-28 | 山东道可化学有限公司 | High-yield synthesis method of cyromazine technical |
| CN112851594B (en) * | 2021-01-27 | 2023-03-07 | 山东道可化学有限公司 | High-yield synthesis method of cyromazine technical |
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| Publication number | Publication date |
|---|---|
| CN1166648C (en) | 2004-09-15 |
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