Hydrogenation of Acetophenone Promoted by Ruthenium Complexes of Modified Glucosamine Derivatives†

doi:10.7503/cjcu20140267

Abstract

Abstract:

The glucosamine acetal derivative L1 and sulfonamide derivatives L2—L4 were synthesized via the reaction of hydroxy and/or amine of glucosamine. The catalytic properties of the catalysts generated in situ from the reaction of Ru(Ⅱ) compounds with glucosamine based ligands were evaluated in the hydrogenation of acetophenone with i-PrOH as hydrogen source. The catalytic activity was enhanced by the introduction of organic group into the glucosamine frame. The effects of reaction temperature, time, molar ratio of acetophenone to catalyst and base on the catalytic reaction of the hydrogenation of acetophenone promoted by the combination of RuCl₂(PPh₃)₃/L4 were explored. The turn over frequency(TOF) was up to 1232 h^-1 at 413 K with n(catalyst):n(KOH):n(acetophenone)=1:10:5000. Among the bases used, the potassium isopropoxide was the best one to activate the precatalyst. The kinetic results revealed that the reaction was the first order respect to acetophenone, and the apparent activition energy was 37.13 kJ/mol. The catalyst system of RuCl₂(PPh₃)₃/L4 was stable in the hydrogenation of acetophenone. The plausible reaction mechanism was proposed.

Key words: Hydrogenation, Glucosamine, Ruthenium, Acetophenone

CLC Number:

O621.3

TrendMD:

LIU Xiaojing, ZHOU Hongyong, LIU Bing, LI Xiaona, SONG Shasha, LI Yunqing, WANG Jiaxi. Hydrogenation of Acetophenone Promoted by Ruthenium Complexes of Modified Glucosamine Derivatives^†[J]. Chem. J. Chinese Universities, 2014, 35(11): 2335.

Figures/Tables 7

References 29

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Entry	Ligand	T/K	Conversion(%)	Entry	Ligand	T/K	Conversion(%)
1	GlcN	363	15.6	4	L3	363	57.8
2	L1	363	57.4	5	L4	363	49.5
3	L2	363	40.0

Entry	Ligand	T/K	Conversion(%)	Entry	Ligand	T/K	Conversion(%)
1	GlcN	363	15.6	4	L3	363	57.8
2	L1	363	57.4	5	L4	363	49.5
3	L2	363	40.0

Entry	T/K	n(S)/n(C)	Conversion(%)	TOF/h^-1
1 ^a	318	1000	4.5	15
2 ^a	333	1000	11.1	37
3 ^a	348	1000	24.3	90
4 ^a	363	1000	49.5	165
5 ^a	368	1000	67.2	224
6 ^a	373	1000	96.6	322
7 ^a	383	1000	96.3	321
8 ^a	393	1000	96.5	322
9 ^a	413	1000	96.9	323
10 ^b	393	5000	51.0	850
11 ^b	413	5000	74.2	1232

Entry	T/K	n(S)/n(C)	Conversion(%)	TOF/h^-1
1 ^a	318	1000	4.5	15
2 ^a	333	1000	11.1	37
3 ^a	348	1000	24.3	90
4 ^a	363	1000	49.5	165
5 ^a	368	1000	67.2	224
6 ^a	373	1000	96.6	322
7 ^a	383	1000	96.3	321
8 ^a	393	1000	96.5	322
9 ^a	413	1000	96.9	323
10 ^b	393	5000	51.0	850
11 ^b	413	5000	74.2	1232

Entry	Base	Conversion(%)	Entry	Base	Conversion(%)
1	NEt₃	0.7	5	KOH	49.5
2	NaOH	16.2	6	i-PrOK	60.3
3	K₂CO₃	19.5	7	i-PrOK+t-BuOH	46.0
4	t-BuOK	34.1