Kinetics of the reaction of decanesulfoperacid with SO2 in the presence of water

A study has been made of the kinetics of the oxidation of SO₂ by decanesulfoperacid in the presence of water in a medium of CH₃CN. Retardation of the process by acids has been observed, the retarding effect decreasing with decreasing strength of acid. A mechanism for the reaction has been suggested which explains the experimental results obtained.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 546–548, March, 1991.     

Kinetics and reaction mechanisms of diazo compounds and iodonium salts as studied by chemically induced dynamic nuclear polarisation

CIDNP phenomena in various reactions of diazo compounds and iodonium salts are described. The various reaction pathways leading to the formation of polarised aromatic products are analysed in detail.     

The products of the reaction of polyphenylene sulfide with SO3 and SOCl2

Two polymer fractions, respectively with 28–38% and 6–9% sulphonated (? SO₃H) phenylene rings, may be isolated in the solid-liquid reaction between p-polyphenylene sulfide and SO₃ in refluxing dichloroethane-liquid SO₂. The products relative yield depends on the experimental conditions of the reaction. No solvent has been found for these polymers. The reaction of the sulphonated polymers with SOCl₂ leads to formation of higher substitution products containing both and functional groups. The polymers in chlorophenyl phenylsulphonylchloride form are soluble in excess SOCl₂ and/or CHCl₃, depending upon the concentration of ring chlorine. The mechanism of sulphonation in the heterogeneous medium and the presence of cross-links in the reaction products are discussed.     

Structure of products of the reaction of 2-cyanoaziridine with carbonyl compounds

The structure of azimexone (3), the product of the reaction of 2-cyanoaziridine with acetone, was confirmed on the basis of¹H and¹³C NMR spectra. The formation of this product is accounted for by the -aziridinoalkylating action of an intermediate containing a good leaving iminoyloxy group. Similar reactions were observed for 1-chloromethylaziridine and a 1-aziridinylmethylammonium salt (6), but not for 1-methoxymethylaziridine (7) and 1-aziridinemethanol.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2136–2139, December, 1993.     

Mechanism of the reactions of diazaphospholes with diazo compounds

Conclusions Diazaphospholes react with diazo compounds by the mechanism of 1,3-dipolar cycloaddition. The reaction of 2-acetyl-5-methyl-1,2,3-diazaphosphole with diphenyldiazomethane proceeds via the intermediate formation of the product of [2 + 3]-cycloaddition.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1376–1380, June, 1987.     

Ruthenium-catalysed carbenoid cyclopropanation reactions with diazo compounds

The transition-metal catalysed cyclopropanation of olefinic bonds using diazo compounds as a carbene source is among the best developed and most useful transformations available to the synthetic organic chemist. Nevertheless, the quest for new catalyst/ligand systems continues in order to further extend the scope of this method and to identify more economical catalytic systems. In this tutorial review, several different ruthenium complexes are presented which have recently emerged as suitable catalysts for carbenoid cyclopropanation. For the model reaction--cyclopropanation of styrene(s) with diazoacetates--and also for some intramolecular cyclopropanation reactions highly remarkable results in terms of catalyst efficiency, product yields, dia- and enantioselectivity have been reported.     

Chemiluminescence in the reaction of diphenylsulfene with SO2

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, p. 2667, November, 1990.     

Fluorescent products of the reaction of mono-substituted guanidino compounds with benzoin-dimethylformamide

The fluorescent products formed from methylguanidine or phenylguanidine and benzoin in the presence of dimethylformamide are shown to be the corresponding 2-substituted amino-4, 5-diphenylimidazoles. They fluoresce most intensely at pH 9–10 and the fluorescence is stabilized by β-mercaptoethanol.     

Formation of spiro-substituted 1,3-dithiolanes and thiiranes in the reaction of 3-aminoindene-1-thiones with aliphatic diazo compounds

3-Aminoindene-1-thiones react readily with diazomethane to give the corresponding 4,4;5,5-dispiro-substituted 1,3-dithiolanes. The production of both 2,2-spiro-substituted thiiranes and products of desulfuration of the latter is possible in the reaction of 3-aminoindene-1-thiones with substituted diazomethanes. The thermolysis, hydrolysis, and salt-forming reactions of the compounds obtained were investigated.Communication VIII from the series , -Unsubstituted Thio Compounds. See [1] for communication VII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 36–42, January, 1978     

Surprising 1,7-cyclization of vinyl carbonyl ylides generated from reaction of indanetrione with vinyl diazo compounds

Reactions of tricarbonyl compounds with vinyl diazo compounds 2 were carried out. Reaction of 1,2,3-indanetrione with 2a,b,c gave the spiroindan-1,3-dione-2,2′-benzodihydrooxepin 7a,b,c, but not normal products oxirane and dihydrofuran derivatives expected from intermediate vinyl carbonyl ylides 4. Formation of 7 requires isomerization of vinyl carbonyl ylides 4 bearing a (Z)-cyanostyryl group to unstable (E)-form 5 and subsequent cyclization to oxepin 6 followed by a 1,5-hydrogen shift. However, reaction of 2 with six-membered cyclic tricarbonyl compounds 1,2,3-trioxo-2,3-dihydrophenalene 11 and dimethylalloxane 13 gave the dioxole 12 and the dihydrofuran 14, respectively, typical products expected from vinyl carbonyl ylides.     

Metal-free cascade boron-heteroatom addition and alkylation with diazo compounds

Transition metal-catalyzed carbene transfer reaction is one of the most notable advances for C-C bond formation reactionsduring the past decade,which has been widely employed in the preparation of C3-substituted indoles,Here,we described an efficient exa mple of catalyst-and metal-free aminobo ration of alkynes and C—C bond formation with diazo compounds to produce C3-substituted indoles,Diverse alkynyla nilines and diazo compounds ca n be utilized for this tandem transfo rmation under mild reaction conditions,re sulting in broad functional group co mpatibility.Additionally,this metal-free strategy can be extended to construct substituted benzofurans.