Preparation of Propargylamines Catalyzed by Heterogeneous Catalysts with Double Catalytic Sites†

doi:10.7503/cjcu20170721

Abstract

Abstract:

The supramolecular coordination polymer Ni₂(2,6-NDC)₂(H₂O)₅∙2H₂O(CP-Ni-NDC) was synthesized by hydrothermal method from 2,6-pyridinedicarboxylic acid and nickelous acetate. Then, Au@CP-Ni-NDC and Ag@CP-Ni-NDC catalysts with double catalytic sites were prepared with HAuCl₄ and AgNO₃ as precursors by impregnation method. The two catalysts were characterized by single crystal X-ray diffraction, powder X-ray diffraction(XRD), infrared spectroscopy(IR), thermogravimetric analysis(TG), transmission electron microscopy(TEM), X-ray photoelectron spectroscopy(XPS), inductivity coupled plasma-atomic emiss ions spectrometry(ICP-AES) and temperature-programmed desorption(NH₃-TPD). X-Ray crystallographic results reveal that CP-Ni-NDC is a one-dimensional chain, which further assembles into a three-dimensional supramolecular network via the π-π stacking interaction and hydrogen bonds. IR spectra, NH₃-TPD and XPS results indicated that 4.49%Au@CP-Ni-NDC and 3.43%Ag@CP-Ni-NDC contains Lewis acid-Au(Ag) double catalytic sites. The catalytic performance of the catalysts were examined in one-pot synthesis of structurally divergent propargylamines by three component coupling of aldehyde, alkyne and amine(A³) in 1,4-dioxane. The substrate scope, catalyst reusability and possible mechanism were investigated. The results indicated that 4.49%Au@CP-Ni-NDC and 3.43%Ag@CP-Ni-NDC displyed good catalytic activity. The yields of propargylamines were 63% and 43% over 4.49%Au@CP-Ni-NDC and 3.43%Ag@CP-Ni-NDC at 120 ℃ within 10 h, respectively. Taking into account the total metal content of the catalyst, the TON numbers calculated were 9.9 and 4.8, respectively. 4.49%Au@CP-Ni-NDC and 3.43%Ag@CP-Ni-NDC have good catalytic activities for aromatic aldehydes and aliphatic aldehydes. And the catalysts of 4.49%Au@CP-Ni-NDC and 3.43%Ag@CP-Ni-NDC could be recovered easily by centrifugation and reused four times.

Key words: Coordination polymer, Double catalytic sites, Catalyst, Propargylamine

CLC Number:

O643

TrendMD:

LIU Lili, TAI Xishi, LIU Junbo, LI Dan, ZHOU Xiaojing, ZHANG Lijun, WEI Xiaofei. Preparation of Propargylamines Catalyzed by Heterogeneous Catalysts with Double Catalytic Sites^†[J]. Chem. J. Chinese Universities, 2018, 39(3): 482.

Figures/Tables 13

References 30

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Entry	Catalyst	Aldehyde	Alkyne	t/h	Yield(%)	TON^b
1		Benzaldehyde	Phenylacetylene	10	2
2	CP-Ni-NDC	Benzaldehyde	Phenylacetylene	10	4
3	0.81%Au@CP-Ni-NDC	Benzaldehyde	Phenylacetylene	1	9	7.7
4	2.03%Au@CP--Ni-NDC	Benzaldehyde	Phenylacetylene	1	22	7.5
5	4.49%Au@CP-Ni-NDC	Benzaldehyde	Phenylacetylene	1	50	7.8
6	4.49%Au@CP-Ni-NDC-Py	Benzaldehyde	Phenylacetylene	1	35	5.5
7	4.49%Au@CP-Ni-NDC	Benzaldehyde	Phenylacetylene	10	63	9.9
8	3.43%Ag@CP-Ni-NDC	Benzaldehyde	Phenylacetylene	1	28	3.1
9	3.43%Ag@CP-Ni-NDC	Benzaldehyde	Phenylacetylene	10	43	4.8

Entry	Catalyst	Aldehyde	Alkyne	t/h	Yield(%)	TON^b
1		Benzaldehyde	Phenylacetylene	10	2
2	CP-Ni-NDC	Benzaldehyde	Phenylacetylene	10	4
3	0.81%Au@CP-Ni-NDC	Benzaldehyde	Phenylacetylene	1	9	7.7
4	2.03%Au@CP--Ni-NDC	Benzaldehyde	Phenylacetylene	1	22	7.5
5	4.49%Au@CP-Ni-NDC	Benzaldehyde	Phenylacetylene	1	50	7.8
6	4.49%Au@CP-Ni-NDC-Py	Benzaldehyde	Phenylacetylene	1	35	5.5
7	4.49%Au@CP-Ni-NDC	Benzaldehyde	Phenylacetylene	10	63	9.9
8	3.43%Ag@CP-Ni-NDC	Benzaldehyde	Phenylacetylene	1	28	3.1
9	3.43%Ag@CP-Ni-NDC	Benzaldehyde	Phenylacetylene	10	43	4.8

Entry	Catalyst	Aldehyde	Alkyne	t/h	Yield(%)	TON^b
1	4.49%Au@CP-Ni-NDC	4-Chlorobenzaldehyde	Phenylacetylene	10	44	6.9
2		4-Methylbenzaldehyde	Phenylacetylene	10	97	15.2
3		4-Methoxybenzaldehyde	Phenylacetylene	10	80	12.5
4		Cyclohexylaldehyde	Phenylacetylene	10	93	14.6
5		n-Octanaldehyde	Phenylacetylene	10	99	15.5
6		n-Heptaldehyde	Phenylacetylene	10	99	15.5
7		Benzaldehyde	4-Ethylphenylacetylene	10	36	5.6
8		Benzaldehyde	4-Butylphenylacetylene	10	32	5.0
9		Benzaldehyde	1-Octyne	10	22	3.4
10	3.43%Ag@CP-Ni-NDC	4-Chlorobenzaldehyde	Phenylacetylene	10	31	3.5
11		4-Methylbenzaldehyde	Phenylacetylene	10	75	8.4
12		4-Methoxybenzaldehyde	Phenylacetylene	10	71	8.0
13		Cyclohexylaldehyde	Phenylacetylene	10	70	7.9
14		n-Octanaldehyde	Phenylacetylene	10	81	9.1
15		n-Heptaldehyde	Phenylacetylene	10	99	11.1
16		Benzaldehyde	4-Ethylphenylacetylene	10	27	3.0
17		Benzaldehyde	4-Butylphenylacetylene	10	32	3.6
18		Benzaldehyde	1-Octyne	10	19	2.1

Entry	Catalyst	Aldehyde	Alkyne	t/h	Yield(%)	TON^b
1	4.49%Au@CP-Ni-NDC	4-Chlorobenzaldehyde	Phenylacetylene	10	44	6.9
2		4-Methylbenzaldehyde	Phenylacetylene	10	97	15.2
3		4-Methoxybenzaldehyde	Phenylacetylene	10	80	12.5
4		Cyclohexylaldehyde	Phenylacetylene	10	93	14.6
5		n-Octanaldehyde	Phenylacetylene	10	99	15.5
6		n-Heptaldehyde	Phenylacetylene	10	99	15.5
7		Benzaldehyde	4-Ethylphenylacetylene	10	36	5.6
8		Benzaldehyde	4-Butylphenylacetylene	10	32	5.0
9		Benzaldehyde	1-Octyne	10	22	3.4
10	3.43%Ag@CP-Ni-NDC	4-Chlorobenzaldehyde	Phenylacetylene	10	31	3.5
11		4-Methylbenzaldehyde	Phenylacetylene	10	75	8.4
12		4-Methoxybenzaldehyde	Phenylacetylene	10	71	8.0
13		Cyclohexylaldehyde	Phenylacetylene	10	70	7.9
14		n-Octanaldehyde	Phenylacetylene	10	81	9.1
15		n-Heptaldehyde	Phenylacetylene	10	99	11.1
16		Benzaldehyde	4-Ethylphenylacetylene	10	27	3.0
17		Benzaldehyde	4-Butylphenylacetylene	10	32	3.6
18		Benzaldehyde	1-Octyne	10	19	2.1