Selective Synthesis of Unsaturated Alcohols over Heterogeneous Metal-Ion Catalysts

多相金属离子催化剂选择性合成不饱和醇

• 批准号: 11650808
• 负责人: NISHIYAMA Satoru
• 金额: $ 2.3万
• 依托单位: Kobe University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11650808/
• 关键词: Tin oxide; Zirconium oxide; MCM-41; Active carbon; Crotonaldehyde; Acetophenone; Hydrogen transfer; Selective reduction; メソポーラス多孔質体; シリカゲル; 不飽和カルボニル化合物; 不飽和アルコール; 選択的還元反応

Mesoporous silicate, MCM-41 was synthesized by using hexadecyl trimethyl ammonium bromide as a template. MCM-41, SiO_2, Al_2O_3, TiO_2 and some zeolites were impregnated with some kinds of tin and zirconium salts. The catalyst were calcined and reduced at prescribed temperatures.The selective reductions of crotonaldehyde and acctophenone were carried out with a secondary alcohol in stainless steel autoclave (30 ml).Hydrogenation of crotonaldehyde over metallic catalysts produces significant amount of butyraldehyde and 1-butanol, corresponding hydrogenates of C=C doublc bond. The addition of Sn was effective to improve the selectivity of crotyl alcohol, corresponding hydrogenate of carbonyl group over metallic catalysts. The supported Sn and Zr catalysts indicated that carbonyl groups were selectivcly reduced via hydrogen transfer reaction from secondary alcohol added as a solvent (MPV reduction). The effects of support and starting salts were investigated. Silica including MCM-41 was suitable for the support of Sn and Zr. Acidic or basic support was not effective. Zirconium supported on active carbon was also highly active. Neutral porous materials should be selected for the supports. Tin acetate for Sn catalysts and zirconium oxychloride for Zr catalysts were ones of the best starting salts, respectively Dependence of reduction temperature on the yicld of unsaturated alcohol indicated that Sn (II) and Zr (IV) were active species for the selective reduction of carbonyl compounds. Enatiomeric-excess of S-1-phenyl ethanol was improved by the addition of cinconidine in the reation mixture.

以十六烷基三甲基溴化铵为模板剂合成了介孔硅酸盐MCM-41。用某些锡盐和锆盐浸渍MCM-41、SiO_2、Al_2O_3、TiO_2和部分沸石。将催化剂在规定的温度下煅烧和还原。在不锈钢高压釜（30ml）中用仲醇选择性还原巴豆醛和苯乙酮。巴豆醛在金属催化剂上加氢产生大量的丁醛和1-丁醇，相应的C=C双键的氢化物。 Sn的添加有效提高了巴豆醇（相应的羰基氢化物）在金属催化剂上的选择性。负载型 Sn 和 Zr 催化剂表明，通过氢转移反应，羰基被作为溶剂添加的仲醇选择性还原（MPV 还原）。研究了支持物和起始盐的影响。包括MCM-41在内的二氧化硅适合作为Sn和Zr的载体。酸性或碱性支持无效。活性炭负载的锆也具有高活性。支撑体应选用中性多孔材料。 Sn催化剂的乙酸锡和Zr催化剂的氯氧化锆分别是最好的起始盐。还原温度对不饱和醇产率的依赖性表明Sn(II)和Zr(IV)是选择性还原羰基的活性物质化合物。通过在反应混合物中添加辛可定来改善S-1-苯基乙醇的对映体过量。

项目成果

S.C.Tsang: "Nanoscopic Tin-Oxygen linings on Mesoporous Silica as Novel Catalyst for Hydrogen Transfer Reaction"Nanostructured Materials. 12(5-8). 999-1002 (1999)

S.C.Tsang：“介孔二氧化硅上的纳米锡氧衬里作为氢转移反应的新型催化剂”纳米结构材料。

R.Burch: "Nanoscopic Tin-oxygen Lining on Mesoporous Silica as a Novel Catalyst for Organie Hydrogen Transfor Reaction"Applied Catalysis A General. 194-195. 297-307 (2000)

R.Burch：“介孔二氧化硅上的纳米锡氧衬里作为有机氢转移反应的新型催化剂”应用催化概述。

S.C.Tsang: "Nanoscopic Tin-Oxygen linings on Mesoporous Silica as Novel Catalyst for Hydrogen Transfer Reaction"Nanostructured Materials. 12(5-8). 999-1002 (1999)

S.C.Tsang：“介孔二氧化硅上的纳米锡氧衬里作为氢转移反应的新型催化剂”纳米结构材料。

西山覚: "担持ZrO_2触媒による不飽和アルデヒドの液相選択還元反応"触媒. 41・6. 389-391 (1999)

Satoru Nishiyama：“使用负载型 ZrO_2 催化剂进行不饱和醛的液相选择性还原”，催化 41・6。

Satoru Nishiyama: "Infrared Spectroscopy Study of Aldehydes Adsorbed on Rh-Sn Bimetallic Systems : Selective Activation of Aldehydes by Tin"The Journal of Physical Chemistry B.. 103. 4431-4439 (1999)

Satoru Nishiyama：“吸附在 Rh-Sn 双金属体系上的醛的红外光谱研究：锡对醛的选择性活化”物理化学杂志 B.. 103. 4431-4439 (1999)