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Trifluoromethyl-substituted azide, amine and heterocyclic compounds and preparation method

A technology for azide compounds and amine compounds, applied in the field of amines and heterocyclic compounds, trifluoromethyl substituted azides, can solve the problems of low atom economy, high reaction risk, long reaction steps, etc., to achieve Good atom economy, high selectivity, and mild reaction conditions

Active Publication Date: 2017-05-17
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] The technical problem to be solved by the present invention is to overcome the defects in the prior art that the compound containing azide and trifluoromethyl is difficult to synthesize, the reaction risk is high, the reaction steps are long, the reaction yield is low, and the atom economy is low. A trifluoromethyl-substituted azide, amine and heterocyclic compounds and a preparation method are provided. The preparation method of the present invention utilizes a relatively mild trifluoromethylation reagent to directly construct a carbon compound through difunctionalization of an alkene -Nitrogen bond and carbon-carbon bond, efficient and highly selective synthesis of trifluoromethyl-substituted azide, amine and heterocyclic compounds, the preparation method of the present invention has cheap and easy-to-obtain raw materials, mild reaction conditions, and good atom economy , high selectivity, simple post-treatment, environmentally friendly, high yield, suitable for industrial production

Method used

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  • Trifluoromethyl-substituted azide, amine and heterocyclic compounds and preparation method
  • Trifluoromethyl-substituted azide, amine and heterocyclic compounds and preparation method
  • Trifluoromethyl-substituted azide, amine and heterocyclic compounds and preparation method

Examples

Experimental program
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Effect test

example 1

[0098] Add Togni reagent (99.2mg, 0.3mmol) to a 10mL sealed tube, weigh the catalyst Cu(CH 3 CN) 4 PF 6 (3.7mg, 0.01mmol), then transfer out of the glove box, add magnets and 1mL solvent under the protection of nitrogen, and then add TMSN 3 (54μL, 0.4mmol) and styrene (0.2mmol) were added to the sealed tube. After the reaction was stirred at room temperature for 6h, 5mL ethyl acetate was added. The reaction solution was washed twice with water (20mL×2), and then washed once with saturated saline (20mL). The organic layer was spin-dried and directly subjected to column chromatography to obtain 37.4 mg of product The total yield is 87%, 1 H NMR, 13 C NMR and 19 The purity of F NMR is greater than 95%.

[0099] 1 H NMR(400MHz, CDCl 3 )δ7.44-7.28(m,5H), 4.77(dd,J=8.4,5.2Hz,1H), 2.65(dqd,J=15.6,10.4,8.4Hz,1H), 2.48(dqd,J=15.6, 10.4, 5.2Hz, 1H). 13 C NMR(100MHz, CDCl 3 )δ137.6,129.2,129.0,126.6,125.2(d,J=276.4Hz), 59.9(q,J=3.2Hz), 40.3(q,J=28.3Hz). 19 F NMR(376MHz, CDCl 3 )δ-64.10(t,J...

example 2

[0102] Add Togni reagent (99.2mg, 0.3mmol) to a 10mL sealed tube, weigh the catalyst Cu(CH 3 CN) 4 PF 6 (3.7mg, 0.01mmol), then transfer out of the glove box, add magnets and 1mL solvent under the protection of nitrogen, and then add TMSN 3 (54μL, 0.4mmol) and (0.2mmol) was added to the sealed tube. After the reaction was stirred at room temperature for 6h, 5mL ethyl acetate was added. The reaction solution was washed twice with water (20mL×2), and then washed once with saturated saline (20mL). The organic layer was spin-dried and directly subjected to column chromatography to obtain 48.6mg of product The total yield is 89%, 1 HNMR, 13 C NMR and 19 The purity of F NMR is greater than 95%.

[0103] 1 H NMR(400MHz, CDCl 3 )δ7.34(d,J=8.1Hz,2H), 7.29(d,J=8.1Hz,2H), 6.21(b,1H), 4.77(dd,J=8.6,5.0Hz,1H), 3.66( s, 2H), 2.61 (dqd, J=15.2, 10.4, 8.6 Hz, 1H), 2.47 (dqd, J=15.2, 10.4, 5.0 Hz, 1H). 13 C NMR(100MHz, CDCl 3 )δ172.9, 136.8, 134.2, 130.2, 126.9, 125.1 (q, J=277.4Hz), 59.5 (q, J...

example 3

[0106] Add Togni reagent (99.2mg, 0.3mmol) to a 10mL sealed tube, weigh the catalyst Cu(CH 3 CN) 4 PF 6 (3.7mg, 0.01mmol), then transfer out of the glove box, add magnets and 1mL solvent under the protection of nitrogen, and then add TMSN 3 (54μL, 0.4mmol) and (0.2mmol) was added to the sealed tube. After the reaction was stirred at room temperature for 6h, 5mL ethyl acetate was added. The reaction solution was washed twice with water (20 mL×2), and then washed once with saturated saline (20 mL). The organic layer was spin-dried and directly subjected to column chromatography to obtain 42.8 mg of product The total yield is 93%, 1 H NMR, 13 C NMR and 19 The purity of F NMR is greater than 95%.

[0107] 1 H NMR(400MHz, CDCl 3 )δ7.49-7.39(m,4H),7.37-7.32(m,1H), 2.66(dq,J=15.6,10.4Hz,1H), 2.60(dq,J=15.6,10.4Hz,1H),1.88 (q,J=0.9Hz,3H). 13 C NMR(100MHz, CDCl 3 )δ141.9,128.7,128.1,125.3,125.0(d,J=278.3Hz), 62.8(q,J=2.1Hz), 45.2(q,J=27.3Hz), 24.2(q,J=1.7Hz). 19 F NMR(376MHz, CDCl 3 )δ-...

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Abstract

The invention discloses trifluoromethyl-substituted azide, amine and heterocycle compounds and preparing methods thereof. The preparing method of the trifluoromethyl-substituted azide compounds includes following steps of: subjecting a trifluoromethylation agent, azidotrimethylsilane and a carbon-carbon double bond of an olefin to addition in an organic solvent under the existence of a catalyst to obtain a compound in which one carbon in the carbon-carbon double bond of the olefin has trifluoromethyl and the other carbon has an azide group. The preparing methods utilize the trifluoromethylation agent which is mild relatively, directly form a carbon-nitrogen bond and a carbon-carbon bond by double-functionalization of olefins, and efficiently synthesize the trifluoromethyl-substituted azide, amine and heterocycle compounds with high selectivity. The preparing methods are easily available in raw materials, mild in reaction conditions, good in atom economy, high in selectivity, simple in after-treatment, environmental friendly, high in yields and suitable for industrial production.

Description

Technical field [0001] The invention relates to trifluoromethyl substituted azide, amine and heterocyclic compounds and preparation methods. Background technique [0002] Nitrogen-containing compounds are widely used in the fields of medicine, pesticides, etc. By introducing trifluoromethyl into these nitrogen-containing molecules, the activity of the drug can be greatly improved and the efficacy of the drug can be improved. Through literature search, a large number of patents and their lead compounds were found to contain trifluoromethyl substituted amines, amides, and nitrogen-containing heterocyclic structures. However, currently there are not many methods for synthesizing these compounds, and there are many problems such as complicated routes, poor substrate compatibility, and harsh conditions. Summary of the invention [0003] The technical problem to be solved by the present invention is to overcome the disadvantages of the prior art, such as difficulty in synthesis of comp...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07B43/00C07C247/12C07C247/10C07C247/14C07D209/48C07J41/00C07D215/42C07H1/00C07H15/203C07B43/04C07C209/42C07C211/37C07B43/06C07C269/04C07C271/24C07D249/04
Inventor 刘国生王飞
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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