Synthesis and study of calix[4]arenes bearing azo moieties at the meta position

Martin Tlustý; Petr Slavík; Hana Dvořáková; Václav Eigner; Pavel Lhoták

doi:10.1016/j.tet.2017.01.025

Synthesis and study of calix[4]arenes bearing azo moieties at the meta position

Martin Tlustý, Petr Slavík, Hana Dvořáková, Václav Eigner, Pavel Lhoták^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

Direct mercuration and subsequent transformation of organomercurial intermediates into the corresponding nitroso derivatives enabled the construction of calix[4]arenes bearing azo moieties at the meta position (to the alkoxy groups). These compounds, representing a unique substitution pattern in calixarene chemistry, showed very unusual dynamic behaviour in solution. Temperature dependent¹H NMR spectra confirmed that the introduction of two bulky moieties (or even just one) into the meta position of calix[4]arene led to the rigidification of the molecule as demonstrated by complete arrest of the typical pinched cone – pinched cone interconversion in solution. The rigidified molecules can be used as ligands capable of cation−π interactions with N-methylpyridinium salts.

Original language	English
Pages (from-to)	1230-1237
Number of pages	8
Journal	Tetrahedron
Volume	73
Issue number	9
Early online date	12 Jan 2017
DOIs	https://doi.org/10.1016/j.tet.2017.01.025
Publication status	Published - 2 Mar 2017

Keywords

Azocompounds
Calixarene
Conformational behaviour
DynamicH NMR
Mercuration
meta-Substitution

Access to Document

10.1016/j.tet.2017.01.025

Cite this

@article{84967faab3794481b61d4f71dfe45b60,

title = "Synthesis and study of calix[4]arenes bearing azo moieties at the meta position",

abstract = "Direct mercuration and subsequent transformation of organomercurial intermediates into the corresponding nitroso derivatives enabled the construction of calix[4]arenes bearing azo moieties at the meta position (to the alkoxy groups). These compounds, representing a unique substitution pattern in calixarene chemistry, showed very unusual dynamic behaviour in solution. Temperature dependent1H NMR spectra confirmed that the introduction of two bulky moieties (or even just one) into the meta position of calix[4]arene led to the rigidification of the molecule as demonstrated by complete arrest of the typical pinched cone – pinched cone interconversion in solution. The rigidified molecules can be used as ligands capable of cation−π interactions with N-methylpyridinium salts.",

keywords = "Azocompounds, Calixarene, Conformational behaviour, DynamicH NMR, Mercuration, meta-Substitution",

author = "Martin Tlust{\'y} and Petr Slav{\'i}k and Hana Dvo{\v r}{\'a}kov{\'a} and V{\'a}clav Eigner and Pavel Lhot{\'a}k",

year = "2017",

month = mar,

day = "2",

doi = "10.1016/j.tet.2017.01.025",

language = "English",

volume = "73",

pages = "1230--1237",

journal = "Tetrahedron",

issn = "0040-4020",

publisher = "Elsevier",

number = "9",

}

TY - JOUR

T1 - Synthesis and study of calix[4]arenes bearing azo moieties at the meta position

AU - Tlustý, Martin

AU - Slavík, Petr

AU - Dvořáková, Hana

AU - Eigner, Václav

AU - Lhoták, Pavel

PY - 2017/3/2

Y1 - 2017/3/2

N2 - Direct mercuration and subsequent transformation of organomercurial intermediates into the corresponding nitroso derivatives enabled the construction of calix[4]arenes bearing azo moieties at the meta position (to the alkoxy groups). These compounds, representing a unique substitution pattern in calixarene chemistry, showed very unusual dynamic behaviour in solution. Temperature dependent1H NMR spectra confirmed that the introduction of two bulky moieties (or even just one) into the meta position of calix[4]arene led to the rigidification of the molecule as demonstrated by complete arrest of the typical pinched cone – pinched cone interconversion in solution. The rigidified molecules can be used as ligands capable of cation−π interactions with N-methylpyridinium salts.

AB - Direct mercuration and subsequent transformation of organomercurial intermediates into the corresponding nitroso derivatives enabled the construction of calix[4]arenes bearing azo moieties at the meta position (to the alkoxy groups). These compounds, representing a unique substitution pattern in calixarene chemistry, showed very unusual dynamic behaviour in solution. Temperature dependent1H NMR spectra confirmed that the introduction of two bulky moieties (or even just one) into the meta position of calix[4]arene led to the rigidification of the molecule as demonstrated by complete arrest of the typical pinched cone – pinched cone interconversion in solution. The rigidified molecules can be used as ligands capable of cation−π interactions with N-methylpyridinium salts.

KW - Azocompounds

KW - Calixarene

KW - Conformational behaviour

KW - DynamicH NMR

KW - Mercuration

KW - meta-Substitution

UR - http://www.scopus.com/inward/record.url?scp=85009911181&partnerID=8YFLogxK

U2 - 10.1016/j.tet.2017.01.025

DO - 10.1016/j.tet.2017.01.025

M3 - Article

AN - SCOPUS:85009911181

SN - 0040-4020

VL - 73

SP - 1230

EP - 1237

JO - Tetrahedron

JF - Tetrahedron

IS - 9

ER -

Synthesis and study of calix[4]arenes bearing azo moieties at the meta position

Abstract

Keywords

Access to Document

Other files and links

Cite this