5340-26-1Relevant articles and documents
METHOD FOR PRODUCING ALCOHOL COMPOUND
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Paragraph 0075; 0076; 0078, (2017/04/28)
PROBLEM TO BE SOLVED: To provide a novel production method that reduces a carboxylic acid derivative to an alcohol compound under a mild reaction condition by using inexpensive copper complex catalysts instead of expensive ruthenium complex catalysts. SOLUTION: An method for producing an alcohol compound comprises a step (2) for reducing a carboxylic acid ester compound with hydrogen in the presence of a copper complex obtained by the reaction of an imidazolium salt (A), a copper compound (B) and a base (C). SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT
Mixed Tishchenko reaction over solid base catalysts
Seki, Tsunetake,Kabashima, Hajime,Akutsu, Kazumasa,Tachikawa, Hiroto,Hattori, Hideshi
, p. 393 - 401 (2007/10/03)
Catalytic behaviors of solid base catalysts for mixed Tishchenko reactions were investigated to elucidate the activity- and selectivity-determining factors in active sites of the catalysts and molecular structures of the reactants. A mixture containing equal amounts of two kinds of aldehydes was allowed to react at 353 K. The aldehydes used were benzaldehyde, pivalaldehyde, and cyclopropanecar-baldehyde. For all the reactions, the catalytic activity of alkaline earth oxides increased in the order of BaO ? MgO 2O3, ZrO2, ZnO, γ-alumina, hydrotalcite, KF/alumina, and KOH/alumina, were all inactive for the mixed Tishchenko reaction of benzaldehyde and pivalaldehyde; not only crossed-condensation products but also self-condensation products hardly formed. Quantum chemical calculations of the positive charges on the carbonyl carbon atoms of aldehydes and the structure parameters of the active species for the ester formations account for the observed selectivities to four Tishchenko dimers. The selectivities to four Tishchenko dimers over MgO and CaO are determined primarily in the step of the nucleophilic addition of the active species (PhCH2O-, tBuCH2O-, and C3H5CH2O-) to the carbonyl carbon atoms of aldehydes. The reaction of the aldehyde having a more positively charged and sterically less-hindered carbonyl carbon atom with the active species having a less-hindered oxygen atom proceeds faster.
Reaction of Organotin Hydrides with Acid Chlorides. Mechanism of Aldehyde and Ester Formation
Lusztyk, J.,Lusztyk, E.,Maillard, B.,Ingold K. U.
, p. 2923 - 2931 (2007/10/02)
Tri-n-butyltin hydride reacts with acid chloride, RCOCl, spontaneously at ambient temperatures to form n-Bu3SnCl, RCHO, RC(O)OCH2R, and a number of minor products.The reaction is not a radical chain process, nor are radicals involved as intermediates.The initial products are n-Bu3SnCl and RCHO; it is not known whether these are formed in a direct reaction between n-Bu3SnH and RCOCl or via an unstable chloroalkyloxytin species, n-Bu3SnOCHClR.The remaining products are formed by subsequent reactions of the aldehyde.Thus, the alkoxytin species, n-Bu3SnOCH2R, is formed from aldehyde and tin hydride.This can react further with RCH2Cl to form the ester RC(O)OCH2R, with RCOCl to form n-Bu3SnOCH(R)OCH2R, and with n-Bu3SnH to form RCH2OH.The aldehyde can also react with RCOCl to form the α'-chloro ester, RC(O)OCHClR.
