Solid base-catalyzed reaction of nitriles with methanol to form. alpha. ,. beta. -unsaturated nitriles 2. Surface base property and reaction mechanism

Journal Article · Thu Nov 01 04:00:00 EST 1990 · Journal of Catalysis; (USA)

DOI:https://doi.org/10.1016/0021-9517(90)90059-S· OSTI ID:5536918

Kurokawa, Hideki; Kato, Tatsuro; Kuwabra, Tetsu; Ueda, Wataru; Morikawa, Yutaka; Moro-Oka, Yoshihiko; Ikawa, Tsuneo ^[1]

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1. Tokyo Inst. of Tech. (Japan)

Solid acid and base properties of magnesium oxides activated by transition metal ions, M-MgO, which are effective catalysts for the reaction of nitriles with methanol to form corresponding {alpha},{beta}-unsaturated nitriles, were studied by temperature-programmed desorption of CO{sub 2} and the reaction of isopropyl alcohol, and the reaction mechanism was studied by isotopic tracer methods. The surface base property of magnesium oxide was modified by the addition of a metal ion; the addition of a metal ion with larger ionic radius than that of Mg{sup 2+} induces surface acid sites without any appreciable changes in the amount of surface base site. Active catalysts were formed in the latter case but not in the former case. It was thought that a surface acid property as well as a surface base property played an important role in the course of the reaction. Reaction of deuterium-substituted acetonitrile and methanol revealed that the exchange reaction between hydroxyl hydrogen of methanol and methyl hydrogen of acetonitrile took place readily under the conditions of acrylonitrile synthesis and the isotopic distribution in acetonitrile after the reaction was very close to that of isotopic equilibrium. No exchange reaction between methyl hydrogen of methanol and that of acetonitrile was observed. It was found, on the other hand, that the isotopic exchange reaction between methyl hydrogen of deuterated methanol and light methanol can occur under the same conditions. The reaction mechanism appears to be dehydrogenation of methanol to adsorbed formaldehyde which then reacts with the acetonitrile anion and, after dehydration, yields acrylonitrile.

• OSTI ID: 5536918
• Journal Information: Journal of Catalysis; (USA), Journal Name: Journal of Catalysis; (USA) Vol. 126:1; ISSN 0021-9517; ISSN JCTLA
• Country of Publication: United States
• Language: English

Related Subjects

10 SYNTHETIC FUELS
102000* -- Synthetic Fuels-- Products & By-Products-- (1990-)
ACETONITRILE
ACRYLONITRILE
ALCOHOLS
ALDEHYDES
ALKALINE EARTH METAL COMPOUNDS
CARBON COMPOUNDS
CARBON DIOXIDE
CARBON OXIDES
CATALYSTS
CATALYTIC EFFECTS
CHALCOGENIDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CONTROL
DEHYDRATION
DEHYDROGENATION
DESORPTION
DEUTERIUM
FORMALDEHYDE
HYDROGEN ISOTOPES
HYDROGEN TRANSFER
HYDROXY COMPOUNDS
ISOTOPE APPLICATIONS
ISOTOPES
ISOTOPIC EXCHANGE
KINETICS
LIGHT NUCLEI
MAGNESIUM COMPOUNDS
MAGNESIUM OXIDES
METHANOL
NITRILES
NUCLEI
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PROPANOLS
REACTION KINETICS
STABLE ISOTOPES
SURFACE PROPERTIES
SYNTHESIS
TEMPERATURE CONTROL
TRACER TECHNIQUES