CN103058956A - Preparation method of 5-amino-1,2,3-thiadiazole - Google Patents
Preparation method of 5-amino-1,2,3-thiadiazole Download PDFInfo
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- CN103058956A CN103058956A CN2013100032101A CN201310003210A CN103058956A CN 103058956 A CN103058956 A CN 103058956A CN 2013100032101 A CN2013100032101 A CN 2013100032101A CN 201310003210 A CN201310003210 A CN 201310003210A CN 103058956 A CN103058956 A CN 103058956A
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Abstract
The invention discloses a preparation method of 5-amino-1,2,3-thiadiazole. The method comprises the steps that: (1) an acidolysis reaction is carried out, wherein methylenedioxy amino acetonitrile is added into an ethanol water solution, and a hydrochloric acid ethanol solution is added and a reaction is carried out, such that a hydrochloride salt is formed; (2) a diazo reaction is carried out, wherein the obtained hydrochloride salt is added into an organic solvent; the temperature is reduced, and a nitrite solution is dropped in, such that the diazotization reaction is carried out, and a diazo acetonitrile mixed liquid is prepared; and (3) a cyclization reaction is carried out, wherein a catalyst is added into the prepared diazo acetonitrile mixed liquid; the temperature is reduced, and a hydrogen sulfide gas is added for carrying out the cyclization reaction, such that an organic solvent mother liquor is removed, and the finished product is prepared. The method provided by the invention has the advantages of low cost, recycling of the mother liquor, cost saving, mild reaction conditions, less side effects, low solvent utilization amount, high yield, simple and feasible production, and low three-waste discharge. Therefore, the requirements of environment protection are satisfied.
Description
Technical field
The present invention relates to the preparation field of medicine intermediate, particularly relate to a kind of preparation method of 5-Amino-1,2,3-Thiadiazoles.
Background technology
The 5-Amino-1,2,3-Thiadiazoles is a kind of important organic chemical industry's intermediate, is widely used in the synthetic of medicine and agrochemicals, is the key intermediate of beta-lactams synthesis antibiotic and plant-growth regulator thidiazuron.
Yet at present 5-Amino-1,2,3-Thiadiazoles synthetic method has multiplely, and general route is long, and raw material is expensive and be not easy to obtain, and mother liquor can not recycle, and side reaction is many, and productive rate is low, and preparation is difficult, and three wastes discharge amount is large, can not form rapidly volume production or industrialization.
Summary of the invention
It is low that the technical problem that the present invention mainly solves provides a kind of production cost, and Recycling Mother Solution use to be saved cost, and side reaction is few, and productive rate is high, the production simple possible, and three waste discharge is few, 5-Amino-1,2,3-Thiadiazoles that can suitability for industrialized production.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is: a kind of preparation method of 5-Amino-1,2,3-Thiadiazoles is provided, may further comprise the steps:
(1) acidolysis reaction: the amino second cyanogen of methylene is dropped in the aqueous ethanolic solution, and stirring is dissolved it fully, and 20 ~ 30 ℃ of control temperature drip ethanol solution hydrochloride again, dropwise rear stirring 3 ~ 5 h, and the centrifugal mother liquor that removes gets the solid salt hydrochlorate, and Recycling Mother Solution is used;
(2) doazo reaction: the hydrochloride that obtains is dropped in the organic solvent, be cooled to less than-5 ℃, then drip nitrite solution generation diazotization reaction, drip and finish to stir 0.3 ~ 1.0 h, remove layering waste water, make diazonium second cyanogen mixed solution;
(3) ring-closure reaction: the control temperature adds catalyzer less than 0 ℃ in the diazonium second cyanogen mixed solution that makes, and reduces temperature to-10 ~-5 ℃, then pass into hydrogen sulfide generation ring-closure reaction, ventilation finishes, and stirs 1 ~ 3 h, remove the organic solvent mother liquor, oven dry makes finished product.
In a preferred embodiment of the present invention, the weight ratio of the amino second cyanogen of described aqueous ethanolic solution, ethanol solution hydrochloride and methylene is 4 ~ 6:1 ~ 1.5:1.
In a preferred embodiment of the present invention, the weight ratio of described nitrite solution and hydrochloride is 1.5 ~ 2.8:1.
In a preferred embodiment of the present invention, described diazonium second cyanogen mixed solution, hydrogen sulfide and catalyst weight ratio are 75 ~ 85:1.7 ~ 2.5:1.
In a preferred embodiment of the present invention, described aqueous ethanolic solution is that mass percent is 90% ~ 98% aqueous ethanolic solution.
In a preferred embodiment of the present invention, described organic solvent is chloroform, methylene dichloride or ethylene glycol.
In a preferred embodiment of the present invention, described ethanol solution hydrochloride is that volume percent is 20% ~ 30% ethanol solution hydrochloride.
In a preferred embodiment of the present invention, described nitrite is Sodium Nitrite or potassium nitrite.
In a preferred embodiment of the present invention, described catalyzer is diethylamine.
The invention has the beneficial effects as follows: production cost of the present invention is low, and Recycling Mother Solution is used and saved cost, and reaction conditions is gentle, and side reaction is few, and solvent load is few, and productive rate is high, the production simple possible, and three waste discharge is few, meets environmental requirement.
Embodiment
The below is described in detail preferred embodiment of the present invention, thereby so that advantages and features of the invention can be easier to be it will be appreciated by those skilled in the art that protection scope of the present invention is made more explicit defining.
Embodiment 1
A kind of preparation method of 5-Amino-1,2,3-Thiadiazoles may further comprise the steps:
(1) acidolysis reaction: it is among 95% aqueous ethanolic solution solvent 500 kg that the amino second cyanogen of methylene 100 kg are dropped into mass percent, stirring is dissolved it fully, 25 ℃ of control temperature, dripping volume percent is 25% ethanol solution hydrochloride, 120 kg again, dropwise rear stirring 4 h, the centrifugal mother liquor that removes gets the solid salt hydrochlorate, and Recycling Mother Solution is used;
(2) doazo reaction: hydrochloride 100 kg that obtain are dropped in the 2000 L chloroforms, be cooled to less than-5 ℃, then dripping mass percent is that diazotization reaction occurs 30% sodium nitrite solution, 215 kg, drips and finishes to stir 0.5 h, remove layering waste water, make diazonium second cyanogen mixed solution;
(3) ring-closure reaction: the control temperature is less than 0 ℃, in diazonium second cyanogen mixed solution 1440 kg that make, add diethylamine catalyzer 18 kg, and reduce temperature to-10 ℃, then pass into hydrogen sulfide 38 kg ring-closure reaction occurs, ventilation finishes, stir 2 h, remove the chloroform mother liquor, oven dry makes finished product.
The 5-Amino-1,2,3-Thiadiazoles outward appearance that makes: white crystalline powder, content: 〉=98%, moisture content :≤0.5%.
Embodiment 2
A kind of preparation method of 5-Amino-1,2,3-Thiadiazoles may further comprise the steps:
(1) acidolysis reaction: it is among 98% aqueous ethanolic solution solvent 400 kg that the amino second cyanogen of methylene 100 kg are dropped into mass percent, stirring is dissolved it fully, 20 ℃ of control temperature, dripping volume percent is 25% ethanol solution hydrochloride, 100 kg again, dropwise rear stirring 3 h, the centrifugal mother liquor that removes gets the solid salt hydrochlorate, and Recycling Mother Solution is used;
(2) doazo reaction: hydrochloride 100 kg that obtain are dropped in the 1800 L chloroforms, be cooled to less than-5 ℃, then dripping mass percent is that diazotization reaction occurs 30% sodium nitrite solution, 150 kg, drips and finishes to stir 0.3 h, remove layering waste water, make diazonium second cyanogen mixed solution;
(3) ring-closure reaction: the control temperature is less than 0 ℃, in diazonium second cyanogen mixed solution 1350 kg that make, add diethylamine catalyzer 18 kg, and reduce temperature to-8 ℃, then pass into hydrogen sulfide 31 kg ring-closure reaction occurs, ventilation finishes, stir 1 h, remove the chloroform mother liquor, oven dry makes finished product.
The 5-Amino-1,2,3-Thiadiazoles outward appearance that makes: white crystalline powder, content: 〉=98%, moisture content :≤0.5%.
Embodiment 3
A kind of preparation method of 5-Amino-1,2,3-Thiadiazoles may further comprise the steps:
(1) acidolysis reaction: it is among 90% aqueous ethanolic solution solvent 600 kg that the amino second cyanogen of methylene 100 kg are dropped into mass percent, stirring is dissolved it fully, 30 ℃ of control temperature, dripping volume percent is 25% ethanol solution hydrochloride, 150 kg again, dropwise rear stirring 5 h, the centrifugal mother liquor that removes gets the solid salt hydrochlorate, and Recycling Mother Solution is used;
(2) doazo reaction: hydrochloride 100 kg that obtain are dropped in the 2200 L chloroforms, be cooled to less than-5 ℃, then dripping mass percent is that diazotization reaction occurs 30% sodium nitrite solution, 280 kg, drips and finishes to stir 1 h, remove layering waste water, make diazonium second cyanogen mixed solution;
(3) ring-closure reaction: the control temperature is less than 0 ℃, in diazonium second cyanogen mixed solution 1530 kg that make, add diethylamine catalyzer 18 kg, and reduce temperature to-5 ℃, then pass into hydrogen sulfide 45 kg ring-closure reaction occurs, ventilation finishes, stir 3 h, remove the chloroform mother liquor, oven dry makes finished product.
The 5-Amino-1,2,3-Thiadiazoles outward appearance that makes: white crystalline powder, content: 〉=98%, moisture content :≤0.5%.
Production cost of the present invention is low, and Recycling Mother Solution is used and saved cost, and reaction conditions is gentle, and side reaction is few, and solvent load is few, and productive rate is high, the production simple possible, and three waste discharge is few, meets environmental requirement.
The above only is embodiments of the invention; be not so limit claim of the present invention; every equivalent structure or equivalent flow process conversion that utilizes specification sheets of the present invention to do, or directly or indirectly be used in other relevant technical fields, all in like manner be included in the scope of patent protection of the present invention.
Claims (9)
1. the preparation method of a 5-Amino-1,2,3-Thiadiazoles is characterized in that, may further comprise the steps:
(1) acidolysis reaction: the amino second cyanogen of methylene is dropped in the aqueous ethanolic solution, and stirring is dissolved it fully, and 20 ~ 30 ℃ of control temperature drip ethanol solution hydrochloride again, dropwise rear stirring 3 ~ 5 h, and the centrifugal mother liquor that removes gets the solid salt hydrochlorate, and Recycling Mother Solution is used;
(2) doazo reaction: the hydrochloride that obtains is dropped in the organic solvent, be cooled to less than-5 ℃, then drip nitrite solution generation diazotization reaction, drip and finish to stir 0.3 ~ 1.0 h, remove layering waste water, make diazonium second cyanogen mixed solution;
(3) ring-closure reaction: the control temperature adds catalyzer less than 0 ℃ in the diazonium second cyanogen mixed solution that makes, and reduces temperature to-10 ~-5 ℃, then pass into hydrogen sulfide generation ring-closure reaction, ventilation finishes, and stirs 1 ~ 3 h, remove the organic solvent mother liquor, oven dry makes finished product.
2. the preparation method of 5-Amino-1,2,3-Thiadiazoles according to claim 1 is characterized in that, the weight ratio of the amino second cyanogen of described aqueous ethanolic solution, ethanol solution hydrochloride and methylene is 4 ~ 6:1 ~ 1.5:1.
3. the preparation method of 5-Amino-1,2,3-Thiadiazoles according to claim 1 is characterized in that, the weight ratio of described nitrite solution and hydrochloride is 1.5 ~ 2.8:1.
4. the preparation method of 5-Amino-1,2,3-Thiadiazoles according to claim 1 is characterized in that, described diazonium second cyanogen mixed solution, hydrogen sulfide and catalyst weight ratio are 75 ~ 85:1.7 ~ 2.5:1.
5. the preparation method of 5-Amino-1,2,3-Thiadiazoles according to claim 1 is characterized in that, described aqueous ethanolic solution is that mass percent is 90% ~ 98% aqueous ethanolic solution.
6. the preparation method of 5-Amino-1,2,3-Thiadiazoles according to claim 1 is characterized in that, described organic solvent is chloroform, methylene dichloride or ethylene glycol.
7. the preparation method of 5-Amino-1,2,3-Thiadiazoles according to claim 1 is characterized in that, described ethanol solution hydrochloride is that volume percent is 20% ~ 30% ethanol solution hydrochloride.
8. the preparation method of 5-Amino-1,2,3-Thiadiazoles according to claim 1 is characterized in that, described nitrite is Sodium Nitrite or potassium nitrite.
9. the preparation method of 5-Amino-1,2,3-Thiadiazoles according to claim 1 is characterized in that, described catalyzer is diethylamine.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106632469A (en) * | 2016-12-06 | 2017-05-10 | 湖北泰盛化工有限公司 | Hydrogen chloride acidolysis technology and device |
| CN106674273A (en) * | 2016-12-02 | 2017-05-17 | 湖北泰盛化工有限公司 | Hydrolysis device for producing glyphosate employing glycine method |
| CN106699808A (en) * | 2016-12-02 | 2017-05-24 | 湖北泰盛化工有限公司 | Acidolysis and solvent recycling process and device for producing glyphosate by using glycine method |
| CN109053633A (en) * | 2018-08-29 | 2018-12-21 | 江苏师范大学 | A kind of synthetic method of 5- amino -1,2,3- thiadiazoles |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4113733A (en) * | 1976-08-13 | 1978-09-12 | Schering Ag | Process for making 5-amino-1,2,3-thiadiazoles |
| US4269982A (en) * | 1979-12-27 | 1981-05-26 | Ube Industries, Ltd. | Process for preparing 5-amino-1,2,3-thiadiazoles |
| CN101397281A (en) * | 2008-09-24 | 2009-04-01 | 江苏省农用激素工程技术研究中心有限公司 | Method for preparing 5-amino-1,2,3-thiadiazoles |
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2013
- 2013-01-06 CN CN2013100032101A patent/CN103058956A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4113733A (en) * | 1976-08-13 | 1978-09-12 | Schering Ag | Process for making 5-amino-1,2,3-thiadiazoles |
| US4269982A (en) * | 1979-12-27 | 1981-05-26 | Ube Industries, Ltd. | Process for preparing 5-amino-1,2,3-thiadiazoles |
| CN101397281A (en) * | 2008-09-24 | 2009-04-01 | 江苏省农用激素工程技术研究中心有限公司 | Method for preparing 5-amino-1,2,3-thiadiazoles |
Non-Patent Citations (1)
| Title |
|---|
| 张大永: "5-氨基-1,2,3-噻二唑的合成", 《南京师范大学学报》, vol. 5, no. 2, 20 June 2005 (2005-06-20), pages 58 - 59 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106674273A (en) * | 2016-12-02 | 2017-05-17 | 湖北泰盛化工有限公司 | Hydrolysis device for producing glyphosate employing glycine method |
| CN106699808A (en) * | 2016-12-02 | 2017-05-24 | 湖北泰盛化工有限公司 | Acidolysis and solvent recycling process and device for producing glyphosate by using glycine method |
| CN106632469A (en) * | 2016-12-06 | 2017-05-10 | 湖北泰盛化工有限公司 | Hydrogen chloride acidolysis technology and device |
| CN106632469B (en) * | 2016-12-06 | 2019-06-04 | 湖北泰盛化工有限公司 | A kind of hydrogen chloride acidolysis process and device |
| CN109053633A (en) * | 2018-08-29 | 2018-12-21 | 江苏师范大学 | A kind of synthetic method of 5- amino -1,2,3- thiadiazoles |
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