An Anomalous Course of the Darzens Reaction Catalyzed with Magnesium Methoxide
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Abstract:
The reaction of benzaldehyde with methyl chloroacetate catalyzed with magnesium methoxide gave beside the expected methyl 2,3-epoxy-3-phenylpropanoate ( I ) also comparable amounts of methyl 2-hydroxy-3-methoxy-3-phenylpropanoate ( II ). The condensation was accompanied by a competing disproportionation of benzaldehyde giving methyl benzoate and benzyl alcohol. The course of the condensation reaction is discussed.Keywords:
Benzaldehyde
Methyl benzoate
Benzyl alcohol
Condensation reaction
The reaction of benzaldehyde with methyl chloroacetate catalyzed with magnesium methoxide gave beside the expected methyl 2,3-epoxy-3-phenylpropanoate ( I ) also comparable amounts of methyl 2-hydroxy-3-methoxy-3-phenylpropanoate ( II ). The condensation was accompanied by a competing disproportionation of benzaldehyde giving methyl benzoate and benzyl alcohol. The course of the condensation reaction is discussed.
Benzaldehyde
Methyl benzoate
Benzyl alcohol
Condensation reaction
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m-Xylene
Mordenite
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Benzaldehyde
Benzyl alcohol
Benzyl benzoate
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In the solvent free oxidation of benzyl alcohol, using supported gold-palladium nanoalloys, toluene is often one of major by-products and it is formed by the disproportionation of benzyl alcohol. Gold-palladium catalysts on acidic supports promote both the disproportionation of benzyl alcohol and oxidative dehydrogenation to form benzaldehyde. Basic supports completely switch off disproportionation and the gold-palladium nanoparticles catalyse the oxidative dehydrogenation reaction exclusively. In an attempt to provide further details on the course of these reactions, we have utilized in situ ATR-IR, in situ DRIFT and inelastic neutron scattering spectroscopic methods, and in this article we present the results of these in situ spectroscopic studies.
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Benzaldehyde
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Methyl benzoate
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The addition of methoxide and hydroxide ions, ammonia, and hydrazine to 7,7-dichlorobicyclo[3,2,0]hept-2-en-6-one (I) has led, by ring opening, to cis-dichloromethylcyclopentenecarboxylic acid derivatives (VI), which in the case of the methyl ester may epimerise to the trans-ester (VIIa). In polar aprotic solvents the ketone (I) gives rise to methyl benzoate, and deuterium labelling indicates that a bicyclo[3,1,0]hex-2-en-4-yl anion is involved.
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Benzyl alcohol
Methyl benzoate
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Noncatalytic Disproportionation and Decarbonylation Reactions of Benzaldehyde in Supercritical Water
Abstract In supercritical water at 400 °C and 0.5 g/cm3 (37 MPa), benzaldehyde is decomposed into benzene and CO at a yield of 16% in 4 h; the latter is considered to be further converted into formic acid in the reaction condition. The decomposition competes against two types of disproportionation reactions. One is cross-disproportionation between benzaldehyde and formic acid, leading to the formation of benzyl alcohol and CO2. The other is self-disproportion of benzaldehyde where benzyl alcohol and benzoic acid are equally generated. The weight of the cross-disproportionation is larger than that of the self-disproportionation. As a result, the yield (6.6%) of benzyl alcohol is ≈2.5 times as large as that of benzoic acid.
Decarbonylation
Benzaldehyde
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The aroma complex of cranberry contains benzaldehyde, benzyl alcohol and benzyl benzoate as major components, and [7-14C] benzoic acid was converted into benzaldehyde, benzyl alcohol, benzyl benzoate, and minor amounts of other benzyl and benzoate esters in tissue slices of ripe cranberry. Hydrolysis of the benzyl benzoate indicated that label was about equally distributed between benzoic acid and benzyl alcohol. [7-14C] benzaldehyde was converted in tissue slices into benzyl alcohol and benzyl benzoate, and hydrolysis of the ester indicated that only the alcohol moiety was labeled. Incubation of cranberry tissue slices with [7-14C] benzyl alcohol yielded primarily benzyl benzoate, and only the alcohol portion of the ester was labeled. All biosynthetic products were identified by radio chromatographic analysis and by preparation of derivatives, and the direct incorporation of precursors into biosynthetic products was demonstrated by chemical degradation studies. These results strongly suggest that, in the biosynthesis of benzyl benzoate, benzoic acid is first reduced to benzaldehyde, followed by reduction of the aldehyde to benzyl alcohol which is subsequently esterified. None of the aforementioned transformations of [14C] benzoic acid and its derivatives could be demonstrated in tissue slices from unripe (green) cranberry, suggesting that development of the ability to synthesize volatile benzenoid compounds is associated with ripening.
Benzaldehyde
Benzyl alcohol
Benzyl benzoate
Benzoic acid
Methyl benzoate
Benzoates
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