氨基葡萄糖衍生物钌络合物催化苯乙酮氢化反应

doi:10.7503/cjcu20140267

摘要/Abstract

摘要：

基于D-氨基葡萄糖氨基及羟基的反应, 制备了缩醛化氨基葡萄糖衍生物L1及磺酰胺基葡萄糖衍生物L2~L4. 将其与Ru(Ⅱ)化合物原位组成催化体系, 考察了该催化体系在苯乙酮氢化反应中的催化活性, 结果表明, 有机基团的引入提高了氨基葡萄糖参与氢化反应的催化活性. 研究了反应温度、时间及碱的种类对RuCl₂(PPh₃)₃/L4催化苯乙酮氢化反应的影响. 动力学研究结果表明, 催化反应对苯乙酮为一级反应, 表观活化能为37.13 kJ/mol, 并提出了可能的反应机理.

关键词: 氢化反应, 氨基葡萄糖, 钌, 苯乙酮

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

中图分类号:

O621.3

TrendMD:

刘晓晶, 周宏勇, 刘兵, 李小娜, 宋沙沙, 李云庆, 王家喜. 氨基葡萄糖衍生物钌络合物催化苯乙酮氢化反应. 高等学校化学学报, 2014, 35(11): 2335.

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^†. Chem. J. Chinese Universities, 2014, 35(11): 2335.

图/表 7

参考文献 29

[1]	Wang C., Wu X. F., Xiao J. L., Chem. Asian J., 2008, 3, 1750—1770
[2]	Malacea R., Poli R., Manoury E., Coord. Chem. Rev., 2010, 254, 729—752
[3]	Li X. N., Zhou H. Y., Feng L., Duan K., Wang J. X., Appl. Organomet. Chem., 2012, 26, 168—174
[4]	Hsu S. F., Plietker B., Chem. Eur. J., 2014, 20, 4242—4245
[5]	Bartoszewicz A., Ahlsten N., Martín-Matute B., Chem. Eur. J., 2013, 19, 7274—7302
[6]	Yang J., Zhao W. B., Yang C. F., Sun X. D., Wang Q., Zhu Y. Q., Chen H., Chem. J. Chinese Universities,2013, 34(7), 1679—1684
	(杨俊, 赵文波, 杨朝芬, 孙晓东, 王齐, 朱艳琴, 陈华. 高等学校化学学报,2013, 34(7), 1679—1684)
[7]	Aydemir M., Meric N., Kayan C., Ok F., Baysal A., Inorg. Chim. Acta,2013, 398, 1—10
[8]	Duan K., Li X. N., Li Y. Q., Wang J. X., Chin. J. Org. Chem., 2012, 32, 1247—1254
	(段凯, 李小娜, 李云庆, 王家喜. 有机化学, 2012, 32, 1247—1254)
[9]	Cheng Z. B., Yu S. L., Li Y. Y., Dong Z. R., Sun G., Huang K. L., Gao J. X., Chem. Res. Chinese Universities,2011, 27(2), 170—173
[10]	Kitamura M., Suga S., Kawai K., Noyori R., J. Am. Chem. Soc., 1986, 108, 6071—6072
[11]	Li X. N., Zhang P. L., Duan K., Wang J. X., Chin. J. Org. Chem., 2012, 32, 19—29
	(李小娜, 张鹏亮, 段凯, 王家喜. 有机化学, 2012, 32, 19—29)
[12]	Wu X. F., Li X. H., McConville M., Saidi O., Xiao J. L., J. Mol. Catal. A: Chem., 2006, 247, 153—158
[13]	Ming Y. H., Fan A. L., Jin Z. L., Jiang J. Y., Xu L., Chem. J. Chinese Universities,2010, 31(8), 1548—1553
	(明燕花, 樊爱丽, 金子林, 蒋景阳, 许禄. 高等学校化学学报,2010, 31(8), 1548—1553)
[14]	Thakur K. G., Ganapathy D., Sekar G., Chem. Commun., 2011, 47, 5076—5078
[15]	Mazuela J., Pàmies O., Diéguez M.,Eur. J. Inorg. Chem., 2013, (12), 2139—2145
[16]	Babin M., Clément R., Gagnon J., Fontaine F. G., New J. Chem., 2012, 36, 1548—1551
[17]	Hallman P. S., Stephenson T. A., Wilkinson G., Inorg. Synth., 1970, 12, 237—240
[18]	Minuth T., Irmak M., Groschner A., Lehnert T., Boysen M. M. K., Eur. J. Org. Chem., 2009, (7), 997—1008
[19]	Bauer T., Tarasiuk J., Pas'niczek K., Tetrahedron: Asymmetry,2002, 13, 77—82
[20]	Coeffard V., Thobie-Gautier C., Beaudet I., Grognec E. L., Quintard J. P., Eur. J. Org. Chem., 2008, (2), 383—391
[21]	Lin C. C., Lin C. H., Wong C. H., Tetrahedron Lett., 1997, 38, 2649—2652
[22]	Bauer T., Smoliński S., Appl. Catal. A: General,2010, 375, 247—251
[23]	Babič A., Pečar S., Synth. Commun., 2008, 38, 3052—3061
[24]	Babič A., Pečar S., Tetrahedron Lett., 2007, 48, 4403—4405
[25]	Xia H. J., Yan H., Shen C., Shen F. Y., Zhang P. F., Catal. Commun., 2011, 16, 155—158
[26]	Nie H. F., Reductive Reaction of Acetophenone Catalyzed by Ruthenium Complex, Hebei University of Technology, Tianjin, 2013
	(聂红芬. 钌络合物催化苯乙酮还原反应的研究, 天津: 河北工业大学, 2013)
[27]	Wu X., Liu J., Li X., Zanotti-Gerosa A., Hancock F., Vinci D., Ruan J., Xiao J., Angew. Chem. Int. Ed., 2006, 45, 6718—6722
[28]	Deshmukh A., Kinage A., Kumar R., Meijboom R., Polyhedron,2010, 29, 3262—3268
[29]	Yamakawa M., Ito H., Noyori R., J. Am. Chem. Soc., 2000, 122, 1466—1478

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