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Intramolecular cyclization of N-(2-hydroxyethyl)propargylamines

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Bulletin of the Academy of Sciences of the USSR, Division of chemical science Aims and scope

Conclusions

  1. 1.

    A study was made of base-catalyzed ring closure in the series of some new N-(2-hydroxyethyl)-propargylamines in order to ascertain the effect of a substituent, attached directly to the nitrogen atom, on the direction of cyclization.

  2. 2.

    Methyl-N-(2-hydroxyethyl)- and bis-N-(2-hydroxyethyl)propargylamines, in contrast to other members in the series, which form 2-vinyl-1, 3-oxazolidines in anhydrous media, are cyclized to the corresponding unsaturated morpholines.

  3. 3.

    The peculiar behavior of bis-N-(2-hydroxyethyl)propargylamine is associated with the possible inhibition of allenic isomerization due to intramolecular reaction between the triple bond and the second hydroxyl group in the transition state.

  4. 4.

    In order to explain the anomalous cyclization of methyl-N-(2-hydroxyethyl)propargylamine the theory was proposed that conjugation of the free electron pair of the nitrogen atom with the adjacent C-H bonds is possible.

  5. 5.

    The conversion of N-(2-hydroxyethyl)propargylamines to oxazolidines under the influence of sodium proceeds with a simultaneous, either partial of complete, hydrogenation of the double bond.

  6. 6.

    The rate of the intramolecular vinylation (cyclization of N-(2-hydroxyethyl)benzylpropargylamine) greatly exceeds the rate of the intermolecular vinylation of the alcohol function by acetylene.

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Authors and Affiliations

  1. Irkutsk Institute of Organic Chemistry, Siberian Branch of the Academy of Sciences of the USSR, USSR

    M. F. Shostakovskii, A. S. Atavin, B. A. Trofimov, Z. T. Dmitrieva & V. G. Sakharovskii

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  1. M. F. Shostakovskii
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  2. A. S. Atavin
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  3. B. A. Trofimov
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  4. Z. T. Dmitrieva
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  5. V. G. Sakharovskii
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Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2100–2108, September, 1970.

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Shostakovskii, M.F., Atavin, A.S., Trofimov, B.A. et al. Intramolecular cyclization of N-(2-hydroxyethyl)propargylamines. Russ Chem Bull 19, 1973–1980 (1970). https://doi.org/10.1007/BF00849784

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  • DOI: https://doi.org/10.1007/BF00849784

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