CN1709877A - 5-substituted aromatic laydrocarbon tetrazole production method - Google Patents
5-substituted aromatic laydrocarbon tetrazole production method Download PDFInfo
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- CN1709877A CN1709877A CN 200510040243 CN200510040243A CN1709877A CN 1709877 A CN1709877 A CN 1709877A CN 200510040243 CN200510040243 CN 200510040243 CN 200510040243 A CN200510040243 A CN 200510040243A CN 1709877 A CN1709877 A CN 1709877A
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- laydrocarbon
- substituted aromatic
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
This invention has disclosed a manufacturing method for 5-substituted aromatic-tetrazole. In existing of the organic solvent and catalyst, arenenitrile reacts with sodium azide to get it. This invention is easy to use, suitable for production for industrialization, craft is simple, the acceptive rate of the products is up to 90-95 percent.
Description
Technical field:
The present invention relates to a kind of nitrogen-containing heterocycle compound and preparation method.
Background technology:
5 substituted aromatic laydrocarbon tetrazoles are widely used in a plurality of fields such as medicine, agricultural chemicals, fine chemistry industry, they not only can be used as cephalosporin and husky smooth class medicine intermediate, and some aryl radical tetrazole can also be used for polymers such as nylon 66 as the whipping agent of chemical, the wetting agent of glass fiber reinforced polycarbonate and the solubilizing agent of mineral oil etc.
Existing 5 substituted aromatic laydrocarbon tetrazole synthesis techniques be from aryl radical nitrile and hydrazoic acid under solvent and catalyst action, react, refining, though yield is higher, hydrazoic acid toxicity is bigger, unsuitable suitability for industrialized production; Another kind of technology is react under solvent and catalyst action, make with extra care from alkyl nitrile and sodiumazide, and its process recovery ratio is lower.
Summary of the invention:
The object of the present invention is to provide a kind of production method that is applicable to suitability for industrialized production, 5 substituted aromatic laydrocarbon tetrazoles that yield is high.
Technical solution of the present invention is:
A kind of production method of 5 substituted aromatic laydrocarbon tetrazoles is characterized in that: under the condition that organic solvent and catalyzer exist, reaction makes by aryl radical nitrile and sodiumazide, and reaction formula is:
Wherein, R=H, 2-Cl, 2-F, 3-Cl, 3-Br, 3-F, 4-Cl, 4-Br, 4-F;
Catalyzer is triethylamine, ammonia chloride or TEBA.
Organic solvent is benzene or toluene.Acid is hydrochloric acid or sulfuric acid.The mol ratio of aryl radical nitrile and sodiumazide is 1: 0.8～1.5, the consumption of organic solvent is 1～10 times of aryl radical nitrile consumption by weight, catalyst consumption is 0.2～50% of aryl radical nitrile consumption by weight, and the aryl radical nitrile is 1: 0.4～1.8 with the mol ratio of acid.Acid is to drip gradually in 2～24 hours.
Technology of the present invention is simple, and is easy to operate, suitability for industrialized production, and product yield is up to 90～95%.
The invention will be further described below in conjunction with embodiment.
Embodiment:
Embodiment 1:
In reactor, with 1 mole cyanobenzene and 1.0 moles (or 0.8 mole, 1.5 sodiumazide mole) joins 5 times (or 1 times, 10 times) in the benzene (or toluene) of cyanobenzene weight, and adding is cyanobenzene consumption 0.2～50% (example 0.2% by weight, 10%, 30%, 50%) catalyzer TEBA (or triethylamine, ammonia chloride), at 10 hours (or 2 hours, 24 hours) interior gradual slow adds 1.3 moles (or 0.4 mole, 1.8 concentrated hydrochloric acid (or vitriol oil) mole), drip and finish back restir 2～12 hours, after reaction finishes, add in the entry and stir, filter, obtain crude product, oven dry obtains product 5-phenyl tetrazole, and yield is 95%.
Reaction formula:
Embodiment 2
In reactor, with 1 mole o-Cyanochlorobenzene and 1.0 moles (or 0.8 mole, 1.5 sodiumazide mole) joins 5 times (or 1 times, 10 times) in the toluene (or benzene) of o-Cyanochlorobenzene weight, and adding is o-Cyanochlorobenzene consumption 0.2～50% (example 0.2% by weight, 10%, 30%, 50%) catalyst of triethylamine (or TEBA, ammonia chloride), gradual slow adds 1.8 moles (or 0.4 mole in 24 hours, 1.2 concentrated hydrochloric acid (or vitriol oil) mole), drip and finish back restir 2～12 hours, after reaction finishes, add in the entry and stir, filter, obtain crude product, oven dry obtains product 5-Chloro-O-Phenyl tetrazole, and yield is 92%.
Reaction formula:
Embodiment 3:
With the aryl radical nitrile
The R base, become 2-Br, 3-Cl, 3-Br, 3-F, 4-Cl, 4-Br or 4-F, all the other steps obtain corresponding 5 substituted aromatic laydrocarbon tetrazoles with embodiment 1, yield is all between 90～95%.
Claims (5)
1, a kind of production method of 5 substituted aromatic laydrocarbon tetrazoles is characterized in that: under the condition that organic solvent and catalyzer exist, reaction makes by aryl radical nitrile and sodiumazide, and reaction formula is:
Wherein, R=H, 2-Cl, 2-F, 3-Cl, 3-Br, 3-F, 4-Cl, 4-Br, 4-F;
Catalyzer is triethylamine, ammonia chloride or TEBA.
2, the production method of 5 substituted aromatic laydrocarbon tetrazoles according to claim 1 is characterized in that: organic solvent is benzene or toluene.
3, the production method of 5 substituted aromatic laydrocarbon tetrazoles according to claim 1 and 2 is characterized in that: acid is hydrochloric acid or sulfuric acid.
4, the production method of 5 substituted aromatic laydrocarbon tetrazoles according to claim 1 and 2, it is characterized in that: the mol ratio of aryl radical nitrile and sodiumazide is 1: 0.8～1.5, the consumption of organic solvent is 1～10 times of aryl radical nitrile consumption by weight, catalyst consumption is 0.2～50% of aryl radical nitrile consumption by weight, and the aryl radical nitrile is 1: 0.4～1.8 with the mol ratio of acid.
5, the production method of 5 substituted aromatic laydrocarbon tetrazoles according to claim 1 and 2 is characterized in that: acid is to drip gradually in 2～24 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100402439A CN1314672C (en) | 2005-05-24 | 2005-05-24 | 5-substituted aromatic laydrocarbon tetrazole production method |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100402439A CN1314672C (en) | 2005-05-24 | 2005-05-24 | 5-substituted aromatic laydrocarbon tetrazole production method |
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| Publication Number | Publication Date |
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| CN1709877A true CN1709877A (en) | 2005-12-21 |
| CN1314672C CN1314672C (en) | 2007-05-09 |
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| CNB2005100402439A Expired - Fee Related CN1314672C (en) | 2005-05-24 | 2005-05-24 | 5-substituted aromatic laydrocarbon tetrazole production method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100591674C (en) * | 2008-02-21 | 2010-02-24 | 南京大学 | Method for catalytic synthesis of 5-substituted tetrazole by tungstate |
| CN101857577A (en) * | 2010-04-27 | 2010-10-13 | 盐城市康乐化工有限公司 | Method for preparing tetrazole compound by taking core-shell magnetic nanoparticles as catalyst |
| CN102145297A (en) * | 2011-01-29 | 2011-08-10 | 浙江金立源药业有限公司 | Solid acid catalyst and method for catalytic synthesis of 5-substituted tetrazole by solid acid catalyst |
| CN102993114A (en) * | 2012-10-11 | 2013-03-27 | 南通市华峰化工有限责任公司 | Method for producing 1H-tetrazole-5-acetic acid |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1238346C (en) * | 2004-03-24 | 2006-01-25 | 南通市华峰化工有限责任公司 | Method for producing 1-ethoxyl-5-mercapto-tetrazole |
-
2005
- 2005-05-24 CN CNB2005100402439A patent/CN1314672C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100591674C (en) * | 2008-02-21 | 2010-02-24 | 南京大学 | Method for catalytic synthesis of 5-substituted tetrazole by tungstate |
| CN101857577A (en) * | 2010-04-27 | 2010-10-13 | 盐城市康乐化工有限公司 | Method for preparing tetrazole compound by taking core-shell magnetic nanoparticles as catalyst |
| CN101857577B (en) * | 2010-04-27 | 2012-07-04 | 盐城市康乐化工有限公司 | Method for preparing tetrazole compound by taking core-shell magnetic nanoparticles as catalyst |
| CN102145297A (en) * | 2011-01-29 | 2011-08-10 | 浙江金立源药业有限公司 | Solid acid catalyst and method for catalytic synthesis of 5-substituted tetrazole by solid acid catalyst |
| CN102993114A (en) * | 2012-10-11 | 2013-03-27 | 南通市华峰化工有限责任公司 | Method for producing 1H-tetrazole-5-acetic acid |
| 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 |
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| CN1314672C (en) | 2007-05-09 |
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Assignee: Jiangsu Defeng Chemical Industry Co., Ltd. Assignor: Huafeng Chemical Co., Ltd., Nantong City Contract fulfillment period: 2009.2.5 to 2015.2.4 contract change Contract record no.: 2009320000118 Denomination of invention: 5-substituted aromatic laydrocarbon tetrazole production method Granted publication date: 20070509 License type: Exclusive license Record date: 2009.2.18 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2009.2.5 TO 2015.2.4; CHANGE OF CONTRACT Name of requester: JIANGSU DEFENG MEDICINE CHEMICAL INDUSTRY CO., LTD Effective date: 20090218 |
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Granted publication date: 20070509 Termination date: 20120524 |