醋酸乙烯氢甲酰化反应工艺中的区域选择性研究
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摘要
醋酸乙烯氢甲酰化是带有多官能团的烯烃氢甲酰化反应,即其主要产物2-乙酰氧基丙醛和3-乙酰氧基丙醛具有双官能团酯基和醛基,经氢化水解可以得到1,2-丙二醇和1,3-丙二醇,或者经氧化水解得到乳酸和3-羟基丙酸等重要的工业原料及产品。对HRh(CO)(PPh_3)_3催化醋酸乙烯氢甲酰化反应进行研究,发现其对醋酸乙烯氢甲酰化反应具有良好的催化活性,且对生成2-乙酰氧基丙醛具有良好的选择性。同时对ROPAC(乙酰丙酮三苯基膦羰基铑)催化体系进行考察,发现使用DIOP(邻苯二甲酸二异辛酯)配体并降低反应温度至100℃时,可以增加3-乙酰氧基丙醛选择性。
Hydroformylation of vinyl acetate is reaction of olefins with multi-functional groups. Its main products are 2-acetoxypropanal and 3-acetoxypropanal having bifunctional groups of esters and aldehydes. Then,1,2-propanediol and 1,3-propanediol can be obtained by hydrogenation hydrolysis,or lactic acid and 3-hydroxypropionic acid can be obtained by oxidation hydrolysis. In this paper,the hydroformylation of vinyl acetate catalyzed by HRh( CO)( PPh_3)_3 was studied. It was found that HRh( CO)( PPh_3)_3 had good catalytic activity for the hydroformylation of vinyl acetate and good selectivity for the formation of 2-acetoxypropanal. At the same time,investigation on the catalytic system of ROPAC found that selectivity of 3-acetoxypropanal could be increased when DIOP ligand was invited and reaction temperature lowered to 100 ℃.
Hydroformylation of vinyl acetate is reaction of olefins with multi-functional groups. Its main products are 2-acetoxypropanal and 3-acetoxypropanal having bifunctional groups of esters and aldehydes. Then,1,2-propanediol and 1,3-propanediol can be obtained by hydrogenation hydrolysis,or lactic acid and 3-hydroxypropionic acid can be obtained by oxidation hydrolysis. In this paper,the hydroformylation of vinyl acetate catalyzed by HRh( CO)( PPh_3)_3 was studied. It was found that HRh( CO)( PPh_3)_3 had good catalytic activity for the hydroformylation of vinyl acetate and good selectivity for the formation of 2-acetoxypropanal. At the same time,investigation on the catalytic system of ROPAC found that selectivity of 3-acetoxypropanal could be increased when DIOP ligand was invited and reaction temperature lowered to 100 ℃.
引文
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[2]Cobley C J,Gardner K,Klosin C,et al. Synthesis and application of a new bisphosphite ligand collection for asymmetric hydroformylation of allyl cyanide[J] Journal of Organic Chemistry,2004,69(12):4031-4040.
[3]Bhatt K,Halligudi S. Hydroformylation of allyl alcohol catalysd by[RH(PPH3)3]+montmorillonite:a kineticstudy[J]. Journal of Molecular Catalysis,1994,91(2):187-194.
[4]Breeden S,Cole-Hamilton D J,Foster D F,et al. Rhodiummediated asymmetric hydroformylation with a novel bis(diazaphospholidine)ligand[J]. Angewandte Chemie International Edition,2000,39(22):4106-4108.
[5]Fell B,Barl M. Hydroformylation of vinyl-acetate to propanediol derivatives[J]. Journal of Molecular Catalysis,1977,2(4):301-306.
[6]Tullo A. Nothing but blue skies[J]. Chemical&Engineering News,2004,82(35):40-41.
[7]Arntz D,Wiegand N. Method of paring 1,3-propanediol:US,5015789[P]. 1991-05-14.
[8]Powell J B,Slaugh L H,Forschner T C,et al.(Shell oil company)cobalt-catalyzed process for preparing 1,3-propanediol using a lipophilic bidentate phosphine promotor:US,5545766[P]. 1996-08-13.
[9]Slaugh L H,Arhancet J P. Process for making 3-hydroxypropanal and 1,3-propanediol:US,5304686[P].1994-04-19.
[10]Laffend L A,Nagarajan V,Nakamura C E. Bioconversion of a fermentable carbon source to 1,3-propanediol by a single microorganism:US,6025184[P]. 2000-02-15
[11]Borole Y L,Chaudhari R V. New route for the synthesis of propylene glycols via hydroformylation of vinyl acetate[J].Industrial&Engineering Chemistry Research,2005,44(25):9601-9668.
[12]Anthony G,Abatjoglou,David R,et al. Rhodium-catalyzed low pressure hydroformylation of vinyl esters:solvent and phosphine effects on catalyst activity,selectivity and stability[J]. Journal of Molecular Catalysis,1983,18:381-390.