三聚氯氰催化及溶剂效应实现温和高效的酮肟贝克曼重排反应

doi:10.6023/cjoc202008018

摘要/Abstract

与其他溶剂的效果显著不同, 以六氟异丙醇为溶剂时, 低用量三聚氯氰可在室温下高效催化酮肟的贝克曼重排反应得到相应的酰胺产物. 本方法操作简便, 催化剂用量少, 溶剂可回收再利用, 条件温和, 官能团兼容性好, 适用底物范围广, 产物收率高, 是一种制备酰胺化合物的相对绿色实用的方法.

关键词: 酮肟, 贝克曼重排, 三聚氯氰, 六氟异丙醇, 温和条件, 酰胺

By using hexafluoroisopropanol as the solvent, a low loading of cyanuric chloride could effectively catalyze the Beckmann rearrangement of ketoximes to obtain the corresponding amide products under mild conditions, such as room temperature and air atmosphere. The effect of hexafluoroisopropanol was greatly different from that of other solvents. This method has the advantages of simple operation, low catalyst loading, recoverability of solvent, mild conditions, good tolerance of the functional groups, broad substrate scope and high product yields. It is a relatively green and practical method for the preparation of amide compounds.

Key words: ketoxime, Beckmann rearrangement, cyanuric chloride, hexafluoroisopropanol, mild condition, amide

引用此文

周婷婷, 刘霞, 叶子航, 周奕鹏, 杨雅淇, 徐清. 三聚氯氰催化及溶剂效应实现温和高效的酮肟贝克曼重排反应[J]. 有机化学, 2021, 41(2): 688-694.

Tingting Zhou, Xia Liu, Zihang Ye, Yipeng Zhou, Yaqi Yang, Qing Xu. Cyanuric Chloride Catalysis and Solvent Effect Leading to a Mild and Efficient Beckmann Rearrangement of Ketoximes[J]. Chinese Journal of Organic Chemistry, 2021, 41(2): 688-694.

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参考文献 31

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Entry	Cat. (mol%)	Solvent	T^b/℃	t/h	Yield^c/%
1	AlCl₃ (20)	CH₃CN	100	6	88
2	ZnCl₂ (20)	CH₃CN	100	6	56
3	FeCl₃ (20)	CH₃CN	100	6	71
4	MoO₃ (20)	CH₃CN	100	6	Trace
5	MnO₂ (20)	CH₃CN	100	6	Trace
6	T_SCl (20)	CH₃CN	100	6	69
7	Phosphonitrilic chloride trimer (20)	CH₃CN	100	6	81
8	Cyanuric chloride (20)	CH₃CN	100	6	84
9	Cyanuric chloride (20)	CH₃CN	100	2	86
10	Cyanuric chloride (20)	DMF	100	2	66
11	Cyanuric chloride (20)	DCE	100	2	75
12	Cyanuric chloride (20)	THF	100	2	76
13	Cyanuric chloride (20)	TFA	100	2	93
14	Cyanuric chloride (20)	HFIP	100	2	95
15	Cyanuric chloride (20)	HFIP	60	2	96
16	Cyanuric chloride (10)	HFIP	60	2	94
17^d	Cyanuric chloride (10)	HFIP	60	2	90
18^d	Cyanuric chloride (10)	HFIP	45	2	91
19^d	Cyanuric chloride (5)	HFIP	45	2	80
20^d	Cyanuric chloride (5)	HFIP	r.t.	2	75
21^d	Cyanuric chloride(1)	HFIP	r.t.	24	95
22^d	Cyanuric chloride (0.5)	HFIP	r.t.	24	89
23^d	Cyanuric chloride (0.3)	HFIP	r.t.	24	77
24^d	—	HFIP	r.t.	24	36

Entry	Cat. (mol%)	Solvent	T^b/℃	t/h	Yield^c/%
1	AlCl₃ (20)	CH₃CN	100	6	88
2	ZnCl₂ (20)	CH₃CN	100	6	56
3	FeCl₃ (20)	CH₃CN	100	6	71
4	MoO₃ (20)	CH₃CN	100	6	Trace
5	MnO₂ (20)	CH₃CN	100	6	Trace
6	T_SCl (20)	CH₃CN	100	6	69
7	Phosphonitrilic chloride trimer (20)	CH₃CN	100	6	81
8	Cyanuric chloride (20)	CH₃CN	100	6	84
9	Cyanuric chloride (20)	CH₃CN	100	2	86
10	Cyanuric chloride (20)	DMF	100	2	66
11	Cyanuric chloride (20)	DCE	100	2	75
12	Cyanuric chloride (20)	THF	100	2	76
13	Cyanuric chloride (20)	TFA	100	2	93
14	Cyanuric chloride (20)	HFIP	100	2	95
15	Cyanuric chloride (20)	HFIP	60	2	96
16	Cyanuric chloride (10)	HFIP	60	2	94
17^d	Cyanuric chloride (10)	HFIP	60	2	90
18^d	Cyanuric chloride (10)	HFIP	45	2	91
19^d	Cyanuric chloride (5)	HFIP	45	2	80
20^d	Cyanuric chloride (5)	HFIP	r.t.	2	75
21^d	Cyanuric chloride(1)	HFIP	r.t.	24	95
22^d	Cyanuric chloride (0.5)	HFIP	r.t.	24	89
23^d	Cyanuric chloride (0.3)	HFIP	r.t.	24	77
24^d	—	HFIP	r.t.	24	36