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One-pot synthesis of p-tert-butylthiacalix[6/8]arenes

Journal of Inclusion Phenomena and Macrocyclic Chemistry volume 81, pages 245–249 (2015)Cite this article

Abstract

Since Miyano and co-workers’ facile synthesis of p-tert-butylthiacalix[4]arene (1), many studies related to 1 have been published. In contrast, because of their extremely low yields, investigation of the larger macrocycles p-tert-butylthiacalix[6]arene (2) and p-tert-butylthiacalix[8]arene (3) has been limited. An improved synthetic method for 1–3 by the heating of p-tert-butylphenol, sulfur, and catalytic NaOH in a one-pot, two-stage procedure is described. The first step (oligomer formation) proceeds optimally at 180 °C for 24 h with 2 mol % NaOH. The second step (cyclization) is conducted at 230 °C with 50 mol % NaOH. Investigations by 1H NMR spectroscopy and matrix-assisted laser desorption-ionization time-of-flight mass spectrometry (MALDI-TOF MS) revealed that 2 and 3 transform into 1 and oligomers at the high temperature required for the cyclization step. Moreover, even 1 transforms into oligomers at high temperature for 48 h. Heating times of 5 and 24 h were optimal for the preparation of 2 (18.1 %) and 3 (4.6 %), respectively. A comparison of the thermal stability of the p-tert-butylthiacalix[n]arenes determined their stability in the order 1, 2, and 3.

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Authors and Affiliations

  1. Department of Applied Chemistry for Environments, Graduate School of Engineering and Resource Science, Akita University, 1-1 Tegatagakuen-machi, Akita, 010-8502, Japan

    Takashi Kimuro & Fumio Hamada

  2. Research Center for Engineering Science, Graduate School of Engineering and Resource Science, Akita University, 1-1 Tegatagakuen-machi, Akita, 010-8502, Japan

    Manabu Yamada

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  1. Takashi Kimuro
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  2. Manabu Yamada
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  3. Fumio Hamada
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Correspondence to Manabu Yamada or Fumio Hamada.

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Kimuro, T., Yamada, M. & Hamada, F. One-pot synthesis of p-tert-butylthiacalix[6/8]arenes. J Incl Phenom Macrocycl Chem 81, 245–249 (2015). https://doi.org/10.1007/s10847-014-0435-1

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