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Fluoro dihydropyrrole or fluoro pyrrole

A technology of fluorinated dihydropyrrole and substituted dihydropyrrole, which is applied in the field of fluorinated dihydropyrrole or fluoropyrrole and its preparation from allenes, and can solve problems such as cumbersome routes, poor substrate compatibility, and harsh conditions , to achieve the effect of simple steps, high yield and easy synthesis

Active Publication Date: 2013-01-09
SHANGHAI INST OF ORGANIC CHEMISTRY - CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, there are not many methods for synthesizing such fluoropyrroles at present, and there are many problems such as cumbersome routes, poor substrate compatibility, and harsh conditions.

Method used

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  • Fluoro dihydropyrrole or fluoro pyrrole

Examples

Experimental program
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Effect test

example 1

[0036] Example 1: Synthesis

[0037] 3.4mg (0.02mmol) of AgNO 3 , 27.6 mg (0.4 mmol) of K 2 CO 3 , 47.5mg (0.3mmol) of NFSI, 37.1mg (0.1mmol) of allene Add it into the reaction tube, replace the nitrogen, add 1.5ml of anhydrous diethyl ether, and stir at 30°C for 8 hours. Then filter, wash the solid with ethyl acetate, combine the filtrate, concentrate, column chromatography, and obtain 33.5mg product with ethyl acetate and petroleum ether gradient washing method The yield was 86%.

[0038] 1 H NMR (400MHz, CDCl3) δ7.40(d, J=8.0Hz, 2H), 7.29-7.22(m, 5H), 7.16(d, J=8.0Hz, 2H), 5.70(dt, J=5.6, 2.0Hz, 1H), 4.48(dt, J=15.6, 2.4Hz, 1H), 4.36(dt, J=15.6, 5.2Hz, 1H), 4.12-3.95(m, 2H), 2.38(s, 3H), 1.10(t, J=7.2Hz, 3H); 13 C NMR (100MHz, CDCl 3 )δ160.5 (d, J=298.2Hz), 160.0 (d, J=3.7Hz), 143.7, 138.9 (d, J=1.5Hz), 134.9, 129.6, 128.3, 128.3, 127.7, 127.1, 110.3, 66.7 (d, J=2.3Hz), 60.8, 50.5 (d, J=28.2Hz), 21.4, 13.8; 19 F NMR (376MHz, CDCl 3 )δ-107.4 (dt, J=5.2, 2.0Hz...

example 2

[0039] Example 2: Synthesis

[0040] 3.4mg (0.02mmol) of AgNO 3 , 27.6 mg (0.4 mmol) of K 2 CO 3 , 47.5mg (0.3mmol) of NFSI, 44.7mg (0.1mmol) of allene Add it into the reaction tube, add 1.5ml of anhydrous diethyl ether after pumping nitrogen, and stir at 30°C for 10 hours. Then filter, wash the solid with ethyl acetate, combine the filtrate, concentrate, column chromatography, and obtain 19.3mg product with ethyl acetate and petroleum ether gradient washing method and 19.3 mg of product The overall yield was 83%.

[0041] trans-4i

[0042] trans-4i

[0043] 1 H NMR (400MHz, CDCl3) δ7.45-7.35(m, 4H), 7.35-7.27(m, 6H), 7.12(d, J=8.4Hz, 2H), 6.98(d, J=8.4Hz, 2H) , 5.91(dd, J=6.4, 1.6Hz, 1H), 5.74(s, 1H), 4.15-3.95(m, 2H), 2.30(s, 3H), 1.07(t, J=7.6Hz, 3H); 13 C NMR (100MHz, CDCl 3 )δ161.1 (d, J=298.9Hz), 160.3, 143.5, 128.8, 135.8, 135.3, 129.2, 128.9, 128.6 (d, J=6.7Hz), 128.4, 128.3, 128.0, 127.3, 125.5 (d, J =6.7Hz), 108.8, 65.7, 65.6 (d, J=24.5Hz), 60.9, 21....

example 3

[0047] Example 3: Synthesis

[0048] 3.4mg (0.02mmol) of AgNO 3 , 27.6 mg (0.4 mmol) of K 2 CO 3 , 47.5mg (0.3mmol) of NFSI, 29.9mg (0.1mmol) of allene Put it into the reaction tube, add 1.5ml of anhydrous diethyl ether after replacing the nitrogen, and stir at 30°C for 24 hours. Then filter, wash the solid with ethyl acetate, combine the filtrate, concentrate, column chromatography, and obtain 20.6mg product with ethyl acetate and petroleum ether gradient washing method The yield is 65%.

[0049] 1 H NMR (400MHz, CDCl3) δ7.77 (d, J = 8.4Hz, 2H), 7.37-7.32 (m, 6H), 7.31-7.24 (m, 1H), 4.43 (dt, J = 4.4, 4.0Hz, 2H), 4.29(dt, J=4.4, 4.0Hz, 2H), 2.42(s, 3H); 13 C NMR (100MHz, CDCl 3 )δ 148.9 (d, J = 278.9Hz), 144.0, 133.3, 130.0, 129.6 (d, J = 4.7Hz), 128.6, 128.1 (d, J = 2.0Hz), 127.5, 126.3 (d, J = 6.3 Hz), 110.1(d, J=2.8Hz), 52.5(d, J=5.1Hz), 50.8(d, J=31.6Hz), 21.5; 19 F NMR (376MHz, CDCl 3 )δ-126.0 (tt, J=4.8, 4.1Hz); HRMS: calculated value of m / z (EI) [M] + :...

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Abstract

The invention relates to a compound of fluoro dihydropyrrole or fluoro pyrrole and a preparation method thereof, in particular to a 4-fluorine-2, 5-dihydropyrrole compound and a 4-fluorine pyrrole compound and a novel preparation method starting from simple nitrogen-containing allene. Under the metal catalysis, N- fluorobenzenesulfonimide (NFSI) is used as oxidant and serves as a fluorine source simultaneously. The 4-fluorine-2, 5-dihydropyrrole compound is obtained in high selection mode through fluorine amination reaction of the allene. Aromatization is performed on the product to obtain the corresponding 4-fluorine pyrrole compound.

Description

technical field [0001] The present invention relates to a kind of fluorinated dihydropyrrole or fluoropyrrole and its new preparation method from allene. Background technique [0002] Nitrogen-containing heterocycles (such as dihydropyrrole and pyrrole, etc.) are widely used in the fields of medicine and pesticides. By introducing fluoride ions into these nitrogen-containing heterocycle molecules, the activity and efficacy of drugs can be greatly improved. Through literature search, it is found that the drugs and their lead compounds described in a large number of patents contain fluorinated dihydropyrrole or fluoropyrrole structure. However, there are not many methods for synthesizing such fluoropyrroles at present, and there are many problems such as cumbersome routes, poor substrate compatibility, and harsh conditions. Contents of the invention [0003] The problem to be solved by the present invention is to provide a fluorodihydropyrrole or fluoropyrrole. [0004] An...

Claims

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Application Information

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IPC IPC(8): C07D207/48C07D207/34
CPCY02P20/55
Inventor 刘国生徐涛
Owner SHANGHAI INST OF ORGANIC CHEMISTRY - CHINESE ACAD OF SCI
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