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New tetrylenes based on substituted diethylenetriamines: synthesis and use as initiators for ε-caprolactone polymerization

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Abstract

The reactions of 3-benzyl-1,5-ditosyl-1,3,5-triazapentane (1) and 3-benzyl-1,5-dimesityl- 1,3,5-triazapentane (2) with one equivalent of Lappert´s germylene or stannylene (M[N(SiMe3)2]2, where M = Ge, Sn) produced germylenes and stannylenes of the general formula PhCH2N(CH2CH2NR)2M, where M = Ge, R = 4-MeC6H4SO2– (3); 2,4,6-Me3C6H2– (5); M = Sn, R = 4-MeC6H4SO2– (4); 2,4,6-Me3C6H2– (6), in satisfactory yields. According to NMR data (1H, 13C, 119Sn), stannylenes 4 and 6 are monomeric in solution, and the coordination number of tin is four. The synthesized stannylenes exhibited very high (compound 4) and moderate (compound 6) activity as initiators for bulk polymerization of ε-caprolactone, resulting in the synthesis of high-molecular-weight polymers with relatively narrow molecular-weight distribution. Previously unknown triamine 2 was synthesized by benzylation of HN(CH2CH2NHMes)2 with benzyl chloride in the presence of K2CO3.

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Authors and Affiliations

  1. N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991, Moscow, Russian Federation

    B. N. Mankaev, K. V. Zaitsev, E. A. Kuchuk, M. V. Vershinina, G. S. Zaitseva, M. P. Egorov & S. S. Karlov

  2. Department of Chemistry, M. V. Lomonosov Moscow State University, 1, Build. 3, Leninskie Gory, 119991, Moscow, Russian Federation

    B. N. Mankaev, K. V. Zaitsev, E. A. Kuchuk, M. V. Vershinina, G. S. Zaitseva & S. S. Karlov

Authors
  1. B. N. Mankaev
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  2. K. V. Zaitsev
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  3. E. A. Kuchuk
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  4. M. V. Vershinina
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  5. G. S. Zaitseva
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  6. M. P. Egorov
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  7. S. S. Karlov
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Correspondence to S. S. Karlov.

Additional information

Dedicated to Academician of the Russian Academy of Sciences A. I. Konovalov on the occasion of his 85th birthday.

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 0389–0393, February, 2019.

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Mankaev, B.N., Zaitsev, K.V., Kuchuk, E.A. et al. New tetrylenes based on substituted diethylenetriamines: synthesis and use as initiators for ε-caprolactone polymerization. Russ Chem Bull 68, 389–393 (2019). https://doi.org/10.1007/s11172-019-2397-3

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  • DOI: https://doi.org/10.1007/s11172-019-2397-3

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