Reaction of N-alkylglycolurils with electrophilic reagents |
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Authors: | A N Kravchenko A S Sigachev G A Gazieva E Yu Maksareva N S Trunova K A Chegaev K A Lyssenko D V Lyubetsky M I Struchkova M M Il’in V A Davankov O V Lebedev N N Makhova V A Tartakovsky |
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Institution: | (1) N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, 117913;(2) A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, 119991 |
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Abstract: | 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.
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Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 411–423, March, 2006. |
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Keywords: | N-Hydroxymethyl(acetyl acetoxymethyl)glycolurils acetic anhydride formaldehyde electrophilic reagents hydroxymethylation and electrophilic substitution of N-alkylglycolurils regioselectivity regiospecificity X-ray analysis enantiomeric analysis |
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