CN103880778B

CN103880778B - The preparation method of Buprofezin

Info

Publication number: CN103880778B
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: 2016-08-03
Anticipated expiration: 2032-12-20
Also published as: CN103880778A

Abstract

The present invention relates to the preparation method of a kind of Buprofezin, including photochemical, chlorination, synthesis, the step of distillation crystallization；The most photochemical step uses dioxane or chloroform, and using dioxane or N chloromethyl N phenyl amino formyl chloride in chlorinating step is solvent；Synthesis step use organic amine participate in condensation, the present invention uses dioxane, chloroform or N chloromethyl N phenyl amino formyl chloride to be good to material dissolution performance during solvent reaction, little to HCL dissolubility, be conducive to the carrying out of reaction, the productivity of production is up to more than 82%；Use organic amine to replace ammonium hydrogencarbonate as the alkali of synthetic reaction, recyclable decrease the discharge of ammonia nitrogen in waste water.

Description

The preparation method of Buprofezin

Technical field

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

Background technology

The chemical name of Buprofezin is 2-tertiary butyl imino group-3-isopropyl-5-phenyl-1, and 3,5-thiadiazine-4-ketone, molecular formula is C16H23N3OS, is a kind of heterocyclic Chitin synthesis inhibitor, and the newborn epidermis destroying insecticide is formed, interference The normal growth of insecticide is grown, and causes insect dead.Tool is tagged, stomach poison function is strong, has permeability.Do not kill adult, but Can reduce and lay eggs and hinder egg hatching.

The production method of existing Buprofezin mainly has optical self-encoding method and non-phosgene synthetic method, and optical self-encoding method is mainly N- Monomethylaniline. and phosgene, chlorine reaction prepare intermediate, under alkaline environment with the latter in the presence of a base with above-mentioned N-chlorine Methyl-N-phenyl formyl chloride reacts, and prepares Buprofezin.

Chinese patent application CN201010526731.1, the preparation method of entitled a kind of Buprofezin, disclose Buprofezin Preparation method use chlorobenzene as solvent, select ammonium hydrogencarbonate condensation Buprofezin, Chinese patent application CN200710191089.4, the synthetic method of entitled a kind of Buprofezin, disclose the synthetic method of Buprofezin, use benzene, Benzene Chloride or its homologue are as solvent.But select one of above-mentioned solvent product HCL dissolubility in a solvent higher It is unfavorable for that the spilling of hydrogen chloride is unfavorable for the raising of productivity, selects ammonium hydrogencarbonate condensation Buprofezin, the ammonia nitrogen in reaction waste Content is higher, and environmental pollution is serious.

Summary of the invention

Present invention aim to address the problems referred to above, it is provided that a kind of solvent using HCL dissolubility little, reaction waste is more Add the preparation method of the Buprofezin of environmental protection.

The technical scheme realizing the object of the invention is the preparation method of a kind of Buprofezin, including photochemical, and chlorination, synthesis, steam Evaporate the step of crystallization；Wherein using dioxane or N-chloromethyl-N-phenyl amino formyl chloride in chlorinating step is solvent；Close Become and step uses organic amine participate in condensation.

The preparation method of above-mentioned Buprofezin, described concrete processing step is: (1) photochemical reaction, puts into photochemical still Solvent dioxane opens stirring, heats up, and temperature controls at 10～20 DEG C, with 10m³/ h is passed through phosgene, is simultaneously added dropwise N-first Base aniline, terminates to reaction, reacting rear material carries out decompression distillation, removes solvent；(2) chlorination reaction, aforementioned Adding solvent dioxane or N-chloromethyl-N-phenyl amino formyl chloride in photochemical still, catalyst azodiisobutyronitrile, by light Change still temperature to control to be passed through chlorine at 0 DEG C, terminate to reaction；(3) synthetic reaction, by all reactant liquors in photochemical still Transfer is put in synthesis reactor, places into fourth propyl thiourea, and organic amine then heats to DEG C, is incubated 10 hours, by reaction material Liquid pump enters in distillating still；(4) distillation crystallization, opens stirring, vacuum valve by distillating still, opens jacket steam and heats up, will Reaction residual organic amine evaporation is reclaimed, and is then pumped into methanol, crystallizes to obtain end product.

The preparation method of above-mentioned Buprofezin, in described step (1) photochemical reaction, solvent is dioxane；Described is organic Amine is triethylamine, tri-n-butyl amine, a kind of in DMA.

The present invention has positive effect: (1) uses dioxane or N-chloromethyl-N-phenyl amino formyl chloride to be that solvent is anti- During Ying, HCL dissolubility be little, the spilling of beneficially HCL, and the productivity of production reaches more than 83%, reaches time higher 88%；(2) using organic amine to replace the ammonium hydrogencarbonate alkali as synthetic reaction, the ammonia-nitrogen content in reaction waste is low, ring Protect.

Detailed description of the invention

(embodiment 1)

(1) photochemical reaction: putting into 1000ml solvent dioxane to photochemical still and open stirring, heat up, temperature controls About 15 DEG C, while be passed through phosgene 300g (96.8%), limit dropping methylphenylamine 240g, the most slowly it is warmed up to 50 degree, Period maintenance is passed through phosgene on a small quantity, then drives unnecessary phosgene and hydrogen chloride away with nitrogen, obtains N-MethYlphenylamino Formyl chloride dioxane solution；

(2) chlorination reaction: add catalyst azo two in aforementioned N-MethYlphenylamino formyl chloride dioxane solution different Butyronitrile 5g, controls photochemical still temperature to be passed through chlorine 190g at 55 DEG C, detects N-dichloromethyl phenyl carbamyl chloride More than 0.5% i.e. with chlorine and the by-product hydrogen chloride of nitrogen purging excess, obtain N-chloromethyl phenyl carbamyl chloride two Alkane solution；

(3) synthetic reaction: put in synthesis reactor by the N-chloromethyl phenyl carbamyl chloride dioxane solution of upper step, throws Enter fourth propyl thiourea 367g, drip triethylamine 448g at 10-20 DEG C, then heat to 40 DEG C, after being incubated 5 hours, Reaction material is cooled to 13-15 DEG C, is filtered to remove the hydrochlorate of triethylamine；Triethylamine hydrochloride goes to reclaim triethylamine.

(4) distillation crystallization, is distilled off dioxane by the filtrate decompression of upper step, and crude product is subsequently adding methanol according to 1:1, Crystallize to obtain end product, gross production rate 84.6%, content 98.5%.

(embodiment 2)

(1) photochemical reaction: putting into 1000ml chloroform to photochemical still and open stirring, heat up, temperature controls on 15 DEG C of left sides The right side, while be passed through phosgene 300g (96.8%), limit dropping methylphenylamine 240g, the most slowly it is warmed up to 50 degree, period Maintain and be passed through phosgene on a small quantity, then drive unnecessary phosgene and hydrogen chloride away with nitrogen, reacting rear material is carried out decompression distillation, N-MethYlphenylamino formyl chloride is obtained after removing solvent chloroform；

(2) chlorination reaction: aforementioned N-MethYlphenylamino formyl chloride is dissolved in 300gN-chloromethyl phenyl carbamyl In chlorine, add catalyst azodiisobutyronitrile 5g, control photochemical still temperature to be passed through chlorine 190g at 55 DEG C, detection N-dichloromethyl phenyl carbamyl chloride i.e. with chlorine and the by-product hydrogen chloride of nitrogen purging excess, obtains N-more than 0.5% Chloromethyl phenyl carbamyl chloride, takes out lower crowd of 300g use, and other goes synthetic reaction；

(3) synthetic reaction: the N-chloromethyl phenyl carbamyl chloride of upper step is put in synthesis reactor while hot, puts into 1000ml Dioxane stirring and dissolving；Put into fourth propyl thiourea 367g, be slowly passed through ammonia 80g at 10-20 DEG C, then heat to 40 DEG C, After being incubated 5 hours, reaction material is cooled to 25 DEG C, is filtered to remove ammonia chloride.

(4) distillation crystallization, is distilled off dioxane by the filtrate decompression of upper step, and crude product is subsequently adding methanol according to 1:1, Crystallize to obtain end product, gross production rate 86.1%, content 98.0%.

(embodiment 3)

(3) synthetic reaction: put in synthesis reactor by the N-chloromethyl phenyl carbamyl chloride dioxane solution of upper step, throws Enter fourth propyl thiourea 367g, drip tri-n-butyl amine 819g at 10-20 DEG C, then heat to 40 DEG C, be incubated 5 hours After, reaction material is cooled to 13-15 DEG C, is filtered to remove the hydrochlorate of tri-n-butyl amine；Tri-n-butyl amine hydrochlorate adds 1000g water neutralizes PH=10 with 50% sodium hydroxide, and layering is reclaimed tri-n-butyl amine 815g and applied mechanically.

(4) distillation crystallization, is distilled off dioxane by the filtrate decompression of upper step, according to crude product: methanol is that 1:1 adds Methanol, crystallizes to obtain end product, gross production rate 85.3%, content 98.2%.

(embodiment 4)

(1) photochemical reaction: putting into 1000ml dioxane to photochemical still and open stirring, heat up, temperature controls at 15 DEG C Left and right, while be passed through phosgene 300g (96.8%), limit dropping methylphenylamine 240g, the most slowly it is warmed up to 50 degree, the phase Between maintain and be passed through phosgene on a small quantity, then drive unnecessary phosgene and hydrogen chloride away with nitrogen, reacting rear material carried out decompression and steams Evaporate, after removing solvent dioxane, obtain N-MethYlphenylamino formyl chloride；

(3) synthetic reaction: the N-chloromethyl phenyl carbamyl chloride of upper step is put in synthesis reactor while hot, puts into 1000ml Dioxane stirring and dissolving；Put into fourth propyl thiourea 367g, drip tri-n-butyl amine 819g at 10-20 DEG C, then heat to 40 DEG C, after being incubated 5 hours, reaction material is cooled to 13-15 DEG C, is filtered to remove the hydrochlorate of tri-n-butyl amine；Three just Butylamine hydrochlorate goes to reclaim tri-n-butyl amine and applies mechanically.

(4) distillation crystallization, is distilled off dioxane by the filtrate decompression of upper step, and crude product is subsequently adding methanol according to 1:1, Crystallize to obtain end product, gross production rate 83.3%, content 98.0%.

(embodiment 5)

(1) photochemical reaction: put into 1000ml solvent dioxane to photochemical still and open stirring, heats up, and temperature controls 15 About DEG C, while be passed through phosgene 300g (96.8%), limit dropping methylphenylamine 240g, the most slowly it is warmed up to 50 degree, Period maintenance is passed through phosgene on a small quantity, then drives unnecessary phosgene and hydrogen chloride away with nitrogen, obtains N-MethYlphenylamino Formyl chloride dioxane solution；

(3) synthetic reaction: put in synthesis reactor by the N-chloromethyl phenyl carbamyl chloride dioxane solution of upper step, throws Enter fourth propyl thiourea 367g, drip tripropylamine 633g at 10-20 DEG C, then heat to 40 DEG C, after being incubated 5 hours, Reaction material is cooled to 13-15 DEG C, is filtered to remove the hydrochlorate of tripropylamine；Tripropylamine hydrochlorate goes to reclaim tripropyl Amine is applied mechanically.

Particular embodiments described above, has been carried out the purpose of the present invention, technical scheme and beneficial effect the most in detail Illustrate, be it should be understood that the specific embodiment that the foregoing is only the present invention, be not limited to the present invention, All within the spirit and principles in the present invention, any modification, equivalent substitution and improvement etc. done, should be included in this Within bright protection domain.

Claims

1. a preparation method for Buprofezin, including photochemical, chlorination, synthesis, distill crystallisation step；It is characterized in that: wherein using the one in dioxane or N-chloromethyl-N-phenyl amino formyl chloride in chlorinating step is solvent；Synthesis step use organic amine or ammonia participate in condensation；

Concrete processing step is: (1) photochemical reaction, puts into two alkane solvents to photochemical still, opens stirring, heats up, and temperature controls at 10～20 DEG C, with 10m³/ h is passed through phosgene, is simultaneously added dropwise methylphenylamine, terminates to reaction, reacting rear material carries out decompression distillation, removes solvent；(2) chlorination reaction, adds solvent dioxane or N-chloromethyl-N-phenyl amino formyl chloride, catalyst azodiisobutyronitrile in aforementioned photochemical still, controls to be passed through chlorine at 0 DEG C by photochemical still temperature, terminate to reaction；(3) all reactant liquors in photochemical still are shifted and put in synthesis reactor, place into fourth propyl thiourea and organic amine or ammonia then heats to 10 DEG C, be incubated 10 hours, entered in distillating still by reaction material liquid pump by synthetic reaction；(4) distillation crystallization, opens stirring, vacuum valve by distillating still, opens jacket steam and heats up, and reaction residual organic amine evaporation is reclaimed, is then pumped into methanol, crystallizes to obtain end product.

The preparation method of Buprofezin the most according to claim 1, it is characterised in that: the organic amine added in described synthetic reaction step is the one in triethylamine, tri-n-butyl amine and DMA.