CN105237490A - Synthesis method of 5-methyl tetrazole - Google Patents
Synthesis method of 5-methyl tetrazole Download PDFInfo
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- CN105237490A CN105237490A CN201510777870.4A CN201510777870A CN105237490A CN 105237490 A CN105237490 A CN 105237490A CN 201510777870 A CN201510777870 A CN 201510777870A CN 105237490 A CN105237490 A CN 105237490A
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- methyl tetrazole
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D257/04—Five-membered rings
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Abstract
The invention relates to a synthesis method of 5-methyl tetrazole. The method includes the steps of adding acetonitrile, sodium azide and a certain amount of catalysts into a high-pressure kettle through green catalyzed synthesis, raising the temperature to 60-180 DEG C, and keeping the temperature for 1-48 hours, wherein the raw material ratio is between 1 to 1 and 1 to 1.5; then, conducting cooling, exhausting and suction filtration to recycle the catalysts, recycling excessive acetonitrile, regulating the pH value to 1 to 2 through hydrochloric acid remaining liquid with the mass concentration of 10%, separating out a crude product, and conducting suction filtration, washing, recrystallization and drying to obtain 5-methyl tetrazole. The method has the advantages that the synthesis method is simple in process and safe and easy to operate, the catalysts used in the reaction process can be recycled, and therefore the production cost can be low; the method is green and environmentally friendly, waste emission is reduced, and the method is suitable for industrial production; meanwhile, the yield of the product synthesized through the method can reach up to 84% at most.
Description
Technical field
The present invention relates to technical field of organic synthesis, particularly a kind of synthetic method of 5-methyl tetrazole.
Background technology
5-methyl tetrazole is used for the antibiotic synthesis of Cephalosporins of new generation, and its intermediate has been widely used at synthetic antifunguses object space mask, also has been widely used at electronic applications.At present, domestic and international manufacturer is nearly all using organic solvents such as DMF, DMSO as reaction system solvent, under the effect of phase-transfer catalyst, through repeatedly extracting, distilling, the complicated operation such as separation obtains 5-methyl tetrazole salt, extraction, distillation, centrifugal, refining, dryly obtains 5-methyl tetrazole fine work.The method of the existing 5-of preparation methyl tetrazole salt also exists that technical process complexity, operation steps are various, exhausted air quantity is large in operating process, and organic solvent loss is many, and waste water is difficult biochemical, to the physical effects of operator.
For above-mentioned phenomenon, China Patent No. is 201310320527.8 water phase synthesis methods proposing a kind of 5-methyl tetrazole, the method comprises the following steps: (1) sodiumazide, acetonitrile, zinc chloride and appropriate deionized water are dropped in synthesis under normal pressure equipment and react, obtain 5-phenyl tetrazole zinc salt after reaction terminates; By step (1) in drip 30% sodium hydroxide solution, stirring reaction in the 5-phenyl tetrazole zinc salt that obtains, reaction terminates rear generation 5-methyl tetrazole sodium salt; By step (2) in drip hydrochloric acid, stirring reaction in the 5-methyl tetrazole sodium salt that obtains, completely add extraction into ethyl acetate, get oil reservoir, distillation, centrifugal, be drying to obtain 5-methyl tetrazole fine work; By step (3) in namely obtain 5-methyl tetrazole finished product after the 5-methyl tetrazole fine work drying process that obtains.This method reduce the generation of the three wastes, alleviate treatment pressure of sewage, the feature of good product quality, but the product yield of the method synthesis is relatively low.
Therefore, research and develop that a kind of technique is simple, environmental protection, production cost is low and the synthetic method of the 5-phenyl tetrazole that product yield is high is necessary.
Summary of the invention
The technical problem to be solved in the present invention is to provide that a kind of technique is simple, environmental protection, production cost is low and the synthetic method of the 5-phenyl tetrazole that product yield is high.
For solving the problems of the technologies described above, technical scheme of the present invention is: a kind of synthetic method of 5-methyl tetrazole, its innovative point is: synthesized by green catalysis, be that the second cyanogen of 1:1 ~ 1:1.5 and sodiumazide and a certain amount of catalyzer add autoclave by proportioning raw materials, add solvent again, be warming up to 60 ~ 180 DEG C, insulation reaction 1 ~ 48 hour; Then be cooled to room temperature, exhaust, the acetonitrile that suction filtration recovery catalyzer is excessive with recovery, finally adjust debris PH to 1 ~ 2 with the hydrochloric acid that mass concentration is 10%, separate out thick product, then suction filtration, washing, recrystallization, obtain 5-methyl tetrazole after drying, reaction formula is:
Further, described catalyzer is the one in acid atlapulgite or acidic ion exchange resin, and the add-on of catalyzer is 5 ~ 50% of sodiumazide.
Further, described solvent is the one in DMF, DMSO, ethanol, methyl alcohol, toluene, benzene or dimethylbenzene.
The invention has the advantages that: the synthetic method of 5-methyl tetrazole of the present invention, technique is simple, and safety is easy to operate, the catalyzer recoverable used in reaction process, and then make production cost low, and this synthetic method environmental protection, greatly reduce discharge of wastewater, be applicable to industrial production; Meanwhile, the product synthesized by the method, product yield reaches as high as 84%.
Embodiment
The following examples can make the present invention of professional and technical personnel's comprehend, but therefore do not limit the present invention among described scope of embodiments.
embodiment 1
Get 300 grams, second cyanogen, sodiumazide 65 grams and acidity of catalyst atlapulgite 20 grams, add autoclave, be warming up to 135 DEG C, react 10 hours at this temperature, be then cooled to room temperature, exhaust, suction filtration reclaims catalyzer and reclaims excessive acetonitrile, finally adjusts debris PH to 1 with the hydrochloric acid that mass concentration is 10%, separates out thick product, suction filtration again, washing, recrystallization, obtains 5-methyl tetrazole 69 grams after drying.
embodiment 2
Get 300 grams, second cyanogen, sodiumazide 65 grams and example 1 reclaim acidity of catalyst atlapulgite, add autoclave, be warming up to 135 DEG C, react 10 hours at this temperature, be then cooled to room temperature, exhaust, suction filtration reclaims catalyzer and reclaims excessive acetonitrile, finally adjusts debris PH to 1 with the hydrochloric acid that mass concentration is 10%, separates out thick product, suction filtration again, washing, recrystallization, obtains 5-methyl tetrazole 67 grams after drying.
embodiment 3
Get 450 grams, second cyanogen, sodiumazide 65 grams and acidity of catalyst atlapulgite 20 grams, add there-necked flask, add solvent DMF 100ml, be warming up to 85 DEG C, react 10 hours at this temperature, then be cooled to room temperature, exhaust, suction filtration reclaims catalyzer and reclaims excessive acetonitrile, finally adjust debris PH to 2 with the hydrochloric acid that mass concentration is 10%, separate out thick product, then suction filtration, washing, recrystallization, obtains 5-methyl tetrazole 54 grams after drying.
Following table is the synthetic method of the 5-methyl tetrazole of embodiment 1 ~ 3 and the contrast of prior synthesizing method sintetics yield:
| Product | Embodiment 1 | Embodiment 2 | Embodiment 3 | Tradition (aqueous phase synthesis method) |
| Yield | 82% | 80% | 84% | 58% |
As can be seen from the above table, the product synthesized by the synthetic method of 5-methyl tetrazole of the present invention, product yield can reach 84%, and the product yield of traditional method synthesis the highlyest reaches 58% only; In addition, be used for the synthesis of 5-methyl tetrazole by the catalyzer reclaimed, the yield of product still can reach more than 80%.
The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and equivalent thereof.
Claims (3)
1. the synthetic method of a 5-methyl tetrazole, it is characterized in that: synthesized by green catalysis, be that the second cyanogen of 1:1 ~ 1:1.5 and sodiumazide and a certain amount of catalyzer add autoclave by proportioning raw materials, then add solvent, be warming up to 60 ~ 180 DEG C, insulation reaction 1 ~ 48 hour; Then be cooled to room temperature, exhaust, the acetonitrile that suction filtration recovery catalyzer is excessive with recovery, finally adjust debris PH to 1 ~ 2 with the hydrochloric acid that mass concentration is 10%, separate out thick product, then suction filtration, washing, recrystallization, obtain 5-methyl tetrazole after drying, reaction formula is:
。
2. the synthetic method of 5-methyl tetrazole according to claim 1, is characterized in that: described catalyzer is the one in acid atlapulgite or acidic ion exchange resin, and the add-on of catalyzer is 5 ~ 50% of sodiumazide.
3. the synthetic method of 5-methyl tetrazole according to claim 1, is characterized in that: described solvent is the one in DMF, DMSO, ethanol, methyl alcohol, toluene, benzene or dimethylbenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510777870.4A CN105237490A (en) | 2015-11-16 | 2015-11-16 | Synthesis method of 5-methyl tetrazole |
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| CN201510777870.4A CN105237490A (en) | 2015-11-16 | 2015-11-16 | Synthesis method of 5-methyl tetrazole |
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| CN201510777870.4A Pending CN105237490A (en) | 2015-11-16 | 2015-11-16 | Synthesis method of 5-methyl tetrazole |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111943899A (en) * | 2020-09-08 | 2020-11-17 | 河北凯力昂生物科技有限公司 | Synthesis method of 5-ethyl formate tetrazole |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4791210A (en) * | 1986-10-11 | 1988-12-13 | Dynamit Nobel Aktiengesellschaft | Process for the production of 5-methyltetrazole |
| CN1718574A (en) * | 2004-07-09 | 2006-01-11 | 浙江工业大学 | 1,2,3, the chemical synthesis process of 4-tetrazole compound |
| CN101260084A (en) * | 2008-03-17 | 2008-09-10 | 江苏德峰医药化工有限公司 | Production technique for preparing 5-alkyltetranitrozole by high pressure method |
| CN103351353A (en) * | 2013-07-25 | 2013-10-16 | 浙江海蓝化工有限公司 | Aqueous phase synthesis method of 5-methyl tetrazole |
-
2015
- 2015-11-16 CN CN201510777870.4A patent/CN105237490A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4791210A (en) * | 1986-10-11 | 1988-12-13 | Dynamit Nobel Aktiengesellschaft | Process for the production of 5-methyltetrazole |
| CN1718574A (en) * | 2004-07-09 | 2006-01-11 | 浙江工业大学 | 1,2,3, the chemical synthesis process of 4-tetrazole compound |
| CN101260084A (en) * | 2008-03-17 | 2008-09-10 | 江苏德峰医药化工有限公司 | Production technique for preparing 5-alkyltetranitrozole by high pressure method |
| CN103351353A (en) * | 2013-07-25 | 2013-10-16 | 浙江海蓝化工有限公司 | Aqueous phase synthesis method of 5-methyl tetrazole |
Non-Patent Citations (2)
| Title |
|---|
| ALIREZA NAJAFI CHERMAHINI等: "Clay-Catalyzed Synthesis of 5-Substituent 1-H-Tetrazoles", 《JOURNAL OF HETEROCYCLIC CHEMISTRY》 * |
| ALIREZA NAJAFI CHERMAHINI等: "Simple and Efficient Synthesis of 5-Substituted 1-H-Tetrazoles Using Metal-Modified Clay Catalysts", 《HETEROATOM CHEMISTRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111943899A (en) * | 2020-09-08 | 2020-11-17 | 河北凯力昂生物科技有限公司 | Synthesis method of 5-ethyl formate tetrazole |
| CN111943899B (en) * | 2020-09-08 | 2023-04-21 | 河北凯诺中星科技有限公司 | Synthesis method of 5-ethyl formate tetrazole |
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Application publication date: 20160113 |