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ISSN 1998-9539

One-pot Synthesis of Mono-substituted Quaternized p-tert- Butylthiacalix[4]arenes

Bulat Kh. Gafiatullin,a Ilya V. Paskevich,a Vladimir A. Burilov,a@ Svetlana E. Solovievab and Igor S. Antipina
aKazan Federal University, 420008 Kazan, Russian Federation
bArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, 420088
Kazan, Russian Federation
@Corresponding author E-mail:


The possibility of one-pot synthesis of mono-substituted quaternized derivatives of p-tert-butylthiacalix[4]arene was demonstrated for the first time by the reaction of distally di-bromopropyl substituted p-tert-butyl thiacalix[4]arene with several nitrogen-containing nucleophiles. The structure and composition of the reaction products were analyzed by modern physical methods, including two-dimensional NMR spectroscopy and high-resolution mass spectrometry. A detailed analysis of the reaction mixtures made it possible to reveal the dealkylation mechanism, which consists in the nucleophilic attack of the bromide ion on the O-CH2 carbon atom, followed by the formation of a brominecontaining adduct, detected by mass spectrometry. Dealkylation does not occur when the classical di-bromopropyl substituted p-tert-butyl calix[4]arene is used as a substrate - the bis-quaternized imidazolium calix[4]arene salt is formed in a high yield. Such a difference in the reactivity of two macrocycles is associated with the difference in the sizes of the macrocycles: in the case of di-substituted thiacalixarene, which has a large size, two unsubstituted hydroxyl groups form a hydrogen bond with only one alkoxy group, while in the classical calix[4]arene, two paired hydrogen bonds are formed. As a result, one of the two alkoxy groups of the thiacalixarene is more accessible for nucleophilic attack; formed thereafter thiacalixarene nucleofuge-anion is stabilized by two hydrogen bonds at once.


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