Thiazolidine-2,4-dione in benzoylation reaction

Chemistry of Heterocyclic Compounds - The direction of the benzoylation reaction of thiazolidine-2,4-dione under the conditions of basic and general acid catalysis was studied. It was shown that...     

Remarks concerning the effect of environment on the properties of CC and CO bonds

The purpose of this paper is to present, in a simple way, some results recently obtained at the “Centre de Mécanique Ondulatoire Appliquée” in studying the effect of environment on CC and CO bonds.     

OH-initiated oxidation of toluene. 1. Quantum chemistry investigation of the reaction path

In this paper we present the results of a detailed quantum chemistry investigation of the toluene-OH-O2 system, mostly at the B3LYP/6-311G(2df,2pd) level. We focus on OH addition followed by H abstraction to O2, a mechanism based on that proposed by Klotz et al. [Phys. Chem. Chem. Phys. 2000, 2, 227] to explain the experimentally observed photolysis products. A notable feature of the calculated minimum energy pathway is the formation of ketone intermediates during the isomerization from the toluene oxides to the cresols. The quantum chemistry results largely support the plausibility of the mechanism proposed by Klotz et al. The system provides a rich set of reactions with which to test statistical kinetic theories.     

Explorations into new reaction chemistry

This Review describes the basic concepts that have guided our exploration of new chemical reactions by giving examples of results from my research group. Our strategy of carrying out research is to investigate three to four different topics at a time so we can gather as many results as possible. These may at first appear unrelated to each other but may have the potential to be united into a greater hypothesis after repeated feedback. Three scenarios from our research are presented: the "oxidative-reductive condensation reaction" devised in 1960, which after an interval of nearly 40 years brought forth the new concept of using compounds of structure Ph(2)POR as reducing reagents; the "TiCl(4)-aldol reaction" of 1973 that eventually led to the present "base-promoted aldol reaction" through a chain of ideas; and the "glycosylation reaction using fluorosugars" from 1984 which recently bloomed into "stereocontrolled glycosylation". Thus, it can be said that by reviewing what we had done before, we were able to expand on it to achieve new outcomes.     

Extending Pummerer reaction chemistry. Synthesis studies in the phakellin alkaloid area

The syntheses of (+/-)-dibromophakellstatin and, from this species, (+/-)-dibromophakellin are described. Oxidative cyclization of a phenylthiolated dihydrooroidin derivative triggered by a Pummerer reaction constitutes the key step in this biomimetic approach to this family of marine alkaloids.     

The benzoylation of uracil and thymine

Uracil and thymine react with benzoyl chloride in acetonitrile-pyridine solution at room temperature to give first their 1-$\text{N}$-benzoyl (2b and 3b) and then their 1-$\text{N}$, 3-$\text{N}$-dibenzoyl derivatives (4a and 4b, respectively); the latter compounds are converted into the corresponding 3-$\text{N}$-benzoyl derivatives (5a and 6a) under mild conditions of basic hydrolysis.     

The chemistry of carbazole. VI. On the formation of N-ethylcarbazoles in the cadogan reaction

Reaction of 2′,6-dimethyl-2-nitrobiphenyl with triethyl phosphite gave 4,5-dimethyl-9-ethylcarbazole besides 4,5-dimethylcarbazole. In this reaction, 4,5-dimethylcarbazole was ethylated by triethyl N-(2′,6-dimethybiphenyl-2-yl)phosphorimidate and diethyl N-(2′,6-dimethylbiphenyl-2-yl)phosphoramidate, which arose from a nitrene-intermediate and triethyl phosphite. Analogous ethylations of carbazole with other phosphorimidate and phosphoramidates were investigated.     

Extending Pummerer reaction chemistry. Application to the oxidative cyclization of indole derivatives

Treatment of 2-(phenylsulfinyl)indoles bearing a pendant nucleophile at C(3) with Tf(2)O/lutidine triggers a Pummerer-like cyclization to furnish 3,3-spirocyclic-2-(phenylthio)indolenine products, which can, in turn, be hydrolyzed to 3,3-spirocyclic oxindoles. [reaction: see text]     

Extending Pummerer reaction chemistry. Application to the oxidative cyclization of tryptophan derivatives

The diastereoselective oxidative cyclization of a beta-oxygenated tryptophan derivative is reported. This process, which utilizes a new variant of the Pummerer reaction, may have application in TMC-95A synthesis.     

Isolation of an inclusion complex of naphthol and its benzoate as an intermediate in the solvent-free benzoylation reaction of naphthol

Solvent-free benzoylation of naphthol was found to proceed via an inclusion complex intermediate of the naphthol and its benzoate by IR spectral monitoring.     

Applications of the luminol chemiluminescent reaction in analytical chemistry

This critical review discusses the results published between 2000 and 2005 on the development of analytical systems based on the luminol chemiluminescent and electrochemiluminescent reactions. An increasing number of non-specific detection systems based on the enhancing, inhibiting or catalysing effect of a large range of compounds have been published. Possible detected compounds and their concomitant presence in samples are discussed. Chemiluminescent and electrochemiluminescent reactions were also found to merge in biochip and microarray development as a possible substitute to the well-established but hardly quantitative fluorescent detections.     

Theoretical studies of reaction mechanism in chemistry

After defining reaction mechanism, reaction path, reaction coordinate, reaction profile, and classical trajectories, dynamic and static approaches suitable (or promising) for analysis of reaction mechanism are critically discussed.     

Solvated positron chemistry. The reaction of hydrated positrons with chloride ions

The reaction of hydrated positrons (c_aq⁺ with cloride ions in aqueous solutions has been studied by means of positron annihilation angular correlation measurements. A rate constant of k = (2.5 ± 0.5) × 10¹⁰ M^?1 s^?1 was found. Probably the reacting positrons annihilated from an e⁺ Cl^? bound state resulting in an angular correlation curve 8% narrower than for the hydrated positron. Carbontetrachloride in benzene seems to give similar, but smaller effect.     

Synthesis of 1,3-diazacyclanes by the benzoylation of bis-schiffs bases

Conclusions Benzoylation of the bisazomethines R-CH=N(CH₂)_nN=CH-R (R=i-C₃H₇, Ph; n=3–6.8) affords NN-dibenzoyl-2-R-1,3-diazacycloalkanes and open-chain amides. The yields of 2-R-1,3-diazacycloalkanes are at a maximum when n=2 and 3, decreasing rapidly as n increases.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1612–1615, July, 1985.