CN102399216B - Method for producing thiacloprid technical - Google Patents
Method for producing thiacloprid technical Download PDFInfo
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- CN102399216B CN102399216B CN201110389533.XA CN201110389533A CN102399216B CN 102399216 B CN102399216 B CN 102399216B CN 201110389533 A CN201110389533 A CN 201110389533A CN 102399216 B CN102399216 B CN 102399216B
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Abstract
The invention discloses a method for producing thiacloprid technical, which comprises the following steps of: synthesizing cyanamide, caustic soda liquid and carbon disulfide which are used as raw materials under the action of a catalyst; then performing a reaction on the obtained product and dimethyl sulfate to obtain N-cyanoimido-S,S-dimethyl-dithiocarbonate; performing a reaction on the obtained N-cyanoimido-S,S-dimethyl-dithiocarbonate and cysteamine hydrochloride to synthesize 2-cyanoimino-1,3-thiazolidine; and finally, performing a reaction on the 2-cyanoimino-1,3-thiazolidine and 2-chloro-5-chloromethylpyridine in a solvent, completing dropwise adding carbon disulfide in a temperature range of 5 DEG C to 20 DEG C and then performing a temperature rising reaction, wherein the catalyst is tetrabutyl ammonium bromide and after being extracted by using chloroform as an extracting solvent, the N-cyanoimido-S,S-dimethyl-dithiocarbonate directly reacts with the cysteamine hydrochloride.
Description
Technical field
The present invention relates to a kind of chloro nicotinic insecticide, particularly the production method of the former medicine of a kind of thiacloprid.
Background technology
Thiacloprid is the chloro nicotinoids new pesticides of Bayer Bitterfeld GmbH agro-chemical companies and Japanese Bayer agro-chemical companies cooperation, effective to piercing mouth parts and some biting mouth parts insects, is the sterilant of interior suction wide spectrum.The chemical name of thiacloprid is: 3-[(6-chloro-3-pyridyl base) methyl]-1,3-thiazoles quinoline-2-base fork cyanogen (acyl) amine or (3-(6-chloro-3-pyridyl base) first
Base-1,3-thiazoline-2-subunit) cyanamide, molecular formula is C
10h
9clN
4s; English common name is: thiacloprid, and structural formula is:
Thiacloprid toxicity test: acute oral LD50 rat (hero): 836mg/kg body weight, (female): 444mg/kg body weight; Acute fatal LD50 (24h) rat (male, female): >2000mg/kg body weight; Acute inhalation LC50 (4h, aerosol) rat (hero): >2535mg/m
3air, (female): ~ 122mg/m
3air.The same with Provado, thiacloprid also acts on nicotinic acetylcholine receptors, and it and common insecticides do not have cross resistance as intended deinsectization polyester, organic phosphates and amino formate, thus can be used for resistance management.In soil, the transformation period of thiacloprid is short, 7-21 days, and movability is low to moderate medium.To birds, fish and multiple beneficial arthropods safety.(4h) is had no stimulation to rabbit skin; (24h) is had no stimulation to lagophthalmos eyeball; To guinea pig skin without sensitization; To rat without carcinogenesis; To rat and the rabbit development toxicity without former; Without heredity and mutagenesis.
Zhang Pin, Wu Daoxin etc. are published in " fine-chemical intermediate " the 40th in December, 2010 volume the 6th phase 23-26 page the synthesising process research of low toxic pesticide thiacloprid " efficient, " in highlight in the lab, with cyanamide, dithiocarbonic anhydride, methyl-sulfate, Mercaptamine etc. for raw material, acid binding agent synthesis 2-itrile group imines-1,3-thiazoles quinoline made by mineral alkali; Then, under n-butanol solvent, thiacloprid is reacted to obtain with CCMP again.Wherein, when synthesizing disodium salt, be that the triethyl benzyl ammonia chloride of employing is catalyzer.Concrete synthetic route is as follows:
the price of catalyzer used in this method and the solvent, n-butanol in later stage is all higher, and propyl carbinol not easily reclaims or cost recovery is too high, is very unsuitable for suitability for industrialized production.
So, technique general adopted in current suitability for industrialized production mainly with cyanamide, liquid caustic soda, dithiocarbonic anhydride for raw material, benzyl trimethyl ammonium chloride is catalyzer, synthesizes disodium salt at a lower temperature, N-cyanogen imido grpup-S is generated again, S-dithiocarbonic acid dimethyl ester with methyl-sulfate effect.In the basic conditions with Mercaptamine cyclization, generating thiazolidine, is finally that solvent and CCMP effect generate product with ethanol.But, also there is following shortcoming:
1) catalyzer can not reclaim, and brings postorder reaction into, causes waste and affects postorder reaction.
2) disodium salt synthesis reaction temperature is low, and the reaction times is longer, generally more than 20 hours.
3) after two Lipase absobed, will carry out the process such as crystallisation by cooling, filtration, washing, drying to product, technical process is comparatively loaded down with trivial details, and loss of product is more.
4) thiacloprid synthesis adopt ethanol as solvent, not easily reclaim or cost recovery too high.
Summary of the invention
In order to solve the deficiencies such as catalyzer can not reclaim, long reaction time, loss of product are many that prior art exists, the invention provides the production method of the former medicine of a kind of thiacloprid, there is disodium salt synthesis used catalyst and can reclaim and cheap, that the reaction times is short, loss of product is few advantage.
Technical scheme of the present invention is: the production method of the former medicine of a kind of thiacloprid, synthesize in the presence of a catalyst (hereinafter referred to as disodium salt) for raw material with cyanamide, liquid caustic soda, dithiocarbonic anhydride, then N-cyanogen imido grpup-S is obtained by reacting with methyl-sulfate, S-dithiocarbonic acid dimethyl ester (abbreviation diester), again with Mercaptamine Reactive Synthesis 2-cyano group imines-1,3-thiazoles alkane; Finally, thiacloprid is reacted to obtain again in a solvent with CCMP, in the temperature range of 5 DEG C ~ 20 DEG C, dithiocarbonic anhydride is dropwised, and then temperature reaction, described catalyzer is Tetrabutyl amonium bromide, by the N-cyanogen imido grpup-S obtained, S-dithiocarbonic acid dimethyl ester is direct after extraction solvent extraction with chloroform and Mercaptamine reacts.
Described solvent is methyl alcohol.
Synthesis
time, temperature of reaction is 30 DEG C ~ 60 DEG C reactions, and during synthesis thiacloprid, temperature of reaction is the reflux temperature of methyl alcohol.
Described Tetrabutyl amonium bromide after the completion of reaction filtering separation re-uses.
Described solvent methanol comes into operation after the reaction after rectification process again.
Described extraction solvent haloform reaction terminates rear negative pressure and distillates recovery.
beneficial effect:
1, in disodium salt synthesis, have selected a kind of new catalyzer Tetrabutyl amonium bromide, not only price is much lower compared with benzyl trimethyl ammonium chloride, and reaction effect is comparatively obvious, and catalyzer adds rear CL and participates in reaction, accelerates speed of response.After reaction terminates, all separate out, directing terminal arrives, and by filter cloth by catalyzer elimination, reuses.Both reduce production cost, can not catalyzer be brought into the next step again, reduce the possibility that negative reaction occurs.
2, in disodium salt synthesis, we adopt and drip off dithiocarbonic anhydride at the temperature of 5 DEG C ~ 20 DEG C, then solution temperature are slowly promoted to 30 DEG C-60 DEG C, react under being allowed to condition at high temperature.Substantially increase speed of response, shorten the reaction times, reduce production cost, improve efficiency.
3, after diester end of synthesis, we adopt chloroform as extraction solvent, by the N-cyanogen imido grpup-S generated, S-dithiocarbonic acid dimethyl ester is dissolved in chloroform, forms chloroform two ester solution, makes diester and aqueous phase separation, the purity of diester is higher, is directly used in the synthesis of lower step thiazolidine.Avoid and crystallisation by cooling, filtration, washing and dry supervisor and the parcel to impurity produced in the process and loss of product are carried out to diester.Only after thiazolidine reaction terminates, chloroform negative pressure need be distillated, can recovery be realized.Simplify operation steps, decreased product and too much lose.And, adopt liquid to drip and replace solid to feed intake, shorten the reaction times, make reaction more abundant.
4, when thiacloprid synthesizes, by selecting, adopt methyl alcohol as solvent, not only price is low but also reduce the temperature of building-up reactions compared with propyl carbinol, make temperature be down to the methanolic reflux temperature of 40 DEG C-65 DEG C by original 70 DEG C-85 DEG C, decrease the waste of the energy, reduce production cost.Also reduce the generation of by product simultaneously, reduce product solubleness in a solvent, improve product content and yield.The rear solvent of reaction comparatively propyl carbinol is easier to recovery, after propyl carbinol uses, due to moisture in system,
levels of n-butanol is down to60-80%wt, to be recycled to 99.9%wt propyl carbinol, cost is too high.Use methanol as solvent, after solvent only need slightly steam by mother liquor in still, then carry out rectifying, be easy to reach more than 99%wt, can realize applying mechanically.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
Agents useful for same is originated:
30%wt cyanamide: Rugao Zhongru Chemical Co., Ltd.
30%wt sodium hydroxide: Xuzhou Tian Cheng chlor-alkali company limited
Dithiocarbonic anhydride: Shanghai White aurification work Group Co., Ltd
Tetrabutyl amonium bromide: Shuyang County Feng Tai Chemical Company
30%wt hydrochloric acid: Yang Mei Heng Tong chemical inc, Shandong
Methyl-sulfate: Linyi Yuan Bo Chemical Co., Ltd.
Chloroform: Jiangsu Meilan Chemical Co
Half Guang ammonia hydrochloric acid salt: An Weixingdong Chemical Co., Ltd.
Methyl alcohol: Xuzhou Xinyi branch office of Yuan Xiang trade of goods and materials company limited
Formaldehyde: Jun Kun resin company limited of Xinyi City
The chloro-picoline of the chloro-5-of 2-: industrial Chemical Co., Ltd. of Langfang in Hebei Province
Synthesis route of the present invention is as follows:
(1) the building-up reactions formula of disodium salt:
(2) N-cyanogen imido grpup-S, the building-up reactions formula of S-dithiocarbonic acid dimethyl ester:
(3) the building-up reactions formula of 2-cyano group imines-1,3-thiazoles alkane:
(4) the building-up reactions formula of thiacloprid:
Under concrete operations are shown in:
embodiment 1:
1, the synthesis procedure of disodium salt
The cyanamide aqueous solution of a certain amount of 30%wt is dropped in reactor, be cooled to 0-5 DEG C, according to mol ratio cyanamide: sodium hydroxide is the sodium hydroxide solution of the ratio dropping 30%wt of 1:1.5 ~ 3.5, after dripping off, add the amount of 0.1-2g four butyl bromation amine according to 1mol cyanamide, add catalyzer four butyl bromation amine, according to mol ratio cyanamide: the ratio of dithiocarbonic anhydride=1:1 ~ 3 drips dithiocarbonic anhydride, material higher than 20 DEG C, after dripping off, must not be slowly warming up to 30 DEG C-60 DEG C by dropping temperature.Stirring reaction 3-10 hour at this temperature.After having reacted, distill out unreacted dithiocarbonic anhydride with the tiny structure of-0.01 ~-0.03MPa.Distillation terminates, by material through suction filtration tank suction surge tank, by catalyzer elimination.
2, N-cyanogen imido grpup-S, S-dithiocarbonic acid dimethyl ester synthesis procedure
Filter pump is squeezed into N-cyanogen imido grpup-S, S-dithiocarbonic acid dimethyl ester synthesis reactor.Be cooled to 10-20 DEG C, in still, add hydrochloric acid regulate pH=7-10 in still, regulate still temperature at 10-30 DEG C. according to mol ratio disodium salt: the ratio of methyl-sulfate=1:1 ~ 3 is added dropwise to methyl-sulfate in still, is finished by methyl-sulfate at above-mentioned temperature and pH value condition.Control temperature in the kettle at 10-30 DEG C, till substantially constant in pH value half an hour in still (about needing 2-5 hour).With chloroform extraction 2 times, first time, extraction was according to 50-90mL chloroform/mole N-cyanogen imido grpup-S, the amount of S-dithiocarbonic acid dimethyl ester adds, second time extraction is according to 10-30mL/ mole of N-cyanogen imido grpup-S, the amount of S-dithiocarbonic acid dimethyl ester adds, and is merged by the extraction liquid of twice, weigh up chloroform layer weight after extraction, sampling analysis N-cyanogen imido grpup-S, S-dithiocarbonic acid dimethyl ester content.
3,2-cyano group imines-1,3-thiazoles alkane synthesis procedure
According to mass ratio half Guang ammonia hydrochloric acid salt: the ratio of water=1:2 ~ 5 is injected water and passes into nitrogen in reactor, according to mol ratio N-cyanogen imido grpup-S, S-dithiocarbonic acid dimethyl ester: the ratio of half Guang ammonia hydrochloric acid salt=1:1 ~ 2 adds Mercaptamine in still.When being cooled to 0-5 DEG C, according to mol ratio: N-cyanogen imido grpup-S, S-dithiocarbonic acid dimethyl ester: the ratio of sodium hydroxide=1:1 ~ 2 drips the sodium hydroxide solution of 30%wt in still, drips off rear insulation 30-60 minute.N-cyanogen imido grpup-S is dripped, the chloroformic solution of S-dithiocarbonic acid dimethyl ester in still. after adding, clock reaction 2-8 hour.After reaction terminates, drive vacuum pump, close nitrogen, by the regulation system acidity of 20-30%wt hydrochloric acid to pH=2-6, open hot water, lift temperature to 40-60 DEG C, chloroform is steamed.Emptying hot water, water flowing is cooled to 0-10 DEG C, puts into whizzer and dries, dry 2-4 hour in discharging to drying plant.The qualified rear discharging of moisture content, sampling analysis, calculated yield.
4, thiacloprid synthesis procedure
In thiacloprid synthesis reactor, a certain amount of anhydrous methanol is squeezed into according to the ratio of 500-1000ml/mol thiazolidine, the 2-cyano group imines-1 of step synthesis in input, 3-thiazolidine, start vacuum pump, according to mol ratio thiazolidine: the ratio of picoline=1:1 ~ 2 is the formaldehyde solution (consumption: 5-10 ‰) (making catalyzer) of 30-40% to suction CCMP in still and mass percent concentration.When passing into steam temperature raising to 40-65 DEG C, drip the liquid caustic soda adjust ph of 30%wt between 7-11, after dripping off, clock reaction 2-4 hour, sampling analysis.After qualified, material is gone to crystallization kettle.Water flowing is cooled to 0-10 DEG C, and feed liquid is put into whizzer, after drying, material is proceeded to washing kettle.By 50-80 DEG C of hot water wash twice, terminate rear centrifuge dripping.Discharging to drying plant, to dry materials 2-5 hour, until moisture qualified (water content≤1%).Cooling discharge.
embodiment 2:
1, the synthesis procedure of disodium salt
The cyanamide aqueous solution of 30%wt is dropped in reactor, be cooled to 10 DEG C, according to mol ratio cyanamide: sodium hydroxide is the sodium hydroxide solution of the ratio dropping 30%wt of 1:1.5, after dripping off, add the amount of 0.1g four butyl bromation amine according to 1mol cyanamide, add catalyzer four butyl bromation amine, according to mol ratio cyanamide: the ratio of dithiocarbonic anhydride=1:1 drips dithiocarbonic anhydride, material higher than 20 DEG C, after dripping off, must not be slowly warming up to 50 DEG C by dropping temperature.Stirring reaction 3-10 hour at this temperature.After having reacted, distill out unreacted dithiocarbonic anhydride with the tiny structure of-0.01 ~-0.03MPa.Distillation terminates, by material through suction filtration tank suction surge tank, by catalyzer elimination.
2, N-cyanogen imido grpup-S, S-dithiocarbonic acid dimethyl ester synthesis procedure
Filtrate is squeezed into N-cyanogen imido grpup-S, S-dithiocarbonic acid dimethyl ester synthesis reactor.Be cooled to 20 DEG C, in still, add hydrochloric acid regulate pH=7-10 in still, still temperature is at 30 DEG C. according to mol ratio disodium salt: the ratio of methyl-sulfate=1:1 is added dropwise to methyl-sulfate in still, after finishing, solution reacted at 30 DEG C of temperature to substantially constant (about needing 2-5 hour) in pH value half an hour.With chloroform extraction 2 times, first time, extraction was according to 50-90mL chloroform/mole N-cyanogen imido grpup-S, the amount of S-dithiocarbonic acid dimethyl ester adds, second time extraction is according to 10-30mL/ mole of N-cyanogen imido grpup-S, the amount of S-dithiocarbonic acid dimethyl ester adds, and is merged by the extraction liquid of twice, weigh up chloroform layer weight after extraction, sampling analysis N-cyanogen imido grpup-S, S-dithiocarbonic acid dimethyl ester content.
3,2-cyano group imines-1,3-thiazoles alkane synthesis procedure
According to mass ratio half Guang ammonia hydrochloric acid salt: the ratio of water=1:2 is injected water and passes into nitrogen in reactor, according to mol ratio N-cyanogen imido grpup-S, S-dithiocarbonic acid dimethyl ester: the ratio of half Guang ammonia hydrochloric acid salt=1:1 adds Mercaptamine in still.When being cooled to 5 DEG C, according to mol ratio: N-cyanogen imido grpup-S, S-dithiocarbonic acid dimethyl ester: the ratio of sodium hydroxide=1:1 drips the sodium hydroxide solution of 30%wt in still, drips off rear insulation 30-60 minute.N-cyanogen imido grpup-S is dripped, the chloroformic solution of S-dithiocarbonic acid dimethyl ester in still. after adding, clock reaction 2-8 hour.After reaction terminates, drive vacuum pump, close nitrogen, by the regulation system acidity of 20-30%wt hydrochloric acid to pH=2-6, open hot water, lift temperature to 60 DEG C, chloroform is steamed.Emptying hot water, water flowing is cooled to 0-10 DEG C, puts into whizzer and dries, imperial material dry 2-4 hour to drying plant.The qualified rear discharging of moisture content, sampling analysis, calculated yield.
4, thiacloprid synthesis procedure
In thiacloprid synthesis reactor, a certain amount of anhydrous methanol is squeezed into according to the ratio of 500-1000ml/mol thiazolidine, the 2-cyano group imines-1 of step synthesis in input, 3-thiazolidine, start vacuum pump, according to mol ratio thiazolidine: the ratio of picoline=1:1 ~ 2 is the formaldehyde solution (consumption: 5-10 ‰) (making catalyzer) of 30-40% to suction CCMP in still and mass percent concentration.When passing into steam temperature raising to 65 DEG C, drip the liquid caustic soda adjust ph of 30%wt between 7-11, after dripping off, clock reaction 2-4 hour, sampling analysis.After qualified, material is gone to crystallization kettle.Water flowing is cooled to 10 DEG C, and feed liquid is put into whizzer, after drying, material is proceeded to washing kettle.By 50-80 DEG C of hot water wash twice, terminate rear centrifuge dripping.Discharging to drying plant, to dry materials 2-5 hour, until moisture qualified (water content≤1%).Cooling discharge.
embodiment 3:
1, the synthesis procedure of disodium salt
The cyanamide aqueous solution of 30%wt is dropped in reactor, be cooled to 15 DEG C, according to mol ratio cyanamide: sodium hydroxide is the sodium hydroxide solution of the ratio dropping 30%wt of 1:1.5 ~ 3.5, after dripping off, add the amount of 0.1-2g four butyl bromation amine according to 1mol cyanamide, add catalyzer four butyl bromation amine, according to mol ratio cyanamide: the ratio of dithiocarbonic anhydride=1:3 drips dithiocarbonic anhydride, material higher than 20 DEG C, after dripping off, must not be slowly warming up to 50 DEG C by dropping temperature.Stirring reaction 3-10 hour at this temperature.After having reacted, distill out unreacted dithiocarbonic anhydride with the tiny structure of-0.01 ~-0.03MPa.Distillation terminates, by material through suction filtration tank suction surge tank, by catalyzer elimination.
2, N-cyanogen imido grpup-S, S-dithiocarbonic acid dimethyl ester synthesis procedure
Filtrate is squeezed into N-cyanogen imido grpup-S, S-dithiocarbonic acid dimethyl ester synthesis reactor.Be cooled to 10-20 DEG C, in still, add hydrochloric acid regulate pH=7-10 in still, still temperature is at 15-30 DEG C. according to mol ratio disodium salt: the ratio of methyl-sulfate=1:1 ~ 3 is added dropwise to methyl-sulfate in still, after finishing, solution reacted at 15-30 DEG C of temperature to substantially constant (about needing 2-5 hour) in pH value half an hour.With the chloroform extraction 2 times reclaimed in embodiment 1, first time, extraction was according to 50-90mL chloroform/mole N-cyanogen imido grpup-S, the amount of S-dithiocarbonic acid dimethyl ester adds, second time extraction is according to 10-30mL/ mole of N-cyanogen imido grpup-S, the amount of S-dithiocarbonic acid dimethyl ester adds, and is merged by the extraction liquid of twice, weigh up chloroform layer weight after extraction, sampling analysis N-cyanogen imido grpup-S, S-dithiocarbonic acid dimethyl ester content.
3,2-cyano group imines-1,3-thiazoles alkane synthesis procedure
According to mass ratio half Guang ammonia hydrochloric acid salt: the ratio of water=1:2 ~ 5 is injected water and passes into nitrogen in reactor, according to mol ratio N-cyanogen imido grpup-S, S-dithiocarbonic acid dimethyl ester: the ratio of half Guang ammonia hydrochloric acid salt=1:1 ~ 2 adds Mercaptamine in still.When being cooled to 0-5 DEG C, according to mol ratio: N-cyanogen imido grpup-S, S-dithiocarbonic acid dimethyl ester: the ratio of sodium hydroxide=1:1 ~ 2 drips the sodium hydroxide solution of 30%wt in still, drips off rear insulation 30-60 minute.N-cyanogen imido grpup-S is dripped, the chloroformic solution of S-dithiocarbonic acid dimethyl ester in still. after adding, clock reaction 2-8 hour.After reaction terminates, drive vacuum pump, close nitrogen, by the regulation system acidity of 20-30%wt hydrochloric acid to pH=2-6, open hot water, lift temperature to 40-60 DEG C, chloroform is steamed.Emptying hot water, water flowing is cooled to 0-10 DEG C, puts into whizzer and dries, imperial material dry 2-4 hour to drying plant.The qualified rear discharging of moisture content, sampling analysis, calculated yield.
4, thiacloprid synthesis procedure
In thiacloprid synthesis reactor, the anhydrous methanol reclaimed in a certain amount of embodiment 1 is squeezed into according to the ratio of 500-1000ml/mol thiazolidine, the 2-cyano group imines-1 of step synthesis in input, 3-thiazolidine, start vacuum pump, according to mol ratio thiazolidine: the ratio of picoline=1:1 ~ 2 is the formaldehyde solution (consumption: 5-10 ‰) (making catalyzer) of 30-40% to suction CCMP in still and mass percent concentration.When passing into steam temperature raising to 40-65 DEG C, drip the liquid caustic soda adjust ph of 30%wt between 7-11, after dripping off, clock reaction 2-4 hour, sampling analysis.After qualified, material is gone to crystallization kettle.Water flowing is cooled to 0-10 DEG C, and feed liquid is put into whizzer, after drying, material is proceeded to washing kettle.By 50-80 DEG C of hot water wash twice, terminate rear centrifuge dripping.Discharging to drying plant, to dry materials 2-5 hour, until moisture qualified (water content≤1%).Cooling discharge.
comparative example 1(benzyl trimethyl ammonium chloride catalyzer)
1, the synthesis procedure of disodium salt
The cyanamide aqueous solution of a certain amount of 30%wt is dropped in reactor, be cooled to 0-10 DEG C, according to mol ratio cyanamide: sodium hydroxide is the sodium hydroxide solution of the 30%wt that the ratio of 1:1.5 ~ 3.5 drips, after dripping off, add the amount of 0.1-2g according to 1mol cyanamide, add a certain amount of benzyl trimethyl ammonium chloride, according to mol ratio cyanamide: the ratio of dithiocarbonic anhydride=1:1 ~ 2 drips dithiocarbonic anhydride, material higher than 20 DEG C, after dripping off, slowly must not be warming up to 20-30 DEG C by dropping temperature.Stirring reaction 10-20 hour at this temperature.After having reacted, stop stirring, leave standstill 2-4 hour, separate unreacted dithiocarbonic anhydride.
After separating dithiocarbonic anhydride, open and stir and temperature of reaction is down to 10-20 DEG C, in still, add hydrochloric acid regulate pH=7-10 in still, still temperature is at 10-30 DEG C. according to mol ratio disodium salt: the ratio of methyl-sulfate=1:1 ~ 3 is added dropwise to methyl-sulfate in still, when the pH value of inspection reaction solution that will be constant after input 2/3 methyl-sulfate, make pH value be held between 7-10, methyl-sulfate is finished.
After finishing, solution is reacted at 10-30 DEG C of temperature substantially constant to pH value half an hour.With chloroform extraction 2 times, first time, extraction was according to 50-90mL chloroform/mole N-cyanogen imido grpup-S, the amount of S-dithiocarbonic acid dimethyl ester adds, second time extraction is according to 10-30mL/ mole of N-cyanogen imido grpup-S, the amount of S-dithiocarbonic acid dimethyl ester adds, and is merged by the extraction liquid of twice, weigh up chloroform layer weight after extraction, sampling analysis N-cyanogen imido grpup-S, S-dithiocarbonic acid dimethyl ester content.
As follows by the diester yield data of benzyl trimethyl ammonium chloride and its brometo de amonio two schemes of four fourths:
Table one: benzyl trimethyl ammonium chloride
| Charging capacity | Diester quality | Two ester contents | Yield |
| 2kmol | 578 | 42% | 83.13% |
| 2kmol | 684 | 37.3% | 87.37% |
| 2kmol | 621 | 40.2% | 85.49% |
| 2kmol | 543 | 44.4% | 82.57% |
| 2kmol | 566 | 45% | 87.22% |
Table two: Tetrabutyl amonium bromide
| Charging capacity | Diester quality | Two ester contents | Yield |
| 2kmol | 676 | 39.2% | 90.75% |
| 2kmol | 631 | 41.5% | 89.68% |
| 2kmol | 572 | 46.3% | 90.7% |
| 2kmol | 546 | 49.2% | 92.0% |
| 2kmol | 541 | 51% | 94.49% |
As can be seen from above table, although benzyl trimethyl ammonium chloride also can be used this reaction, be not as good as Tetrabutyl amonium bromide in effect.
comparative example 2(toluene, ethylene dichloride, methylene dichloride, cyclohexane give extraction solvent)
1, the synthesis procedure of disodium salt
The cyanamide aqueous solution of a certain amount of 1mo 30%wt is dropped in reaction flask, be cooled to 0-10 DEG C, according to mol ratio cyanamide: sodium hydroxide is the sodium hydroxide solution of the 30%wt that the ratio of 1:1.5 ~ 3.5 drips, after dripping off, the amount of 0.1-2g four butyl bromation amine is added according to 1mol cyanamide, add a certain amount of catalyzer, according to mol ratio cyanamide: the ratio of dithiocarbonic anhydride=1:1 ~ 2 drips dithiocarbonic anhydride, dropping temperature must not higher than 20 DEG C, after dripping off, material is slowly warming up to 30-50 DEG C.Stirring reaction 3-10 hour at this temperature.After having reacted, tiny structure distills out unreacted dithiocarbonic anhydride.Distillation terminates, by material through suction filtration tank suction surge tank, by catalyzer elimination.
2, N-cyanogen imido grpup-S, S-dithiocarbonic acid dimethyl ester synthesis procedure
Pour filtrate into flask, be cooled to 10-20 DEG C, in bottle, add hydrochloric acid regulate pH=7-10 in still, still temperature is at 10-30 DEG C. according to mol ratio disodium salt: the ratio of methyl-sulfate=1:1 ~ 3 is added dropwise to methyl-sulfate in bottle, after finishing, solution reacted at 10-30 DEG C of temperature to substantially constant (about needing 2-3 hour) in pH value half an hour.
3, the extraction of diester
After diester has reacted, be that solvent extracts with toluene, ethylene dichloride, methylene dichloride and cyclohexane give respectively.Extraction results is as follows: table three
| Cyanamide charging capacity | Diester yield | Solvent for use | Consume volume |
| 1mol | In 90% | Chloroform | 80ml |
| 1mol | In 90% | Toluene | 210ml |
| 1mol | In 90% | Methylene dichloride | 110ml |
| 1mol | In 90% | Ethylene dichloride | 135ml |
| 1mol | In 90% | Hexanaphthene | Substantially insoluble |
As can be seen from above table: toluene, ethylene dichloride, methylene dichloride all can use as extraction solvent, if but use toluene, these two kinds of solvent extractions of ethylene dichloride, can toluene and ethylene dichloride be brought into the next step, treat that thiazolidine reaction terminates, these two kinds of solvents need be steamed.But the boiling point of these two kinds of solvents is all higher, all higher than 80 DEG C (ethylene dichloride 83.3 DEG C, toluene 110 DEG C).And experiment proves that thiazolidine is higher than being resolvent when 80 DEG C.Therefore to be steamed, not only to consume a large amount of energy, and impact is being had on the yield of next step thiazolidine, therefore can not with these two kinds of solvent extractions.Although the boiling point of methylene dichloride is lower, the solubleness of methylene dichloride in water is 2.5 times of chloroform.Methylene dichloride is being separated in effect not as chloroform as extraction agent.So chloroform is best extraction solvent.
comparative example 3(ethanol as solvent)
4, thiacloprid synthesis procedure
In thiacloprid synthesis reactor, a certain amount of dehydrated alcohol is squeezed into according to the ratio of 500-1000ml/mol thiazolidine, the 2-cyano group imines-1 of step synthesis in input, 3-thiazolidine, start vacuum pump, according to mol ratio thiazolidine: the ratio of picoline=1:1 ~ 2 is the formaldehyde solution (consumption: 5-10 ‰) (making catalyzer) of 30-40% to suction CCMP in still and mass percent concentration.When passing into steam temperature raising to 40-65 DEG C, drip the liquid caustic soda adjust ph of 30%wt between 7-11, after dripping off, clock reaction 2-4 hour, sampling analysis.After qualified, material is gone to crystallization kettle.Water flowing is cooled to 0-10 DEG C, and feed liquid is put into whizzer, after drying, material is proceeded to washing kettle.By 50-80 DEG C of hot water wash twice, terminate rear centrifuge dripping.Discharging to drying plant, to dry materials 2-5 hour, until moisture qualified (water content≤1%).Cooling discharge.With methyl alcohol and ethanol as solvent, the data of gained thiacloprid are as follows:
Table four: use ethanol as solvent
| Thiazolidine throwing amount | Product content | Product yield | Quality product |
| 2kmol | 95.7% | 73.65% | 372.3kg |
| 2kmol | 96.4% | 74.75% | 377.9kg |
| 2kmol | 96.9% | 74.55% | 376.9kg |
| 2kmol | 96.2% | 75.15% | 380kg |
| 2kmol | 96.7% | 75.75% | 382.9kg |
Table five: use methanol as solvent
| Thiazolidine throwing amount | Product content | Product yield | Quality product |
| 2kmol | 97.5% | 79.45% | 401.7kg |
| 2kmol | 97.9% | 80.75% | 408.2kg |
| 2kmol | 98.2% | 80% | 404.6kg |
| 2kmol | 98% | 81.4% | 411.6kg |
| 2kmol | 98.3% | 79.9% | 404kg |
As can be seen from experimental data above: use methanol as solvent, product content can be made to improve 1-2%, make product yield improve 3-5%.Simultaneously from commercially available price, anhydrous methanol price is at about 2500 yuan/ton, and dehydrated alcohol price is at about 6500 yuan/ton.No matter from cost, or from product content and qualitatively, use methyl alcohol all effective than use ethanol.
In sum, four embodiments, only have example one no matter can reach best effect from each step yield, content and cost, can draft as the former medicine production method of the reliable thiacloprid of one.
Claims (3)
1. the production method of the former medicine of thiacloprid, synthesize in the presence of a catalyst for raw material with cyanamide, liquid caustic soda, dithiocarbonic anhydride, be then obtained by reacting N-cyanogen imido grpup-S with methyl-sulfate, S-dithiocarbonic acid dimethyl ester, again with Mercaptamine Reactive Synthesis 2-cyano group imines-1,3-thiazoles alkane; Finally, thiacloprid is reacted to obtain again in a solvent with CCMP, it is characterized in that, in the temperature range of 5 DEG C ~ 20 DEG C, dithiocarbonic anhydride is dropwised, and then temperature reaction, wherein said catalyzer is Tetrabutyl amonium bromide, and by the N-cyanogen imido grpup-S obtained, S-dithiocarbonic acid dimethyl ester is direct after extraction solvent extraction with chloroform and Mercaptamine reacts; Described solvent is methyl alcohol, and described solvent comes into operation after the reaction after rectification process again; Described Tetrabutyl amonium bromide after the completion of reaction filtering separation re-uses; Described extraction solvent reaction terminates rear negative pressure and distillates recovery.
2. the production method of the former medicine of thiacloprid as claimed in claim 1, is characterized in that, synthesis (NaS)
2during C=N-C ≡ N, temperature of reaction is 30 DEG C ~ 60 DEG C reactions; During synthesis thiacloprid, temperature of reaction is the reflux temperature of methyl alcohol.
3. the production method of the former medicine of thiacloprid as claimed in claim 1, is characterized in that, 2-cyano group imines-1,3-thiazoles alkane and CCMP react the temperature of reaction of thiacloprid is the reflux temperature of methyl alcohol.
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| WO2008125410A2 (en) * | 2007-04-12 | 2008-10-23 | Basf Se | Pesticidal mixtures comprising cyanosulfoximine compounds |
| CN101792439A (en) * | 2010-03-25 | 2010-08-04 | 环境保护部南京环境科学研究所 | Method for synthesizing thiacloprid amide by using thiacloprid |
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