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Reaction of N-alkylglycolurils with electrophilic reagents

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Chemistry of Heterocyclic Compounds Aims and scope

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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Authors and Affiliations

  1. N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, 117913

    A. N. Kravchenko, A. S. Sigachev, G. A. Gazieva, E. Yu. Maksareva, N. S. Trunova, K. A. Chegaev, M. I. Struchkova, O. V. Lebedev, N. N. Makhova & V. A. Tartakovsky

  2. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, 119991

    K. A. Lyssenko, D. V. Lyubetsky, M. M. Il’in & V. A. Davankov

Authors
  1. A. N. Kravchenko
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  2. A. S. Sigachev
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  3. G. A. Gazieva
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  4. E. Yu. Maksareva
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  5. N. S. Trunova
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  6. K. A. Chegaev
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  7. K. A. Lyssenko
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  8. D. V. Lyubetsky
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  9. M. I. Struchkova
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  10. M. M. Il’in
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  11. V. A. Davankov
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  12. O. V. Lebedev
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  13. N. N. Makhova
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  14. V. A. Tartakovsky
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__________

Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 411–423, March, 2006.

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Kravchenko, A.N., Sigachev, A.S., Gazieva, G.A. et al. Reaction of N-alkylglycolurils with electrophilic reagents. Chem Heterocycl Compd 42, 365–376 (2006). https://doi.org/10.1007/s10593-006-0094-2

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  • DOI: https://doi.org/10.1007/s10593-006-0094-2

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