CN103880778A

CN103880778A - Preparation method of buprofezin

Info

Publication number: CN103880778A
Application number: CN201210556903.9A
Authority: CN
Inventors: 陆明若; 张中泽; 马志荣; 王卫华; 田庆海
Original assignee: JIANGSU CHANGLONG CHEMICALS CO Ltd
Current assignee: JIANGSU CHANGLONG CHEMICALS CO Ltd
Priority date: 2012-12-20
Filing date: 2012-12-20
Publication date: 2014-06-25
Anticipated expiration: 2032-12-20
Also published as: CN103880778B

Abstract

The invention relates to a preparation method of buprofezin, which comprises the following steps of actinism, chlorination, synthesis and distillation crystallization. The actinism step employs dioxane or chloroform, the chlorination step employs dioxane or N-chloromethyl-N-phenyl carbamyl chloride as a solvent; and the synthesis step employs organic amine to participate in condensation. According to the invention, dioxane, chloroform or N-chloromethyl-N-phenyl carbamyl chloride are employed as the solvents, so that good dissolving performance is provided to the raw material, and the dioxane, chloroform or N-chloromethyl-N-phenyl carbamyl chloride has little solubility to HCL and is in favor of reaction, the production yield can reach as high as more than 82%; organic amine is employed for replacing ammonium bicarbonate as alkali for synthesis reaction, and can be recovered so that the discharge of ammonia nitrogen in waste water is reduced.

Description

The preparation method of Buprofezin

Technical field

The present invention relates to a kind of preparation method of Buprofezin.

Background technology

The chemical name of Buprofezin is 2-tertiary butyl imino--3-sec.-propyl-5-phenyl-1,3,5-thiadiazine-4-ketone, molecular formula is C16H23N3OS, is a kind of heterocyclic Chitin synthesis inhibitor, and the newborn epidermis that destroys insect forms, the normal growth of interference insect is grown, and causes insect death.Tool is tagged, stomach poison function is strong, tool perviousness.Do not kill adult, lay eggs and hinder ovum hatching but can reduce.

The production method of existing Buprofezin mainly contains phosgene synthesis method and non-phosgene synthesis method, phosgene synthesis method is mainly methylphenylamine and phosgene, chlorine reaction make intermediate, under alkaline environment, react with above-mentioned N-chloromethyl-N-phenyl amino formyl chloride under alkali exists with the latter, make Buprofezin.

Chinese patent application CN201010526731.1, name is called a kind of preparation method of Buprofezin, the preparation method who discloses Buprofezin adopts chlorobenzene as solvent, select ammonium hydrogencarbonate condensation Buprofezin, Chinese patent application CN200710191089.4, name is called a kind of synthetic method of Buprofezin, discloses the synthetic method of Buprofezin, adopts benzene, Benzene Chloride or its homologue as solvent.But select, the solubleness of one of above-mentioned solvent product HCL in solvent is higher is unfavorable for that overflowing of hydrogenchloride is unfavorable for the raising of productive rate, selects ammonium hydrogencarbonate condensation Buprofezin, and the ammonia-nitrogen content in reaction waste is higher, and environmental pollution is serious.

Summary of the invention

The object of the invention is to address the above problem, provide a kind of HCL of employing solubleness little solvent, reaction waste is the preparation method of the Buprofezin of environmental protection more.

The technical scheme that realizes the object of the invention is a kind of preparation method of Buprofezin, comprise photochemical, chlorination, synthetic, the step of distillation crystallization; Wherein in chlorinating step, adopting diox or N-chloromethyl-N-phenyl amino formyl chloride is solvent; In synthesis step, adopt organic amine to participate in condensation.

The preparation method of above-mentioned Buprofezin, described concrete processing step is: (1) photochmeical reaction, put into Rong Ji diox to photochemical still and open stirring, heat up, temperature is controlled at 10 ~ 20 ℃, passes into phosgene with 10m3/h, drip methylphenylamine simultaneously, to reaction end, reacting rear material is carried out to underpressure distillation, remove solvent; (2) chlorination reaction adds Rong Ji diox or N-chloromethyl-N-phenyl amino formyl chloride in aforementioned photochemical still, and catalyzer Diisopropyl azodicarboxylate is controlled at 0 ℃ by photochemical still temperature and passes into chlorine, to reaction end; (3) building-up reactions, shifts all reaction solutions in photochemical still to put into synthesis reactor, then put into toluene, fourth propyl thiourea, and then organic amine is warming up to ℃, is incubated 10 hours, and reaction material liquid pump is entered in still kettle; (4) distillation crystallization, opens stirring, vacuum valve by still kettle, opens jacket steam and heats up, and will react residual organic amine evaporation and reclaim, and then pumps into methyl alcohol, and crystallization obtains final product.

The preparation method of above-mentioned Buprofezin, in described step (1) photochmeical reaction, solvent is diox; Described organic amine is triethylamine, and tri-n-butyl amine is a kind of in N-N-xylidine.

The present invention has positive effect: (1) adopts diox or N-chloromethyl-N-phenyl amino formyl chloride is that in solvent reaction process, HCL solubleness is little, is conducive to overflowing of HCL, and the productive rate of production reaches more than 83%, reaches 88% when higher; (2) adopt organic amine to replace the alkali of ammonium hydrogencarbonate as building-up reactions, the ammonia-nitrogen content in reaction waste is low, environmental protection.

Embodiment

embodiment

(embodiment 1)

(1) photochmeical reaction: put into 1000ml Rong Ji diox to photochemical still and open stirring, heat up, temperature is controlled at 15 ℃ of left and right, limit passes into phosgene 300g (96.8%), limit drips methylphenylamine 240g, is then slowly warmed up to 50 degree, maintains during this time and passes on a small quantity phosgene, then drive unnecessary phosgene and hydrogenchloride away with nitrogen, obtain N-aminomethyl phenyl urea chloride dioxane solution;

(2) chlorination reaction: add catalyzer Diisopropyl azodicarboxylate 5g in aforementioned N-aminomethyl phenyl urea chloride dioxane solution, photochemical still temperature is controlled to 55 ℃ and passes into chlorine 190g, detection N-dichloromethyl phenyl urea chloride is greater than 0.5% and uses the excessive chlorine of nitrogen purging and by-product hydrogen chloride, obtains N-chloromethyl phenyl urea chloride dioxane solution;

(3) building-up reactions: the N-chloromethyl phenyl urea chloride dioxane solution of upper step is put into synthesis reactor, drop into fourth propyl thiourea 367g, drip triethylamine 448g at 10-20 ℃, then be warming up to 40 ℃, be incubated after 5 hours, reaction material is cooled to 13-15 ℃, removes by filter the hydrochloride of triethylamine; Triethylamine hydrochloride removes to reclaim triethylamine.

(4) distillation crystallization, removes diox by the filtrate decompression distillation of upper step, and then crude product adds methyl alcohol according to 1:1, and crystallization obtains final product, overall yield 84.6%, content 98.5%.

(embodiment 2)

(1) photochmeical reaction: put into 1000ml chloroform to photochemical still and open stirring, heat up, temperature is controlled at 15 ℃ of left and right, limit passes into phosgene 300g (96.8%), and limit drips methylphenylamine 240g, is then slowly warmed up to 50 degree, maintain during this time and pass on a small quantity phosgene, then drive unnecessary phosgene and hydrogenchloride away with nitrogen, reacting rear material is carried out to underpressure distillation, obtain N-aminomethyl phenyl urea chloride after removing solvent chloroform;

(2) chlorination reaction: aforementioned N-aminomethyl phenyl urea chloride is dissolved in 300gN-chloromethyl phenyl urea chloride, add catalyzer Diisopropyl azodicarboxylate 5g, photochemical still temperature is controlled to 55 ℃ and passes into chlorine 190g, detection N-dichloromethyl phenyl urea chloride is greater than 0.5% and uses the excessive chlorine of nitrogen purging and by-product hydrogen chloride, obtain N-chloromethyl phenyl urea chloride, take out lower batch of use of 300g, other goes building-up reactions;

(3) building-up reactions: the N-chloromethyl phenyl urea chloride of upper step is put into synthesis reactor while hot, put into 1000ml diox stirring and dissolving; Drop into fourth propyl thiourea 367g, slowly pass into ammonia 80g at 10-20 ℃, be then warming up to 40 ℃, be incubated after 5 hours, reaction material is cooled to 25 ℃, remove by filter ammonia chloride.

(4) distillation crystallization, removes diox by the filtrate decompression distillation of upper step, and then crude product adds methyl alcohol according to 1:1, and crystallization obtains final product, overall yield 86.1%, content 98.0%.

(embodiment 3)

(3) building-up reactions: the N-chloromethyl phenyl urea chloride dioxane solution of upper step is put into synthesis reactor, drop into fourth propyl thiourea 367g, drip tri-n-butyl amine 819g at 10-20 ℃, then be warming up to 40 ℃, be incubated after 5 hours, reaction material is cooled to 13-15 ℃, removes by filter the hydrochloride of tri-n-butyl amine; Tri-n-butyl amine hydrochloride adds 1000g water to neutralize PH=10 with 50% sodium hydroxide, and layering is reclaimed tri-n-butyl amine 815g and applied mechanically.

(4) distillation crystallization, removes diox by the filtrate decompression distillation of upper step, according to crude product: methyl alcohol is that 1:1 adds methyl alcohol, and crystallization obtains final product, overall yield 85.3%, content 98.2%.

(embodiment 4)

(1) photochmeical reaction: put into 1000ml diox to photochemical still and open stirring, heat up, temperature is controlled at 15 ℃ of left and right, limit passes into phosgene 300g (96.8%), and limit drips methylphenylamine 240g, is then slowly warmed up to 50 degree, maintain during this time and pass on a small quantity phosgene, then drive unnecessary phosgene and hydrogenchloride away with nitrogen, reacting rear material is carried out to underpressure distillation, obtain N-aminomethyl phenyl urea chloride after removing Rong Ji diox;

(3) building-up reactions: the N-chloromethyl phenyl urea chloride of upper step is put into synthesis reactor while hot, put into 1000ml diox stirring and dissolving; Drop into fourth propyl thiourea 367g, drip tri-n-butyl amine 819g at 10-20 ℃, be then warming up to 40 ℃, be incubated after 5 hours, reaction material is cooled to 13-15 ℃, remove by filter the hydrochloride of tri-n-butyl amine; Tri-n-butyl amine hydrochloride removes to reclaim tri-n-butyl amine and applies mechanically.

(4) distillation crystallization, removes diox by the filtrate decompression distillation of upper step, and then crude product adds methyl alcohol according to 1:1, and crystallization obtains final product, overall yield 83.3%, content 98.0%.

(embodiment 5)

(3) building-up reactions: the N-chloromethyl phenyl urea chloride dioxane solution of upper step is put into synthesis reactor, drop into fourth propyl thiourea 367g, drip tripropylamine 633g at 10-20 ℃, then be warming up to 40 ℃, be incubated after 5 hours, reaction material is cooled to 13-15 ℃, removes by filter the hydrochloride of tripropylamine; Tripropylamine hydrochloride goes to reclaim tripropylamine and applies mechanically.

Above-described specific embodiment; object of the present invention, technical scheme and beneficial effect are further described; institute is understood that; the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any modification of making, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.

Claims

1. a preparation method for Buprofezin, comprise photochemical, chlorination, synthetic, distillation crystallisation step; It is characterized in that: wherein in chlorinating step, adopting the one in diox, chloroform or N-chloromethyl-N-phenyl amino formyl chloride is solvent; In synthesis step, adopt organic amine to participate in condensation.

2. the preparation method of Buprofezin according to claim 1, it is characterized in that: concrete processing step is: (1) photochmeical reaction, put into solvent to photochemical still, open and stir, heat up, temperature is controlled at 10 ~ 20 ℃, pass into phosgene with 10m3/h, drip methylphenylamine simultaneously, to reaction end, reacting rear material is carried out to underpressure distillation, remove solvent; (2) chlorination reaction adds Rong Ji diox or N-chloromethyl-N-phenyl amino formyl chloride in aforementioned photochemical still, and catalyzer Diisopropyl azodicarboxylate is controlled at 0 ℃ by photochemical still temperature and passes into chlorine, to reaction end; (3) building-up reactions, shifts all reaction solutions in photochemical still to put into synthesis reactor, then puts into toluene, fourth propyl thiourea and organic amine and be then warming up to 10 ℃, is incubated 10 hours, and reaction material liquid pump is entered in still kettle; (4) distillation crystallization, opens stirring, vacuum valve by still kettle, opens jacket steam and heats up, and will react residual organic amine evaporation and reclaim, and then pumps into methyl alcohol, and crystallization obtains final product.

3. the preparation method of Buprofezin according to claim 2, is characterized in that: in described step (1) photochmeical reaction, solvent is diox.

4. the preparation method of Buprofezin according to claim 2, is characterized in that: the organic amine adding in described building-up reactions step is the one in triethylamine, tri-n-butyl amine, ammonia and N-N-xylidine.