First example of phosphorylation of macrocyclic azomethine with secondary phosphine oxides

Full text of DOI:10.1134/S1070363213120244

ISSN 1070-3632, Russian Journal of General Chemistry, 2013, Vol. 83, No. 12, pp. 2345–2346. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © Yu.G. Trishin, A.I. Kudryavtseva, M.V. Shafeeva, E.A. Avdeeva, E.A. Karpova, 2013, published in Zhurnal Obshchei Khimii, 2013,
Vol. 83, No. 12, pp. 2062–2063.
LETTERS
TO THE EDITOR
First Example of Phosphorylation of Macrocyclic Azomethine
with Secondary Phosphine Oxides
Yu. G. Trishin, A. I. Kudryavtseva, M. V. Shafeeva, E. A. Avdeeva, and E. A. Karpova
St. Petersburg State Technological University of Plant Polymers,
ul. Ivana Chernykh 4, St. Petersburg, 198095 Russia
e-mail: trish@YT4470.spb.edu
Received September 30, 2013
DOI: 10.1134/S1070363213120244
Macrocyclic azomethines are classical host mole-
cules of supramolecular systems [1]. Broad prospects
for their use in this capacity have resulted from the
development of template-free methods of the synthesis
of such compounds [2]. In the last decade, the
compounds with different ring sizes, various number
of the C=N bonds, structure of hydrocarbon moiety
(aliphatic, cycloaliphatic, or aromatic) in the ring have
been obtained.
Hitherto such compounds have not been synthesized
and used as hosts for the creation of supramolecular
systems. At the same time it is known that aminophos-
phoryl compounds containing only one P(O)–C–NH
group show high efficiency and selectivity in the
solvent extraction processes of metal ions and mineral
acids, and also in the membrane transport of organic
and mineral acidic substrates [3]. These properties are
largely conditioned by the ability of aminophosphoryl
group to form five-membered chelate structures. In
macrocyclic aminophosphoryl compounds these pro-
perties may be significantly expanded and enhanced
through a combination of the chelate and macrocyclic
effects, which are known to increase significantly the
thermodynamic stability of the host-guest complex.
One of the most important transformations in
organophosphorus chemistry is Pudovik reaction
consisting in the addition of hydrophosphoryl com-
pounds to multiple bonds. The addition to the C=N
bond leads to the formation of α-aminophosphoryl
compounds possessing unique biologically active
properties and complexing ability [3].
In this work, we first carried out the phos-
phorylation of macrocyclic azomethine with secondary
phosphine oxides by an example of hexaimine I ob-
tained via [3+3]-cyclization of terephthalaldehyde and
1,2-diaminocyclohexane. Diphenylphosphine oxide II
was used as a secondary phosphine oxide. The reaction
In this regard, it seemed appropriate to perform the
phosphorylation of macrocyclic Schiff bases to
produce new compounds, in which the nitrogen atom
is a part of a heterocycle, and the phosphoryl group
bonded to the adjacent carbon atom is exocyclic.
CH
P(O)Ph
H C
Ph (O)P
3
3
2
2
N
N
N
H
N
H
O
H
P
+
Ph (O)P
2 H C
P(O)Ph
CH
2
3
3
N
HN
N
NH
H
N
H
N
N
N
Ph (O)P
2 H C
CH
P(O)Ph
3
3
2
I
II
III
2345

2346
TRISHIN et al.
was performed under prolonged reflux of the reaction
mixture at a ratio azomethine : dichloromethane :
diphenylphosphine oxide = 1 : 6.
of cis- and trans-isomers) according to [4] at an
increased reaction time. Diphenylphosphine oxide II
was obtained by hydrolysis of diphenylchlorophos-
phine (Acros Organics, 98%) with 1 N hydrochloric
acid under argon atmosphere [5]. Methylene chloride
was purchased from JSC “Vekton” (purum, TU 2631-
019-44493179-98).
The reaction progress was monitored by decrease in
the signal intensity of diphenylphosphine oxide in the
1
31P NMR spectrum (δР 21.3 ppm, JPH 482 Hz). It
should be noted that adding diphenylphisphine oxide
to all C=N bonds requires prolonged heating; 95%
conversion of the starting organophosphorus com-
pound was achieved in 30 h.
Compound (III). A mixture of 2.02 g (10 mmol) of
diphenylphosphine oxide II in 5 mL of anhydrous
methylene chloride and 1.05 g (1.66 mmol) of
hexaimine I in 17 mL of methylene chloride was re-
fluxed for 35 h under argon. Then the solvent was
removed on a rotary evaporator. Yield 3.03 g (98.6%),
a yellowish cream solid, mp > 230°C. IR spectrum, ν,
The structure of the obtained α-aminophosphoryl
macrocyclic product III containing six P(O)Ph2 groups
1
on the macrocycle rim was confirmed by IR, H, 13C,
31P NMR spectroscopy and mass spectrometry. Thus,
the IR spectrum contains strong absorption bands of
NH (3428 cm–1) and P=O groups (1190 cm–1). In the
31P NMR spectrum there are two signals of equal
intensity at 31.1 and 31.6 ppm characteristic of the
tertiary phosphine with two phenyl groups at the
phosphorus atom and pointing to a different spatial
arrangement of these groups with respect to the ring
1
cm–1: 3428 (NH), 1190 (P=O). H NMR spectrum, δ,
ppm: 1.2–1.6 m (12H, СН2), 2.1–2.4 m (6H,
NCHcyclohexyl), 4.6 m (6H, РCH), 6.8–8.0 m (72H, Ar).
13С NMR spectrum, δC, ppm: 24.4, 29.6, 33.1 (12СH2);
54.1, 56.9 (6NCHcyclohexyl); 58.7, 61.0 (6РCH), 128.3–
132.6 (Ar). 31Р NMR spectrum, δР, ppm: 31.1, 31.6.
Found, %: С 73.87; Н 6.42; N 4.51; P 9.78. C114H114
·
N6O6P6. Calculated, %: С 74.01; Н 6.21; N 4.54; P 10.05.
1
fragments. H NMR spectrum contains broad signals
owing to large molecular weight of III. The spectrum
contains characteristic signal of the methine protons of
P(O)CH groups at 4.6 ppm. The signals of methine
protons of cyclohexane ring were observed in the
range of 2.1–2.4 ppm that differs from their position in
the spectrum of the starting hexaimine (δ 3.4 ppm).
The protons of methylene groups resonate as multi-
plets in the range of 1.2–1.6 ppm. In the 13C NMR
spectrum there are the signals of the carbon atoms of
P(O)CH (δC 58.7, 61.0 ppm), CH2 (δC 24.4, 29.6,
33.1 ppm) and NHCH groups (δC 54.1, 56.9 ppm), of
the benzene rings at 128.3–132.6 ppm and no signals
of the carbon atoms of the C=N group of hexaimine I
(δC 160.4 ppm).
1H, 13C and 31P NMR spectra (CDCl3) were re-
corded on a Bruker Avance-400 spectrometer operat-
ing at 400.13, 100.61, and 161.98 MHz, respectively.
31P chemical shifts were measured with respect to 85%
H3PO4. IR spectrum was taken on a Shimadzu FTIR-
8400S instrument from KBr pellets. Mass spectrum
(ESI) was obtained on a Bruker Customer Microtof
10223 instrument using methanol as solvent.
Elemental analysis was performed on an automated
CHNS-analyzer Vario Microcube Elementar; phos-
phorus content was determined by spectrophotometry.
ACKNOWLEDGMENTS
This work was supported by the Russian Founda-
tion for Basic Research (grant no. 11-03-00648).
The mass spectrum of compound III contains a
peak with m/z 1872.7638 corresponding to the ion
[М – Na]+ and confirming the molecular weight of the
nitrogen-containing macrocycle with six diphenylphos-
phine groups. There are also peaks at m/z 1670.6935,
1467.6256, 1265.5615, 1061.6718, 849.5355, and 637.4048
corresponding to the fragments with split-off one, two,
three, four, five, and six diphenylphosphine groups,
respectively.
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 12 2013