Salt structures in a series of hexacoordinated phosphorus polycyclic derivatives

Full text of DOI:10.1134/S1070363211020277

ISSN 1070-3632, Russian Journal of General Chemistry, 2011, Vol. 81, No. 2, pp. 429–430. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © L.K. Kibardina, S.A. Terent’eva, A.R. Burilov, M.A. Pudovik, 2011, published in Zhurnal Obshchei Khimii, 2011, Vol. 81, No. 2,
pp. 331–332.
LETTERS
TO THE EDITOR
Salt Structures in a Series
of Hexacoordinated Phosphorus Polycyclic Derivatives
L. K. Kibardina, S. A. Terent’eva, A. R. Burilov, and M. A. Pudovik
Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center,
Russian Academy of Sciences, ul. Arbuzova 8, Kazan, Tatarstan, 420088 Russia
e-mail: pudovik@iopc.knc.ru
Received July 20, 2010
DOI: 10.1134/S1070363211020277
Recently we synthesized polycyclic framework
structures of new type formed via the nitrogen–
phosphorus intramolecular coordination bonding [1].
The presence of a secondary amino group connected
with the phosphorus atom through a carbon atom
(aminoalkylphosphonate analog) determines a pos-
sibility to form a salt structure on this basis.
Compounds Ia–Id were found to react with dibromo-
acetic and picric acids in a solvent at room temperature
to afford the compounds of salt structure IIa–IId. The
chemical shift of the phosphorus atom is observed in
the range of –113 to –116 ppm, which is characteristic
of the compounds of the hexacoordinated phosphorus
atom.
H
C
H
C
N
R
N
R
O
O
+ HX
O
O
X _
+
HN
H
H2N
P
P
C
O
C
O
H
.
.
O
O
Iа, Ib
IIа−IId
Iа, R = cyclohexyl; Ib, R = (CH2)2; IIа R = cyclohexyl, X– = CHBr2C(O)O; IIb, R = cyclohexyl, X = 2,4,6-(NO2)3C6H2O;
IIc, R = (CH2)2, X– = CHBr2C(O)O; IId, R = (CH2)2, X = 2,4,6-(NO2)3C6H2O.
The structure of compounds obtained was
1,1-Ethylenedioxy-3,4,11,12-dibenzo-6-aza-7,8-
tetramethyleno-9-ammonia-2,13-dioxa-1-phospha
[8.3.01,10]tridecatri-3,5,11-ene dibromoacetate (IIа).
A solution of 0.41 g of compound Iа and 0.22 g of
dibromoacetic acid in 5 ml of methylene chloride was
maintained for 6 h at 20°С. The target product was
precipitated from ether. Yield 0.40 g (64%), mp 116°С.
IR spectrum (KBr), ν, cm–1 33 (C=N), 1732 [С(O)O],
2580–2700 (NH2+). 31Р NMR spectrum (CDCl3), δР,
1
confirmed by the Н, 31Р NMR, IR spectroscopy, and
composition, by the elemental analysis. Due to the salt
structure, in the 1Н spectra the protons of these
compounds appear as poorly resolved broad signals.
Therefore only a group analysis can be made based on
the chemical shifts without considering their fine
structure. The compounds obtained undergo changes at
prolonged contact with air.
429

430
KIBARDINA et al.
ppm: –114.29. Found, %: Br 25.63; N 4.59; P 4.79.
C24H27Br2N2O6P. Calculated, %: Br 25.39; N 4.44; P
4.92.
(2Н), 3.69–3.74 m (1Н), 3.77–3.79 m (1Н), 3.96–4.02
m (1Н), 4.32–4.38 m (1Н), 4.48–4.55 m (1Н), 6.81–
7.75 m (8Н). 31Р NMR spectrum (CDCl3), δР, ppm:
–116.66. Found, %: Br 27.21;
C20H21Br2N2O6P. Calculated, %: Br 27.77; P 5.38.
P
5.87.
1,1-Ethylenedioxy-3,4,11,12-dibenzo-6-aza-7,8-
tetramethyleno-9-ammonia-2,13-dioxa-1-phospha
[8.3.01,10]tridecatri-3,5,11-ene picrate (IIb) was prepared
similarly from 0.41 g of compound Iа and 0.23 g of
picric acid. Yield 0.3 g (47%), mp 170–174°С. IR
spectrum (KBr), ν, cm–1: 1633 (C=N), 2490–2854
(NH2+). 31Р NMR spectrum (CDCl3), δР, ppm: –113.96.
Found, %: N 10.95; P 4.93. C28H28N5O11P. Calculated,
%: N 10.92; P 4.83.
1,1-Ethylenedioxy-3,4,11,12-dibenzo-6-aza-9-
ammonia-2,13-dioxa-1-phospha[8.3.01,10]tridecatri-
3,5,11-ene picrate (IId) was prepared similarly from
0.36 g of compound Ib and 0.23 g of picric acid. Yield
0.40 g (69%), mp 102–106°С. IR spectrum (KBr), ν,
+
cm–1: 1630 (C=N), 2480–2857 (NH2 ). 31Р NMR
spectrum (CDCl3), δР, ppm: –115.91. Found, %: N
11.45; P 4.87. C24H22N5O11P. Calculated, %: N 11.92;
P 5.28.
1,1-Ethylenedioxy-3,4,11,12-dibenzo-6-aza-9-
ammonia-2,13-dioxa-1-phospha[8.3.01,10]tridecatri-
3,5,11-ene dibromoacetate (IIc) was prepared
similarly from 0.36 g of compound Ib and 0.22 g of
dibromoacetic acid. Yield 0.31 g (53%), mp 214–218°С.
IR spectrum (KBr), ν, cm–1: 1628 (C=N), 1734
[С(O)O], 2480–2856 (NH2+). 1Н NMR spectrum
(СDCl3), δ, ppm: 3.42–3.47 m (2Н), 3.48–3.54 m
REFERENCES
1. Kibardina, L.K., Terent’eva, S.A., Kataeva, O.N.,
Burilov, A.R., and Pudovik, M.A., Zh. Obshch. Khim.,
2010, vol. 80, no. 2, p. 341.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 2 2011