CN101993401B - Preparation method of 1-isopropyl-3-tertiary butyl thiocarbamide - Google Patents
Preparation method of 1-isopropyl-3-tertiary butyl thiocarbamide Download PDFInfo
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- CN101993401B CN101993401B CN201010523124XA CN201010523124A CN101993401B CN 101993401 B CN101993401 B CN 101993401B CN 201010523124X A CN201010523124X A CN 201010523124XA CN 201010523124 A CN201010523124 A CN 201010523124A CN 101993401 B CN101993401 B CN 101993401B
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- tertiary butyl
- thiocarbamide
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Abstract
The invention relates to a preparation method of 1-isopropyl-3-tertiary butyl thiocarbamide, which is characterized by using chlorobenzene as a solvent in the process of preparing the 1-isopropyl-3-tertiary butyl thiocarbamide. The method comprises the following concrete steps: adding tert-butyl isothiocyanate to the chlorobenzene and stirring; cooling, dropwise adding isopropylamine, and insulating and reacting after dropwise adding the isopropylamine to obtain the solution of the 1-isopropyl-3-tertiary butyl thiocarbamide; and after cooling, centrifuging and drying to obtain the 1-isopropyl-3-tertiary butyl thiocarbamide. The invention has safer and simpler technological operation, no three wastes and high yield, and is more environment-friendly and more suitable for industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of pesticide intermediate, the preparation method of particularly a kind of 1-sec.-propyl-3-tertiary butyl thiocarbamide.
Background technology
1-sec.-propyl-3-tertiary butyl thiocarbamide is the key intermediate of preparation PP618, and 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.
The building-up reactions equation of 1-sec.-propyl of the prior art-3-tertiary butyl thiocarbamide is:
Consider yield and manufacturing cost, the solvent of synthetic 1-sec.-propyl-3-tertiary butyl thiocarbamide is used toluene mostly, and 1,2-ethylene dichloride or solvent oil.And toluene is precursor chemicals, and the vp of these several kinds of solvents is all higher, therefore is prone to produce industrial accident, 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, provides a kind of cost low, the preparation method of 1-sec.-propyl-3-tertiary butyl thiocarbamide that yield is higher.
Technical problem to be solved by this invention is to realize through following technical scheme.The present invention is the preparation method of a kind of 1-sec.-propyl-3-tertiary butyl thiocarbamide, is characterized in: in the preparation process of 1-sec.-propyl-3-tertiary butyl thiocarbamide, use chlorobenzene to make solvent.
Technical problem to be solved by this invention can also further realize through following technical scheme.Above-described preparation method is characterized in, its concrete steps are following: 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 the solution of 1-sec.-propyl-3-tertiary butyl thiocarbamide; Centrifugal after being cooled to 0-20 ℃, drying obtains 1-sec.-propyl-3-tertiary butyl thiocarbamide.
Technical problem to be solved by this invention can also further realize through following technical scheme.Above-described preparation method is characterized in: 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 the solution of 1-sec.-propyl-3-tertiary butyl thiocarbamide; Centrifugal after being cooled to 10 ℃, drying obtains 1-sec.-propyl-3-tertiary butyl thiocarbamide.
Compared with prior art,, make and reduced danger in the production plant production process because the present invention used chlorobenzene to make solvent in reaction, operation safe, environmentally friendly, quality product has reached international standard.And synthesis technique of the present invention is more reasonable, and it is low to have a cost, and quality is high, and the overall yield of reaction of this method can reach more than 76.5% in ammonium thiocyanide, is more suitable in suitability for industrialized production.
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.The preparation method of a kind of 1-sec.-propyl-3-tertiary butyl thiocarbamide in the preparation process of 1-sec.-propyl-3-tertiary butyl thiocarbamide, uses chlorobenzene to make solvent.
Embodiment 2.Among the embodiment 1 described preparation method, its concrete steps are following: 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 ℃ of insulation reaction 2 hours, obtain the solution of 1-sec.-propyl-3-tertiary butyl thiocarbamide; Centrifugal after being cooled to 0 ℃, drying obtains 1-sec.-propyl-3-tertiary butyl thiocarbamide.
Embodiment 3.Among the embodiment 1 described preparation method, its concrete steps are following: 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 the solution of 1-sec.-propyl-3-tertiary butyl thiocarbamide; Centrifugal after being cooled to 20 ℃, drying obtains 1-sec.-propyl-3-tertiary butyl thiocarbamide.
Embodiment 4.Among the embodiment 1 described preparation method, its concrete steps are following: 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 the solution of 1-sec.-propyl-3-tertiary butyl thiocarbamide; Centrifugal after being cooled to 10 ℃, drying obtains 1-sec.-propyl-3-tertiary butyl thiocarbamide.
Embodiment 5.The preparation experiment of 1-sec.-propyl-3-tertiary butyl thiocarbamide.
Experiment one.Adopt the inventive method to carry out the preparation of 1-sec.-propyl-3-tertiary butyl thiocarbamide.
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, centrifugal 1-sec.-propyl-3-tertiary butyl thiocarbamide 45.5 grams that obtain, chlorobenzene is used for next batch.
Experiment two.Adopt the inventive method to carry out the preparation of 1-sec.-propyl-3-tertiary butyl thiocarbamide.
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, centrifugal 1-sec.-propyl-3-tertiary butyl thiocarbamide 180 grams that obtain, chlorobenzene is used for next batch.
Experiment three.The 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.
Can find out from above experiment contrast; Because the boiling point of chlorobenzene is than toluene high (132.2 ℃＞110.6 ℃); Saturation steam pressure ratio toluene low (1.33 kPa＜9.970 kPa) in the time of 20 ℃, flash-point are than toluene high (28 ℃＞4 ℃), so the dangerous chlorobenzene of producing is lower than toluene.
Claims (1)
1. the preparation method of 1-sec.-propyl-3-tertiary butyl thiocarbamide is characterized in that: in the preparation process of 1-sec.-propyl-3-tertiary butyl thiocarbamide, use chlorobenzene to make solvent; Its concrete steps are following: 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 the solution of 1-sec.-propyl-3-tertiary butyl thiocarbamide; Centrifugal after being cooled to 10 ℃, drying obtains 1-sec.-propyl-3-tertiary butyl thiocarbamide.
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| CN201010523124XA CN101993401B (en) | 2010-10-28 | 2010-10-28 | Preparation method of 1-isopropyl-3-tertiary butyl thiocarbamide |
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| 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 |
| CN114150335B (en) * | 2021-08-20 | 2022-12-06 | 韶关学院 | Electrochemical method for preparing thiourea compound by using tertiary amine |
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