CN102993114A - Method for producing 1H-tetrazole-5-acetic acid - Google Patents

Method for producing 1H-tetrazole-5-acetic acid Download PDF

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Publication number
CN102993114A
CN102993114A CN2012103833535A CN201210383353A CN102993114A CN 102993114 A CN102993114 A CN 102993114A CN 2012103833535 A CN2012103833535 A CN 2012103833535A CN 201210383353 A CN201210383353 A CN 201210383353A CN 102993114 A CN102993114 A CN 102993114A
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tetrazole
acetic acid
acid
production
catalyzer
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CN102993114B (en
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王德峰
朱小飞
王炳才
张耀斌
石飞
俞健钧
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Jiang Shulin
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HUAFENG CHEMICAL CO Ltd NANTONG CITY
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Abstract

The invention discloses a method for producing 1H-tetrazole-5-acetic acid, which is characterized by comprising two steps: 1) based on cyanoacetic acid as an initial material, reacting with a chloro-compound at 0-30 DEG C for 1-3h with presence of solvent and catalyst to obtain an intermediate product; and 2) adding sodium azide in the intermediate product obtained from the step 1, increasing the temperature to 60-150 DEG C with presence of the solvent and the catalyst, reacting for 6-8h, reducing the temperature to 30 DEG C after the reaction, acidizing the solution with an acid until the pH value of the solution is 1-2, reducing the temperature to 0-5 DEG C once again, and filtering to obtain the target product 1H-tetrazole-5-acetic acid. The method for producing 1H-tetrazole-5-acetic acid has the advantages that the method, which adopts low-cost raw materials, is safe and toxic-free, simple in production process, easy in operation, and high in product yield to 75-85%.

Description

The production method of a kind of 1H-TETRAZOLE-5-acetic acid
Technical field
The present invention relates to the production method of a kind of 1H-TETRAZOLE-5-acetic acid.
Background technology
1H-TETRAZOLE-5-acetic acid, molecular formula are C 3H 4N 4O 2, be a kind of white powder.At present, existing document (Inorganic Chemistry Communications, 2010,13:250-253) reported the production method of 1H-TETRAZOLE-5-acetic acid, take 1H-TETRAZOLE-5-ethyl acetate as raw material, make 1H-TETRAZOLE-5-acetic acid through zinc chloride or Cadmium chloride fine powder hydrolysis, the method product yield is low, the highlyest can only reach 54%, and the raw materials for production price, the zinc chloride of use or Cadmium chloride fine powder are dangerous poisonous, difficulty and product separation cause the method to be unfavorable for applying.Therefore, in order to reduce raw materials cost and to avoid using hazardous agents, seek an operational path that more is fit to industrialization, thereby the yield and the quality that improve 1H-TETRAZOLE-5-acetic acid will extremely there be Research Significance.
Summary of the invention
The production method that the purpose of this invention is to provide the 1H-TETRAZOLE that a kind of raw materials cost is low, technique is simple and safe, product yield is high-5-acetic acid.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is: the production method of a kind of 1H-TETRAZOLE-5-acetic acid, it is characterized in that: the method is reacted in two steps: 1) take cyanoacetic acid as initial substance, in the presence of solvent and catalyzer, react with the chloro thing first, temperature of reaction is 0-30 ℃, and the time is that 1-3h obtains intermediate; 2) will add sodiumazide in the step 1 gained intermediate, in the presence of solvent and catalyzer, be warming up to 60-150 ℃ of reaction 6-8h, reaction is cooled to 30 ℃ after finishing, between sour souring soln pH to 1-2, again be cooled to 0-5 ℃, filter and obtain target product 1H-TETRAZOLE-5-acetic acid, its reactional equation is as follows:
Wherein, described R is pivaloyl group or trimethyl silicon based.
Further, the described catalyzer of step 1) is tertiary amine compounds, described solvent benzol or toluene.
Further, described tertiary amine compounds is triethylamine, N, N-dipropyl-1-propylamine or DMA.
Further, step 2) described catalyzer is ammonium chloride or imines class catalyzer, described solvent benzol or toluene.
Further, step 2) described acid is dilute hydrochloric acid or dilute sulphuric acid.
Further, described dilute hydrochloric acid or dilute sulphuric acid concentration are 15%.
The invention has the advantages that: the present invention adopts low-cost raw material, safety non-toxic, and production technique is simple, easy to operate, and product yield is high, reaches 75-85%.
Embodiment
In order to make the public can fully understand technical spirit of the present invention and beneficial effect; the applicant will describe in detail the specific embodiment of the present invention below; but the applicant is not restriction to technical scheme to the description of embodiment, anyly makes form and immaterial variation all should be considered as protection scope of the present invention according to the present invention's design.
Embodiment 1
Add benzene 500ml, cyanoacetic acid 85g and triethylamine 138ml in the there-necked flask of 1000ml cleaning, stir the dirty pivaloyl chloride 123ml that adds, whole process temperature must not surpass 30 ℃, and is reinforced complete, in 20~30 ℃ of reaction 2h, and for subsequent use in this temperature insulation.
In the flask of another 2000ml cleaning, add benzene 200ml, sodiumazide 71.5g and ammonium chloride 59g, dispersed with stirring, the cyanoacetic acid reaction solution is transferred in the above-mentioned mixed solution, reinforced complete, slowly be warming up to 80 ℃, and in this thermotonus 6h, be cooled to 30 ℃ of hydrochloric acid with interior usefulness 15% and transfer pH to 1-2, slow stirred crystallization, temperature is down to 0-5 ℃ of filtration, filter cake is drained with frozen water 50ml * 3 time rinsing, drying gets white crystals shape solid 103g, and yield is 80.4%.
Embodiment 2
In the there-necked flask of 1000ml cleaning, add toluene 500ml, cyanoacetic acid 85g and triethylamine 138ml, stir the dirty trimethylchlorosilane 86.4ml that adds, whole process temperature must not surpass 30 ℃, and is reinforced complete, in 25~30 ℃ of reaction 2h, and for subsequent use in this temperature insulation.
In the flask of another 2000ml cleaning, add toluene 200ml, sodiumazide 71.5g and succinimide 35g, dispersed with stirring, the cyanoacetic acid reaction solution is transferred in the above-mentioned mixed solution, reinforced complete, slowly be warming up to 110 ℃, and in this thermotonus 7h, be cooled to 30 ℃ of dilute sulphuric acids with interior usefulness 15% and transfer pH to 1-2, slow stirred crystallization, temperature is down to 0-5 ℃ of filtration, filter cake is drained with frozen water 50ml * 3 time rinsing, drying gets white crystals shape solid 98g, yield 76.5%.
Embodiment 3
In the there-necked flask of 1000ml cleaning, add benzene 500ml, cyanoacetic acid 85g and xylidine 121ml, stir the dirty trimethylchlorosilane 86.4ml that adds, whole process temperature must not surpass 30 ℃, and is reinforced complete, in 25~30 ℃ of reaction 3h, and for subsequent use in this temperature insulation.
In the flask of another 2000ml cleaning, add benzene 200ml, sodiumazide 71.5g and succinimide 35g, dispersed with stirring, the cyanoacetic acid reaction solution is transferred in the above-mentioned mixed solution, reinforced complete, slowly be warming up to 80 ℃, and in this thermotonus 7h, be cooled to 30 ℃ of hydrochloric acid with interior usefulness 15% and transfer pH to 1-2, slow stirred crystallization, temperature is down to 0-5 ℃ of filtration, filter cake is drained with frozen water 50ml * 3 time rinsing, drying gets white crystals shape solid 100g, yield 78%.

Claims (6)

1. the production method of 1H-TETRAZOLE-5-acetic acid, it is characterized in that: the method is reacted in two steps: 1) take cyanoacetic acid as initial substance, in the presence of solvent and catalyzer first with the reaction of chloro thing, temperature of reaction is 0-30 ℃, the time is that 1-3h obtains intermediate; 2) will add sodiumazide in the step 1 gained intermediate, in the presence of solvent and catalyzer, be warming up to 60-150 ℃ of reaction 6-8h, reaction is cooled to 30 ℃ after finishing, between sour souring soln pH to 1-2, again be cooled to 0-5 ℃, filter and obtain target product 1H-TETRAZOLE-5-acetic acid, its reactional equation is as follows:
Wherein, described R is pivaloyl group or trimethyl silicon based.
2. the production method of a kind of 1H-TETRAZOLE according to claim 1-5-acetic acid, it is characterized in that: the described catalyzer of step 1) is tertiary amine compounds, described solvent benzol or toluene.
3. the production method of a kind of 1H-TETRAZOLE according to claim 2-5-acetic acid, it is characterized in that: described tertiary amine compounds is triethylamine, N, N-dipropyl-1-propylamine or DMA.
4. the production method of a kind of 1H-TETRAZOLE according to claim 1-5-acetic acid is characterized in that: step 2) described catalyzer is ammonium chloride or imines class catalyzer, described solvent benzol or toluene.
5. the production method of a kind of 1H-TETRAZOLE according to claim 1-5-acetic acid is characterized in that: step 2) described acid is dilute hydrochloric acid or dilute sulphuric acid.
6. the production method of a kind of 1H-TETRAZOLE according to claim 5-5-acetic acid, it is characterized in that: described dilute hydrochloric acid or dilute sulphuric acid concentration are 15%.
CN201210383353.5A 2012-10-11 2012-10-11 A kind of production method of 1H-TETRAZOLE-5-acetic acid Expired - Fee Related CN102993114B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103351352A (en) * 2013-07-15 2013-10-16 南通市华峰化工有限责任公司 Novel synthetic method for 5-phenyl tetrazole
CN103508971A (en) * 2013-09-09 2014-01-15 南通市华峰化工有限责任公司 1H-tetrazole-5-acetic acid one-step synthesis production method
CN103508969A (en) * 2013-09-09 2014-01-15 南通市华峰化工有限责任公司 Synthesis production method of high-purity 1H-tetrazole-5-acetic acid
CN105037330A (en) * 2015-06-23 2015-11-11 西安近代化学研究所 Synthesis method of 4,5-di(1H-5-tetrazol)-1,2,3-triazole

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1709877A (en) * 2005-05-24 2005-12-21 南通市华峰化工有限责任公司 5-substituted aromatic laydrocarbon tetrazole production method
WO2009057139A2 (en) * 2007-10-29 2009-05-07 Natco Pharma Limited Novel 4-(tetrazol-5-yl)-quinazoline derivatives as anti cancer agents

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1709877A (en) * 2005-05-24 2005-12-21 南通市华峰化工有限责任公司 5-substituted aromatic laydrocarbon tetrazole production method
WO2009057139A2 (en) * 2007-10-29 2009-05-07 Natco Pharma Limited Novel 4-(tetrazol-5-yl)-quinazoline derivatives as anti cancer agents

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MEI-FENG WU等: "Hydrothermal syntheses, structures and luminescent properties of group IIB metal coordination polymers based on bifunctional 1H-tetrazolate-5-acetic acid ligand", 《INORGANIC CHEMISTRY COMMUNICATIONS》, 26 November 2009 (2009-11-26), XP026858622 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103351352A (en) * 2013-07-15 2013-10-16 南通市华峰化工有限责任公司 Novel synthetic method for 5-phenyl tetrazole
CN103351352B (en) * 2013-07-15 2015-10-21 南通市华峰化工有限责任公司 A kind of 5-phenyl tetrazole novel synthesis
CN103508971A (en) * 2013-09-09 2014-01-15 南通市华峰化工有限责任公司 1H-tetrazole-5-acetic acid one-step synthesis production method
CN103508969A (en) * 2013-09-09 2014-01-15 南通市华峰化工有限责任公司 Synthesis production method of high-purity 1H-tetrazole-5-acetic acid
CN105037330A (en) * 2015-06-23 2015-11-11 西安近代化学研究所 Synthesis method of 4,5-di(1H-5-tetrazol)-1,2,3-triazole

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