- REACTIVITY OF THE SULFUR-CONTAINING ANALOGS OF ORTHO ESTERS IN FREE-RADICAL REACTIONS
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The effect of the structure and the nature of the heteroatom on the reactivity of thioorthoformates in radical transformations was studied by the method of competing reactions.In the series of diethoxyalkylthiomethanes the activity increases with increase in the chain length of the alkyl substituent.The reactivity increases with substitution of the sulfur atom by a nitrogen atom and decreases if any alkoxy group is present instead of an alkylthio group.The reactivity of the 2-ethoxy-1,3-oxaheterocyclopentanes increases in the following order: 1,3-dioxacyclopentane 1,3-oxathiacyclopentane 1,3-oxaazacyclopentane.
- Taganlyev, A.,Rol'nik, L. Z.,Pastushenko, E. V.,Zlot-skii, S. S.,Rakhmankulov, D. L.
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p. 270 - 272
(2007/10/02)
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- N-NITROSAMINES AS REAGENTS FOR THE =C=S=C=O TRANSFORMATION
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N-nitrosopiperidine and N-nitroso-N-methylaniline react in acidic solution with thiocarbonyl compounds to give the corresponding carbonyl analogues.Secondary- and tertiary thioamides, xanthione, thio- and dithiobutyrolactone, thiocoumarin, certain thiourea derivatives, dithio-O,O-thiocarbonic, S,S-trithiocarbonic- and N,N disubstituted thiocarbamic esters are all converted into the corresponding O-analogues.Thiobenzamide and N-phenylthiourea yield 1,2,4-thiadiazoles.All the reactions are run with iodide (I-) as NO+-carrier.The kinetics of the reaction have been studied under pseudo-first order conditions, and the reaction rate is proportional to the Pearson's nucleophilicity parameter of ions.The =C=S =C=O transformation is also found to take place in gastric juice.
- Jorgensen, K. A.,El-Wassimy, M. T. M.,Lawesson, S. -O.
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p. 469 - 474
(2007/10/02)
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- EFFECT OF STRUCTURAL FACTORS ON THE KINETICS OF THE REACTION OF ALKYL CHLOROFORMATES WITH ALIPHATIC-AROMATIC AMINES
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As a result of investigation of the effect of the structure of the reagents on the kinetics of acylation of aliphatic-aromatic amines by alkyl chloroformates it was shown that the reaction takes place by an addition-elimination mechanism without a controlling stage.The kinetic data obey the two-parameter Taft equation.
- Orlov, S. I.,Chimishkyan, A. L.,Lapin, A. S.,Grabarnik, M. S.
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p. 1905 - 1908
(2007/10/02)
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