CN101973962B - Preparation method of buprofezin - Google Patents
Preparation method of buprofezin Download PDFInfo
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- CN101973962B CN101973962B CN2010105267311A CN201010526731A CN101973962B CN 101973962 B CN101973962 B CN 101973962B CN 2010105267311 A CN2010105267311 A CN 2010105267311A CN 201010526731 A CN201010526731 A CN 201010526731A CN 101973962 B CN101973962 B CN 101973962B
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Abstract
The invention discloses a preparation method of buprofezin, which is characterized in that chlorobenzene is uniformly used as a solvent in all reaction steps requiring the solvent. The preparation method specifically comprises the steps of preparation of isosulfocyanic acid butyl ester, preparation of a 1-isopropyl-3-tert-butyl thiourea solution, preparation of an N-chloromethyl-N-phenyl carbamyl chloride solution and preparation of raw buprofezin powder. In the invention, the chlorobenzene is uniformly used as the solvent in all steps requiring the solvent for preparing the buprofezin so that dangers are reduced in a production process in a production department, the purpose of environmental-friendliness is achieved, and product quality reaches an international standard. The preparation method in the invention is simple, convenient, environmental-friendly and more reasonable, has low cost and high quality, and is more suitable for industrialized production. The total reaction yield of the method can reach more than 68.5% if taking ammonium thiocyanate as reference.
Description
Technical field
The present invention relates to a kind of preparing method's of pesticide material, particularly a kind of PP618 preparation method.
Background technology
The chemistry of PP618 is called 2-tertiary butyl imino--3-sec.-propyl-5-phenyl-1,3, and 5-thiadiazine-4-ketone is a kind of diazthines insect growth regulator(IGR), belongs to the insect molting suppressor factor.Through suppressing the synthetic and interference metabolism of chitin, insect can not normally be casted off a skin with abnormal and dead gradually.Have high reactivity, highly selective, the characteristics in the long longevity of residure.Tool is tagged, stomach poison function is strong, the tool perviousness; Do not kill adult, but can reduce the heterocyclic insect chitin synthetic inhibitor of laying eggs and hindering the ovum hatching.
PP618 is the agricultural insecticide that Coleoptera, part Homoptera and acarina is had the long-lasting larvicidal activity.Can prevent and treat Cicadellidae, Delphacidae on the paddy rice effectively; Cicadellidae on the yam; Aleyrodidae on citrus, cotton and the vegetables; Insects such as a red-spotted lizard section on the citrus, armored scale material and Pseudococcidae.Be applicable to paddy rice, fruit tree, tea tree, vegetable crop.
PP618 reaction equation of the prior art is following:
Consider yield and manufacturing cost, the solvent of synthetic N-chloromethyl-N-phenyl amino formyl chloride is used tetracol phenixin mostly, and the solvent of synthetic PP618 is mostly with toluene or 1, the 2-ethylene dichloride.Country bans use of tetracol phenixin now, and toluene is precursor chemicals, and uses multiple solvent in the production process, is prone to produce industrial accident, brings difficulty both for the buying of raw material, also handles to the three wastes and brings difficulty.
Summary of the invention
Technical problem to be solved by this invention is the deficiency to prior art, and a kind of preparation method of the new PP618 that cost is low, yield is higher is provided, and its technology is easy, and is environmentally friendly.
Technical problem to be solved by this invention is to realize through following technical scheme.The present invention is a kind of preparation method of PP618, is characterized in, need be in the process of preparation PP618 with all reactions step of solvent in the unified chlorobenzene that uses make solvent.Concrete steps are following:
(1) preparation of tert.-butyl isothiocyanate: get ammonium thiocyanide and add in the entry, the weight ratio of ammonium thiocyanide and water is 1:0.5-2, opens to stir to make its dissolving; Add the trimethyl carbinol again, stirred 10-40 minute, the mol ratio of the trimethyl carbinol and ammonium thiocyanide is 1:0.9-1.2; Slowly be warming up to 70-90 ℃, then under the backflow situation, drip technical hydrochloric acid, dripped time 1-3 hour, the mol ratio of the trimethyl carbinol and hydrochloric acid is 1:1-2.0, drips the end back and under the backflow situation, is incubated 2-4 hour; Be cooled to 40-70 ℃ then, layering, acid waste water removes purification tank for liquid waste; The upper strata oil reservoir adds the alkaline aqueous solution washing; The alkaline matter in the alkaline aqueous solution and the mol ratio of the trimethyl carbinol are 1:0.1-0.5, wash to pH6.8-7.2 again, and light yellow oil reservoir liquid comes back in the reaction kettle that the reflux water-dividing system is housed; Intensification refluxes band water until anhydrous, obtains light yellow transparent liquid; In light yellow transparent liquid, adding weight is the lewis acidity catalyzer of the 0.5-5% of the trimethyl carbinol, is warming up to 100-140 ℃, and insulation reaction 3-6 hour, the elimination insolubles obtained tert.-butyl isothiocyanate;
(2) preparation of 1-sec.-propyl-3-tertiary butyl thiourea solution: tert.-butyl isothiocyanate is added in the chlorobenzene, and the weight ratio of tert.-butyl isothiocyanate and chlorobenzene is 1:4-8, stirs 10-40 minute; Be cooled to 0-30 ℃, drip Isopropylamine, the dropping time is 0.5-2 hour; The mol ratio of Isopropylamine and tert.-butyl isothiocyanate is 1:0.9-1.1; Drip off after the Isopropylamine at 20-50 ℃ of insulation reaction 2-6 hour, obtain 1-sec.-propyl-3-tertiary butyl thiourea solution;
(3) preparation of N-chloromethyl-N-phenyl amino formyl chloride solution: methylphenylamine adds in the chlorobenzene, and the weight ratio of methylphenylamine and chlorobenzene is 1:4-7, then stirring and dissolving; Slowly be warming up to 30-60 ℃, begin logical phosgene, do not have methylphenylamine, just stop logical phosgene until gas chromatographic detection; Then begin logical chlorine, when gas chromatographic detection produces N-dichloromethyl-N-phenyl amino formyl chloride, stop logical chlorine; Water circulating vacuum pump is taken out remaining chlorine and hydrogen chloride gas in the dereaction liquid, then boils off the solution that partial solvent obtains N-chloromethyl-N-phenyl amino formyl chloride with Sprengel pump;
(4) preparation of the former powder of PP618: bicarbonate of ammonia adds in the entry, and the weight ratio of bicarbonate of ammonia and water is 1:0.8-1.4, stirring and dissolving; Add in the chlorobenzene again; 1-sec.-propyl-3-the tertiary butyl thiourea solution that adds above-mentioned preparation; Be cooled to 0 ℃, at 0-20 ℃ of solution that drips N-chloromethyl-N-phenyl amino formyl chloride; The mol ratio 3-4:1.0-1.2:1.0 of bicarbonate of ammonia and 1-sec.-propyl-3-tertiary butyl thiocarbamide, N-chloromethyl-N-phenyl amino formyl chloride; The dropping time is 1-2 hour; After the solution of N-chloromethyl-N-phenyl amino formyl chloride drips off, be warming up to 20-50 ℃, insulation reaction 3-6 hour; After insulation finishes, layering; Water layer removes purification tank for liquid waste, adds water in the oil reservoir, the water yield be bicarbonate of ammonia weight 0.8-1.2 doubly, stirred 20-40 minute, secondary clearing again, water layer removes purification tank for liquid waste, oil reservoir removes the molecular distillation still; Under-0.09--1.0MPa in distillating recovering solvent chlorobenzene to the reaction kettle warm 100-120 ℃; Distillation finishes postcooling to 60-90 ℃, add weight and be bicarbonate of ammonia 0.5-0.8 methyl alcohol doubly, then slowly cool to 0-20 ℃, centrifugal, drying obtains PP618.
Among the preparation method of above-described PP618, preferred technical characterictic is:
1, in the step (1), the mol ratio of the trimethyl carbinol and ammonium thiocyanide is 1:0.95-1.1; The mol ratio of the trimethyl carbinol and hydrochloric acid is 1:1.0-1.1.
2, in the step (1), the weight percent concentration of technical hydrochloric acid is 29-36%.
3, in the step (1), the upper strata oil reservoir adds the alkaline aqueous solution washing, washes to pH7.0 again.
4, in the step (1), the washing soda property aqueous solution is the aqueous solution such as sodium hydroxide, yellow soda ash, sodium hydrogencarbonate.
5, in the step (1), described lewis acidity catalyzer is Zinc Chloride Anhydrous, aluminum chloride or iron trichloride; The weight of the lewis acidity catalyzer that in light yellow transparent liquid, adds is the 1-2% of the trimethyl carbinol.
6, in the process of preparation N-chloromethyl-N-phenyl amino formyl chloride and 1-sec.-propyl-3-tertiary butyl thiocarbamide, need not remove solvent, directly be used for next step reaction.
Compared with prior art, all need all use chlorobenzene to make solvent with the place of solvent is unified in preparation PP618 process in the present invention, make to have reduced danger in the production plant production process, and environmentally friendly, quality product has reached international standard.Preparing method's technology of the present invention is more reasonable, easy, and it is low to have a cost, and quality is high, and environmental friendliness is more suitable in suitability for industrialized production.The overall yield of reaction of the inventive method can reach more than 68.5% in ammonium thiocyanide.
Embodiment
Below further describe the concrete technical scheme of the utility model,, and do not constitute restriction its right so that those skilled in the art understands the present invention further.
Embodiment 1.A kind of preparation method of PP618, need be in the process of preparation PP618 with all reactions step of solvent in the unified chlorobenzene that uses make solvent.
Embodiment 2.The preparation method of embodiment 1 described a kind of PP618, concrete steps are following:
(1) preparation of tert.-butyl isothiocyanate: get ammonium thiocyanide and add in the entry, the weight ratio of ammonium thiocyanide and water is 1:0.5, opens to stir to make its dissolving; Add the trimethyl carbinol again, stirred 10 minutes, the mol ratio of the trimethyl carbinol and ammonium thiocyanide is 1:0.9; Slowly be warming up to 70 ℃, then under the backflow situation, drip technical hydrochloric acid, 1 hour dropping time, the mol ratio of the trimethyl carbinol and hydrochloric acid is 1:1, drips the end back and under the backflow situation, is incubated 2 hours; Be cooled to 40 ℃ then, layering, acid waste water removes purification tank for liquid waste; The upper strata oil reservoir adds the alkaline aqueous solution washing; The alkaline matter in the alkaline aqueous solution and the mol ratio of the trimethyl carbinol are 1:0.1, wash to pH6.8 again, and light yellow oil reservoir liquid comes back in the reaction kettle that the reflux water-dividing system is housed; Intensification refluxes band water until anhydrous, obtains light yellow transparent liquid; In light yellow transparent liquid, add weight and be 0.5% lewis acidity catalyzer of the trimethyl carbinol, be warming up to 100 ℃, insulation reaction 3 hours, the elimination insolubles obtains tert.-butyl isothiocyanate;
(2) preparation of 1-sec.-propyl-3-tertiary butyl thiourea solution: tert.-butyl isothiocyanate is added in the chlorobenzene, and the weight ratio of tert.-butyl isothiocyanate and chlorobenzene is 1:4, stirs 10 minutes; Be cooled to 0 ℃, drip Isopropylamine, the dropping time is 0.5 hour; The mol ratio of Isopropylamine and tert.-butyl isothiocyanate is 1:0.9; Drip off after the Isopropylamine 20-50 ℃ of insulation reaction 2 hours, obtain 1-sec.-propyl-3-tertiary butyl thiourea solution;
(3) preparation of N-chloromethyl-N-phenyl amino formyl chloride solution: methylphenylamine adds in the chlorobenzene, and the weight ratio of methylphenylamine and chlorobenzene is 1:4, then stirring and dissolving; Slowly be warming up to 30 ℃, begin logical phosgene, do not have methylphenylamine, just stop logical phosgene until gas chromatographic detection; Then begin logical chlorine, when gas chromatographic detection produces N-dichloromethyl-N-phenyl amino formyl chloride, stop logical chlorine; Water circulating vacuum pump is taken out remaining chlorine and hydrogen chloride gas in the dereaction liquid, then boils off the solution that partial solvent obtains N-chloromethyl-N-phenyl amino formyl chloride with Sprengel pump;
(4) preparation of the former powder of PP618: bicarbonate of ammonia adds in the entry, and the weight ratio of bicarbonate of ammonia and water is 1:0.8, stirring and dissolving; Add in the chlorobenzene again; Be cooled to 0 ℃, at 0 ℃ of solution that drips N-chloromethyl-N-phenyl amino formyl chloride; The mol ratio 3:1.0:1.0 of bicarbonate of ammonia and 1-sec.-propyl-3-tertiary butyl thiocarbamide, N-chloromethyl-N-phenyl amino formyl chloride; The dropping time is 1 hour; After the solution of N-chloromethyl-N-phenyl amino formyl chloride drips off, be warming up to 20 ℃, insulation reaction 3 hours; After insulation finishes, layering; Water layer removes purification tank for liquid waste, adds water in the oil reservoir, and the water yield is 0.8 times of bicarbonate of ammonia weight, stirred 20 minutes, and secondary clearing again, water layer removes purification tank for liquid waste, and oil reservoir removes the molecular distillation still; Under-0.09 MPa in distillating recovering solvent chlorobenzene to the reaction kettle temperature 100 ℃; Distillation finishes postcooling to 60 ℃, add weight and be bicarbonate of ammonia 0.5 times methyl alcohol, then slowly cool to 0 ℃, centrifugal, drying obtains PP618.
Embodiment 3.The preparation method of embodiment 1 described a kind of PP618, concrete steps are following:
(1) preparation of tert.-butyl isothiocyanate: get ammonium thiocyanide and add in the entry, the weight ratio of ammonium thiocyanide and water is 1:2, opens to stir to make its dissolving; Add the trimethyl carbinol again, stirred 40 minutes, the mol ratio of the trimethyl carbinol and ammonium thiocyanide is 1:1.2; Slowly be warming up to 90 ℃, then under the backflow situation, drip technical hydrochloric acid, 3 hours dropping time, the mol ratio of the trimethyl carbinol and hydrochloric acid is 1:2.0, drips the end back and under the backflow situation, is incubated 4 hours; Be cooled to 70 ℃ then, layering, acid waste water removes purification tank for liquid waste; The upper strata oil reservoir adds the alkaline aqueous solution washing; The alkaline matter in the alkaline aqueous solution and the mol ratio of the trimethyl carbinol are 1:0.5, wash to pH7.2 again, and light yellow oil reservoir liquid comes back in the reaction kettle that the reflux water-dividing system is housed; Intensification refluxes band water until anhydrous, obtains light yellow transparent liquid; In light yellow transparent liquid, add weight and be 5% lewis acidity catalyzer of the trimethyl carbinol, be warming up to 140 ℃, insulation reaction 6 hours, the elimination insolubles obtains tert.-butyl isothiocyanate;
(2) preparation of 1-sec.-propyl-3-tertiary butyl thiourea solution: tert.-butyl isothiocyanate is added in the chlorobenzene, and the weight ratio of tert.-butyl isothiocyanate and chlorobenzene is 1:8, stirs 40 minutes; Be cooled to 30 ℃, drip Isopropylamine, the dropping time is 2 hours; The mol ratio of Isopropylamine and tert.-butyl isothiocyanate is 1:1.1; Drip off after the Isopropylamine 50 ℃ of insulation reaction 6 hours, obtain 1-sec.-propyl-3-tertiary butyl thiourea solution;
(3) preparation of N-chloromethyl-N-phenyl amino formyl chloride solution: methylphenylamine adds in the chlorobenzene, and the weight ratio of methylphenylamine and chlorobenzene is 1:7, then stirring and dissolving; Slowly be warming up to 60 ℃, begin logical phosgene, do not have methylphenylamine, just stop logical phosgene until gas chromatographic detection; Then begin logical chlorine, when gas chromatographic detection produces N-dichloromethyl-N-phenyl amino formyl chloride, stop logical chlorine; Water circulating vacuum pump is taken out remaining chlorine and hydrogen chloride gas in the dereaction liquid, then boils off the solution that partial solvent obtains N-chloromethyl-N-phenyl amino formyl chloride with Sprengel pump;
(4) preparation of the former powder of PP618: bicarbonate of ammonia adds in the entry, and the weight ratio of bicarbonate of ammonia and water is 1:1.4, stirring and dissolving; Add in the chlorobenzene again; 1-sec.-propyl-3-the tertiary butyl thiourea solution that adds above-mentioned preparation; Be cooled to 0 ℃, at 20 ℃ of solution that drip N-chloromethyl-N-phenyl amino formyl chloride; The mol ratio 4:1.2:1.0 of bicarbonate of ammonia and 1-sec.-propyl-3-tertiary butyl thiocarbamide, N-chloromethyl-N-phenyl amino formyl chloride; The dropping time is 2 hours; After the solution of N-chloromethyl-N-phenyl amino formyl chloride drips off, be warming up to 50 ℃, insulation reaction 6 hours; After insulation finishes, layering; Water layer removes purification tank for liquid waste, adds water in the oil reservoir, and the water yield is 1.2 times of bicarbonate of ammonia weight, stirred 40 minutes, and secondary clearing again, water layer removes purification tank for liquid waste, and oil reservoir removes the molecular distillation still; 120 ℃ of temperature in distillating recovering solvent chlorobenzene to the reaction kettle under-1.0MPa; Distillation finishes postcooling to 90 ℃, add weight and be bicarbonate of ammonia 0.8 times methyl alcohol, then slowly cool to 20 ℃, centrifugal, drying obtains PP618.
Embodiment 4.The preparation method of embodiment 1 described a kind of PP618, concrete steps are following:
(1) preparation of tert.-butyl isothiocyanate: get ammonium thiocyanide and add in the entry, the weight ratio of ammonium thiocyanide and water is 1:1, opens to stir to make its dissolving; Add the trimethyl carbinol again, stirred 20 minutes, the mol ratio of the trimethyl carbinol and ammonium thiocyanide is 1:1; Slowly be warming up to 80 ℃, then under the backflow situation, drip technical hydrochloric acid, 2 hours dropping time, the mol ratio of the trimethyl carbinol and hydrochloric acid is 1:1.5, drips the end back and under the backflow situation, is incubated 3 hours; Be cooled to 55 ℃ then, layering, acid waste water removes purification tank for liquid waste; The upper strata oil reservoir adds the alkaline aqueous solution washing; The alkaline matter in the alkaline aqueous solution and the mol ratio of the trimethyl carbinol are 1:0.3, wash to pH7.0 again, and light yellow oil reservoir liquid comes back in the reaction kettle that the reflux water-dividing system is housed; Intensification refluxes band water until anhydrous, obtains light yellow transparent liquid; In light yellow transparent liquid, add weight and be 2% lewis acidity catalyzer of the trimethyl carbinol, be warming up to 120 ℃, insulation reaction 4.5 hours, the elimination insolubles obtains tert.-butyl isothiocyanate;
(2) preparation of 1-sec.-propyl-3-tertiary butyl thiourea solution: tert.-butyl isothiocyanate is added in the chlorobenzene, and the weight ratio of tert.-butyl isothiocyanate and chlorobenzene is 1:6, stirs 25 minutes; Be cooled to 15 ℃, drip Isopropylamine, the dropping time is 1 hour; The mol ratio of Isopropylamine and tert.-butyl isothiocyanate is 1:1; Drip off after the Isopropylamine 35 ℃ of insulation reaction 4 hours, obtain 1-sec.-propyl-3-tertiary butyl thiourea solution;
(3) preparation of N-chloromethyl-N-phenyl amino formyl chloride solution: methylphenylamine adds in the chlorobenzene, and the weight ratio of methylphenylamine and chlorobenzene is 1:5, then stirring and dissolving; Slowly be warming up to 45 ℃, begin logical phosgene, do not have methylphenylamine, just stop logical phosgene until gas chromatographic detection; Then begin logical chlorine, when gas chromatographic detection produces N-dichloromethyl-N-phenyl amino formyl chloride, stop logical chlorine; Water circulating vacuum pump is taken out remaining chlorine and hydrogen chloride gas in the dereaction liquid, then boils off the solution that partial solvent obtains N-chloromethyl-N-phenyl amino formyl chloride with Sprengel pump;
(4) preparation of the former powder of PP618: bicarbonate of ammonia adds in the entry, and the weight ratio of bicarbonate of ammonia and water is 1:1.2, stirring and dissolving; Add in the chlorobenzene again; 1-sec.-propyl-3-the tertiary butyl thiourea solution that adds above-mentioned preparation; Be cooled to 0 ℃, at 10 ℃ of solution that drip N-chloromethyl-N-phenyl amino formyl chloride; The mol ratio 3.5:1.1:1.0 of bicarbonate of ammonia and 1-sec.-propyl-3-tertiary butyl thiocarbamide, N-chloromethyl-N-phenyl amino formyl chloride; The dropping time is 1.5 hours; After the solution of N-chloromethyl-N-phenyl amino formyl chloride drips off, be warming up to 35 ℃, insulation reaction 4 hours; After insulation finishes, layering; Water layer removes purification tank for liquid waste, adds water in the oil reservoir, and the water yield is 1.0 times of bicarbonate of ammonia weight, stirred 30 minutes, and secondary clearing again, water layer removes purification tank for liquid waste, and oil reservoir removes the molecular distillation still; 110 ℃ of temperature in distillating recovering solvent chlorobenzene to the reaction kettle under-0.5MPa; Distillation finishes postcooling to 75 ℃, add weight and be bicarbonate of ammonia 0.65 times methyl alcohol, then slowly cool to 10 ℃, centrifugal, drying obtains PP618.
Embodiment 5.In the preparing method's of embodiment 2 described PP618s the step (1), the mol ratio of the trimethyl carbinol and ammonium thiocyanide is 1:0.95; The mol ratio of the trimethyl carbinol and hydrochloric acid is 1:1.1.
Embodiment 6.In the preparing method's of any one described PP618 of embodiment 2-4 the step (1), the weight percent concentration of technical hydrochloric acid is 29-36%.
Embodiment 7.In the preparing method's of any one described PP618 of embodiment 2-4 the step (1), the washing soda property aqueous solution is sodium hydroxide, yellow soda ash or sodium bicarbonate aqueous solution.
Embodiment 8.In the preparing method's of any one described PP618 of embodiment 2-4 the step (1), described lewis acidity catalyzer is Zinc Chloride Anhydrous, aluminum chloride or iron trichloride; The weight of the lewis acidity catalyzer that in light yellow transparent liquid, adds is the 1-2% of the trimethyl carbinol.
Embodiment 9.Preparing method's experiment of PP618.
Experiment one.Preparing method's experiment of the PP618 that carries out with the inventive method.
Tap funnel is being housed and is stirring in the 250ml four-hole bottle, adding entry 35g and ammonium thiocyanide 40g, opening stirring, the dissolving back adds the 50g trimethyl carbinol, then slowly is warming up to 80 ℃; And, about 1 hour of dropping time, then under this temperature, be incubated 3 hours at the dripping hydrochloric acid 70g down that refluxes.
Insulation is cooled to 50 ℃ after finishing; Layering, acid waste water goes wastewater treatment, and the upper strata oil reservoir adds the saturated aqueous solution of sodium bicarbonate washing; Wash again to the PH7; Light yellow oil reservoir liquid comes back in the four-hole reaction flask that the reflux water-dividing system is housed, and heats up to reflux band water until anhydrous, obtains light yellow transparent liquid.
Above-mentioned gained liquid is cooled to 80 ℃, then adds catalyzer 1.0g Zinc Chloride Anhydrous, and obtained the 52.4g tert.-butyl isothiocyanate in 4 hours 100 ℃ of insulation reaction.
In the 250ml four-hole bottle of whisking appliance, TM and tap funnel is housed, add 30 gram tert.-butyl isothiocyanates, chlorobenzene 100ml opens stirring, is cooled to 0 ℃, drips Isopropylamine 15 grams.Drip and finish, be warming up to 30 ℃, continue insulation 5 hours, obtain the chlorobenzene solution of 1-sec.-propyl-3-tertiary butyl thiocarbamide.Subsequent use.
In the 250ml four-hole bottle of exhaust treatment system and whisking appliance, TM is housed, add methylphenylamine 20 grams and chlorobenzene 140 grams, open stirring; Be warming up to 50 ℃; Begin logical phosgene, do not have methylphenylamine, just stop logical phosgene until gas chromatographic detection; Begin logical chlorine, when gas chromatographic detection produces N-dichloromethyl-N-phenyl amino formyl chloride, stop logical chlorine.Water circulating vacuum pump is taken out remaining chlorine and hydrogen chloride gas in the dereaction liquid, then boils off chlorobenzene with Sprengel pump and obtains N-chloromethyl-N-phenyl amino formyl chloride 36.2 grams.
In the 500ml reaction flask, add entry 40 grams, bicarbonate of ammonia 60 grams; Add above-mentioned 1-sec.-propyl-3-tertiary butyl thiocarbamide chlorobenzene solution after the stirring and dissolving; Stir half a hour, and be cooled to 0 ℃, the solution that beginning Dropwise 50 gram muriate and 40 gram chlorobenzenes are formed; Finish and be warming up to 35 ℃, and 40 ℃ of insulation reaction 5 hours.Then carry out layering, washing, the vacuum distilling precipitation is finished, and cooling adding methyl alcohol 50 restrains slightly, dissolving, crystallisation by cooling filters, and is dry that PP618 49 restrains content 96.5%.
Experiment two.Preparing method's experiment of the PP618 that carries out with the inventive method.
Have tap funnel and stirring in the 100ml four-hole bottle, adding entry 150g and ammonium thiocyanide 150g, opening stirring, the dissolving back adds the 135g trimethyl carbinol, then slowly is warming up to 80 ℃; And, about 1 hour of dropping time, then under this temperature, be incubated 3 hours at the dripping hydrochloric acid 300g down that refluxes.
Insulation is cooled to 60 ℃ after finishing; Layering, acid waste water goes wastewater treatment, the washing of upper strata oil reservoir hydro-oxidation sodium water solution; Wash again to the PH7; Light yellow oil reservoir liquid comes back in the four-hole reaction flask that the reflux water-dividing system is housed, and heats up to reflux band water until anhydrous, obtains light yellow transparent liquid.
Above-mentioned gained liquid is cooled to 80 ℃, then adds catalyzer 5.0g Zinc Chloride Anhydrous, and obtained the 209g tert.-butyl isothiocyanate in 4 hours 100 ℃ of insulation reaction.
In the 1000ml four-hole bottle of whisking appliance, TM and tap funnel is housed, add 120 gram tert.-butyl isothiocyanates, chlorobenzene 500ml opens stirring, is cooled to 0 ℃, drips Isopropylamine 65 grams.Drip and finish, be warming up to 40 ℃, continue insulation 5 hours, obtain the chlorobenzene solution of 1-sec.-propyl-3-tertiary butyl thiocarbamide.Subsequent use.
In the 1000ml four-hole bottle of exhaust treatment system and whisking appliance, TM is housed, add methylphenylamine 90 grams and chlorobenzene 600 grams, open stirring; Be warming up to 60 ℃; Begin logical phosgene, do not have methylphenylamine, just stop logical phosgene until gas chromatographic detection; Begin logical chlorine, when gas chromatographic detection produces N-dichloromethyl-N-phenyl amino formyl chloride, stop logical chlorine.Water circulating vacuum pump is taken out remaining chlorine and hydrogen chloride gas in the dereaction liquid, then boils off the chlorobenzene solution that the part chlorobenzene obtains N-chloromethyl-N-phenyl amino formyl chloride with vacuum pump.Subsequent use.
In the 1000ml reaction flask, add entry 250 grams, bicarbonate of ammonia 250 grams; Add above-mentioned 1-sec.-propyl-3-tertiary butyl thiocarbamide chlorobenzene solution after the stirring and dissolving; Stir half a hour, and be cooled to 0 ℃, begin to drip the chlorobenzene solution of N-chloromethyl-N-phenyl amino formyl chloride; Finish and be warming up to 40 ℃, and 50 ℃ of insulation reaction 5 hours.Then carry out layering, washing, the vacuum distilling precipitation is finished, and cooling adding methyl alcohol 200 restrains slightly, dissolving, crystallisation by cooling filters, and is dry that PP618 201 restrains content 97.2%.
Experiment three, contrast experiment.
Have tap funnel and stirring in the 250ml four-hole bottle, adding entry 35g and ammonium thiocyanide 40g, opening stirring, the dissolving back adds the 50g trimethyl carbinol, then slowly is warming up to 80 ℃; And, about 1 hour of dropping time, then under this temperature, be incubated 3 hours at the dripping hydrochloric acid 70g down that refluxes.
Insulation is cooled to 50 ℃ after finishing; Layering, acid waste water goes wastewater treatment, and the upper strata oil reservoir adds the saturated aqueous solution of sodium bicarbonate washing; Wash again to the PH7; Light yellow oil reservoir liquid comes back in the four-hole reaction flask that the reflux water-dividing system is housed, and heats up to reflux band water until anhydrous, obtains light yellow transparent liquid.
Above-mentioned gained liquid is cooled to 80 ℃, then adds catalyzer 1.0g Zinc Chloride Anhydrous, and obtained the 52.4g tert.-butyl isothiocyanate in 4 hours 100 ℃ of insulation reaction.
In having the 250ml four-hole bottle of whisking appliance, TM and tap funnel, add 30 gram tert.-butyl isothiocyanates, toluene 100ml opens stirring, is cooled to 0 ℃, drips Isopropylamine 15 grams.Drip and finish, be warming up to 30 ℃, continue insulation 5 hours, be cooled to the 10 ℃ of centrifugal 1-of obtaining sec.-propyls-3-tertiary butyl thiocarbamide 44.2 grams.
In having the 250ml four-hole bottle of exhaust treatment system, whisking appliance, TM and reflux exchanger, add methylphenylamine 20 grams and tetracol phenixin 200 grams, open stirring; Be warming up to 50 ℃, open water coolant, begin logical phosgene; There is not methylphenylamine until gas chromatographic detection; Just stop logical phosgene, then begin logical chlorine, when gas chromatographic detection produces N-dichloromethyl-N-phenyl amino formyl chloride, stop logical chlorine.Water circulating vacuum pump is taken out remaining chlorine and hydrogen chloride gas in the dereaction liquid, then boils off tetracol phenixin with Sprengel pump and obtains N-chloromethyl-N-phenyl amino formyl chloride 36.2 grams.
In the 500ml reaction flask, add entry 40 grams, bicarbonate of ammonia 60 grams, add 1 after the stirring and dissolving, 2-ethylene dichloride 50 grams and 1-sec.-propyl-3-tertiary butyl thiocarbamide 50 grams; Stir half a hour; And be cooled to 0 ℃, muriatic 100 grams 1 of beginning Dropwise 50 gram, 2-ethylene dichloride; Finish and be warming up to 35 ℃, and 40 ℃ of insulation reaction 5 hours.Then carry out layering, washing, the vacuum distilling precipitation is finished, and cooling adding methyl alcohol 50 restrains slightly, dissolving, crystallisation by cooling filters, and is dry that PP618 48 restrains content 97.5%.
Compare and can find out through above-mentioned experiment, technology of the present invention need not filter out 1-sec.-propyl-3-tertiary butyl thiocarbamide, and the solvent in N-chloromethyl-N-phenyl amino formyl chloride does not need all to steam, so only need adopt the conventional vacuum pump.
And 1-sec.-propyl in the simultaneous test-3-tertiary butyl thiocarbamide must be centrifugal or filters out, and the gas that is produced when centrifugal is inflammable, smell is choked the people very much; And need a large amount of human and material resources of cost.And the solvent in N-chloromethyl-N-phenyl amino formyl chloride must all boil off, in order to avoid be to contain two kinds of compositions in the recovered solvent doing PP618.So need to use Sprengel pump, purchase, the Abschreibungskosten of equipment are higher.
Claims (6)
1. the preparation method of a PP618 is characterized in that: the unified chlorobenzene that uses is made solvent in need be with all reactions step of solvent in the process of preparation PP618; Concrete steps are following:
(1) preparation of tert.-butyl isothiocyanate: get ammonium thiocyanide and add in the entry, the weight ratio of ammonium thiocyanide and water is 1: 0.5-2, open stirring and make its dissolving; Add the trimethyl carbinol again, stirred 10-40 minute, the mol ratio of the trimethyl carbinol and ammonium thiocyanide is 1: 0.9-1.2; Slowly be warming up to 70-90 ℃, then under the backflow situation, drip technical hydrochloric acid, dripped time 1-3 hour, the mol ratio of the trimethyl carbinol and hydrochloric acid is 1: 1.0-2.0 drips the end back and under the backflow situation, is incubated 2-4 hour; Be cooled to 40-70 ℃ then, layering, acid waste water removes purification tank for liquid waste; The upper strata oil reservoir adds the alkaline aqueous solution washing; The alkaline matter in the alkaline aqueous solution and the mol ratio of the trimethyl carbinol are 1: 0.1-0.5, to wash again to pH6.8-7.2, and light yellow oil reservoir liquid comes back in the reaction kettle that the reflux water-dividing system is housed; Intensification refluxes band water until anhydrous, obtains light yellow transparent liquid; In light yellow transparent liquid, adding weight is the lewis acidity catalyzer of the 0.5-5% of the trimethyl carbinol, is warming up to 100-140 ℃, and insulation reaction 3-6 hour, the elimination insolubles obtained tert.-butyl isothiocyanate;
(2) preparation of 1-sec.-propyl-3-tertiary butyl thiourea solution: tert.-butyl isothiocyanate is added in the chlorobenzene, and tert.-butyl isothiocyanate and chlorobenzene weight ratio are 1: 4-8, stirred 10-40 minute; Be cooled to 0-30 ℃, drip Isopropylamine, the dropping time is 0.5-2 hour; The mol ratio of Isopropylamine and tert.-butyl isothiocyanate is 1: 0.9-1.1; Drip off after the Isopropylamine at 20-50 ℃ of insulation reaction 2-6 hour, obtain 1-sec.-propyl-3-tertiary butyl thiourea solution;
(3) preparation of N-chloromethyl-N-phenyl amino formyl chloride solution: methylphenylamine adds in the chlorobenzene, and the weight ratio of methylphenylamine and chlorobenzene is 1: 4-7, then stirring and dissolving; Slowly be warming up to 30-60 ℃, begin logical phosgene, do not have methylphenylamine, just stop logical phosgene until gas chromatographic detection; Then begin logical chlorine, when gas chromatographic detection produces N-dichloromethyl-N-phenyl amino formyl chloride, stop logical chlorine; Water circulating vacuum pump is taken out remaining chlorine and hydrogen chloride gas in the dereaction liquid, then boils off the solution that partial solvent obtains N-chloromethyl-N-phenyl amino formyl chloride with vacuum pump;
(4) preparation of the former powder of PP618: bicarbonate of ammonia adds in the entry, and the weight ratio of bicarbonate of ammonia and water is 1: 0.8-1.4, stirring and dissolving; Add in the chlorobenzene again; 1-sec.-propyl-3-the tertiary butyl thiourea solution that adds above-mentioned preparation; Be cooled to 0 ℃, at 0-20 ℃ of solution that drips N-chloromethyl-N-phenyl amino formyl chloride; The mol ratio 3-4 of bicarbonate of ammonia and 1-sec.-propyl-3-tertiary butyl thiocarbamide, N-chloromethyl-N-phenyl amino formyl chloride: 1.0-1.2: 1.0; The dropping time is 1-2 hour; After the solution of N-chloromethyl-N-phenyl amino formyl chloride drips off, be warming up to 20-50 ℃, insulation reaction 3-6 hour; After insulation finishes, layering; Water layer removes purification tank for liquid waste, adds water in the oil reservoir, the water yield be bicarbonate of ammonia weight 0.8-1.2 doubly, stirred 20-40 minute, secondary clearing again, water layer removes purification tank for liquid waste, oil reservoir removes the molecular distillation still; Under-0.09--1.0MPa in distillating recovering solvent chlorobenzene to the reaction kettle warm 100-120 ℃; Distillation finishes postcooling to 60-90 ℃, and adding weight is the 0.5-0.8 methyl alcohol doubly of bicarbonate of ammonia, then slowly cools to 0-20 ℃, and centrifugal, drying obtains PP618.
2. the preparation method of PP618 according to claim 1, it is characterized in that: in the step (1), the mol ratio of the trimethyl carbinol and ammonium thiocyanide is 1: 0.95-1.1; The mol ratio of the trimethyl carbinol and hydrochloric acid is 1: 1.0-1.2.
3. the preparation method of PP618 according to claim 1, it is characterized in that: in the step (1), the weight percent concentration of technical hydrochloric acid is 29-36%.
4. the preparation method of PP618 according to claim 1 is characterized in that: in the step (1), the upper strata oil reservoir adds the alkaline aqueous solution washing, washes to pH7.0 again.
5. the preparation method of PP618 according to claim 1, it is characterized in that: in the step (1), the washing soda property aqueous solution is the aqueous solution of sodium hydroxide, yellow soda ash or sodium hydrogencarbonate.
6. the preparation method of PP618 according to claim 1, it is characterized in that: in the step (1), described lewis acidity catalyzer is Zinc Chloride Anhydrous, aluminum chloride or iron trichloride; The weight of the lewis acidity catalyzer that in light yellow transparent liquid, adds is the 1-2% of the trimethyl carbinol.
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| CN103214400B (en) * | 2013-04-15 | 2014-12-31 | 衢州学院 | Preparation method of hexaflumuron |
| CN105017114B (en) * | 2014-04-30 | 2017-01-11 | 连云港市金囤农化有限公司 | Preparation method of 1-isopropyl-3-tert-butylthiourea |
| CN108530388A (en) * | 2018-03-28 | 2018-09-14 | 江苏安邦电化有限公司 | A kind of preparation method of Buprofezin |
| CN112625005A (en) * | 2020-12-24 | 2021-04-09 | 安道麦安邦(江苏)有限公司 | Method and device for improving yield of pediculicide and environmental friendliness |
| CN112694419A (en) * | 2020-12-25 | 2021-04-23 | 安道麦安邦(江苏)有限公司 | Synthesis process and synthesis equipment for mixture of buprofezin intermediate tert-butyl thiocyanate and tert-butyl isocyanate |
| CN112724056A (en) * | 2020-12-28 | 2021-04-30 | 安道麦安邦(江苏)有限公司 | Method and device for effectively utilizing buprofezin intermediate 1-isopropyl-3-tert-butylthiourea mother liquor to improve yield |
| CN113651771A (en) * | 2021-08-10 | 2021-11-16 | 安徽广信农化股份有限公司 | Synthesis method of combined buprofezin |
| CN113717126B (en) * | 2021-09-08 | 2023-08-01 | 安徽广信农化股份有限公司 | Buprofezin medicament for killing insects and production process thereof |
| CN114573487A (en) * | 2022-03-11 | 2022-06-03 | 南京先进生物材料与过程装备研究院有限公司 | Method for preparing butylpropylthiourea |
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