Trifluoromethyl-substituted azide, amine and heterocycle compounds and preparing methods thereof

A technology for azide compounds and amine compounds, which is applied in the field of amines and heterocyclic compounds, trifluoromethyl-substituted azides, and can solve problems such as difficult synthesis, high reaction risk, and long reaction steps

Active Publication Date: 2015-05-27
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 heterocycle compounds and preparing methods thereof
  • Trifluoromethyl-substituted azide, amine and heterocycle compounds and preparing methods thereof
  • Trifluoromethyl-substituted azide, amine and heterocycle compounds and preparing methods thereof

Examples

Experimental program
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Effect test

example 1

[0098] Add Togni reagent (99.2mg, 0.3mmol) into a 10mL sealed tube, weigh the catalyst Cu(CH 3 EN) 4 PF 6 (3.7mg, 0.01mmol) and transferred out of the glove box, under the protection of nitrogen, add magneton and 1mL solvent, and then add TMSN 3 (54μL, 0.4mmol) and styrene (0.2mmol) were added to the sealed tube, and after the reaction was stirred at room temperature for 6h, 5mL of ethyl acetate was added. The reaction solution was washed twice with water (20mL×2), and once with saturated brine (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,...

example 2

[0102] Add Togni reagent (99.2mg, 0.3mmol) into a 10mL sealed tube, weigh the catalyst Cu(CH 3 EN) 4 PF 6 (3.7mg, 0.01mmol) and transferred out of the glove box, under the protection of nitrogen, add magneton and 1mL solvent, and then add TMSN 3 (54 μL, 0.4 mmol) and (0.2mmol) was added to the sealed tube, and after the reaction was stirred at room temperature for 6h, 5mL of ethyl acetate was added. The reaction solution was washed twice with water (20mL×2), and once with saturated brine (20mL). The organic layer was spin-dried and directly subjected to column chromatography to obtain 48.6 mg of product The total yield is 89%, 1 H NMR, 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=15.2,10.4,8.6Hz,1H),2.47(dqd,J=15.2,10.4,5.0Hz,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=3.1Hz),...

example 3

[0106] Add Togni reagent (99.2mg, 0.3mmol) into a 10mL sealed tube, weigh the catalyst Cu(CH 3 EN) 4 PF 6 (3.7mg, 0.01mmol) and transferred out of the glove box, under the protection of nitrogen, add magneton and 1mL solvent, and then add TMSN 3 (54 μL, 0.4 mmol) and (0.2mmol) was added to the sealed tube, and after the reaction was stirred at room temperature for 6h, 5mL of ethyl acetate was added. The reaction solution was washed twice with water (20mL×2), and once with saturated brine (20mL). 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 (376MH...

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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 a preparation method. Background technique [0002] Nitrogen-containing compounds are widely used in medicine, pesticides and other fields. By introducing trifluoromethyl into these nitrogen-containing molecules, the activity of drugs can be greatly improved and the efficacy of drugs can be improved. Through literature search, it is found that the drugs and their lead compounds described in a large number of patents contain trifluoromethyl-substituted amines, amides, and nitrogen-containing heterocyclic structures. However, there are not many methods for synthesizing these compounds at present, and there are many problems such as cumbersome routes, poor substrate compatibility, and harsh conditions. Contents of the invention [0003] The technical problem to be solved by the present invention is to overcome the defects in the prior art that the compound ...

Claims

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Application Information

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Patent Type & Authority Applications(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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