Thermoregulated phase transfer ligands and catalysis XVIII:: synthesis of N,N-dipolyoxyethylene-substituted-2-(diphenylphosphino)phenylamine (PEO-DPPPA) and the catalytic activity of its rhodium complex in the aqueous-organic biphasic hydroformylation of 1-decene

被引:41
作者
Liu, C [1 ]
Jiang, JY [1 ]
Wang, YH [1 ]
Cheng, F [1 ]
Jin, ZL [1 ]
机构
[1] Dalian Univ Technol, State Key Lab Fine Chem, Dalian 116012, Peoples R China
基金
中国国家自然科学基金;
关键词
thermoregulated phase transfer catalysis; hydroformylation; thermoregulated phosphine; high olefins;
D O I
10.1016/S1381-1169(02)00601-5
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
A novel water soluble phosphine,N,N-dipolyoxyethylene-substituted-2-(diphenylphosphino)phenylamine (PEO-DPPPA), was synthesized by a two-step ethoxylation of 2-(diphenylphosphino)phenylamine (2-Ph2P-C6H4NH2, DPPPA). In the first step, DPPPA was ethoxylated without catalyst to give an intermediate with an average polyethylene glycol (PEG) chain length (L = m + n) of 3. Thereafter, this intermediate was further ethoxylated by using KOH as a catalyst to obtain the products with needed values of L. The solubility of the products in water increases with increasing of L. When L is more than 35, the products are water-soluble and possess the property of inverse temperature-dependent solubility in water (cloud point, C-p) as nonionic surfactants. The PEO-DPPPA/Rh complex catalyst formed in situ by RhCl3.3H(2)O and PEO-DPPPA (L = 45) has been applied to the aqueous-organic biphasic hydroformylation of 1-decene. The conversion of olefin and the yield of aldehyde are 99.5 and 99.0%, respectively, under the conditions of 120 degreesC, 5.0 MPa (CO/H-2 = 1), P/Rh = 4 (molar ratio), 1-decene/Rh = 1000 (molar ratio) and 5 h. Recycling test shows that both the conversion of olefin and the yield of aldehyde are still higher than 94.0% even after the catalyst has been recycled 20 times. The high reactivity of PEO-DPPPA/Rh complex can be attributed to a process termed thermoregulated phase transfer catalysis. (C) 2002 Elsevier Science B.V. All rights reserved.
引用
收藏
页码:23 / 27
页数:5
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