α,β-Vicinal Bromoamine Compounds Converted into α,β-Dehydroamino Derivatives Promoted by Combination of Potassium Carbonate and Thiouea in Water†

doi:10.7503/cjcu20131129

Abstract

Abstract:

In order to promote further development of green chemistry, an easy and efficient new method for the synthesis of fuctionalized enamines from α,β-vicinal bromoamine compounds promoted by combination of potassium carbonate and thiouea in water at room temperature was developed, and the nearly quantitative yields of much products were obtained(up to 99%). 23 structurally different substrates were investigated. The results indicate that the protocol could tolerate various vicinal bromoamine compounds including α,β-vicinal bromoamine esters and ketones. During the elimination process of HBr from vicinal bromoamine compounds, the corresponding intermediate aziridines must be formed. Herein, no matter the substrate was α-amino-β-bromo or α-bromo-β-amino in structurally, the aziridines skeleton in structurally was similar to each other formed from the intramolecular nucleophilic replacement reaction fashion. Because of ring-open reaction of the aziridines have full regiospecificity, the obtained final products are full regiospecificity, too. The structures of all products were confirmed by ¹H NMR, ¹³C NMR and HRMS analysis. When the gram level substrate was tested with this protocol, the nearly quantitative yield of the product was obtained, too. This result indicated that the new method could be possible applied in the industrialization.

Key words: Thiourea, Potassium carbonate, αβ-Vicinal bromoamine, Fuctionalized enamine

CLC Number:

O626.3

TrendMD:

CHEN Zhanguo, WANG Yingjie, LIU De’e, LIU Yali, LI Ya’nan, WANG Dan, GE Miao. α,β-Vicinal Bromoamine Compounds Converted into α,β-Dehydroamino Derivatives Promoted by Combination of Potassium Carbonate and Thiouea in Water^†[J]. Chem. J. Chinese Universities, 2014, 35(7): 1458.

Figures/Tables 6

References 28

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Entry	Base (molar fraction, %)	Accelerator(molar fraction, %)	t/h	Yield^b(%)
1	K₂CO₃(50)	Thiourea(50)	48	45
2	K₂CO₃(200)	Thiourea(200)	24	99
3	Na₂CO₃(200)	Thiourea(200)	24	80
4	NaOAc(200)	Thiourea(200)	24	60
5	K₃PO₄(200)	Thiourea(200)	24	90
6	NaOH(200)	Thiourea(200)	24	Mix.^c
7	KOH(200)	Thiourea(200)	24	Mix.^c
8	0	Thiourea(200)	48	NR^d
9	K₂CO₃(200)	Thiourea(0)	48	NR^d
10	K₂CO₃(100)	Thiourea(200)	48	68
11	K₂CO₃(100)	Thiourea(100)	48	65
12	K₂CO₃(200)	Thiourea(100)	24	99
13	K₂CO₃(200)	Thiourea(50)	48	58
14	K₂CO₃(200)	Urea(100)	24	30^e
15	K₂CO₃(200)	Succinimide(100)	48	NR^d
16	K₂CO₃(200)	Acetamide(100)	48	NR^d
17	K₂CO₃(200)	Benzoylamine(100)	48	NR^d

Entry	Base (molar fraction, %)	Accelerator(molar fraction, %)	t/h	Yield^b(%)
1	K₂CO₃(50)	Thiourea(50)	48	45
2	K₂CO₃(200)	Thiourea(200)	24	99
3	Na₂CO₃(200)	Thiourea(200)	24	80
4	NaOAc(200)	Thiourea(200)	24	60
5	K₃PO₄(200)	Thiourea(200)	24	90
6	NaOH(200)	Thiourea(200)	24	Mix.^c
7	KOH(200)	Thiourea(200)	24	Mix.^c
8	0	Thiourea(200)	48	NR^d
9	K₂CO₃(200)	Thiourea(0)	48	NR^d
10	K₂CO₃(100)	Thiourea(200)	48	68
11	K₂CO₃(100)	Thiourea(100)	48	65
12	K₂CO₃(200)	Thiourea(100)	24	99
13	K₂CO₃(200)	Thiourea(50)	48	58
14	K₂CO₃(200)	Urea(100)	24	30^e
15	K₂CO₃(200)	Succinimide(100)	48	NR^d
16	K₂CO₃(200)	Acetamide(100)	48	NR^d
17	K₂CO₃(200)	Benzoylamine(100)	48	NR^d

Entry	Substrate	Product	t/h	Yield^b(%)
1			24	99
	1a	2a
2			24	98
	1b	2b
3			24	99
	1c	2c
4			24	99
	1d	2d
5			24	99
	1e	2e
6			24	99
	1f	2f
7			24	98
	1g	2g
8			24	96^c
	1h	2h
9			24	98
	1i	2i
10			24	99
	1j	2j
11			24	99
	1k	2k
12			24	99
	1l	2l
13			24	99
	1m	2m
14			24	99
	1n	2n
15			24	98
	1o	2o
16			24	99
	1p	2p
17			24	99
	1q	2q
18			24	97 ^c
	1r	2r
19			24	98
	1s	2s
20			24	99
	1t	2t
21			48	82^c
	1u	2u
22			48	74^c
	1v	2v
23			48	66^c
	1w	2w

Entry	Substrate	Product	t/h	Yield^b(%)
1			24	99
	1a	2a
2			24	98
	1b	2b
3			24	99
	1c	2c
4			24	99
	1d	2d
5			24	99
	1e	2e
6			24	99
	1f	2f
7			24	98
	1g	2g
8			24	96^c
	1h	2h
9			24	98
	1i	2i
10			24	99
	1j	2j
11			24	99
	1k	2k
12			24	99
	1l	2l
13			24	99
	1m	2m
14			24	99
	1n	2n
15			24	98
	1o	2o
16			24	99
	1p	2p
17			24	99
	1q	2q
18			24	97 ^c
	1r	2r
19			24	98
	1s	2s
20			24	99
	1t	2t
21			48	82^c
	1u	2u
22			48	74^c
	1v	2v
23			48	66^c
	1w	2w