CN102442961A - Production method of 1-methyl tetrazole - Google Patents
Production method of 1-methyl tetrazole Download PDFInfo
- Publication number
- CN102442961A CN102442961A CN201010537157XA CN201010537157A CN102442961A CN 102442961 A CN102442961 A CN 102442961A CN 201010537157X A CN201010537157X A CN 201010537157XA CN 201010537157 A CN201010537157 A CN 201010537157A CN 102442961 A CN102442961 A CN 102442961A
- Authority
- CN
- China
- Prior art keywords
- tetrazole
- methyl
- solvent
- methyl tetrazole
- working method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OMAFFHIGWTVZOH-UHFFFAOYSA-N 1-methyltetrazole Chemical compound CN1C=NN=N1 OMAFFHIGWTVZOH-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 150000003536 tetrazoles Chemical class 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000010992 reflux Methods 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 11
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 5
- 235000015320 potassium carbonate Nutrition 0.000 claims description 5
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- VRESBNUEIKZECD-UHFFFAOYSA-N 2-methyltetrazole Chemical compound CN1N=CN=N1 VRESBNUEIKZECD-UHFFFAOYSA-N 0.000 description 4
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 238000003810 ethyl acetate extraction Methods 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- -1 nitrogen-containing heterocycle compound Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Plural Heterocyclic Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses a production method of 1-methyl tetrazole, which is characterized by comprising the following steps: 1-methyl tetrazole is generated by the reaction of tetrazole and dimethyl carbonate under the condition of reflux reaction in a weakly alkaline catalyst and a solvent, and a target product is obtained by post-treatment. The method has the advantages of simple process, easy operation and high product yield which is 50-82.5%.
Description
Technical field:
The present invention relates to a kind of preparation method of nitrogen-containing heterocycle compound.
Background technology:
Existing 1-methyl tetrazole is produced; As: Zhurnal Organicheskoi Khimii (1984), 20 (2), 398-404. has introduced with the adjusting refluxed reaction at acetic acid of aqueous methylamine solution, triethyl orthoformate and sodiumazide; Processing obtains 1-methyl tetrazole; This technology is used sodiumazide and acetic acid, not only blast easily, and also also very big to corrosion on Equipment property; Mendeleev Communications, (1), 10-11; 1995 grades have been introduced to be reacted under alkaline condition by tetrazole and methyl-sulfate and have been obtained 1-methyl tetrazole, use the methyl-sulfate severe toxicity in the technology.
Summary of the invention:
The object of the present invention is to provide a kind of technology simple, the working method of the 1-methyl tetrazole that yield is high.
Technical solution of the present invention is:
The working method of 1-methyl tetrazole, its characteristic: in weakly alkaline catalyzer, solvent, under the back flow reaction condition, react generation 1-methyl tetrazole, reaction formula by tetrazole and methylcarbonate:
Further, reaction is under the reflux condition, to carry out.
Further, the weakly alkaline catalyzer is meant: yellow soda ash or salt of wormwood or sodium hydrogencarbonate or saleratus.
Further, solvent is meant: the alcoholic solvent of THF or 2-methyltetrahydrofuran or N or toluene or benzene or C1-10.
Further, the mol ratio of tetrazole, methylcarbonate, catalyzer, solvent is: tetrazole: methylcarbonate: catalyzer: solvent=1: 0.6～20: 0.6～20: 2～100.
Technology of the present invention is simple, and is easy to operate, and product yield is high, reaches 50～82.5%.
Below in conjunction with embodiment the present invention is done into-goes on foot explanation:
Embodiment:
Embodiment 1:
1 mole tetrazole, 1.5 moles methylcarbonate, 1.1 moles salt of wormwood joined in 600 milliliters the N, be heated to 130 ℃ of back flow reaction 18 hours, reaction finishes the most of solvent of back pressure reducing and steaming; In debris, add 1000 ml waters; Stirred 1 hour, and, merged organic layer with 400 milliliters ethyl acetate extraction four times; Concentrating under reduced pressure desolvates; Product is collected in decompression, obtains 1-methyl tetrazole 58.5 grams (yield 69.6%), 2-methyl tetrazole 14.2 grams (yield 16.9%).
Embodiment 2:
1 mole tetrazole, 1.5 moles methylcarbonate, 1.1 moles salt of wormwood joined in 800 milliliters the toluene, heated 130 ℃ of back flow reaction 24 hours, reaction finishes the back and adds 1000 ml waters; Stirred 1 hour, layering, water layer is used 400 milliliters twice of methylbenzene extraction again; Merge organic layer, concentrating under reduced pressure desolvates, and product is collected in decompression; Obtain 1-methyl tetrazole 69.3 grams (yield 82.5%), 2-methyl tetrazole 5.2 grams (yield 6.2%).
Embodiment 3:
1 mole tetrazole, 1.5 moles methylcarbonate, 1.1 moles salt of wormwood joined in 600 milliliters the THF, be heated to 130 ℃ of back flow reaction 48 hours, reaction finishes the most of solvent of back pressure reducing and steaming; In debris, add 1000 ml waters; Stirred 1 hour, and, merged organic layer with 400 milliliters ethyl acetate extraction four times; Concentrating under reduced pressure desolvates; Product is collected in decompression, obtains 1-methyl tetrazole 58.5 grams (yield 69.6%), 2-methyl tetrazole 18.1 grams (yield 21.5%).
Embodiment 4:
1 mole tetrazole, 1.5 moles methylcarbonate, 1.1 moles yellow soda ash joined in 600 milliliters the N, be heated to 130 degree reactions 18 hours, reaction finishes the most of solvent of back pressure reducing and steaming; In debris, add 1000 ml waters; Stirred 1 hour, and, merged organic layer with 400 milliliters ethyl acetate extraction four times; Concentrating under reduced pressure desolvates; Product is collected in decompression, obtains 1-methyl tetrazole 43.5 grams (yield 51.8%), 2-methyl tetrazole 25.1 grams (yield 29.9%).
Claims (5)
1. the working method of a 1-methyl tetrazole is characterized in that: in weakly alkaline catalyzer, solvent under the back flow reaction condition, reaction generates 1-methyl tetrazole, reaction formula by tetrazole and methylcarbonate:
2. the working method of 1-methyl tetrazole according to claim 1 is characterized in that: reaction is under the reflux condition, to carry out, said Heating temperature 100-140 ℃.
3. the working method of 1-methyl tetrazole according to claim 1 is characterized in that: said weakly alkaline catalyzer is meant: yellow soda ash or salt of wormwood or sodium hydrogencarbonate or saleratus.
4. the working method of 1-methyl tetrazole according to claim 1 is characterized in that: said solvent is meant: the alcoholic solvent of THF or 2-methyltetrahydrofuran or N or toluene or benzene or C1-10.
5. the working method of 1-methyl tetrazole according to claim 1 is characterized in that: the mol ratio of tetrazole, methylcarbonate, catalyzer, solvent is: tetrazole: methylcarbonate: catalyzer: solvent=1: 0.6～20: 0.6～20: 2～100.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010537157XA CN102442961A (en) | 2010-11-10 | 2010-11-10 | Production method of 1-methyl tetrazole |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010537157XA CN102442961A (en) | 2010-11-10 | 2010-11-10 | Production method of 1-methyl tetrazole |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102442961A true CN102442961A (en) | 2012-05-09 |
Family
ID=46005941
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010537157XA Pending CN102442961A (en) | 2010-11-10 | 2010-11-10 | Production method of 1-methyl tetrazole |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102442961A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103508972A (en) * | 2013-09-09 | 2014-01-15 | 南通市华峰化工有限责任公司 | 2-methyl-5-aminotetrazole synthesis production method |
| CN103524445A (en) * | 2013-09-09 | 2014-01-22 | 南通市华峰化工有限责任公司 | Method for synthetic production of 1-methyl-5-aminotetrazole |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1860117A (en) * | 2003-07-28 | 2006-11-08 | 詹森药业有限公司 | Benzimidazole, benzthiazole and benzoxazole derivatives and their use as lta4h modulators |
-
2010
- 2010-11-10 CN CN201010537157XA patent/CN102442961A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1860117A (en) * | 2003-07-28 | 2006-11-08 | 詹森药业有限公司 | Benzimidazole, benzthiazole and benzoxazole derivatives and their use as lta4h modulators |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103508972A (en) * | 2013-09-09 | 2014-01-15 | 南通市华峰化工有限责任公司 | 2-methyl-5-aminotetrazole synthesis production method |
| CN103524445A (en) * | 2013-09-09 | 2014-01-22 | 南通市华峰化工有限责任公司 | Method for synthetic production of 1-methyl-5-aminotetrazole |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103665032A (en) | Preparation method of glufosinate | |
| TW201918474A (en) | Method for preparing azoxystrobin intermediates | |
| CN102391114B (en) | Method for synthesizing n-decanal ester | |
| CN111187154A (en) | Synthetic method of sitagliptin intermediate 2,4, 5-trifluoro phenylacetic acid | |
| CN111440133A (en) | Method for preparing D, L-pantoic acid lactone by normal pressure reduction | |
| CN102627608A (en) | Preparation method for analgesic and antipyretic drug-analgin | |
| CN102442961A (en) | Production method of 1-methyl tetrazole | |
| CN102816076A (en) | Synthetic method of p-hydroxyphenylglycine | |
| CN116178136B (en) | A kind of preparation method of 2-hexyldecanoic acid | |
| CN104326988B (en) | A kind of synthetic method of 2,4-dichloro-5-methoxy pyrimidines | |
| CN104262160B (en) | A kind of preparation method of 2-nitro-2-methyl isophthalic acid-propyl alcohol | |
| CN102531897A (en) | Method for preparing alpha-replacing malonic acid diacetoxyiodo derivative | |
| CN102391083A (en) | Method for synthesizing decyl acetal aldehyde | |
| CN105566257A (en) | Industrial preparation method of acetyl tetrahydrofuran with high optical purity | |
| CN102442962A (en) | Production method of 1-alkyl tetrazole | |
| CN104277027A (en) | Preparation method of (R)-propylene carbonate | |
| CN106478431B (en) | A kind of method of synthesis of trans hexamethylene dimethylamine | |
| CN103755706B (en) | A kind of environment-friendly preparation method synthesizing folic acid | |
| CN105254574B (en) | A kind of simple and convenient process for preparing of the cyanopyrimidine of 2 methyl of vitamin B1 key intermediate, 4 amino 5 | |
| CN102558071A (en) | Method for synthesizing (+/-)-thiopental | |
| CN110498781A (en) | A kind of synthetic method of D, L- pantolactone | |
| CN102020600B (en) | Synthetic method of indole-2-carboxylic acid | |
| CN104151161B (en) | A kind of 2-(2-allyl group) preparation method of amylene-4-acid methyl esters | |
| CN102775319B (en) | Method for preparing methyldopa through microwave basic hydrolysis 5-methyl-5-(3,4-dimethoxy benzyl) hydantoin | |
| CN105175320A (en) | Preparation method of 3-hydroxypyridine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120509 |