Pyruvic acid and its isomers, including the enol tautomers and enantiomeric lactone structures, have been investigated at the B3LYP/6-311 + + G(3df,3pd) level, and it is found that a keto form with trans C(methyl)C(keto)C(acid)O(hydroxyl) and cis C(keto)C(acid)OH, and with one methyl hydrogen in a synperiplanar position with respect to the keto oxygen, is the most stable. This agrees with previous theoretical and experimental determinations. However, no minimum corresponding to protonated pyruvate could be located, although previous semiempirical calculations had found such structures. Decarboxylation by different possible routes was then studied. It was found that the direct formation of acetaldehyde, the most stable of the resulting C2H4O isomers, via a four-center-like transition state is the most feasible, although there is a high activation barrier of 70 kcal mol(-1). In contrast to semiempirical calculations, it is found that no hydroxyethylidene-carbon dioxide complex exists as a product, and no transition state leading to the dissociation to hydroxethylidene could be located.

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We carried out an experiment in order to obtain the InfraRed (IR) spectra of methyl propionate (CH3CH2COOCH3) in astrochemical conditions and present the IR spectra for future identification of this molecule in the InterStellar Medium (ISM). The experimental IR spectrum is compared with the theoretical spectrum and an attempt was made to assign the observed peak positions to their corresponding molecular vibrations in condensed phase. Moreover, our calculations suggest that methyl propionate must be synthesized efficiently within the complex chemical network of the ISM and therefore be present in cold dust grains, awaiting identification.

In this paper, authors report the synthesis of nanocrystalline hierarchical zeolite ZSM-5 and its application as a heterogeneous catalyst in the alkylation of phenol with cyclohexene. The catalyst was synthesized by vacuum-concentration coupled hydrothermal technique in the presence of two templates. This synthetic route could successfully introduce pores of higher hierarchy in the zeolite ZSM-5 structure. Hierarchical ZSM-5 could catalyse effectively the industrially important reaction of cyclohexene with phenol. We ascribe the high efficiency of the catalyst to its conducive structural features such as nanoscale size, high surface area, presence of hierarchy of pores and existence of Lewis sites along with Brønsted acid sites. The effect of various reaction parameters like duration, catalyst amount, reactant mole ratio and temperature were assessed. Under optimum reaction conditions, the catalyst showed up to 65% selectivity towards the major product, cyclohexyl phenyl ether. There was no discernible decline in percent conversion or selectivity even when the catalyst was re-used for up to four runs. Kinetic studies were done through regression analysis and a mechanistic route based on LHHW model was suggested.

The current paper reports the application of nanocrystalline form of zeolite ZSM-5 in lieu of Friedel Crafts catalysts in the benzylation of anisole using benzyl alcohol. There are many problems associated with the use and disposal of conventional catalysts due to their toxicity, corrosiveness and non-recyclability. Nanocrystalline zeolites can be a less polluting alternative to the conventional Friedel Crafts catalysts. Nanocrystalline ZSM-5 was synthesized by a facile method and was characterized using SEM, XRD and FTIR. The prepared nanocrystalline zeolite was then evaluated for its efficiency and selectivity in liquid phase benzylation of anisole. Optimum conditions of reaction time, temperature, quantity of catalyst and mole ratio of reactants were obtained. Kinetic studies were done to propose a mechanistic model for the catalyzed reaction. Results of this study suggest that the synthesized nanocrystals of zeolites are efficient, selective, stable, consistent and reusable catalysts. This catalyst thus holds the possibility of being a better alternative to homogeneous catalysts, from environmental and economic perspectives.