Synthesis of novel macrocyclic ligands containing phosphoryl and aminoacetal fragments

Article abstract of DOI:10.1080/10426507.2012.740699

A method for the synthesis of novel phosphorylated aminoacetals was developed. The latter are involved in Mannich reaction as amine component with calix[4]resorcinol and formaldehyde to form tetrasubstituted macrocycles containing four acetal groups and four phosphonate (phosphine oxide) fragments on the upper rim of molecule with high yields.

Full text of DOI:10.1080/10426507.2012.740699

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Phosphorus, Sulfur, and Silicon and the
Related Elements
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Synthesis of Novel Macrocyclic Ligands
Containing Phosphoryl and Aminoacetal
Fragments
Liudmila K. Kibardina a , Liliya I. Vagapova a , Alexander R. Burilov a
, Airat R. Garyfzyanov b & Michael A. Pudovik a
a State Budgetary-Funded Institution of Science, A. E. Arbuzov
Institute of Organic and Physical Chemistry of Kazan, Scientific
Center of Russian Academy of Sciences, Arbuzov Str. 8 , Kazan ,
420088 , Russian Federation
b Kazan (Volga region) Federal University, Kremlyovskaya Str. 18 ,
Kazan , 420008 , Russian Federation
Accepted author version posted online: 01 Nov 2012.Published
online: 08 May 2013.
To cite this article: Liudmila K. Kibardina , Liliya I. Vagapova , Alexander R. Burilov , Airat R.
Garyfzyanov & Michael A. Pudovik (2013): Synthesis of Novel Macrocyclic Ligands Containing
Phosphoryl and Aminoacetal Fragments, Phosphorus, Sulfur, and Silicon and the Related Elements,
188:1-3, 10-12
To link to this article: http://dx.doi.org/10.1080/10426507.2012.740699
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Phosphorus, Sulfur, and Silicon, 188:10–12, 2013
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2012.740699
SYNTHESIS OF NOVEL MACROCYCLIC LIGANDS
CONTAINING PHOSPHORYL AND AMINOACETAL
FRAGMENTS
Liudmila K. Kibardina,1 Liliya I. Vagapova,1 Alexander R.
Burilov,1 Airat R. Garyfzyanov,2 and Michael A. Pudovik1
1State Budgetary-Funded Institution of Science, A. E. Arbuzov Institute of Organic
and Physical Chemistry of Kazan, Scientific Center of Russian Academy of
Sciences, Arbuzov Str. 8, Kazan 420088, Russian Federation
2Kazan (Volga region) Federal University, Kremlyovskaya Str. 18, Kazan 420008,
Russian Federation
GRAPHICAL ABSTRACT
Abstract A method for the synthesis of novel phosphorylated aminoacetals was developed.
The latter are involved in Mannich reaction as amine component with calix[4]resorcinol and
formaldehyde to form tetrasubstituted macrocycles containing four acetal groups and four
phosphonate (phosphine oxide) fragments on the “upper” rim of molecule with high yields.
Keywords Aminophosphonate; aminophosphine oxide; calix[4]resorcinol; Mannich reaction
The development of methods for the selective synthesis of novel macrocyclic lig-
ands is a key problem of organic and supramolecular chemistry. Macrocycles as well as
calixarenes containing aminophosphoryl groups are of particular importance among these
receptors.1,2 They exhibit various biological activities3 and are used as extragents of rare-
earth metals4 as well as transmitters in membrane extraction.2,5
Received 16 July 2012; accepted 7 October 2012.
The work was supported by the Russian Foundation for Basic Research (grant 11-03-00416-а).
Address correspondence to Michael A. Pudovik, State Budgetary-Funded Institution of Science, A. E.
Arbuzov Institute of Organic and Physical Chemistry of Kazan, Scientific Center of Russian Academy of Sciences,
Arbuzov Str. 8, Kazan 420088, Russian Federation. E-mail: pudovik@iopc.ru
10

SYNTHESIS OF NOVEL MACROCYCLIC LIGANDS
11
In earlier investigations, we developed methods for the synthesis of tetrasubstituted
calix[4]resorcinols containing aminophosphonate6 and aminoacetal7,8 groups on the upper
rim of the molecule. These macromolecules are able to undergo chemical modification9
as well as to form supramolecular aggregates having catalytic activity in the hydrolysis of
phosphonates,10 the complexation of Cu(II) and La(III) ions,11 and the extraction of La(III)
and Gd(III) ions.5
With the aim to synthesize macrocyclic polydentate ligands having phosphoryl frag-
ments in addition to acetyl groups, we developed a method for a single-step synthesis
of phosphorylated aminoacetals and investigated their reaction with formaldehyde and
calix[4]resorcinol.
The synthesis of compounds 3а–d was performed by the condensation of aminoacetal
1 with paraformaldehyd and dialkylphosphites (dialkylphosphinic acids) 2a–d according
to Kabachnik–Fields reaction (Scheme 1).
Scheme 1
As a result of the reaction of phosphorylated aminoacetals 3а–d with
calix[4]resorcinol 4 and formaldehyde (Mannich reaction), new tetrasubstituted
macrocycles 5a–d containing phosphine oxide (phosphonate) fragments with various
substituents at the phosphorus atom on the “upper” rim of the molecule were obtained
with the yields from 88 to 99%.
The presence of four phosphoryl and four acetal groups on the “upper” rim of
compounds 5а--d makes it possible to consider them as promising polydentate ligands.
The structure of the compounds synthesized was proved by 31Р and 1Н NMR spec-
troscopy; the composition was confirmed by correct elemental analysis data.

12
LIUDMILA K. KIBARDINA ET AL.
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