M. S. Yusubov

New oxidative transformations of alkenes and alkynes under the action of diacetoxyiodobenzene

Treatment of alkenes and alkynes with diacetoxyiodobenzene activated by mineral and organic acids predominantly results in oxidative rearrangement. 1,4-Diphenylbutadiene in MeOH gives 3,4-dimethoxy-1,4-diphenylbut-1-ene.

(Dichloroiodo)benzene—An Easily Available Reagent for Chloro‐ and Iodoalkoxylation, Iodohydroxylation, and Iodochlorination of Alkenes

Abstract A convenient synthesis of vicinal methoxychlorides, methoxyiodides, iodhydrines and iodocloride from alkenes using PhICl2/CH3OH, I2/PhICl2/CH3OH, I2/PhICl2/CH3CN/H2O and I2/PhICl2/CH2Cl2 is described.

Iodosobenzene dichloride, a convenient reagent for chloro-and iodomethoxylation of double and triple bonds

The reaction with a-methylstyrene (VIII) was less selective and afforded in 70% overall yield an inseparable mixture of two isomers IX and X in 75 : 25 ratio according to GC-MS and H NMR data. The formation of reaction product X is an evidence of a contribution from free-radical chlorination of the methyl group in compound IX [or in initial a-methylstyrene (VIII)] effected by PhICl2. It turned out that reaction of styrene (II) with PhICl2 in methanol in the presence of iodine took another route easily providing a product of iodomethoxylation of the double bond XI in 80% yield. Obviously here the iodosobenzene dichloride acted as oxidant for iodine providing its electrophilic intermediates (I + , ICl, or CH3OI). This reaction is perhaps the first example of a simple iodoalkoxylation of alkenes with the use of compounds of polyvalent iodine, and it opens new opportunities for the synthesis of commonly less available iodoalkoxyalkanes [4, 5].

Simple synthesis of 3-acyl-5-alkyl(aryl)isoxazoles from terminal alkynes and nitrates of alkaline metals or ammonium

A simple and general synthesis of 3-acyl-5-alkyl(aryl)isoxazoles by reaction of terminal alkynes with nitrates in acetic acid in the presence of SO3 or alkaline salts is described.

The reaction of alkynes with dimethyl sulfoxide, halogenated hydrocarbons and sulfur trioxide

1,2-Disubstituted alkynes are converted in CCl4 or CHCl3 with dimethyl sulfoxide in the presence of sulfur trioxide into the corresponding (E, Z)-1-chloro-2-methylthio-ethenes. The reaction of 1,2-diphenylethyne with CHBr3, DMSO, and dioxane sulfotrioxide gives (E, Z)-1,2-dimethylthio-1,2-diphenylethene.

A new synthetic application of (dichloroiodo)benzene in reactions with alkenes and alkynes

A convenient synthesis of vicinal methoxychlorides, methoxyiodides from alkenes and alkynes using PhICl/sub 2//CH/sub 3/OH, I/sub 2//PhICl/sub 2//CH/sub 3/OH is described.

Halogenation and nitration of aromatics and unsaturated compounds by halides and nitrates of alkali metals

We have discovered that KVNaN03 and KBr/NaN03 in AcOH possesse Balqenation and nitration properties towards to 9-methylcarbazole in depending on tempemre. So KBr/NaN03 has bromination activity at r.L but it is nitration agent at 8OoC. On the other hand KI/NaN03 provides the mixture of iodand nitrocarbazoles at 8OoC, and arising temperature up 80C gives only 3-nitroand 3,6-dinitro-9-methylcarbazoles. We suppose that weak iodination ability of KUNaN03 is due to the fact that the intermediate nitriliodide INOt does not produce r but has a tendency to free-radical rupture. It was confirmed by ab initio quantum-chemical computations of nitrilhalogenides X-N02 (X=F,CI,Br,I).