Preparation method of compound containing C(sp2)-Br bond

A compound, -br technology, applied in the field of organic synthesis, can solve the problems of poor selectivity, using a large amount of oxidants, etc., and achieve the effects of saving production costs, being environmentally friendly, and having high yields

Inactive Publication Date: 2020-04-17
WUYI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

For this reason, the present invention proposes a kind of containing C (sp 2 The preparation method of )-Br bond compound can overcome the C(sp 2 )-H bond into C(sp 2 )-Br bond poor selectivity, need to use a large amount of oxidant and other defects

Method used

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  • Preparation method of compound containing C(sp2)-Br bond
  • Preparation method of compound containing C(sp2)-Br bond
  • Preparation method of compound containing C(sp2)-Br bond

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1-1

[0076]

[0077] The electrolysis was carried out in a room equipped with two platinum electrodes (4.0×4.0cm 2 ) in an undivided electrolytic cell. 8-aminoquinoline amide derivative 1c (1.104g, 5.34mmol), NH 4 Br(6.23g, 64.08mmol), Cu(OAc) 2 (96.73 mg, 0.534 mmol), DMF (80 mL) was added to the electrolytic cell. Electrolysis was carried out at 60 °C with a constant current of 20 mA for 80 h. After the reaction was complete, it was quenched with ice-cold water and extracted with EtOAc. The combined organic extracts were dried over anhydrous sodium sulfate and filtered, and the solvent was evaporated under reduced pressure to obtain a crude product, which was separated and purified by silica gel column chromatography to obtain a white solid 3c (1.704 g, 93%, purity greater than 95%). 1 H NMR (400MHz, CDCl 3 )δ10.57(s,1H),8.78(dd,J=4.2,1.2Hz,1H),8.75(d,J=8.4Hz,1H),8.42(dd,J=8.6,1.2Hz,1H), 7.84-7.73(m,3H),7.48(dd,J=8.2,4.4Hz,1H),7.42-7.32(m,2H),2.45(s,3H). 13 C NMR (100MH...

Embodiment 1-2

[0079]

[0080] The electrolysis was carried out in a cell equipped with two platinum electrodes (1.0×1.0cm 2 ) in an undivided electrolytic cell. 8-aminoquinoline amide derivative 1h (64.8mg, 0.2mmol), NH 4 Br(232.8mg, 2.4mmol), Cu(OAc) 2 (3.62mg, 0.02mmol), DMF (3mL) was added to the electrolytic cell. The electrolysis was performed at 60 °C for 34 h at a constant current of 3 mA. The progress of the reaction was monitored by TLC. After the reaction was complete, it was quenched with ice-cold water and extracted with EtOAc. The combined organic extracts were dried over anhydrous sodium sulfate and filtered, and the solvent was evaporated under reduced pressure to obtain a crude product, which was separated and purified by silica gel column chromatography to obtain a white solid 2h (79.3 mg, 98%, purity greater than 95%). 1 H NMR (400MHz, CDCl 3 ):δ10.70(s,1H),8.84(dd,J=4.0,1.2Hz,1H),8.81(d,J=8.4Hz,1H),8.49(dd,J=8.4,1.2Hz,1H) ,8.12(d,J=8.0Hz,2H),7.81(d,J=8.0Hz,1H),7...

Embodiment 1-3

[0082]

[0083] Using the same reaction conditions as above, starting from 1i (59.6 mg, 0.25 mmol), electrolysis for 33 h gave 2i (71.0 mg, 94%, purity greater than 95%) as a white solid. 1 H NMR (400MHz, CDCl 3 ):δ10.40(s,1H),8.94(d,J=8.4Hz,1H), 8.75(dd,J=4.4,1.6Hz,1H),8.56-8.50(m,2H),8.01(d, J=8.4Hz,1H),7.95-7.86(m,3H), 7.62-7.51(m,4H); 13 C NMR (101MHz, CDCl 3 ): δ167.68, 148.78, 139.26, 135.97, 134.69, 134.29, 133.86, 131.34, 130.93, 130.27, 128.44, 127.41, 127.25, 126.58, 125.56, 125.45, 112.74.16, 9.12 1 H NMR spectrum as Figure 5 shown; 13 C NMR spectrum as Figure 6 shown.

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Abstract

The invention discloses a preparation method of a compound containing a C(sp2)-Br bond, wherein the compound containing the C(sp2)-Br bond is a compound represented by a formula II. The method comprises the following steps: in the presence of a copper catalyst and a bromide, carrying out a constant-current electrolytic reaction on an 8-aminoquinoline amide derivative represented by a formula I andused as a substrate to obtain the compound containing the C(sp2)-Br bond and represented by the formula II. According to the preparation method disclosed by the invention, an expensive, toxic or dangerous oxidant can be prevented from being used, the C(sp2)-H bond compound can be converted into the product of the C(sp2)-Br bond at high selectivity, and the method is environment-friendly, high inyield, good in purity and suitable for industrial production.

Description

technical field [0001] The invention relates to the field of organic synthesis, in particular to a C(sp 2 )-Br bond compound preparation method. Background technique [0002] Under catalytic conditions, aromatic C(sp 2 )-H into C(sp 2 )-Br bond has always been one of the very important challenges in synthetic chemistry. Over the past decade, regioselective C–H functionalization under transition metal-catalyzed conditions has emerged as an effective method for constructing C–C bonds and C–X (heteroatom) bonds. Especially the transition metal-catalyzed C–H halogenation of arenes as a reaction for building C–X bonds has received much attention. [0003] In 2013, Yu Jinquan's research group reported the use of I 2 Pd-catalyzed C–H iodination as the sole oxidant. In 2015, the Glorius group reported Rh-catalyzed C–H halogenation using NXS. In 2016, Shi Bingfeng's research group reported the use of lithium halide and KMnO 4 Ni-catalyzed C–H halogenation was achieved. Howev...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C25B3/06
CPCC25B3/27
Inventor 梅天胜王向阳徐学涛张焜李冬利
Owner WUYI UNIV
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