628-73-9Relevant articles and documents
Impact of sulfur heteroatoms on the activity of quaternary ammonium salts as phase transfer catalysts for nucleophilic displacement reactions
West, Christy Wheeler,O'Brien, Richard A.,Salter, E. Alan,Hollingsworth, Brian E.,Huynh, Thai L.,Sweat, Rachel E.,Griffin, Nathan J.,Wierzbicki, Andrzej,Davis, James H.
, p. 282 - 288 (2015)
The application of a new class of alkylammonium salts as phase-transfer catalysts was investigated. These salts are tetra(4-thiaalkyl) ammonium bromides, and the key questions of the study focus on how the incorporation of a sulfur atom in the alkyl chains affects the efficacy of the salts as phase-transfer catalysts. Employing the nucleophilic substitution of cyanide for bromide on 1-bromopentane as a model reaction, reaction rate constants and activation energies are evaluated. The kinetic parameters obtained using the tetrathiaalkylammonium salts are compared to those obtained using their tetraalkylammonium analogs. The general trend is that the presence of sulfur in the alkyl chains reduces the reaction rates and increases activation energies. This trend is analyzed both in terms of computational modeling and experimental distribution coefficients to determine the cause of the slower reaction rates. Thiaquats are shown to distribute more into the aqueous phase than traditional quat salts of similar chain length, resulting in lower organic phase concentrations. Quantum calculations indicate stronger ion pairing for the thiaquats, increasing activation energies and slowing reaction rates. Thus, differences in rate enhancements are attributable both to phase distribution and ion pairing effects.
Chemoenzymatic one-pot reaction from carboxylic acid to nitrile: Via oxime
Hecko, Sebastian,Horvat, Melissa,Klempier, Norbert,Martínková, Ludmila,Pátek, Miroslav,R?disch, Robert,Rudroff, Florian,Schiefer, Astrid,Weilch, Victoria,Wilding, Birgit,Winkler, Margit
, p. 62 - 66 (2022/01/22)
We report a new chemoenzymatic cascade starting with aldehyde synthesis by carboxylic acid reductase (CAR) followed by chemical in situ oxime formation. The final step to the nitrile is catalyzed by aldoxime dehydratase (Oxd). Full conversions of phenylacetic acid and hexanoic acid were achieved in a two-phase mode.
METHOD FOR PRODUCING NITRILE
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Paragraph 0080; 0084; 0095-0099, (2021/02/05)
The present invention provides a method of producing a nitrile from a primary amide, characterized in that the primary amide is subjected to a dehydration reaction in a supercritical fluid in the presence of an acid catalyst. The present invention achieves the object of reducing the corrosion of a reactor and the thermal decomposition of raw materials, as well as provides the effect of improving the reaction rate and nitrile selectivity.
A new reagent for efficient synthesis of nitriles from aldoximes using methoxymethyl bromide
ULUDAG, Nesimi,GIDEN, Ozge NUR
, p. 993 - 998 (2021/02/05)
This study outlines an efficient, high-yielding, and rapid method by which to access diverse nitriles from aldoximes with methoxymethyl bromide (MOM-Br) in THF. It represents the first application of MOM-Br as a deoximation reagent to synthesize nitriles. The reaction was performed at reflux to ensure excellent yield (79-96%) of the nitriles within 20-45 minutes. Furthermore, this method has been successfully applied to the synthesis of the synthesis precursor of aromatic, heteroaromatic, cyclic, and acyclic aliphatic.