N-无保护苯胺电化学硒醚化反应构建4-(烃基硒代)苯胺

doi:10.6023/cjoc202109044

摘要/Abstract

报道了一种无过渡金属催化剂、无化学氧化剂条件下N-无保护苯胺的电化学硒醚化反应. 该反应在非分隔电解槽中进行, 实现了温和电化学条件下4-(芳基硒代)苯胺和4-(烷基硒代)苯胺化合物的高效合成. 该反应具有良好的官能团兼容性和易放大等优点, 为合成4-(烃基硒代)苯胺类化合物提供了绿色实用的合成方法.

关键词: N-无保护苯胺, 二烃基二硒醚, 电化学合成, 温和条件, 绿色化学

A transition-metal-free and chemical oxidant-free method was developed for the uniform synthesis of 4-arylselanylanilines and 4-alkylselanylanilines through electrolytic selenylation of N-unprotected anilines with diorganyl diselenides under mild conditions in an undivided cell. The present approach had good functional group compatibility, which made it to be a green and practical method to synthesize 4-(organylselanyl)anilines.

Key words: N-unprotected anilines, diorganyl diselenides, electrochemical synthesis, mild conditions, green chemistry

引用此文

李文艺, 唐胤恒, 欧阳文韬, 陆雨函, 陈锦杨, 何卫民. N-无保护苯胺电化学硒醚化反应构建4-(烃基硒代)苯胺[J]. 有机化学, 2021, 41(12): 4766-4772.

Wenyi Li, Yinheng Tang, Wentao Ouyang, Yuhan Lu, Jinyang Chen, Weimin He. Electrochemical Selenylation of N-Unprotected Anilines for Consturcing 4-(Organylselanyl)anilines[J]. Chinese Journal of Organic Chemistry, 2021, 41(12): 4766-4772.

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参考文献 16

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Entry	Variation from the standard reaction conditions	Yield/%
1	None	95
2	C (+)\|Pt (–) instead of Pt (+)\|Pt (–)	80
3	RVC (+)\|Pt (–) instead of Pt (+)\|Pt (–)	63
4	C (+)\|C (–) instead of Pt (+)\|Pt (–)	63
5	RVC (+)\|RVC (–) instead of Pt (+)\|Pt (–)	34
6	Pt (+)\|Ni foam (–) instead of Pt (+)\|Pt (–)	81
7	ⁿBu₄NBF₄ instead of KI	Trace
8	ⁿBu₄NBr instead of KI	Trace
9	Et₄NClO₄ instead of KI	Trace
10	LiBF₄ instead of KI	Trace
11	ⁿBu₄NI instead of KI	61
12	I₂ (10 mol) instead of KI	70
13	DMF as the solvent	77
14	DMA as the solvent	49
15	DCM as the solvent	16
16	THF as the solvent	9
17	10 mol of KI, 12 h	46
18	30 mol of KI, 6 h	95
19	4 mA instead of 6 mA, 12 h	40
20	12 mA instead of 6 mA, 6 h	89
21	No electric current	N.D.
22	N₂atmosphere instead of air atmosphere	95

Entry	Variation from the standard reaction conditions	Yield/%
1	None	95
2	C (+)\|Pt (–) instead of Pt (+)\|Pt (–)	80
3	RVC (+)\|Pt (–) instead of Pt (+)\|Pt (–)	63
4	C (+)\|C (–) instead of Pt (+)\|Pt (–)	63
5	RVC (+)\|RVC (–) instead of Pt (+)\|Pt (–)	34
6	Pt (+)\|Ni foam (–) instead of Pt (+)\|Pt (–)	81
7	ⁿBu₄NBF₄ instead of KI	Trace
8	ⁿBu₄NBr instead of KI	Trace
9	Et₄NClO₄ instead of KI	Trace
10	LiBF₄ instead of KI	Trace
11	ⁿBu₄NI instead of KI	61
12	I₂ (10 mol) instead of KI	70
13	DMF as the solvent	77
14	DMA as the solvent	49
15	DCM as the solvent	16
16	THF as the solvent	9
17	10 mol of KI, 12 h	46
18	30 mol of KI, 6 h	95
19	4 mA instead of 6 mA, 12 h	40
20	12 mA instead of 6 mA, 6 h	89
21	No electric current	N.D.
22	N₂atmosphere instead of air atmosphere	95