CN108530388A - A kind of preparation method of Buprofezin - Google Patents
A kind of preparation method of Buprofezin Download PDFInfo
- Publication number
- CN108530388A CN108530388A CN201810262751.9A CN201810262751A CN108530388A CN 108530388 A CN108530388 A CN 108530388A CN 201810262751 A CN201810262751 A CN 201810262751A CN 108530388 A CN108530388 A CN 108530388A
- Authority
- CN
- China
- Prior art keywords
- added
- preparation
- buprofezin
- water
- tert
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/15—Six-membered rings
- C07D285/16—Thiadiazines; Hydrogenated thiadiazines
- C07D285/34—1,3,5-Thiadiazines; Hydrogenated 1,3,5-thiadiazines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of preparation methods of Buprofezin, including step 1）：Sodium sulfocyanate and water are added in esterifying kettle to dissolving；It adds the tert-butyl alcohol and hydrochloric acid obtains mixed ester, then tert-butyl isothiocyanate is obtained by the reaction through indexing and catalysis；Step 2）：Tert-butyl isothiocyanate is added in chlorobenzene and is stirred, isopropylamine is added dropwise, obtains 1 isopropyl, 3 tertiary butyl thiocarbamide solution；Step 3）：N methylanilines are added in chlorobenzene；Sequentially thang-kng gas and chlorine obtain the solution of N chloromethyl N phenyl amino formyl chlorides；Step 4）：Sodium bicarbonate is added to the water, and adds in chlorobenzene；1 isopropyl, 3 tertiary butyl thiocarbamide solution is added；The solution of N chloromethyl N phenyl amino formyl chlorides is added dropwise, chlorobenzene is boiled off by filtering, layering, high vacuum, then it is crystallized, centrifuge, be dried to obtain Buprofezin.Average yield is replaced to reach 90% or more in the preparation process of the Buprofezin of the application, finished product Buprofezin content generates in preparation process without ammonia nitrogen waste water up to 98.0% or more.
Description
Technical field
The invention belongs to chemical products synthesis technical fields, and in particular to a kind of preparation method of Buprofezin.
Background technology
The chemical name of Buprofezin is 2- tertiary butyl imino group -3- isopropyl -5- phenyl -1,3, and 5- thiadiazine -4- ketone divides
Minor is C16H23N3OS, is a kind of heterocyclic Chitin synthesis inhibitor, and the newborn epidermis for destroying insect is formed, interference
The normal growth and development of insect causes pest dead.Tool is tagged, stomach poison function is strong, has permeability.Adult is not killed, but can be reduced
It lays eggs and hinders egg hatching.
The preparation process of Buprofezin prepares isothiocyanic acid uncle using ammonium thiocyanate and the tert-butyl alcohol as raw material first in the prior art
Butanol is condensed finally by ammonium hydrogencarbonate and Buprofezin is made by esterification, indexing, addition, chlorination and photochemical；Due to thiocyanic acid
Ammonium and ammonium hydrogencarbonate use so that generate a large amount of ammonia nitrogen waste water in Buprofezin production process, and due to the high ammonia nitrogen of the waste water,
High COD, with high salt, intractability is larger, manufacturing enterprise mostly use it is clear under water-reducible method it is up to standard after outer row, do not reduce total discharge
Amount, to environmental effects.
Invention content
Based on the above prior art, the purpose of the present invention is to provide a kind of preparation methods of Buprofezin, are given birth in Buprofezin
Ammonium thiocyanate is substituted using sodium sulfocyanate during production, ammonium hydrogen carbonate is substituted using sodium bicarbonate, to reduce ammonia nitrogen waste water production
It is raw.
In order to achieve the goal above, the technical solution adopted by the present invention is：
A kind of preparation method of Buprofezin, includes the following steps：
Step 1)：The preparation of tert-butyl isothiocyanate
Sodium sulfocyanate and water are added in esterifying kettle, stirring makes sodium sulfocyanate be completely dissolved；It is equal to add tert-butyl alcohol stirring
It is even；It is to slowly warm up to 70-90 DEG C, technical hydrochloric acid is added dropwise in reflux, 2-4 hours are kept the temperature in reflux after completion of dropwise addition；
Then it is cooled to 40-70 DEG C, layering, acid waste water goes purification tank for liquid waste, upper layer oil reservoir that alkaline aqueous solution is added to wash, then carries out water
It is 6.8-7.2 to be washed till pH, and light yellow oil reservoir liquid comes back in the reaction kettle equipped with reflux water-dividing system, and heating flows back
It is with water until anhydrous, obtain light yellow clear liquid；Lewis acidity catalyst is added into light yellow clear liquid, is warming up to
100-140 DEG C, insulation reaction 3-6 hours filters off insoluble matter, obtains tert-butyl isothiocyanate；
Step 2)：The preparation of 1- isopropyl -3- tertiary butyl thiocarbamide solution
Tert-butyl isothiocyanate is added in chlorobenzene and is stirred 10-40 minutes；It is cooled to 0-30 DEG C, isopropylamine is added dropwise, is added dropwise
Time is 0.5-2 hours；It drips off after isopropylamine in 20-50 DEG C of insulation reaction 2-6 hours, obtains 1- isopropyl -3- tertiary butyl sulphur
Urea solution；
Step 3)：The preparation of N- chloromethyl-N-phenyl amino formyl chloride solution
Methylphenylamine is added in chlorobenzene, stirring and dissolving；It is to slowly warm up to 30-60 DEG C, starts thang-kng gas, until gas phase color
Spectrum detection just stops thang-kng gas without methylphenylamine；Then start logical chlorine, until gas chromatographic detection generates N- dichloromethanes
Stop leading to chlorine when base-N- phenyl amino formyl chlorides；Remaining chlorine and hydrogen chloride gas in reaction solution are pumped with water circulation vavuum pump, is connect
It and boils off partial solvent with high-vacuum pump and obtain the solution of N- chloromethyl-N-phenyl amino formyl chlorides；
Step 4)：The preparation of Buprofezin original powder
Sodium bicarbonate is added to the water, and stirring makes sodium bicarbonate dissolve；It adds in chlorobenzene；Above-mentioned steps 2 are added) prepare
1- isopropyl -3- tertiary butyl thiocarbamide solution；It is cooled to 0 DEG C, the molten of N- chloromethyl-N-phenyl amino formyl chlorides is added dropwise at 0-20 DEG C
Liquid, time for adding are 1-2 hours；After the solution of N- chloromethyl-N-phenyl amino formyl chlorides drips off, it is warming up to 20-50 DEG C, heat preservation
Reaction 3-6 hours；After heat preservation, layering；Water layer removes purification tank for liquid waste, and it is sodium bicarbonate weight that water, water are added in oil reservoir
It 0.8-1.2 times, stirs 20-40 minutes, then secondary clearing, water layer go purification tank for liquid waste, oil reservoir to remove high vacuum distillation kettle；(-
0.09) 100-120 DEG C of temperature in solvent chlorobenzene to reaction kettle is distilled to recover under-(- 1.0MPa)；60-90 is cooled to after distillation
DEG C, 0.5-0.8 times of the methanol that weight is sodium bicarbonate is added, then slowly cools to 0-20 DEG C, centrifuges, is dried to obtain thiophene
Piperazine ketone.
Further, the molar ratio of sodium sulfocyanate, the tert-butyl alcohol and hydrochloric acid is 1 in the step 1)：(0.8-1.2)：(1-
2.0)。
Further, the mass ratio of tert-butyl isothiocyanate and chlorobenzene is 1 in the step 2):(5-7).
Further, the molar ratio of isopropylamine and tert-butyl isothiocyanate is 1 in the step 2)：(0.9-1.1).
Further, the mass ratio of methylphenylamine and chlorobenzene is 1 in the step 3):(4-8).
Further, ammonium hydrogen carbonate and 1- isopropyl -3- tertiary butyl thiocarbamides, N- Chloromethyl-N-phenyls in the step 4)
The molar ratio (3-4) of carbamyl chloride:(1.0-1.2)：1.0.
Further, the lewis acidity catalyst is anhydrous zinc chloride, alchlor or ferric trichloride；It is described
Lewis acidity catalyst charge is the 1-2% of tert-butyl alcohol quality.
Compared with prior art, the device have the advantages that it is as follows：
The preparation method of Buprofezin of the present invention substitutes Buprofezin production process respectively by using sodium sulfocyanate, sodium bicarbonate
Middle ammonium thiocyanate, ammonium hydrogen carbonate, wherein sodium sulfocyanate substitute ammonium thiocyanate as the raw material in the different ester production process of Buprofezin, lead to
1- isopropyl -3- tertiary butyl thiocarbamides are obtained after crossing substitution, indexing, addition reaction；Using sodium bicarbonate substitute ammonium hydrogen carbonate as
Raw material in Buprofezin cyclization production process, by obtaining Buprofezin finished product after being condensed, post-processing.The present invention is in above-mentioned technique item
Average yield is replaced to reach 90% or more under part, finished product Buprofezin content is entirely capable of substituting ammonium thiocyanate, carbon up to 98.0% or more
Sour hydrogen ammonium carries out Buprofezin industrialized production.And ammonia can be reduced as reaction raw materials using sodium sulfocyanate, sodium bicarbonate
The generation of nitrogen waste water, therefore be conducive to environmental protection.
Specific implementation mode
The preparation process of the present invention is described in further detail with reference to specific embodiment.
Embodiment one
A kind of preparation method of Buprofezin, includes the following steps：
Step 1)：The preparation of tert-butyl isothiocyanate
Sodium sulfocyanate and water are added in esterifying kettle, stirring makes sodium sulfocyanate be completely dissolved；It is equal to add tert-butyl alcohol stirring
It is even；80 DEG C are to slowly warm up to, technical hydrochloric acid is added dropwise in reflux, keeps the temperature 2 hours in reflux after completion of dropwise addition, the sulphur
The molar ratio of Zassol, the tert-butyl alcohol and hydrochloric acid is 1：1：1.5；Then 50 DEG C are cooled to, layering, acid waste water goes wastewater treatment
Pond, upper layer oil reservoir add alkaline aqueous solution to wash, then carry out being washed to pH being 7.0, and light yellow oil reservoir liquid, which comes back to, to be equipped with back
In the reaction kettle of flow point water system, heating carries out reflux band water until anhydrous, obtains light yellow clear liquid；To light yellow clear
Anhydrous zinc chloride is added in liquid, is warming up to 120 DEG C, insulation reaction 5 hours filters off insoluble matter, obtains tert-butyl isothiocyanate；
Step 2)：The preparation of 1- isopropyl -3- tertiary butyl thiocarbamide solution
Tert-butyl isothiocyanate is added in chlorobenzene and is stirred 20 minutes, the mass ratio of tert-butyl isothiocyanate and chlorobenzene is 1:
6；10 DEG C are cooled to, isopropylamine is added dropwise, time for adding is 1 hour, and the molar ratio of the isopropylamine and tert-butyl isothiocyanate is
1：1；It drips off after isopropylamine in 30 DEG C of insulation reactions 4 hours, obtains 1- isopropyl -3- tertiary butyl thiocarbamide solution；Step 3)：N- chlorine
The preparation of methyl-N-phenyl formyl solutions of chlorine
Methylphenylamine is added in chlorobenzene, and the mass ratio of methylphenylamine and chlorobenzene is 1:5, stirring and dissolving；Slowly heating
To 40 DEG C, start thang-kng gas, until gas chromatographic detection just stops thang-kng gas without methylphenylamine；Then start logical chlorine, directly
Stop leading to chlorine when generating N- dichloromethyl-N- phenyl amino formyl chlorides to gas chromatographic detection；It is pumped instead with water circulation vavuum pump
Remaining chlorine and hydrogen chloride gas in liquid are answered, then boiling off partial solvent with high-vacuum pump obtains N- Chloromethyl-N-phenyl amino first
The solution of acyl chlorides；
Step 4)：The preparation of Buprofezin original powder
Sodium bicarbonate is added to the water, and stirring makes sodium bicarbonate dissolve；It adds in chlorobenzene；Above-mentioned steps 2 are added) prepare
1- isopropyl -3- tertiary butyl thiocarbamide solution；It is cooled to 0 DEG C, the molten of N- chloromethyl-N-phenyl amino formyl chlorides is added dropwise at 10 DEG C
Liquid, time for adding are 1.5 hours；The ammonium hydrogen carbonate and 1- isopropyl -3- tertiary butyl thiocarbamides, N- Chloromethyl-N-phenyl amino
The molar ratio 3.5 of formyl chloride:1.1：1.After the solution of N- chloromethyl-N-phenyl amino formyl chlorides drips off, 30 DEG C are warming up to, heat preservation
Reaction 4 hours；After heat preservation, layering；Water layer removes purification tank for liquid waste, and it is the 1.1 of sodium bicarbonate weight that water, water are added in oil reservoir
Times, it stirs 30 minutes, then secondary clearing, water layer go purification tank for liquid waste, oil reservoir to remove high vacuum distillation kettle；(- 0.09)-(-
110 DEG C of temperature in solvent chlorobenzene to reaction kettle is distilled to recover under 1.0MPa)；80 DEG C are cooled to after distillation, addition weight is carbon
0.6 times of methanol of sour hydrogen sodium, then slowly cools to 5 DEG C, centrifuges, is dried to obtain Buprofezin.
Embodiment two
A kind of preparation method of Buprofezin, includes the following steps：
Step 1)：The preparation of tert-butyl isothiocyanate
Sodium sulfocyanate and water are added in esterifying kettle, stirring makes sodium sulfocyanate be completely dissolved；It is equal to add tert-butyl alcohol stirring
It is even；70 DEG C are to slowly warm up to, technical hydrochloric acid is added dropwise in reflux, keeps the temperature 3 hours in reflux after completion of dropwise addition, the sulphur
The molar ratio of Zassol, the tert-butyl alcohol and hydrochloric acid is 1：0.8：1.2；Then 40 DEG C are cooled to, layering, acid waste water goes wastewater treatment
Pond, upper layer oil reservoir add alkaline aqueous solution to wash, then carry out being washed to pH being 6.8, and light yellow oil reservoir liquid, which comes back to, to be equipped with back
In the reaction kettle of flow point water system, heating carries out reflux band water until anhydrous, obtains light yellow clear liquid；To light yellow clear
Anhydrous zinc chloride is added in liquid, is warming up to 100 DEG C, insulation reaction 6 hours filters off insoluble matter, obtains tert-butyl isothiocyanate；
Step 2)：The preparation of 1- isopropyl -3- tertiary butyl thiocarbamide solution
Tert-butyl isothiocyanate is added in chlorobenzene and is stirred 10 minutes, the mass ratio of tert-butyl isothiocyanate and chlorobenzene is 1:
5；It is cooled to 0 DEG C, isopropylamine is added dropwise, time for adding is 0.5 hour, and the molar ratio of the isopropylamine and tert-butyl isothiocyanate is
1：0.9；It drips off after isopropylamine in 30 DEG C of insulation reactions 4 hours, obtains 1- isopropyl -3- tertiary butyl thiocarbamide solution；
Step 3)：The preparation of N- chloromethyl-N-phenyl amino formyl chloride solution
Methylphenylamine is added in chlorobenzene, and the mass ratio of methylphenylamine and chlorobenzene is 1:6, stirring and dissolving；Slowly heating
To 30 DEG C, start thang-kng gas, until gas chromatographic detection just stops thang-kng gas without methylphenylamine；Then start logical chlorine, directly
Stop leading to chlorine when generating N- dichloromethyl-N- phenyl amino formyl chlorides to gas chromatographic detection；It is pumped instead with water circulation vavuum pump
Remaining chlorine and hydrogen chloride gas in liquid are answered, then boiling off partial solvent with high-vacuum pump obtains N- Chloromethyl-N-phenyl amino first
The solution of acyl chlorides；
Step 4)：The preparation of Buprofezin original powder
Sodium bicarbonate is added to the water, and stirring makes sodium bicarbonate dissolve；It adds in chlorobenzene；Above-mentioned steps 2 are added) prepare
1- isopropyl -3- tertiary butyl thiocarbamide solution；It is cooled to 0 DEG C, the solution of N- chloromethyl-N-phenyl amino formyl chlorides is added dropwise at 0 DEG C,
Time for adding is 1 hour；The ammonium hydrogen carbonate and 1- isopropyl -3- tertiary butyl thiocarbamides, N- chloromethyl-N-phenyl amino formyl chlorides
Molar ratio 3.5:1.1：1.After the solution of N- chloromethyl-N-phenyl amino formyl chlorides drips off, 20 DEG C are warming up to, insulation reaction 4
Hour；After heat preservation, layering；Water layer removes purification tank for liquid waste, and it is 0.8 times of sodium bicarbonate weight that water, water are added in oil reservoir, is stirred
20 minutes, then secondary clearing are mixed, water layer goes purification tank for liquid waste, oil reservoir to remove high vacuum distillation kettle；It is steamed at (- 0.09)-(- 1.0MPa)
Evaporate 100 DEG C of temperature in recycling design chlorobenzene to reaction kettle；80 DEG C are cooled to after distillation, it is sodium bicarbonate that weight, which is added,
0.6 times of methanol then slowly cools to 0 DEG C, centrifuges, is dried to obtain Buprofezin.
Embodiment three
A kind of preparation method of Buprofezin, includes the following steps：
Step 1)：The preparation of tert-butyl isothiocyanate
Sodium sulfocyanate and water are added in esterifying kettle, stirring makes sodium sulfocyanate be completely dissolved；It is equal to add tert-butyl alcohol stirring
It is even；90 DEG C are to slowly warm up to, technical hydrochloric acid is added dropwise in reflux, keeps the temperature 4 hours in reflux after completion of dropwise addition, the sulphur
The molar ratio of Zassol, the tert-butyl alcohol and hydrochloric acid is 1：0.8：1.2；Then 70 DEG C are cooled to, layering, acid waste water goes wastewater treatment
Pond, upper layer oil reservoir add alkaline aqueous solution to wash, then carry out being washed to pH being 7.2, and light yellow oil reservoir liquid, which comes back to, to be equipped with back
In the reaction kettle of flow point water system, heating carries out reflux band water until anhydrous, obtains light yellow clear liquid；To light yellow clear
Anhydrous zinc chloride is added in liquid, is warming up to 140 DEG C, insulation reaction 5 hours filters off insoluble matter, obtains tert-butyl isothiocyanate；
Step 2)：The preparation of 1- isopropyl -3- tertiary butyl thiocarbamide solution
Tert-butyl isothiocyanate is added in chlorobenzene and is stirred 40 minutes, the mass ratio of tert-butyl isothiocyanate and chlorobenzene is 1:
7；30 DEG C are cooled to, isopropylamine is added dropwise, time for adding is 2 hours, and the molar ratio of the isopropylamine and tert-butyl isothiocyanate is
1：1.1；It drips off after isopropylamine in 50 DEG C of insulation reactions 2 hours, obtains 1- isopropyl -3- tertiary butyl thiocarbamide solution；
Step 3)：The preparation of N- chloromethyl-N-phenyl amino formyl chloride solution
Methylphenylamine is added in chlorobenzene, and the mass ratio of methylphenylamine and chlorobenzene is 1:8, stirring and dissolving；Slowly heating
To 60 DEG C, start thang-kng gas, until gas chromatographic detection just stops thang-kng gas without methylphenylamine；Then start logical chlorine, directly
Stop leading to chlorine when generating N- dichloromethyl-N- phenyl amino formyl chlorides to gas chromatographic detection；It is pumped instead with water circulation vavuum pump
Remaining chlorine and hydrogen chloride gas in liquid are answered, then boiling off partial solvent with high-vacuum pump obtains N- Chloromethyl-N-phenyl amino first
The solution of acyl chlorides；
Step 4)：The preparation of Buprofezin original powder
Sodium bicarbonate is added to the water, and stirring makes sodium bicarbonate dissolve；It adds in chlorobenzene；Above-mentioned steps 2 are added) prepare
1- isopropyl -3- tertiary butyl thiocarbamide solution；It is cooled to 0 DEG C, the solution of N- chloromethyl-N-phenyl amino formyl chlorides is added dropwise at 0 DEG C,
Time for adding is 1 hour；The ammonium hydrogen carbonate and 1- isopropyl -3- tertiary butyl thiocarbamides, N- chloromethyl-N-phenyl amino formyl chlorides
Molar ratio 3.5:1.1：1.After the solution of N- chloromethyl-N-phenyl amino formyl chlorides drips off, 50 DEG C are warming up to, insulation reaction 4
Hour；After heat preservation, layering；Water layer removes purification tank for liquid waste, and it is 0.8 times of sodium bicarbonate weight that water, water are added in oil reservoir, is stirred
20 minutes, then secondary clearing are mixed, water layer goes purification tank for liquid waste, oil reservoir to remove high vacuum distillation kettle；It is steamed at (- 0.09)-(- 1.0MPa)
Evaporate 120 DEG C of temperature in recycling design chlorobenzene to reaction kettle；90 DEG C are cooled to after distillation, it is sodium bicarbonate that weight, which is added,
0.8 times of methanol then slowly cools to 20 DEG C, centrifuges, is dried to obtain Buprofezin.
Substitution average yield reaches 90% or more in the preparation process of the Buprofezin prepared by above-described embodiment, finished product thiophene
Piperazine ketone content generates in preparation process without ammonia nitrogen waste water up to 98.0% or more, is conducive to environmental protection.
Finally it should be noted that：The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention,
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used
With technical scheme described in the above embodiments is modified or equivalent replacement of some of the technical features.
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in the present invention's
Within protection domain.
Claims (7)
1. a kind of preparation method of Buprofezin, which is characterized in that include the following steps：
Step 1）：The preparation of tert-butyl isothiocyanate
Sodium sulfocyanate and water are added in esterifying kettle, stirring makes sodium sulfocyanate be completely dissolved；The tert-butyl alcohol is added to stir evenly；It is slow
Slowly it is warming up to 70-90 DEG C, technical hydrochloric acid is added dropwise in reflux, 2-4 hours are kept the temperature in reflux after completion of dropwise addition；Then it drops
Temperature is to 40-70 DEG C, and layering, acid waste water goes purification tank for liquid waste, upper layer oil reservoir that alkaline aqueous solution is added to wash, then carries out being washed to pH
For 6.8-7.2, light yellow oil reservoir liquid comes back in the reaction kettle equipped with reflux water-dividing system, and it is straight that heating carries out reflux band water
It is extremely anhydrous, obtain light yellow clear liquid；Lewis acidity catalyst is added into light yellow clear liquid, is warming up to 100-
140 DEG C, insulation reaction 3-6 hours filters off insoluble matter, obtains tert-butyl isothiocyanate；
Step 2）：The preparation of 1- isopropyl -3- tertiary butyl thiocarbamide solution
Tert-butyl isothiocyanate is added in chlorobenzene and is stirred 10-40 minutes；It is cooled to 0-30 DEG C, isopropylamine, time for adding is added dropwise
It is 0.5-2 hours；It drips off after isopropylamine in 20-50 DEG C of insulation reaction 2-6 hours, it is molten to obtain 1- isopropyl -3- tertiary butyl thiocarbamides
Liquid；
Step 3）：The preparation of N- chloromethyl-N-phenyl amino formyl chloride solution
Methylphenylamine is added in chlorobenzene, stirring and dissolving；It is to slowly warm up to 30-60 DEG C, starts thang-kng gas, until gas-chromatography is examined
It surveys without methylphenylamine, just stops thang-kng gas；Then start logical chlorine, until gas chromatographic detection generates N- dichloromethyls-N-
Stop leading to chlorine when phenyl amino formyl chloride；Remaining chlorine and hydrogen chloride gas in reaction solution are pumped with water circulation vavuum pump, is then used
High-vacuum pump boils off partial solvent and obtains the solution of N- chloromethyl-N-phenyl amino formyl chlorides；
Step 4）：The preparation of Buprofezin original powder
Sodium bicarbonate is added to the water, and stirring makes sodium bicarbonate dissolve；It adds in chlorobenzene；Above-mentioned steps 2 are added）The 1- of preparation is different
Propyl -3- tertiary butyl thiocarbamide solution；It is cooled to 0 DEG C, the solution of N- chloromethyl-N-phenyl amino formyl chlorides is added dropwise at 0-20 DEG C,
Time for adding is 1-2 hours；After the solution of N- chloromethyl-N-phenyl amino formyl chlorides drips off, it is warming up to 20-50 DEG C, heat preservation is anti-
It answers 3-6 hours；After heat preservation, layering；Water layer removes purification tank for liquid waste, and it is sodium bicarbonate weight that water, water are added in oil reservoir
It 0.8-1.2 times, stirs 20-40 minutes, then secondary clearing, water layer go purification tank for liquid waste, oil reservoir to remove high vacuum distillation kettle；（-
0.09）-（-1.0MPa）100-120 DEG C of temperature in lower distillation recovery solvent chlorobenzene to reaction kettle；60-90 is cooled to after distillation
DEG C, 0.5-0.8 times of the methanol that weight is sodium bicarbonate is added, then slowly cools to 0-20 DEG C, centrifuges, is dried to obtain thiophene
Piperazine ketone.
2. the preparation method of Buprofezin according to claim 1, which is characterized in that the step 1）Middle sodium sulfocyanate, uncle
The molar ratio of butanol and hydrochloric acid is 1：（0.8-1.2）：（1-2.0）.
3. the preparation of Buprofezin according to claim 1, which is characterized in that the step 2）Middle tert-butyl isothiocyanate with
The mass ratio of chlorobenzene is 1:（5-7）.
4. the preparation of Buprofezin according to claim 1, which is characterized in that the step 2）Middle isopropylamine and isothiocyanic acid
The molar ratio of the tert-butyl ester is 1：（0.9-1.1）.
5. the preparation of Buprofezin according to claim 1, which is characterized in that the step 3）Middle methylphenylamine and chlorine
The mass ratio of benzene is 1:（4-8）.
6. the preparation of Buprofezin according to claim 1, which is characterized in that the step 4）Middle ammonium hydrogen carbonate and 1- isopropyls
The molar ratio of base -3- tertiary butyl thiocarbamides, N- chloromethyl-N-phenyl amino formyl chlorides（3-4）:（1.0-1.2）：1.0.
7. the preparation of Buprofezin according to claim 1, which is characterized in that the lewis acidity catalyst is anhydrous
Zinc chloride, alchlor or ferric trichloride；The lewis acidity catalyst charge is the 1-2% of tert-butyl alcohol quality.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810262751.9A CN108530388A (en) | 2018-03-28 | 2018-03-28 | A kind of preparation method of Buprofezin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810262751.9A CN108530388A (en) | 2018-03-28 | 2018-03-28 | A kind of preparation method of Buprofezin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108530388A true CN108530388A (en) | 2018-09-14 |
Family
ID=63485335
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810262751.9A Pending CN108530388A (en) | 2018-03-28 | 2018-03-28 | A kind of preparation method of Buprofezin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108530388A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110041289A (en) * | 2019-05-15 | 2019-07-23 | 北京颖泰嘉和生物科技股份有限公司 | A kind of synthetic method of Buprofezin |
| 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 |
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR810001411B1 (en) * | 1978-06-08 | 1981-10-20 | 아리따 마사후미 | Process for preparing tetrahydro-1,3,5-thiadiazin-4-one derivative |
| CN101177418A (en) * | 2007-12-07 | 2008-05-14 | 江苏安邦电化有限公司 | Method for synthesizing thiazine ketone |
| CN101973962A (en) * | 2010-11-01 | 2011-02-16 | 连云港市金囤农化有限公司 | Preparation method of buprofezin |
| CN103880778A (en) * | 2012-12-20 | 2014-06-25 | 江苏常隆农化有限公司 | Preparation method of buprofezin |
-
2018
- 2018-03-28 CN CN201810262751.9A patent/CN108530388A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR810001411B1 (en) * | 1978-06-08 | 1981-10-20 | 아리따 마사후미 | Process for preparing tetrahydro-1,3,5-thiadiazin-4-one derivative |
| CN101177418A (en) * | 2007-12-07 | 2008-05-14 | 江苏安邦电化有限公司 | Method for synthesizing thiazine ketone |
| CN101973962A (en) * | 2010-11-01 | 2011-02-16 | 连云港市金囤农化有限公司 | Preparation method of buprofezin |
| CN103880778A (en) * | 2012-12-20 | 2014-06-25 | 江苏常隆农化有限公司 | Preparation method of buprofezin |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110041289A (en) * | 2019-05-15 | 2019-07-23 | 北京颖泰嘉和生物科技股份有限公司 | A kind of synthetic method of Buprofezin |
| CN110041289B (en) * | 2019-05-15 | 2020-12-25 | 北京颖泰嘉和生物科技股份有限公司 | Synthesis method of buprofezin |
| 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 |
| 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 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108530388A (en) | A kind of preparation method of Buprofezin | |
| CN101973962B (en) | Preparation method of buprofezin | |
| CN105921161B (en) | A kind of catalyst and preparation method thereof preparing 2,5- chlorophenesic acids for paracide hydroxylating | |
| CN103044431A (en) | Novel preparation method of penoxsulam | |
| CN108329211A (en) | The preparation method of 5- chloro-2-nitroanilines | |
| CN103880778B (en) | The preparation method of Buprofezin | |
| CN104292122A (en) | Method for reducing generation of by-product ethyl 3-(phenylamino)but-2-enoate in production of N-acetoacetanilide | |
| CN111217765A (en) | Synthesis process of 3-methyl-4-nitroiminoperhydro-1,3,5-oxadiazine | |
| CN116606259B (en) | Preparation method of Sha Mizhu key intermediate of anti-insect veterinary drug | |
| CN106380414B (en) | A kind of mefenamic acid and its synthesis technology | |
| CN107445869A (en) | A kind of synthetic method of Metformin hydrochloride | |
| CN111039828A (en) | Production method of organic guanidine bactericide | |
| CN104402795A (en) | Synthetic method of substituted indol-2-formic acid | |
| CN106699591A (en) | Clean production process of glycine and co-produced ammonium chloride | |
| CN103254150A (en) | Preparation method of azole acetone with high yield and low emission | |
| CN106187855B (en) | A method of 2- (hetero) aryl indole class compound is prepared using deep eutectic solvent | |
| Shiraiwa et al. | Asymmetric transformation of (RS)-cysteine via formation of (RS)-4-thiazolidinecarboxylic acids | |
| CN113045424B (en) | Synthesis method of 2- (5-fluoro-2-nitrophenoxy) acetate compound | |
| CN104447433A (en) | Method for synthesizing 3,5-dibromoparatoluensulfonyl chloride | |
| CN106565560A (en) | Synthesis process of mesotrione | |
| CN112521344A (en) | Method for producing bentazone | |
| CN1219760C (en) | Methyleneseleno propanel method for preparing selenoic methionine | |
| US4007221A (en) | Manufacture of nuclear-iodinated iodine compounds of aromatic character | |
| CN111004173A (en) | Preparation method of hydroxyl-niatone | |
| CN105037060A (en) | Clean synthesis process of alpha-amino acid compounds |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |