Synthesis of N-Ester Carbazoles Using Diethyl Azodicarboxylate as Carbon Source

doi:10.6023/cjoc202506008

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (2): 612-623.DOI: 10.6023/cjoc202506008 Previous Articles Next Articles

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以偶氮二甲酸二乙酯为碳源合成N-酯基咔唑

樊良鑫^a, 时梦瑶^a, 刘兴源^a, 潘振良^a, 杨国玉^a, 吴璐璐^a, 薛晓平^a^,^*(), 代莉^b^,^*(), 徐翠莲^a^,^*()

^a 河南农业大学理学院郑州 450002
^b 河南农业大学林学院郑州 450046

收稿日期:2025-06-04 修回日期:2025-08-18 发布日期:2025-10-09
通讯作者: 薛晓平, 代莉, 徐翠莲
基金资助:
国家自然科学基金(22301064); 中原教学名师(21XM0429); 河南省博士后科研启动项目(25XM0040); 河南农业大学专项创新基金(KJCX2021C05); 河南省研究生教育改革与质量提升工程项目(YJS2024AL060); 河南省研究生教育改革与质量提升工程项目(YJS2025KC21); 河南农业大学研究生教育教学改革研究与实践项目(2025YJSJGSJ024); 河南省科技攻关(252102111107)

Synthesis of N-Ester Carbazoles Using Diethyl Azodicarboxylate as Carbon Source

Liangxin Fan^a, Mengyao Shi^a, Xingyuan Liu^a, Zhenliang Pan^a, Guoyu Yang^a, Lulu Wu^a, Xiaoping Xue^a^,^*(), Li Dai^b^,^*(), Cuilian Xu^a^,^*()

^a College of Sciences, Henan Agricultural University, Zhengzhou 450002
^b College of Forestry, Henan Agricultural University, Zhengzhou 450046

Received:2025-06-04 Revised:2025-08-18 Published:2025-10-09
Contact: Xiaoping Xue, Li Dai, Cuilian Xu
Supported by:
National Natural Science Foundation of China(22301064); Central Plains Teaching Master Project(21XM0429); Postdoctoral Research Launch Project of Henan Province(25XM0040); Special Innovation Fund of Henan Agricultural University(KJCX2021C05); Postgraduate Education Reform and Quality Improvement Project of Henan Province(YJS2024AL060); Postgraduate Education Reform and Quality Improvement Project of Henan Province(YJS2025KC21); Graduate Education Reform Project of Henan Agricultural University(2025YJSJGSJ024); Science and Technology Research Project of Henan Province(252102111107)

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Abstract

A novel strategy for the N-acylation of secondary arylamines using diethyl azodicarboxylate (DEAD) as the carbon source under base promotion is presented. Carbazole compounds and DEAD were utilized as substrates, affording a series of diverse N-ester carbazole compounds in 15%~94% yields. This approach proceeds under transition metal-free conditions, and offers the advantages of commercially available and inexpensive starting materials, green and mild reaction conditions, operational simplicity, broad substrate scope, and short reaction times. It provides a convenient method for the simple and efficient synthesis of N-substituted carbazoles. The practical application of this method was demonstrated by the gram-scale (10 mmol) synthesis and product derivatizations. Investigation of reaction mechanism suggests that the reaction proceeds via deprotonation of carbazole under basic conditions, followed by nucleophilic attack of the resulting nitrogen anion on DEAD, and subsequent elimination.

Key words: carbazole, N-acylation, diethyl azodicarboxylate

Cite this article

Liangxin Fan, Mengyao Shi, Xingyuan Liu, Zhenliang Pan, Guoyu Yang, Lulu Wu, Xiaoping Xue, Li Dai, Cuilian Xu. Synthesis of N-Ester Carbazoles Using Diethyl Azodicarboxylate as Carbon Source[J]. Chinese Journal of Organic Chemistry, 2026, 46(2): 612-623.

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Fig. & Tab. 7

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Entry	Substrate	Base	Solvent	T/℃	Yield^b/%
1	1~6	Na₂CO₃	DMSO	80	NR
2	7	Na₂CO₃	DMSO	80	44
3	8	Na₂CO₃	DMSO	80	NR
4	9	Na₂CO₃	DMSO	80	15
5	10	Na₂CO₃	DMSO	80	NR
6	11	Na₂CO₃	DMSO	80	23
7	12	Na₂CO₃	DMSO	80	32
8	13	Na₂CO₃	DMSO	80	92
9	13	Li₂CO₃	DMSO	80	75
10	13	NaOAc	DMSO	80	39
11	13	Na₃PO₄	DMSO	80	73
12	13	NaHCO₃	DMSO	80	54
13	13	Na₂HPO₄	DMSO	80	10
14	13	KHCO₃	DMSO	80	63
15	13	K₂CO₃	DMSO	80	58
16	13	K₃PO₄	DMSO	80	67
17	13	^tBuONa	DMSO	80	51
18	13	Et₃N	DMSO	80	NR
19	13	Na₂CO₃	DCE	80	46
20	13	Na₂CO₃	Toluene	80	51
21	13	Na₂CO₃	1,4-dioxane	80	67
22	13	Na₂CO₃	THF	80	Trace
23	13	Na₂CO₃	DMF	80	73
24	13	Na₂CO₃	MeCN	80	21
25	13	Na₂CO₃	Sulfolane	80	63
26	13	Na₂CO₃	DMSO	70	65
27	13	Na₂CO₃	DMSO	90	91
28^c	13	Na₂CO₃	DMSO	80	78
29^d	13	Na₂CO₃	DMSO	80	70
30^e	13	Na₂CO₃	DMSO	80	Trace

Entry	Substrate	Base	Solvent	T/℃	Yield^b/%
1	1~6	Na₂CO₃	DMSO	80	NR
2	7	Na₂CO₃	DMSO	80	44
3	8	Na₂CO₃	DMSO	80	NR
4	9	Na₂CO₃	DMSO	80	15
5	10	Na₂CO₃	DMSO	80	NR
6	11	Na₂CO₃	DMSO	80	23
7	12	Na₂CO₃	DMSO	80	32
8	13	Na₂CO₃	DMSO	80	92
9	13	Li₂CO₃	DMSO	80	75
10	13	NaOAc	DMSO	80	39
11	13	Na₃PO₄	DMSO	80	73
12	13	NaHCO₃	DMSO	80	54
13	13	Na₂HPO₄	DMSO	80	10
14	13	KHCO₃	DMSO	80	63
15	13	K₂CO₃	DMSO	80	58
16	13	K₃PO₄	DMSO	80	67
17	13	^tBuONa	DMSO	80	51
18	13	Et₃N	DMSO	80	NR
19	13	Na₂CO₃	DCE	80	46
20	13	Na₂CO₃	Toluene	80	51
21	13	Na₂CO₃	1,4-dioxane	80	67
22	13	Na₂CO₃	THF	80	Trace
23	13	Na₂CO₃	DMF	80	73
24	13	Na₂CO₃	MeCN	80	21
25	13	Na₂CO₃	Sulfolane	80	63
26	13	Na₂CO₃	DMSO	70	65
27	13	Na₂CO₃	DMSO	90	91
28^c	13	Na₂CO₃	DMSO	80	78
29^d	13	Na₂CO₃	DMSO	80	70
30^e	13	Na₂CO₃	DMSO	80	Trace

以偶氮二甲酸二乙酯为碳源合成N-酯基咔唑

Synthesis of N-Ester Carbazoles Using Diethyl Azodicarboxylate as Carbon Source

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