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Process for production of 1-aryl-5-(trifluoromethyl)-1h- tetrazoles

A kind of aryl, trifluoroimidoacetyl technology, applied in directions such as organic chemistry, can solve problems such as difficult to remove, not favorable

Inactive Publication Date: 2006-11-15
TOYOBO CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

But this method produces two or more times the weight of the target product as solid triphenylphosphine oxide and is difficult to remove
Also, the method is not industrially favorable since the yield is only 76%

Method used

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  • Process for production of 1-aryl-5-(trifluoromethyl)-1h- tetrazoles
  • Process for production of 1-aryl-5-(trifluoromethyl)-1h- tetrazoles
  • Process for production of 1-aryl-5-(trifluoromethyl)-1h- tetrazoles

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0061] N-phenyl-2,2,2-trifluoroiminoacetyl chloride

[0062]

[0063] 7g (37.0mmol) 2,2,2-trifluoro-N-phenylacetamide, 19.84g (74.0mmol) diphenyl chlorophosphate, 7.44g (74.0mmol) triethylamine and 28ml acetonitrile were added to 100ml React in the flask for 15 hours while refluxing (82°C). After the reaction, the reaction solution was cooled to room temperature, 28 ml of ethyl acetate was added thereto, and then the precipitate was removed by filtration. The filtrate was evaporated to remove the solvent, and the obtained crude product was purified by column chromatography (silica gel, ethyl acetate: hexane = 3: 7) to obtain 6.24 g of N-phenyl-2,2,2-trifluoroimino Yellow liquid of acetyl chloride (yield: 81.2%).

[0064] IR (pure, cm -1 ): 1697, 1489, 1286, 1223, 1196, 1161, 947, 766, 725, 691

[0065] 1 H-NMR (CDCl 3 ): δ7.41-7.24 (m, 3H), 7.08-7.05 (m, 2H)

[0066] 13 C-NMR (CDCl 3 ): δ143.47, 131.94 (q, J=42.8Hz), 129.12, 127.40, 120.63, 116.86 (q, J=275.8Hz)

Embodiment 2

[0068] 1-Phenyl-5-(trifluoromethyl)-1H-tetrazole

[0069]

[0070] 5g (24.1mmol) of N-phenyl-2,2,2-trifluoroiminoacetyl chloride obtained in Example 1, 2.83g (43.4mmol) of sodium azide, 1.66g (12.1mmol) of hydrochloric acid tris Ethylamine and 40ml of toluene were added into a 100ml flask and reacted at 80°C for 16.5 hours. After the reaction, the reaction solution was cooled to room temperature and washed with water (30ml×3). The organic phase was dried over anhydrous magnesium sulfate for 1 hour, filtered and the solvent was evaporated. The obtained crude product was purified by column chromatography (silica gel, ethyl acetate: hexane = 3: 7) to obtain 4.81 g of 1-phenyl-5-(trifluoromethyl)-1H-tetrazole as a pale yellow oil (Yield: 93.2%).

[0071] IR (pure, cm -1 ): 3071, 1531, 1499, 1312, 1207, 1167, 1013, 766, 691

[0072] 1 H-NMR (CDCl 3 ): δ7.60-7.54(m, 3H), 7.38(d, J=8.7Hz, 2H), 7.06(d, J=8.7Hz, 2H), 3.89(s, 3H)

[0073] 13 C-NMR (CDCl 3 ): δ145.90 (q, J=42....

Embodiment 3

[0079] N-(4-methylphenyl)-2,2,2-trifluoroiminoacetyl chloride

[0080]

[0081] 7g (34.5mmol) 2,2,2-trifluoro-N-(4-methylphenyl) acetamide, 18.49g (68.9mmol) diphenyl chlorophosphate, 6.97g (68.9mmol) triethylamine and 35ml of acetonitrile was added into a 100ml flask to react for 18 hours while refluxing (82°C). After the reaction, the reaction solution was cooled to room temperature, 25 ml of ethyl acetate was added, and the precipitate was removed by filtration. The filtrate was evaporated to remove the solvent, and the obtained crude product was purified by column chromatography (silica gel, ethyl acetate: hexane = 3: 7) to obtain 6.77 g of N-(4-methylphenyl)-2,2,2 - Yellow liquid of trifluoroacetyl chloride (yield: 88.6%).

[0082] IR (pure, cm -1 ): 1684, 1506, 1286, 1223, 1196, 1159, 949, 934, 820

[0083] 1 H-NMR (CDCl 3 ): δ7.26-7.22(m, 2H), 7.10-7.04(m, 2H), 2.39(s, 3H)

[0084] 13 C-NMR (CDCl 3 ): δ140.61, 137.85, 130.55 (q, J=42.8Hz), 129.69, 121.23, 11...

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Abstract

A process for the production of N-aryl-2,2,2-trifluoro- acetimidoyl chloride represented by the general formula (2) by reacting a 2,2,2-trifluoro-N-arylacetamide represented by the general formula (1) with both at least one member selected from the group consisting of phosphorus oxychloride and diphenyl- phosphoric acid chloride and a tertiary amine in an organic solvent; and a process for the production of 1-aryl-5 -(trifluoromethyl)-1H-tetrazoles represented by the general formula (4) by reacting an N-aryl-2,2,2-trifluoroacetimidoyl chloride represented by the general formula (2) with an azide in an aromatic hydrocarbon solvent in the presence of an amine salt.

Description

technical field [0001] The invention relates to a preparation method of 1-aryl-5-(trifluoromethyl)-1H-tetrazole and its production intermediate, that is, N-aryl-2,2,2-trifluoroiminoacetyl chloride. 1-Aryl-5-(trifluoromethyl)-1H-tetrazole is an important intermediate of various drugs. Background technique [0002] A known method for preparing tetrazole compounds is to blow hydrogen azide gas into imidoyl chloride compounds at 200° C. or higher (J.Am.Chem.Soc., vol.80, 1958, P.4647). Other known methods include: using sodium azide to react in an aqueous solvent (J.Org.Chem., vol.23, 1958, p.1909); utilizing aprotic polar solvents such as DMF, acetonitrile, etc. to react (Synth .Commun., vol.1, 1971, p.1; J.Org.Chem., vol.19, 1979, p.3281; J.Fluorine Chem., vol.99, 1999, p.83); and similar method. [0003] However, the method of blowing hydrogen azide gas at 200° C. or higher allows toxic hydrogen azide to escape from the reaction system, and thus poses a major safety hazar...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C257/02C07D257/04
Inventor 萩谷一刚佐藤安浩小黑清人光井顺
Owner TOYOBO CO LTD
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