New P-containing linear and macrocyclic polyphenols

Article abstract of DOI:10.1080/10426507.2010.537289

We synthesized new phosphorus-containing linear and macrocyclic polyphenols using organic compounds containing phosphorus-carbon bonds and the phosphorus atom of various coordination, and also with reactive acetal, aldehyde, vinylethoxy, and methylene qui

Full text of DOI:10.1080/10426507.2010.537289

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Phosphorus, Sulfur, and Silicon and the
Related Elements
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New P-Containing Linear and Macrocyclic
Polyphenols
Alexander R. Burilov a , Irina R. Knyazeva a , Elmira M. Kasymova a
, Yulia M. Sadykova a , Michael A. Pudovik a , Wolf D. Habicher b
Oleg G. Sinyashin a
&
a A.E. Arbuzov Institute of Organic and Physical Chemistry, Kazan
Scientific Center of the Russian Academy of Sciences, Kazan, Russia
b Drezden University of Technology Institute of Organic Chemistry,
Drezden, Germany
Version of record first published: 25 Apr 2011.
To cite this article: Alexander R. Burilov , Irina R. Knyazeva , Elmira M. Kasymova , Yulia M.
Sadykova , Michael A. Pudovik , Wolf D. Habicher & Oleg G. Sinyashin (2011): New P-Containing
Linear and Macrocyclic Polyphenols, Phosphorus, Sulfur, and Silicon and the Related Elements, 186:4,
884-887
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Phosphorus, Sulfur, and Silicon, 186:884–887, 2011
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2010.537289
NEW P-CONTAINING LINEAR AND MACROCYCLIC
POLYPHENOLS
Alexander R. Burilov,1 Irina R. Knyazeva,1 Elmira M.
Kasymova,1 Yulia M. Sadykova,1 Michael A. Pudovik,1
Wolf D. Habicher,2 and Oleg G. Sinyashin1
1A.E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center
of the Russian Academy of Sciences, Kazan, Russia
2Drezden University of Technology Institute of Organic Chemistry,
Drezden, Germany
Abstract We synthesized new phosphorus-containing linear and macrocyclic polyphenols
using organic compounds containing phosphorus-carbon bonds and the phosphorus atom of
various coordination, and also with reactive acetal, aldehyde, vinylethoxy, and methylene
quinone fragments as starting materials. These achievements are briefly summarized.
Keywords Calixarenes; condensation; intermolecular cyclization; phosphorylation; resorcinol
and its derivatives
Recently macrocyclic and open chain compounds with phosphorus–carbon bonds,
containing phenolic fragments in their structure, and also phosphorus-containing
counterparts of natural compounds, have been intensively studied. Compounds with
phosphorus–carbon bonds can be considered formal counterparts of phosphates with the
difference that their biological action is substantially higher and more varied due to certain
difficulties of enzyme-promoted cleavage of phosphorus–carbon bonds in comparison
with phosphorus–oxygen bonds. In this article, we will show the most recent data on the
synthesis of new linear and macrocyclic polyphenols with phosphorus–carbon bonds.1,2
The interaction of triamidophosphites, containing linear and cyclic amino groups at
a phosphorus atom, with diethylacetal of bromoacetaldehyde leads to the formation of new
triamidophosphonium acetals 1а–e. The structure of compounds 1a and 1c was established
on the basis of X-ray analysis data. Condensation of triamidophosphonium acetals 1а–d
with resorcinol and its derivatives in the presence of acids results in the formation of
new compounds of diarylmethane type 2а–e, 3а–e, and 4а–d (Scheme 1). The formation
of linear structures instead of expected calix[4]resorcinols is probably determined by the
Received 13 September 2010; accepted 31 October 2010.
The authors are grateful to the Russian Foundation for Basic Research for support of this work (grant no.
08-03-00512).
Address correspondence to Alexander R. Burilov, A.E. Arbuzov Institute of Organic and Physical Chemistry,
Kazan Scientific Center of the Russian Academy of Sciences, Arbuzov St. 8, Kazan 420088, Russia. E-mail:
burilov@iopc.ru
884

NEW P-CONTAINING LINEAR AND MACROCYCLIC POLYPHENOLS
885
Scheme 1
steric factors—the presence of large substituents at phosphorus atoms, which interfere in
the further condensation of the product obtained in macrocyclic structure.
Varying the nature of phosphorus-containing acetals and aldehydes in condensa-
tion reactions of resorcinol and its derivatives, we have chosen the aldehydes from 5 to
10 as new subjects of research, which include phosphoric and aldehyde fragments sepa-
rated by an aromatic spacer. For the synthesis of thiophosphorylated calixarenes 11–16,
bearing bulky phosphorus-containing fragments on the lower rim of the molecule, we
carried out the condensation reactions of thiophosphatoaldehydes 5–10, synthesized by a
known procedure, with resorcinol, 2-methylresorcinol, and pyrogallol in acidic conditions
(Scheme 2).
The formation of the phosphorus-containing calixarene matrix was realized in one
step by the interaction of resorcinol, 2-methylresorcinol, or pyrogallol with dithiophosphate
acetal 17 in trifluoroacetic acid, which was used both as the catalyst and solvent (Scheme 3).
Scheme 2

886
A. R. BURILOV ET AL.
Scheme 3
As a result, the first representatives of calix[4]resorcinols 18a–c containing dithiophosphate
methyl fragments on the lower rim of the molecule were obtained.3
For the first time, we studied the condensation of aminophosphonate acetal with
resorcinol and 2-methylresorcinol in acidic conditions. As a result, the main product,
phosphorus-containing polyphenol of diarylmethane type 19, was obtained. However, a
detailed study of the reaction revealed that in the case of aminophosphonate acetal, along
with condensation, the second direction of reaction is realized—intermolecular cyclization
of aminophosphonate with the formation of piperazine derivative 20 (Scheme 4).
We have developed a convenient one-step method for the synthesis of new skeleton,
phosphonates 21a–c, by the condensation of available 2-ethoxyvinyldichlorophosphonate
with resorcinol and its derivatives in dichloromethane in the presence of trifluoroacetic
acid (Scheme 5). The compounds obtained contain several hydroxyl groups; that makes
these cyclic phosphonates interesting as starting compounds for the synthesis of new
Scheme 4

NEW P-CONTAINING LINEAR AND MACROCYCLIC POLYPHENOLS
887
Scheme 5
polymeric and macrocyclic structures. It is necessary to note that during condensation of 2-
ethoxyvinyldichlorophosphonate with 3-methyl-2-ethoxyphenol, the products are bicyclic
phosphonate and oxaphosphorine 22 in 1:1 ratio and also oxaphosphorine 23, which was
isolated in pure state with 5% yield. The structure of compound 22 was also established on
the basis of X-ray analysis data.4
The structure and composition of the products obtained were confirmed by 1H, 31P,
IR, and mass spectrometry data; X-ray analysis data; and elemental analysis.
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