The new type of calix[4]resorcines bearing phosphonates and phosphonium fragments at the lower rim

Article abstract of DOI:10.1080/10426500701764940

Two approaches to the synthesis of calix[4]resorcines bearing phosphonates and phosphonium fragments at the lower rim were elaborated. One of the approaches based on methodology for synthesis of octols by fourfold condensation of 4-substituted benzaldehydes with resorcinol and its derivatives. The calixaren matrix was used as a starting material for functionalization in another method. Both approaches based on the reaction of phosphorylation of arylhalides by the derivatives of P(III) acids in the presence of Ni(II) compounds. Phosphorylated calyx[4]resorcines were further modified at the upper rim with amine groups. Copyright Taylor & Francis Group, LLC.

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The New Type of
Calix[4]Resorcines
Bearing Phosphonates and
Phosphonium Fragments at The
Lower Rim
E. L. Gavrilova a , A. A. Naumova a , N. I. Shatalova a
, E. A. Krasilnikova a , A. R. Burilov b , M. A. Pudovik
b & A. I. Konovalov b
a Kazan State Technological University , Kazan,
Russia
b A. E. Arbuzov Institute of Organic and Physical
Chemistry , Kazan Scientific Centre of Russian
Academy of Science , Kazan, Russia
Published online: 20 Jun 2008.
To cite this article: E. L. Gavrilova , A. A. Naumova , N. I. Shatalova , E. A.
Krasilnikova , A. R. Burilov , M. A. Pudovik & A. I. Konovalov (2008) The New Type of
Calix[4]Resorcines Bearing Phosphonates and Phosphonium Fragments at The Lower
Rim, Phosphorus, Sulfur, and Silicon and the Related Elements, 183:2-3, 561-565, DOI:
10.1080/10426500701764940
To link to this article: http://dx.doi.org/10.1080/10426500701764940
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Phosphorus, Sulfur, and Silicon, 183:561–565, 2008
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500701764940
The New Type of Calix[4]Resorcines Bearing
Phosphonates and Phosphonium Fragments
at The Lower Rim
E. L. Gavrilova,1 A. A. Naumova,1 N. I. Shatalova,1
E. A. Krasilnikova,1 A. R. Burilov,2 M. A. Pudovik,2
and A. I. Konovalov2
1Kazan State Technological University, Kazan, Russia
2A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan
Scientific Centre of Russian Academy of Science, Kazan, Russia
Two approaches to the synthesis of calix[4]resorcines bearing phosphonates and
phosphonium fragments at the lower rim were elaborated. One of the approaches
based on methodology for synthesis of octols by fourfold condensation of 4-
substituted benzaldehydes with resorcinol and its derivatives. The calixaren ma-
trix was used as a starting material for functionalization in another method.
Both approaches based on the reaction of phosphorylation of arylhalides by the
derivatives of P(III) acids in the presence of Ni(II) compounds. Phosphorylated ca-
lyx[4]resorcines were further modified at the upper rim with amine groups.
Keywords Calix[4]resorcinols; derivatives of P(III) acids; phosphorylation;
condensation
INTRODUCTION
The modification of calixarenes by the introduction of phosphorus–
containing groups has attracted considerable attention during the past
years. Depending on the phosphorus-containing fragments those my-
crocycles can possess interesting properties such as physiological activ-
ity, complexing ability towards transition metals.
RESULTS AND DISCUSSION
Calix[4]resorcines are phenolic macrocyclic compounds and readily
available from resorcinols and aldehydes.1 The present work deals with
The support of the RFBR (grant No 04-03-32512) is gratefully acknowledged.
Address correspondence to Kazan State Technological University, Karl Marx str., 68,
420015, Kazan, Russia. E-mail: gavrilova elena @mail.ru
561

562
E. L. Gavrilova et al.
synthetic methodology, that allows the preparation of calyx[4]resorcines
bearing phosphonates and phosphonium groups at the aromatic frag-
ments disposed at the lower rim. Two approaches were elaborated:
using the calixarene matrix as the starting material and the fourfold
condensation of 4-phosphorylated benzaldehydes with resorcinol. Both
approaches based on the reaction of phosphorylation of arylhalides by
the derivatieves of P(III) acids in the presence of Ni(II) compounds. The
method of phosphorylation of arylhalides was work out on the simple
aromatic systems.2-- 6
When calixarene matrix was used as the starting material, the ca-
lyx[4]resorcine 1 was employed7 in conformations bowl and chair. As
phosphorylating reagents PPh3, P(OEt)3, P(OisoPr)3,PhnP(NEt 2)3 (n =
0–2) were used. In order to avoid the decomposition of P(III) derivatives
the hydroxyl groups of calixarene 1 were protected with trimethylsilil
groups using hexamethyldisilazane. It was found that only isomer in
conformation chair undergoes O-sililation and gives 2.
In the reaction of 1 in conformations bowl and chair with PPh3 only
isomer in conformation chair yields the calyx[4]resorcine 3 with four
triphenylphosphoniophenyl groups (Scheme 1).
SCHEME 1

The New Type of Calix[4]Resorcines Bearing Phosphonates and Phosphonium 563
The reaction of 2 with P(OEt)3, P(OisoPr)3 and PhnP(NEt2)3 (n = 0–2)
leads to corresponding phosphorylated calyx[4]resorcine 4–8 with eight
phenolic groups (Scheme 2). We believe that introduction of phosphorus-
containing groups to 2 leads to hydrolytic unstability of intermediate
O-sililated derivatieves.
SCHEME 2
For the purpose of preparation of phosphorylated calyx[4]resorcines
via methodology for synthesis of octols by fourfold condensation
of 4-phosphorylated benzaldehydes with resorcinol, the number of
phosphorus-substituted benzaldehydes were synthesized.8 With suc-
cess the 4-phosphorylated benzaldehydes 9–14 were used in conden-
sation with resorcinol (Scheme 3). The calyx[4]resorcines bearing four
triphenylphosphoniophenyl groups 3 and four aminophosphoniophenyl
groups 6–8 were isolated in conformation chair. The products 4, 5 de-
rived from condensation of 9, 10 with resorcinol were found to exist in
conformation bowl.
Conformers bowl and chair could be easily distinguished by their
characteristic 1H- and 13C-n.m.r. pattern.

564
E. L. Gavrilova et al.
SCHEME 3
Mannich reaction of 3–8 with diethylamine and formaldehyde in an
alcoholic-benzene solution leads to tetra aminomethyl derivatives 15–
20 (Scheme 4) in corresponding conformations.
SCHEME 4
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The New Type of Calix[4]Resorcines Bearing Phosphonates and Phosphonium 565
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