Phosphacyclanes in reactions of bis(ortho-formylphenyl) phenylthioxophosphonate with diamines

Full text of DOI:10.1134/S1070363214070366

ISSN 1070-3632, Russian Journal of General Chemistry, 2014, Vol. 84, No. 7, pp. 1461–1462. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © M.A. Pudovik, S.A. Terentyeva, L.K. Kibardina, E.M. Pudovik, A.R. Burilov, 2014, published in Zhurnal Obshchei Khimii, 2014,
Vol. 84, No. 7, pp. 1221–1222.
LETTERS
TO THE EDITOR
Phosphacyclanes in Reactions
of Bis(ortho-formylphenyl)phenylthioxophosphonate
with Diamines
M. A. Pudovika, S. A. Terentyevaa, L. K. Kibardinaa, E. M. Pudovikb, and A. R. Burilova
a
Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center,
Russian Academy of Sciences, ul. Akademika Arbuzova 8, Kazan, Tatarstan, 420088 Russia
e-mail: pudovik@iopc.ru
b Kazan (Volga Region) Federal University, Kazan, Tatarstan, Russia
Received April 10, 2014
Keywords: bis(ortho-formylphenyl)phenylthioxophosphonate, diamines, condensation, phosphacyclanes
DOI: 10.1134/S1070363214070366
Phosphorus-containing macrocycles are widely
used in supramolecular chemistry for studying the
molecular recognition processes and complex forma-
tion [1–4]. Macromolecules containing azomethine
fragments, which are usually involved into complex
formation, are of particular interest. As a rule, their
synthesis is carried out by reacting hydrazides of thio-
phosphonic and phosphonic acids with dialdehydes [5–8].
(o-formylphenyl)phenylthioxophosphonate I with aro-
matic diamines IIa–IIc in benzene under heating.
When the reaction was performed in ethanol, bis-
azomethine IVb and diethylthioxophenylphosphonate
V were obtained. Apparently, this was due to etha-
nolysis of macrocycle IIIb. However, it is not im-
probable that the formation of IVb is caused by the
reaction of thiophosphonates with ethanol to give
salicylaldehyde, which reacts with diamines. A
possibility of dialdehyde I ethanolysis under heating
was found in a special experiment. The starting
We prepared macrocycles containing phosphorus
atoms and azomethine fragments via the reaction of bis-
Scheme 1.
S
S
R
C6H6
O
O
CH=N
CH=N
N=HC
N=HC
O
O
PhP
PPh
R
S
O
O
CHO
CHO
PhP
+ H2N−R−NH2
IIа−IIc
IIIа−IIIc
R
S
CH2=N
OH
N=CH
HO
C2H5OH
+ PhP(OEt)2
I
V
IVb
R = C6H4-para (а), С6H4CH2С6H4-para (b), (CH2)4 (c).
1461

1462
PUDOVIK et al.
dialdehyde I was obtained by reacting phenyldichloro-
thiophosphonate with salicylaldehyde in the presence
of a base (Scheme 1).
tetraene (IIIc). A mixture of 3.8 g of aldehyde I, 0.88
g of diamine IIc, and 30 mL of benzene was heated for
0.5 h at 60°C. The solvent was removed, and the
residue was washed with cold petroleum ether. Yield
6.6 g (77%). IR spectrum, ν, cm–1: 1621 (C=N). 31Р
NMR spectrum (DMSO-d6): δP 84.35 ppm. Mass
spectrum (MALDI-TOF), m/z: 869 [M + Н]+.
The composition and structures of the reaction
products were confirmed by elemental analysis, mass
spectrometry, IR, 1H and 31P NMR spectroscopy.
Bis(o-formylphenyl)phenylthioxophosphonate (I).
To a solution of 4.9 g of salicylaldehyde and 4.1 g of
triethylamine in 50 mL of diethyl ether was added
dropwise a solution of 4.2 g of phenyldichlorothioxo-
phosphonate. After 24 h the precipitated triethylamine
hydrochloride was filtered off. Next, the solvent was
removed, and the residue was chromatographed on
silica gel eluting with a hexane-–ethyl acetate mixture
(2 : 1). Yield 4.9 g (66%), mp 72°C. 31Р NMR spec-
trum: δР 86.53 ppm. Mass spectrum (MALDI-TOF),
m/z: 421 [M + K]+. Found, %: P 8.59; S 7.94. C20 H15O4PS.
Calculated, %: P 8.11; S 8.37.
Reaction of dialdehyde I with 4,4'-diamino-
diphenylmethane IIb in ethanol. A mixture of 0.7 g
of I, 0.4 g of diamine IIb and 20 mL of ethanol was
heated for 1 h at 60°C to yield 0.43 g (89%) of IVb
(mp 221°C [9]) and 0.34 g (81%) of phosphonate V.
31P NMR spectrum (DMSO-d6): δP 85.25 ppm.
The IR spectra were recorded on a Bruker Vector-
22 spectrometer in the range of 400–3600 cm–1 from
KBr pellets. The 1H NMR spectra were registered on a
Bruker Avance 600 instrument operating at 600.13 MHz
relative to the signals of residual protons of the
deuterated solvent (CDCl3). The 31P NMR spectra
were taken on a Bruker MSL-400 Fourier spectrometer
(100.62 MHz). Mass spectra (MALDI-TOF) were
obtained on a Ultraflex III TOF/TOF Bruker instru-
ment using p-nitroaniline as a matrix.
2,12-Dithioxa-2,12-diphenyl-2,12-diphospha-1,3,-
11,13-tetraoxa-6,8,16,18-tetraaza-4,10,14,20-tetra(1,2)-
phentylene-7,17-bis(1,4)phenylenecyclocosaphan-
5,8,15,18-tetraene (IIIa). A mixture of 1.9 g of al-
dehyde I, 0.54 g of diamine IIa, and 15 mL of benzene
was refluxed for 1 h with water separation. The solvent
was removed, and the residue was recrystallized from
methylene chloride. Yield 1.51 g (67%), mp 123–125°C.
ACKNOWLEDGMENTS
This work was financially supported by the Russian
Foundation for Basic Research (grant no. 12-03-00204).
31
IR spectrum, ν, cm–1: 1619 (C=N). Р NMR spectrum
(DMSO-d6): δP 85.33 ppm. Mass spectrum (MALDI-
TOF), m/z: 910 [M + 1]+. Found, %: P 6.83; S 7.17.
C50H38O4P2S2. Calculated, %: P 7.06; S 7.10.
REFERENCES
1. Habicher, W.D. and Bauer, I., Tetrahedron Lett., 2002,
no. 43, p. 5245.
2,14-Dithioxa-2,14-diphenyl-2,14-diphospha-
1,3,13,15-tetraoxa-6,10,18,22-tetraaza-4,12,16,24-
tetra(1,2)phenylene-7,9,19,21-tetra(1,4)phenylene-
cyclocosaphan-5,10,17,22-tetraene (IIIb). A mixture
of 2.4 g of aldehyde I, 1.24 g of diamine IIb and
20 mL of benzene was refluxed for 1 h with water
separation. The solvent was removed, and the residue
was treated with petroleum ether. After 12 h, the
precipitated product was separated. Yield 2.7 g (78%),
2. Ekici, S., Nieger, M., Clauni, R., and Niecke, E.,
Angew. Chem. Int. Ed., 2003, vol. 42, p. 435.
3. Cherenok, S., Dutasta, J.P., Kalchenko, V., Curr. Org.
Chem., 2006, vol. 10, p. 2307.
4. Simulesku, V. and Ilia, G.J., Incl. Phenom. Macrocycl.
Chem., 2010, vol. 66, p. 3.
5. Gonce, F., Caminade, A.-M., Boutonnet, F., and
Majoral, J.-P., J. Org. Chem., 1992, vol. 57, p. 970.
1
mp 138–140°C. IR spectrum, ν, cm–1: 1618 (C=N). Н
6. Majoral, J.-P., Badri, M., Caminade, A.-M., Delmas, M.,
and Gasett, A., Inorg. Chem., 1988, vol. 27, p. 3815.
NMR spectrum (CDCl3), δ, ppm: 3.85 br.s (4Н), 8.45 s
(4Н). 31Р NMR spectrum (DMSO-d6): δP 85.01 ppm.
Mass spectrum (MALDI-TOF), m/z: 1089 [M + Н]+.
Found, %: N 4.87; P 5.74; S 5.59. C66H50N4O4P2S2.
Calculated, %: N 5.14; P 5.69; S 5.88.
7. Colombo-Khater, D., Caminade, A.-M., Delavaux-
Nicot, B., and Majoral, J.-P., Organometallics, 1993,
vol. 12, p. 2861.
8. Badri, M., Majoral, J.-P., Caminade, A.-M., Caset, M.,
Gorgues, A., and Jaudt, J., J. Am. Chem. Soc., 1990,
vol. 112, p. 5618.
2,15-Dithioxa-2,15-diphenyl-2,15-diphospha-
1,3,14,16-tetraoxa-6,11,19,24-tetraaza-4,13,17,26-
tetra(1,2)phenylenecyclohexacosaphan-5,11,18,24-
9. Yoshida Noboru, Ito Tasuku, and Oshio Hiroki, J. Chem.
Soc. Perkin Trans 2, 1999, no. 5, p. 975.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 7 2014