Reaction of N-alkylglycolurils with electrophilic reagents

The N-hydroxymethylation, N-acetylation, and N-acetoxymethylation of mono-, di-, and trialkylglycolurils by reaction with the electrophilic reagents formaldehyde and acetaldehyde have been studied. General methods have been developed for the preparation of mono-, di-, and tri-N-hydroxymethylglycolurils by treatment of differently substituted N-alkylglycolurils with formaldehyde (as hemiformal in methanol) and the synthesis of di-N-and tri-N-acetyl-or N-acetoxymethylglycolurils via the electrophilic substitution of hydrogen atoms for an acetyl group at the nitrogen or oxygen atoms in the hydroxymethyl groups of glycolurils using acetic anhydride. The regioselectivity of the reaction of the 2-t-Bu-and 2-c-C₆H₁₁-glycolurils with formaldehyde has been shown to yield a 4,6-di(hydroxymethyl) derivative. It was found that the hydroxymethylation of 2,4-and 2,6-dialkylglycolurils occurs regioselectively with a stoichiometric ratio of glycoluril to hemiformal and permits preparation of their mono-and dihydroxymethyl derivatives. The enantiomeric analysis of the obtained compounds has been carried out for the first time using HPLC on chiral phases. X-ray analysis has been carried out on the previously unreported racemic 2,6-diacetoxymethyl-4,8-dimethylglycoluril. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 411–423, March, 2006.     

Reaction of O-acyl derivatives of polynitroalkanes with electrophilic reagents

Conclusions The O-acyl derivatives of polynitroalkanes (trinitromethane, dinitromethane and 1,1-dinitroethane) react with various electrophilic reagents to give the corresponding trinitro- and dinitromethyl derivatives.Translated from Izvestiya Akademiya Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 344–350, February, 1973.     

Reaction of 3,5-diamino-4-nitropyrazole with electrophilic reagents

The interaction of 3,5-diamino-4-nitropyrazole with such electrophilic reagents as acetic anhydride, dimethylformamide acetal, orthoformic ester, and ketones has been studied. Derivatives of pyrazolol[1,5-a]pyrimidines were formed on reaction with 1,3-diketones and some of their properties have been studied.Center for Drug Chemistry, All-Russian Chemical and Pharmaceutical Research Institute (VNIKhFI), Moscow 119815. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 329–335, March, 1997.     

Reaction of 2,4,6-trialkylpyrimidine 1,3-dioxides with electrophilic reagents

The nitrosation of 2,4,6-trimethylpyrimidine 1,3-dioxide and the bromination of 2,4,6-trimethyl- and 2-ethyl-4,6-dimethylpyrimidine 1,3-dioxides take place primarily at the methyl groups in the 4 and 6 positions of the heteroring. In the reaction of 2,4,6-trimethylpyrimidine 1,3-dioxide with phosphorus oxychloride chlorine is incorporated in the methyl group in the 2 position of the heteroring, while in the reaction with acetic anhydride an acetoxy group is incorporated in the methyl group in the 2 position and in the 5 position of the heteroring, whereas in the case of tosyl chloride a tosyloxy group is incorporated in the 5 position of the heteroring.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 110–116, January, 1981.     

Reaction of α-polynitroalkyl sulfones with nucleophilic and electrophilic reagents

Conclusions Under mild conditions -polynitroalkyl sulfones with the general formula RSO₂C(NO₂)₂R are split at the C-SO₂ bond under the action of both nucleophilic (alcohols, water, and bases) and electrophilic (the halogens, SO)₂Cl₂, BrONO₂, and HC1) reagents to form the corresponding polynitroalkane and sulfonic acid derivatives. The attack of the nucleophiles is directed at the sulfur atom, and that of the electrophiles is directed at the -carbon atom bonded to the nitro groups.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 375–380, February, 1977.We thank G. V. Antoshina and E. S. Shpiro for recording and interpreting the x-ray photoelectron spectra.     

Reaction of benzo[b]quinuclidine with electrophilic reagents

Bromination of benzo[b]quinuclidine yields its perbromide and a molecular complex with bromine, while nitration and chlorosulfonation form 7-nitro- and 7-chlorosulfobenzo[b]-quinuclidines. The results of electrophilic substitution attest to the absence in benzo[b]-quinuclidine of a mesomeric interaction between the free electron pair of nitrogen and the electrons of the benzene ring.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 385–388, March, 1971.     

Reaction of 2-substituted 5,5-dimethyl-4-oxo-1-pyrroline-1-oxides with electrophilic reagents

The reaction of -oxonitrones, derivatives of pyrroline, with electrophilic reagents can proceed either at the oxygen atom of the nitrone group in the composition of the heterocyclic ring, or at the carbon atom between the carbonyl and nitrone group.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 395–400, February, 1990.     

Reaction of alkylacetylenic complexes of gallium of the type MGaEt3 C≡CR with electrophilic reagents

Summary The introduction of gallium complexes MGaEt₃CCC₅H₁₁ (M=Li, Na) with electrophilic reagents such as HCl, I₂, , and ethylene oxide occurred with fission of the Ga-alkyne bond and the formation of the corresponding acetylenic compounds.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2354–2356, October, 1981.     

Synthesis of novel DOXYL labelling reagents with electrophilic groups

The oxalic acid salt of 2-aminomethyl-3-oxyl-2,4,4-trimethyl-1,3-oxazolidine has been synthesised from 1-chloroacetone. Being water soluble, the salt is a promising candidate for varied applications. It has been functionalised with electrophilic groups generating novel spin labelling reagents.