Michael Addition of Aminothiophenols to α,β-Unsaturated Ketones with High Steric Hindrance Catalyzed by CeCl3·7H2O-NaI†

doi:10.7503/cjcu20130646

Abstract

Abstract:

In this paper, the Michael additions of o-aminothiophenol, p-chloro-o-aminothiophenol, m-aminothiophenol, p-aminothiophenol and p-methylthiophenol to α,β-unsaturated ketones(1a—1o) catalyzed by CeCl₃·7H₂O-NaI were systematically studied. The results show that the CeCl₃·7H₂O-NaI-SiO₂ system works well for the reaction of the o-aminothiophenol and p-chloro-o-aminothiophenol to the α,β-unsaturated ketones(1a—1o). Under the optimal reaction conditions, i.e., n(CeCl₃·7H₂O):n(NaI):n(α,β-unsaturated ketones)=1:2:2, m(CeCl₃·7H₂O):m(SiO₂)=1:1.6, the reaction time of 2 h, at reflux temperature and CHCl₃ as solvent, the reactions proceed with moderate yields(43.1%—58.8%). The catalyst is basically stable after recycling the conjugate addition reaction four times. In addition, the possible catalytic mechanism was proposed.

Key words: CeCl3·7H2O-NaI, Catalysis, Michael addition, Aminothiophenol, Catalytic mechanism

CLC Number:

O626

TrendMD:

LIU Qian, LI Wenhong, QIU Zhaolai, LI Yuan. Michael Addition of Aminothiophenols to α,β-Unsaturated Ketones with High Steric Hindrance Catalyzed by CeCl₃·7H₂O-NaI^†[J]. Chem. J. Chinese Universities, 2014, 35(3): 538.

Figures/Tables 8

References 25

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Entry	Catalyst	Molar ratio of catalyst to 1d	Solvent	Time/h	Yield(%)
1	TsOH	1:10	CH₃OH	2	0^b
2	TsOH	1:10	CHCl₃	2	Trace^b
3	TsOH	1:10	CHCl₃	6	Trace^b
4	FeCl₃	1:10	CHCl₃	2	0^b
5	HClO₄-SiO₂	1:10	CH₃OH	2	0^b
6	HClO₄-SiO₂	1:10	CHCl₃	2	0^b
7	HOAc	1:10	CHCl₃	2	0^b
8	HOAc	1:10	CH₃OH	2	0^b
9	CeCl₃·7H₂O-NaI	1:3	CHCl₃	2	42.8^c
10	CeCl₃·7H₂O-NaI	1:2	CHCl₃	2	50.9^c
11	CeCl₃·7H₂O	1:3	CHCl₃	2	Trace^b
12	(CH₃)₃COK	1:3	CHCl₃	2	0^b
13	(CH₃CH₂)₃N	1:3	CHCl₃	2	0^b
14	(CH₃CH₂)₃N	1:3	CH₃OH	2	0^b
15	(CH₃CH₂)₃N	1:3	CH₃OH	8	0^b
16	DIPEA	1:3	CHCl₃	2	0^b
17	EtONa	1:10	DMF	2	0^b
18	EtONa	1:10	CHCl₃	2	0^b
19	Montmorillonite K10	2%^d	CHCl₃	2	0^b

Entry	Catalyst	Molar ratio of catalyst to 1d	Solvent	Time/h	Yield(%)
1	TsOH	1:10	CH₃OH	2	0^b
2	TsOH	1:10	CHCl₃	2	Trace^b
3	TsOH	1:10	CHCl₃	6	Trace^b
4	FeCl₃	1:10	CHCl₃	2	0^b
5	HClO₄-SiO₂	1:10	CH₃OH	2	0^b
6	HClO₄-SiO₂	1:10	CHCl₃	2	0^b
7	HOAc	1:10	CHCl₃	2	0^b
8	HOAc	1:10	CH₃OH	2	0^b
9	CeCl₃·7H₂O-NaI	1:3	CHCl₃	2	42.8^c
10	CeCl₃·7H₂O-NaI	1:2	CHCl₃	2	50.9^c
11	CeCl₃·7H₂O	1:3	CHCl₃	2	Trace^b
12	(CH₃)₃COK	1:3	CHCl₃	2	0^b
13	(CH₃CH₂)₃N	1:3	CHCl₃	2	0^b
14	(CH₃CH₂)₃N	1:3	CH₃OH	2	0^b
15	(CH₃CH₂)₃N	1:3	CH₃OH	8	0^b
16	DIPEA	1:3	CHCl₃	2	0^b
17	EtONa	1:10	DMF	2	0^b
18	EtONa	1:10	CHCl₃	2	0^b
19	Montmorillonite K10	2%^d	CHCl₃	2	0^b

Entry	Solvent	Molar ratio of CeCl₃·7H₂O to 1d	Yield(%)	Entry	Solvent	Molar ratio of CeCl₃·7H₂O to 1d	Yield(%)
1	CHCl₃	1:1	44.6^b	6	DMSO	1:1	0^c
2	C₆H₆	1:1	35.6^b	7	THF	1:1	Trace^c
3	CH₃OH	1:1	Trace^c	8	CHCl₃	1:5	40.5^b
4	CH₃CN	1:1	0^c	9	CHCl₃	1:3	42.8^b
5	DMF	1:1	0^c	10	CHCl₃	1:2	50.9^b

Entry	Solvent	Molar ratio of CeCl₃·7H₂O to 1d	Yield(%)	Entry	Solvent	Molar ratio of CeCl₃·7H₂O to 1d	Yield(%)
1	CHCl₃	1:1	44.6^b	6	DMSO	1:1	0^c
2	C₆H₆	1:1	35.6^b	7	THF	1:1	Trace^c
3	CH₃OH	1:1	Trace^c	8	CHCl₃	1:5	40.5^b
4	CH₃CN	1:1	0^c	9	CHCl₃	1:3	42.8^b
5	DMF	1:1	0^c	10	CHCl₃	1:2	50.9^b

Chalcone	Amino thiophenol	Product	Yield^b (%)	Chalcone	Amino thiophenol	Product	Yield^b (%)
1a	2a	3aa	53.6	1j	2a	3ja	48.1
1b	2a	3ba	50.9	1k	2a	3ka	48.3
1c	2a	3ca	48.7	1g	2b	3gb	58.8
1a	2b	3ab	43.5	1h	2b	3hb	43.1
1b	2b	3bb	44.3	1i	2b	3ib	48.3
1c	2b	3cb	45.7	1j	2b	3jb	46.4
1d	2a	3da	50.9	1k	2b	3kb	45.7
1e	2a	3ea	44.9	1l	2a	3la	47.6
1f	2a	3fa	47.3	1m	2a	3ma	43.1
1d	2b	3db	53.9	1n	2a	3na	57.0
1e	2b	3eb	46.6	1l	2b	3lb	45.5
1f	2b	3fb	49.5	1m	2b	3mb	47.5
1g	2a	3ga	43.2	1n	2b	3nb	45.1
1h	2a	3ha	51.2	1o	2a	3oa	48.6
1i	2a	3ia	52.8	1o	2b	3ob	46.9

Michael Addition of Aminothiophenols to α,β-Unsaturated Ketones with High Steric Hindrance Catalyzed by CeCl₃·7H₂O-NaI^†

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Chalcone	Aminothiophenol	Molar ratio^b	Time/h	Product	Yield(%)
1g	2d	1:2	2	5gd	Trace^d
1g	2d	1:2	5	5gd	30.3^e
1i	2d	1:2	5	5id	18.4^e
1g	2e	1:1	5	6ge^c	Trace^d
1g	2e	1:5	5	6ge^c	Trace^d
1g	2e	1:2	5	6ge^c	30.6^e
1g	2e	1:2	8	6ge^c	30.6^e
1f	2e	1:2	5	6fe^c	8.4^e

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