Synthesis of New Calix[4]arenes Functionalizated by Acetylhydrazide Groups

Podyachev, Sergey N.; Syakaev, Victor V.; Sudakova, Svetlana N.; Shagidullin, R. R.; Osyanina, D.V.; Avvakumova, L. V.; Бузыкин, Б. И.; Latypov, Shamil K.; Бауер, И.; Habicher, Wolf D.; Коновалов, А. И.

doi:10.1007/s10847-006-9117-y

Cited by 21 publications

(8 citation statements)

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“…The IR spectra of crystalline samples of tetrathiacalix [4]arenes IIb and IIIa-IIId were similar to those of previously reported hydrazides and aromatic aldehyde N 2 -(4-tert-butylphenoxy)hydrazones [16,18,19]. On the other hand, the spectra of calix [4]arenes were characterized by broadened absorption bands, as compared to their simpler analogs, which may be due to greater diversity of conformational states and hydrogen bonds.…”

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confidence: 81%

“…The subsequent reaction of ester Ia with hydrazine hydrate in THF-EtOH [16] 82% yield. The synthesis of tetrahydrazides IIa and IIb based on tetrathiacalix [4]arene in the 1,3-alternate conformation required a longer time and higher temperature, as compared to their analogs having cone conformation [18]. Obviously, access to reaction centers at the side of the benzene rings in the 1,3-alternate conformer is hindered, so that the reaction rate is lower.…”

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Synthesis of new hydrazones based on tetrathiacalix[4]arene in the 1,3-alternate conformation

et al. 2010

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Reactions of 1,3-alternate stereoisomers of tetrathiacalix [4]arene and 4-tert-butyltetrathiacalix[4]-arene, functionalized by hydrazide groups, with benzaldehyde and pyridin-2-carbaldehyde gave new tetrathiacalix[4]arene tetrahydrazone derivatives as promising receptors for transition and toxic heavy metal ions.Molecular design of artificial receptors is one of the most important problems in modern chemistry [1,2]. To perform the simplest receptor function, i.e., recognition of one or another substrate, several preorganized coordination centers should be present in a receptor molecule. A convenient base structure for the design of such molecules is provided by calix [n]arenes that are compounds with three-dimensional spatially organized structures [3][4][5].Functionalization of calix[n]arenes could considerably extend the scope of their practical application. In particular, functionalization of macrocyclic compounds with hydrazide and hydrazone groups gives rise to potential biologically active substances [6-8] and highly efficient extractants for transition metal ions [9, 10]; in addition, other nitrogen-containing compounds may be obtained on the basis of functionalized calix[n]arenes [11,12]. For example, by condensation of hydrazides with aldehydes we previously synthesized acetylhydrazone derivatives of calix[4]resorcinol [13], which ensured highly efficient binding of transition metal ions and showed especially high selectivity in the extraction of toxic mercury ions. However, analogous reaction with aldehydes of tetrathiacalix-[4]arene in the cone conformation resulted in preferential formation of bis-acetylhydrazone calix[4]arene derivatives with intramolecular N,N′-diacetylhydrazine bridge [14,15]. The target tetrahydrazone was isolated only in the reaction with pyridine-2-carbaldehyde. Presumably, unusual behavior of the cone conformer is determined by spatial proximity of the endo-oriented hydrazide groups. We presumed that the target tetrahydrazones could be obtained using 1,3-alternate conformer of calix[4]arene. The synthesis of such derivatives was also stimulated by the fact that 1,3-alternate conformers of calix[4]arenes are generally more selective receptors for metal ions. This was observed by us previously for tetrahydrazide derivatives [16]. The use of tetrathiacalix[4]arene scaffold (rather than classical calix[4]arene structure) seemed to be preferred due to simpler preparation of the macrocyclic compound in a required conformation. Apart from 4-tert-butyltetrathiacalix[4]arene derivatives, it was interesting to synthesize their analogs with distant tert-butyl groups. Enhanced flexibility of a receptor molecule and reduction of steric hindrances to coordination with metal ions could favor their more efficient binding.In the present communication we report on the synthesis of acetylhydrazone tetrathiacalix[4]arene and 4-tert-butyltetrathiacalix[4]arene derivatives having 1,3-alternate conformation (Scheme 1). In the first step, tetraesters Ia and Ib were synthesized by reactions of unsubsti...

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Synthesis of new hydrazones based on tetrathiacalix[4]arene in the 1,3-alternate conformation

et al. 2010

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“…201 ± 205 Tetranonylcalix [4]resorcinarenes 67, which bear acetylhydrazone groups, were found to be effective reagents for the liquid ± liquid extraction of various metal ions (e.g., Li + , Na + , K + , Cs + , Ca 2+ , Pb 2+ , Co 2+ , Ni 2+ , Cu 2+ , Zn 2+ , Cd 2+ , Hg 2+ , La 3+ , Gd 3+ and Lu 3+ ). 206,207 When dissolved in dichloroethane and heptan-1-ol, dimethylaminomethylated resorcinarene 68 was found to extract the Am III and Eu III ions from neutral aqueous Tetrathiophosphonate-calix [4]resorcinarene host 69 exhibited excellent extraction properties toward soft metal ions. Specifically, it showed a better affinity for Ag + (91%), than for Tl + (38%) and Hg 2+ (16%).…”

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confidence: 99%

Chemistry of calix[4]resorcinarenes

Jain¹,

Kanaiya

2011

Russ. Chem. Rev.

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The review demonstrates the progress in the The review demonstrates the progress in the chemistry of calix[4]resorcinarenes over the last decade. chemistry of calix[4]resorcinarenes over the last decade. Special attention is paid to their synthesis, conformational Special attention is paid to their synthesis, conformational behaviour, functionalization and ability to serve as cavi-behaviour, functionalization and ability to serve as cavitands and capsules, to form monolayers and host ± guest tands and capsules, to form monolayers and host ± guest complexes. Practical applications of calix[4]resorcinarenes complexes. Practical applications of calix[4]resorcinarenes and their derivatives in various fields are surveyed. The and their derivatives in various fields are surveyed. The bibliography includes 296 references bibliography includes 296 references.

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“…27 The reactions of ethyl bromoacetate with pyrogallol and calix [4]pyrogallol afforded esters of the corresponding arene 1,2,3 triyl tris(hydroxyacetic acids), which were transformed by the subsequent treatment with excess hydrazine hydrate into hydrazides 1 and 2 according to a procedure described by us earlier. 17 All measurements were carried out in a water-DMF (30 vol.%) medium at 30 °C. Electrical conductivity was mea sured on a CDM 2d conductometer (Denmark).…”

Section: Methodsmentioning

confidence: 99%

“…17 Its structural analog 2 possess similar properties. Therefore, these compounds are of interest in studying the influence of aggregation and preorganization of the functional groups on their reactivity in aqueous and aqueous organ ic media.…”

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Effect of structural preorganization on the reactivity of carbazoylmethyl derivatives of pyrogallol and calix[4]pyrogallol

et al. 2007

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The aggregation behavior of carbazoylmethyl derivatives of pyrogallol and calix[4]pyrogallol was studied by conductometry and dynamic light scattering in water-DMF media. The for mation of mixed nanoaggregates in the presence of cationic surfactants was revealed. The effect of structural preorganization of these compounds on their reactivity in the acylation by 4 nitrophenylacetate and the catalytic activity in the hydrolysis of phosphorus acid esters was studied.

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Synthesis of New Calix[4]arenes Functionalizated by Acetylhydrazide Groups

Cited by 21 publications

References 12 publications

Synthesis of new hydrazones based on tetrathiacalix[4]arene in the 1,3-alternate conformation

Synthesis of new hydrazones based on tetrathiacalix[4]arene in the 1,3-alternate conformation

Chemistry of calix[4]resorcinarenes

Effect of structural preorganization on the reactivity of carbazoylmethyl derivatives of pyrogallol and calix[4]pyrogallol

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