CN103613565A - Synthetic method of 3-bromine-1,2,4-thiadiazole-5-amine - Google Patents
Synthetic method of 3-bromine-1,2,4-thiadiazole-5-amine Download PDFInfo
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- CN103613565A CN103613565A CN201310622346.0A CN201310622346A CN103613565A CN 103613565 A CN103613565 A CN 103613565A CN 201310622346 A CN201310622346 A CN 201310622346A CN 103613565 A CN103613565 A CN 103613565A
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- amine
- thiadiazoles
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- 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
- C07D285/01—Five-membered rings
- C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
- C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
- C07D285/08—1,2,4-Thiadiazoles; Hydrogenated 1,2,4-thiadiazoles
Abstract
The invention discloses a synthetic method of 3-bromine-1,2,4-thiadiazole-5-amine. The synthetic method comprises the following step of: reacting with alcohol liquor of an ammonia gas to directly generate 3-bromine-1,2,4-thiadiazole-5-amine by one step by taking 3-bromine-5-chlorine-1,2,4-thiadiazole as the material. According to the synthetic method of the 3-bromine-1,2,4-thiadiazole-5-amine provided by the invention, the 3-bromine-1,2,4-thiadiazole-5-amine is generated by adopting the 3-bromine-5-chlorine-1,2,4-thiadiazole to react with the alcohol liquor of the ammonia gas. A reaction product is solid, reaction is carried out under a microwave environment, the material is promoted to react sufficiently and yield is improved. And meanwhile, the shortest reaction route by one-step synthesis is realized by controlling reaction conditions, and byproducts are less.
Description
Technical field
The present invention relates to a kind of 3-bromo-1,2, the synthetic method of 4-thiadiazoles-5-amine.
Background technology
3 – phenyl-1,2,4-thiazole-5-propylhomoserin is the important intermediate of synthetic multiple compounds, and 3-is bromo-1,2,4-thiadiazoles-5-amine is synthetic 3 – phenyl-1, the necessary raw material of 2,4-thiazole-5-propylhomoserin.The shortcomings such as it is long that chemical synthesis process in the past often has synthetic route, and yield is low.
Summary of the invention
The technical problem to be solved in the present invention is to overcome existing defect, provides a kind of yield is high, route is short 3-bromo-1,2, the synthetic method of 4-thiadiazoles-5-amine.
Object of the present invention is carried out specific implementation by the following technical programs:
A kind of 3-is bromo-1,2, the synthetic method of 4-thiadiazoles-5-amine, and chloro-1,2 with the bromo-5-of 3-, 4-thiadiazoles is raw material, reacts with the alcoholic solution of ammonia, it is bromo-1,2 that a step directly generates 3-, 4-thiadiazoles-5-amine,
The bromo-5-of described 3-is chloro-1,2, and the mol ratio of 4-thiadiazoles raw material and ammonia is 1:1.5-2.5,
Concrete reaction conditions is: under microwave condition, react, temperature of reaction is controlled at 67-75 ℃, and the reaction times is controlled at 20-40min.
Reaction formula is as follows:
As preferred version:
The bromo-5-of described 3-is chloro-1,2, and the mol ratio of 4-thiadiazoles raw material and ammonia is 1:2.
Concrete reaction conditions is: under microwave condition, react, temperature of reaction is controlled at 70 ℃, and the reaction times is controlled at 30min.
The alcoholic solution of described ammonia is methyl alcohol or ethanolic soln.Preferred alcohol solution.
Beneficial effect of the present invention:
3-provided by the invention is bromo-1,2, and the synthetic method of 4-thiadiazoles-5-amine adopts the bromo-5-of 3-chloro-1,2, and 4-thiadiazoles reacts with the alcoholic solution of ammonia, and generation 3-is bromo-1,2,4-thiadiazoles-5-amine.Because reaction product is solid, by reacting under microwave environment, impel raw material reaction abundant, improve productive rate.Meanwhile, by the control to reaction conditions, realized the short reaction route of one-step synthesis, and by product is few.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, for explaining the present invention, is not construed as limiting the invention together with embodiments of the present invention.In the accompanying drawings:
Fig. 1 is that the 3-for preparing of the embodiment of the present invention 1 is bromo-1,2, the HNMR collection of illustrative plates of 4-thiadiazoles-5-amine;
Fig. 2 is that the 3-for preparing of the embodiment of the present invention 1 is bromo-1,2, the CNMR collection of illustrative plates of 4-thiadiazoles-5-amine.
Embodiment
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein, only for description and interpretation the present invention, is not intended to limit the present invention.
embodiment 1:
The bromo-5-of 3-is chloro-1,2,4-thiadiazoles (2.6 g, 0.013 mol, 1.00 equiv) add ethanolic soln (2 M, 13 mL, 0.026 mol of ammonia, 2.00 equiv) in, the microwave tube of sealing is heated to 70 ° of C, under microwave environment, reacts 0.5 hour.Reaction is cooled to then suction filtration of room temperature after finishing, ether and water washing post-drying for gained solid after filtering, and gained white powder 1.85 g, are product 3-bromo-1,2,4-thiadiazoles-5-amine, yield 79.1 %.
Product HNMR collection of illustrative plates is referring to accompanying drawing 1: in product structure, contain one group of hydrogen atom, and its chemical shift and product structure coincide, chemical shift is 5 NH at the unimodal of 8.50ppm place
2h peak.
Product C NMR collection of illustrative plates is referring to accompanying drawing 2: in product structure, contain two groups of carbon atoms, and its chemical shift and product structure coincide, chemical shift is the C peak of 5 C at 183.925ppm place, and chemical shift is the C peak of 3 C at 140.641ppm place.
embodiment 2:
The bromo-5-of 3-is chloro-1,2,4-thiadiazoles (2.6 g, 0.013 mol, 1.00 equiv) add ethanolic soln (2 M, 16.25 mL, 0.0325 mol of ammonia, 2.5 equiv) in, the microwave tube of sealing is heated to 70 ° of C, under microwave environment, reacts 0.5 hour.Reaction is cooled to then suction filtration of room temperature after finishing, ether and water washing post-drying for gained solid after filtering, and gained white powder 1.76 g, are product 3-bromo-1,2,4-thiadiazoles-5-amine, yield 75.3 %.
embodiment 3:
The bromo-5-of 3-is chloro-1,2,4-thiadiazoles (2.6 g, 0.013 mol, 1.00 equiv) add ethanolic soln (2 M, 9.75 mL, 0.0195 mol of ammonia, 1.5 equiv) in, the microwave tube of sealing is heated to 70 ° of C, under microwave environment, reacts 0.5 hour.Reaction is cooled to then suction filtration of room temperature after finishing, ether and water washing post-drying for gained solid after filtering, and gained white powder 1.73g, is product 3-bromo-1,2,4-thiadiazoles-5-amine, yield 73.7 %.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, although the present invention is had been described in detail with reference to previous embodiment, for a person skilled in the art, its technical scheme that still can record aforementioned each embodiment is modified, or part technical characterictic is wherein equal to replacement.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (5)
1. a 3-is bromo-1,2, the synthetic method of 4-thiadiazoles-5-amine, it is characterized in that: chloro-1,2 with the bromo-5-of 3-, 4-thiadiazoles is raw material, react with the alcoholic solution of ammonia, a step directly generates 3-bromo-1,2,4-thiadiazoles-5-amine, the bromo-5-of described 3-chloro-1,2, the mol ratio of 4-thiadiazoles and ammonia is 1:1.5-2.5, concrete reaction conditions is: under microwave condition, react, temperature of reaction is controlled at 67-75 ℃, and the reaction times is controlled at 20-40min.
2. 3-according to claim 1 is bromo-1,2, and the synthetic method of 4-thiadiazoles-5-amine, is characterized in that: the bromo-5-of described 3-is chloro-1,2, and the mol ratio of 4-thiadiazoles and ammonia is 1:2.
3. 3-according to claim 1 and 2 is bromo-1,2, and the synthetic method of 4-thiadiazoles-5-amine, is characterized in that: concrete reaction conditions is: under microwave condition, react, temperature of reaction is controlled at 70 ℃, and the reaction times is controlled at 30min.
4. 3-according to claim 1 is bromo-1,2, and the synthetic method of 4-thiadiazoles-5-amine, is characterized in that: the alcoholic solution of described ammonia is methyl alcohol or ethanolic soln.
5. 3-according to claim 4 is bromo-1,2, and the synthetic method of 4-thiadiazoles-5-amine, is characterized in that: the alcoholic solution of described ammonia is ethanolic soln.
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| CN201310622346.0A CN103613565B (en) | 2013-11-30 | 2013-11-30 | The synthetic method of bromo-1,2, the 4-thiadiazoles-5-amine of a kind of 3- |
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| CN201310622346.0A CN103613565B (en) | 2013-11-30 | 2013-11-30 | The synthetic method of bromo-1,2, the 4-thiadiazoles-5-amine of a kind of 3- |
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| CN103613565B CN103613565B (en) | 2015-08-19 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012129338A1 (en) * | 2011-03-22 | 2012-09-27 | Amgen Inc. | Azole compounds as pim inhibitors |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012129338A1 (en) * | 2011-03-22 | 2012-09-27 | Amgen Inc. | Azole compounds as pim inhibitors |
Non-Patent Citations (1)
| Title |
|---|
| PAUL M. WHEN ET.A: "《Facile Synthesis of Substituted5-Amino- and 3-Amino-1, 2, 4-Thiadiazolesfrom a Common Precursor》", 《ORG. LETT.》, vol. 11, no. 24, 31 December 2009 (2009-12-31), pages 5666 - 5669 * |
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