Synthesis of 4, 5-Dihydropyrrole from γ-Nitro-nitrile

doi:10.6023/cjoc201905031

Chinese Journal of Organic Chemistry ›› 2019, Vol. 39 ›› Issue (11): 3162-3168.DOI: 10.6023/cjoc201905031 Previous Articles Next Articles

由γ-硝基腈合成4, 5-二氢吡咯衍生物

文婷, 康梦, 陈战国*()

陕西师范大学化学化工学院陕西省大分子科学重点实验室西安 710119

收稿日期:2019-05-14 发布日期:2019-07-17
通讯作者: 陈战国 E-mail:chzhg@snnu.edu.cn
基金资助:
陕西省自然科学基金(2009JM2011)

Synthesis of 4, 5-Dihydropyrrole from γ-Nitro-nitrile

Wen Ting, Kang Meng, Chen Zhanguo*()

Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710119

Received:2019-05-14 Published:2019-07-17
Contact: Chen Zhanguo E-mail:chzhg@snnu.edu.cn
Supported by:
the Natural Science Foundation of Shaanxi Province(2009JM2011)

1. Supporting Information.pdf(1780KB)

Abstract

A new method for the synthesis of 4, 5-dihydropyrrole derivatives from γ-nitro-nitriles is described. In this procedure, the nitro groups of nitro-nitriles were reduced into aminoes under Fe+HCl systerm in methanol at 30℃ firstly. And then the amino-groups reacted with cyano groups to form target compounds via intramolecular nucleophilic addition reaction and rearrangement reaction. Under the optimized conditions, all γ-nitro-nitriles can be easily converted into 4, 5-dihydropyrrole derivatives in satisfactory yield. It shows that the reaction has better universality. Based on the experimental results, the possible reaction mechanism was proposed.

Key words: 4, 5-dihydropyrrole derivative, γ-nitro-nitrile, malonitrile, ethyl cyanoacetate

Cite this article

Wen Ting, Kang Meng, Chen Zhanguo. Synthesis of 4, 5-Dihydropyrrole from γ-Nitro-nitrile[J]. Chinese Journal of Organic Chemistry, 2019, 39(11): 3162-3168.

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Fig. & Tab. 6

References 9

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Entry	Ar	Product	Yield^b/%
1	C₆H₅	4a-1	59
2	4-CH₃C₆H₄	4a-2	63
3	3, 4-(CH₃)₂C₆H₃	4a-3	53
4	4-CH₃OC₆H₄	4a-4	51
5	3-CH₃OC₆H₄	4a-5	52
6	3, 4, 5-(CH₃O)₃C₆H₂	4a-6	46
7	4-FC₆H₄	4a-7	71
8	4-ClC₆H₄	4a-8	66
9	4-BrC₆H₄	4a-9	65
10	2-Naphthyl	4a-10	45
11	C₆H₅	4b-1	62
12	4-CH₃C₆H₄	4b-2	65
13	3, 4-(CH₃)₂C₆H₃	4b-3	53
14	4-CH₃OC₆H₄	4b-4	65
15	3-CH₃OC₆H₄	4b-5	66
16	3, 4, 5-(CH₃O)₃C₆H₂	4b-6	48
17	4-FC₆H₄	4b-7	65
18	4-ClC₆H₄	4b-8	66
19	4-BrC₆H₄	4b-9	64
20	2-Naphthyl	4b-10	45
21	2-Furyl	4b-11	47
22	3, 4-(CH₃O)₂C₆H₃	4b-12	58


Entry	Ar	Product	Yield^b/%
1	C₆H₅	4a-1	59
2	4-CH₃C₆H₄	4a-2	63
3	3, 4-(CH₃)₂C₆H₃	4a-3	53
4	4-CH₃OC₆H₄	4a-4	51
5	3-CH₃OC₆H₄	4a-5	52
6	3, 4, 5-(CH₃O)₃C₆H₂	4a-6	46
7	4-FC₆H₄	4a-7	71
8	4-ClC₆H₄	4a-8	66
9	4-BrC₆H₄	4a-9	65
10	2-Naphthyl	4a-10	45
11	C₆H₅	4b-1	62
12	4-CH₃C₆H₄	4b-2	65
13	3, 4-(CH₃)₂C₆H₃	4b-3	53
14	4-CH₃OC₆H₄	4b-4	65
15	3-CH₃OC₆H₄	4b-5	66
16	3, 4, 5-(CH₃O)₃C₆H₂	4b-6	48
17	4-FC₆H₄	4b-7	65
18	4-ClC₆H₄	4b-8	66
19	4-BrC₆H₄	4b-9	64
20	2-Naphthyl	4b-10	45
21	2-Furyl	4b-11	47
22	3, 4-(CH₃O)₂C₆H₃	4b-12	58

由γ-硝基腈合成4, 5-二氢吡咯衍生物

Synthesis of 4, 5-Dihydropyrrole from γ-Nitro-nitrile

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Entry	T/℃	Solvent	t/h	Yield^b/%
1	30	CH₃CH₂OH	3	49
2	30	CH₃OH	3	59
3	30	CH₃COCH₃	2	37
4	30	THF	1.5	30
5	30	DMSO	24	Trace
6	30	DMF	2	Trace
7	30	CH₂Cl₂	12	20
8	30	Toluene	12	NR^c
9	30	H₂O	24	NR^c
10	80	H₂O	24	26
11	30	V(CH₃CH₂OH):V(THF)＝1:1	24	55
12	0	CH₃OH	24	36
13	50	CH₃OH	24	42
14	80	CH₃OH	24	16