CN101293858A - Method for synthesizing 'dimilin' with phosgene as raw material - Google Patents
Method for synthesizing 'dimilin' with phosgene as raw material Download PDFInfo
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- CN101293858A CN101293858A CNA2007100215249A CN200710021524A CN101293858A CN 101293858 A CN101293858 A CN 101293858A CN A2007100215249 A CNA2007100215249 A CN A2007100215249A CN 200710021524 A CN200710021524 A CN 200710021524A CN 101293858 A CN101293858 A CN 101293858A
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- young urea
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Abstract
The invention relates to a synthetic method of isocyanate and a condensation reaction of the isocyanate and amide compounds, particularly to a synthetic method of substituted benzyl-benzoyl carbamide (diflubenzuron) with high content. The synthetic method comprises the steps of: synthesizing p-chlorophenyl isocyanate from carbonyl chloride as a starting raw material with reasonable process under optimal reaction conditions, and performing a condensation reaction with substituted benzamides to obtain substituted benzyl-benzoyl carbamide with high content, wherein the two steps of isocyanation and condensation are operated in one pot.
Description
Technical field:
The present invention relates to the condensation reaction of synthetic and the isocyanic ester and the amide compound of isocyanic ester, particularly a kind of " young urea goes out " synthetic method.
Background technology:
Inst. of Plant Protection, Jilin Prov. Academy of Agricultural Sciences, Plant Protection institute, Chinese Academy of Agricultral Sciences, Agricultural University Of Shenyang, plant protection institute of Hebei province Academy of Agricultural Sciences rise to unite the young urea that goes out are studied nineteen eighty-three, and the research young urea control mythimna separata of finding to go out has special efficacy.By indoor and outdoor test and large area control demonstration, clear and definite the effective dose of control armyworm larvae (every mu of pure medicine 1～2 gram), prevent and treat optimum period and resistance of rainwater washing against, the longevity of residure reach 20 surplus day and characteristics such as killed natural enemies not, proposed a cover and be suitable for technical regulation and the method that ground and aircraft spray.Make mythimna separata chemical prevention and protection utilize the contradiction of natural enemy to be readily solved, the coordination of being convenient to chemoprevention and biological and ecological methods to prevent plant disease, pests, and erosion is used, and has improved mythimna separata integrated control technique level.Totally applied more than 40 ten thousand mu by 1984, obtain significant social, economy and ecological benefits, and for China develop the 4th generation agricultural chemicals made important model.
Go out young urea III number be a kind of benzoylphenylurea insecticides, people lack understanding to its behavior in environment for a long time.This achievement to its residual, degraded in water, soil and crop, migration and to phreatic pollution tendencies prediction carried out system, deep research, finish 13 pieces of papers.Result of study shows, this agricultural chemicals is the sterilant of perishability, low residue, efficient, low toxicity, safety.This achievement is not only significant to production, the promotion and application of this agricultural chemicals, and provides the environmental toxicology data for entering the world market.Aspect the evaluation of this agricultural chemicals microbiological deterioration and product thereof in soil and environment toxicological study, help protecting environment and HUMAN HEALTH, provide scientific basis for using scientifically and rationally.
The young urea that goes out is the sterilant of substituted-phenyl benzoyl urea compound, belongs to the biological pesticide of insect growth regulator(IGR) type.Its general structure is:
Wherein: No. 1 R.R ' of young urea that goes out is F.F; No. 2 R.R ' of young urea that go out are C1.C1; No. 3 R.R ' of young urea that go out are C1.H.
This compound normally halogeno-benzene isocyanic ester and chloro aminobenzen condensation forms, and wherein the isocyanation esterification reaction is to adopt halobenzamides and oxalyl chloride to react and get, and this method disadvantage is the raw materials cost height,
Using method and the goods and the production method of young urea preparation " enhancing go out " of Ge Gang town, Qixian County, Henan Province Chao Xi village Guo Jun moral, Guo Dongliang invention, this method, wherein goods and production method are to have added natural percutaneous promotor at the young urea that goes out, and solve to prepare the high difficult problem of young urea cost of going out.
Goal of the invention:
The objective of the invention is process modification, invent the go out method of young urea of a kind of feedstock production cheap and easy to get isocyanation esterification reaction.
Summary of the invention:
It is the reaction conditions that starting raw material and p-Chlorobenzoic acid amide carry out the isocyanation esterification reaction with the phosgene that the technology of the present invention provides a kind of.This reaction conditions provides rational material proportion, gentle reactive mode, best temperature of reaction and reaction times.Therefore, the technology of the present invention provides intermediate objective compound synthetic best mode and condition.
The technology of the present invention provides the synthetic method that chlorobenzene ester and the condensation of replacement stupid methane amide " one kettle way " is made the young urea that goes out with isocyanic ester.This method provides the very easily method of purification of mode, reaction mass proportioning, temperature of reaction reaction times and the target compound of operation, obtains high-load target compound.
Reaction equation:
R is in the formula:
Embodiment:
Following embodiment only is that the present invention prepares one of a kind of method of young urea of going out, is stressed that, and be that " young urea goes out " synthetic method of raw material all is protection contents of the present invention as long as adopt phosgene.
Isocyanic acid is synthetic to the stupid ester of chlorine:
In the reaction flask that agitator, thermometer, dropping funnel, reflux condensing tube, air-intake duct and offgas duct are housed, drop into 125ml toluene, and temperature when being lower than 0 ℃ in being cooled to, feed phosgene 50g, stop logical light, under agitation slowly drip the solution of forming by 30g p-Chlorobenzoic acid amide and 100ml toluene, drip speed control system temperature of reaction and be no more than 10 ℃, drip and finish, cryostat modify-water bath slowly is heated to 95 ℃, and kept 1 hour, reaction is finished and is as cold as room temperature, and it is 8～9% that reactant records the content of p-chlorophenyl isocyanate in toluene with volumetry.
The synthetic of young urea of going out:
On the device of above-mentioned reaction, remove air-intake duct, in former reaction soln, continue to drop into and the equimolar substituted benzamide of p-chlorophenyl isocyanate, be heated to backflow, and kept 8 hours, cooling, filtration, filter cake recrystallization in acetone, the young urea crystallization of must going out.Go out No. 1 mp:220～222 of young urea ℃; Go out No. 2 mp:222～223 of young urea ℃; Go out No. 3 mp:197～199 of young urea ℃.The total recovery of 2 steps reaction counts 82% with p-Chlorobenzoic acid amide, and sample is analyzed through the high pressure liquid chromatograph marker method, and content is 〉=95%.
Claims (7)
1, a kind of phosgene that adopts is " young urea goes out " synthetic method for preparing the young urea sterilant that goes out of raw material, it is characterized in that its reaction equation is:
2, adopting phosgene according to claim 1 is " young urea goes out " synthetic method for preparing the young urea sterilant that goes out of raw material, it is characterized in that the R in the claim 1 is:
3, adopting phosgene according to claim 1 is " young urea goes out " synthetic method for preparing the young urea sterilant that goes out of raw material, it is characterized in that the content of phosgene-toluene solution is controlled to be 18～20%.
4, adopting phosgene according to claim 1 is " young urea goes out " synthetic method for preparing the young urea sterilant that goes out of raw material, it is characterized in that phosgene and p-Chlorobenzoic acid amide mol ratio are 2: 1.
5, adopting phosgene according to claim 1 is " young urea goes out " synthetic method for preparing the young urea sterilant that goes out of raw material, it is characterized in that not purifying after the intermediate objective compound synthesizes, and exists in the toluene solution mode.
6, adopting phosgene according to claim 1 and 3 and 4 and 5 is " young urea goes out " synthetic method for preparing the young urea sterilant that goes out of raw material, it is characterized in that obtaining toluene solution from synthetic p-chlorophenyl isocyanate, with " one kettle way " synthesising target compound.
7, adopting phosgene according to claim 1 and 3 and 4 and 5 is go out method of young urea sterilant of " young urea goes out " synthetic preparation of raw material, it is characterized in that p-chlorophenyl isocyanate and substituted benzamide mole through being 1: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100215249A CN101293858A (en) | 2007-04-28 | 2007-04-28 | Method for synthesizing 'dimilin' with phosgene as raw material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100215249A CN101293858A (en) | 2007-04-28 | 2007-04-28 | Method for synthesizing 'dimilin' with phosgene as raw material |
Publications (1)
| Publication Number | Publication Date |
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| CN101293858A true CN101293858A (en) | 2008-10-29 |
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| CNA2007100215249A Pending CN101293858A (en) | 2007-04-28 | 2007-04-28 | Method for synthesizing 'dimilin' with phosgene as raw material |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102180813A (en) * | 2011-04-02 | 2011-09-14 | 连云港市金囤农化有限公司 | Method for preparing diflubenzuron serving as pesticide |
| CN104926694A (en) * | 2015-05-15 | 2015-09-23 | 重庆大学 | Synthesis method of N-acylurea derivatives |
| CN112876384A (en) * | 2021-01-20 | 2021-06-01 | 安阳市安林生物化工有限责任公司 | Synthesis process and application of diflubenzuron |
| CN113773230A (en) * | 2021-09-07 | 2021-12-10 | 京博农化科技有限公司 | Method for synthesizing diflubenzuron by one-pot method |
| CN113861079A (en) * | 2021-09-14 | 2021-12-31 | 泰州百力化学股份有限公司 | Preparation method of high-yield and high-purity pesticide diflubenzuron |
| CN114380719A (en) * | 2022-01-06 | 2022-04-22 | 坛墨质检科技股份有限公司 | Preparation method of stable isotope labeled chlorbenzuron internal standard reagent |
-
2007
- 2007-04-28 CN CNA2007100215249A patent/CN101293858A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102180813A (en) * | 2011-04-02 | 2011-09-14 | 连云港市金囤农化有限公司 | Method for preparing diflubenzuron serving as pesticide |
| CN102180813B (en) * | 2011-04-02 | 2013-04-17 | 连云港市金囤农化有限公司 | Method for preparing diflubenzuron serving as pesticide |
| CN104926694A (en) * | 2015-05-15 | 2015-09-23 | 重庆大学 | Synthesis method of N-acylurea derivatives |
| CN112876384A (en) * | 2021-01-20 | 2021-06-01 | 安阳市安林生物化工有限责任公司 | Synthesis process and application of diflubenzuron |
| CN113773230A (en) * | 2021-09-07 | 2021-12-10 | 京博农化科技有限公司 | Method for synthesizing diflubenzuron by one-pot method |
| CN113861079A (en) * | 2021-09-14 | 2021-12-31 | 泰州百力化学股份有限公司 | Preparation method of high-yield and high-purity pesticide diflubenzuron |
| CN113861079B (en) * | 2021-09-14 | 2023-10-10 | 泰州百力化学股份有限公司 | Preparation method of high-yield and high-purity pesticide diflubenzuron |
| CN114380719A (en) * | 2022-01-06 | 2022-04-22 | 坛墨质检科技股份有限公司 | Preparation method of stable isotope labeled chlorbenzuron internal standard reagent |
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Application publication date: 20081029 |