TY - JOUR

T1 - Oxidation, oxidative esterification and ammoxidation of acrolein over metal oxides

T2 - Do these reactions include nucleophilic acyl substitution?

AU - Koltunov, Konstantin Yu

AU - Sobolev, Vladimir I.

AU - Bondareva, Valentina M.

N1 - Publisher Copyright: © 2016 Elsevier B.V.

PY - 2017/1/1

Y1 - 2017/1/1

N2 - It is known that nucleophilic acyl substitution in the RCOX compounds with “good leaving” groups X is a fundamental and energetically favorable route to carboxylic acid derivatives. When water, alcohols and ammonia are used as nucleophiles, carboxylic acids, esters and amides (or nitriles) are obtained, respectively. On the other hand, the same products are derived from aldehydes upon their catalytic aerobic oxidation, on condition that water, alcohols and ammonia are present in the feed gas. Therefore, one can surmise that nucleophilic substitution reactions are involved intrinsically in the catalytic oxidation reactions. In agreement with this hypothesis we have shown, as an example, that the selfsame catalyst, MoVTeNb mixed oxides, enables successful oxidation, oxidative esterification and ammoxidation of acrolein. The mechanistic aspects of these reactions are considered based on established organic and general chemistry principles.

AB - It is known that nucleophilic acyl substitution in the RCOX compounds with “good leaving” groups X is a fundamental and energetically favorable route to carboxylic acid derivatives. When water, alcohols and ammonia are used as nucleophiles, carboxylic acids, esters and amides (or nitriles) are obtained, respectively. On the other hand, the same products are derived from aldehydes upon their catalytic aerobic oxidation, on condition that water, alcohols and ammonia are present in the feed gas. Therefore, one can surmise that nucleophilic substitution reactions are involved intrinsically in the catalytic oxidation reactions. In agreement with this hypothesis we have shown, as an example, that the selfsame catalyst, MoVTeNb mixed oxides, enables successful oxidation, oxidative esterification and ammoxidation of acrolein. The mechanistic aspects of these reactions are considered based on established organic and general chemistry principles.

KW - Acrolein

KW - Acrylic acid

KW - Acrylonitrile

KW - Methyl acrylate

KW - Nucleophilic acyl substitution

KW - Vanadium mixed oxide catalyst

KW - MIXED OXIDES

KW - SELECTIVE OXIDATION

KW - PROPANE AMMOXIDATION

KW - HYDROGEN-ATOM TRANSFER

KW - METHANOL OXIDATION

KW - FLOW REACTOR

KW - ACETIC-ACID

KW - CATALYTIC-PROPERTIES

KW - ACRYLIC-ACID

KW - PD CATALYST

UR - http://www.scopus.com/inward/record.url?scp=84993138288&partnerID=8YFLogxK

U2 - 10.1016/j.cattod.2015.12.030

DO - 10.1016/j.cattod.2015.12.030

M3 - Article

AN - SCOPUS:84993138288

VL - 279

SP - 90

EP - 94

JO - Catalysis Today

JF - Catalysis Today

SN - 0920-5861

ER -