Phosphorus-containing salicylalalkylene(arylene)diamines

Full text of DOI:10.1134/S1070363213010258

ISSN 1070-3632, Russian Journal of General Chemistry, 2013, Vol. 83, No. 1, pp. 134–135. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © R.Kh. Bagautdinova, L.K. Kibardina, A.R. Burilov, M.A. Pudovik, 2013, published in Zhurnal Obshchei Khimii, 2013, Vol. 83,
No. 1, pp. 142–143.
LETTERS
TO THE EDITOR
Phosphorus-containing Salicylalalkylene(arylene)diamines
R. Kh. Bagautdinova, L. K. Kibardina, A. R. Burilov, and M. A. Pudovik
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
Received July 2, 2012
DOI: 10.1134/S1070363213010258
In recent years the metal complex compounds on
the basis of hydroxyl diimines and a wide range of the
metal salts were intensively studied. The metal
complexes of this type showed catalytic properties in
various chemical processes [1–6]. Some metal com-
plexes possess a high fungicidal, antibacterial, anti-
microbial, and anti-cancer activity [7–12]. The hyd-
roxy-containing bisazomethines are promising starting
substances for the synthesis of the pincer phosphorus-
containing compounds. The pincer complexes of
various types are used in versatile applications, pre-
dominantly as the catalysts and biologically active
compounds [13]. There are poor data on phos-
phorylation of the hydroxylated bisazomethines. We
developed a method for the synthesis of diphos-
phorylated diimines including the preliminary prepara-
tion of phosphorylated salicylaldehyde III via the
reaction of salicylaldehyde I with cyclic chloro-
phosphate II. Then compound III reacts with aliphatic
and aromatic diamines to give the phosphorylated
diimines IVa and IVb. The structure of the latter was
1
confirmed by the IR, H and 31P NMR spectroscopy,
and mass spectrometry; the composition was proved
by the elemental analysis data.
CHO
CHO
OH
O
O
O
Me
Me
Et3N
O
+
P
Et3N HCl
O
Cl
Me
O
P
Me
N
O
II
III
CH
I
CH N R
O
O
P
H N R NH
2III +
2
2
−2H2O
O
O
O
O
Me
Me
Me
Me
O
O
P
IVа, IVb
IV: R = (CH2)4 (а); para-С6Н4 (b).
The IR spectra of diimines IVa and IVb contain the
absorption bands at 1300 and 1614–1640 cm–1
belonging to the phosphoryl and C=N moieties,
respectively. The chemical shift of the phosphorus
nuclei of compounds IVa and IVb is characteristic of
the phosphate derivatives (δР –14 ppm).
2-Oxo-2-(2-formylphenoxy)-(5,5-dimethyl-1,3,2-
dioxaphosphorinane (III). To a solution of 2.15 g of
salicylaldehyde and 2.61 g of triethylamine in 20 ml of
anhydrous benzene was added a solution of 3.26 g of
the acid chloride II in 10 ml of anhydrous benzene.
After 6 days, the precipitated triethylamine hydro-
134

135
PHOSPHORUS-CONTAINING SALICYLALALKYLENE(ARYLENE)DIAMINES
1
chloride was filtered off, and the solvent was removed
in a vacuum. Yield 2.37 g (91%), viscous substance.
IR spectrum (KBr), ν, cm–1: 1602 (Ph), 1695 (C=О).
1Н NMR spectrum [(CD3)2CO], δ, ppm (J, Hz ): 0.95 s
(3Н, CH3), 1.32 s (3Н, CH3), 4.08–4.16 m (2H,
dispersion of samples in mineral oil. The H NMR
spectra were taken on an Avance 600 instrument
(600.13 MHz), the residual protons signals of CDCl3
serving as internal reference. The 31P NMR spectra
were registered on a Bruker MSL-400 NMR Fourier
spectrometer (100.62 MHz). The MALDI-TOF mass
spectra were obtained on a ULTRAFLEX III
spectrometer using p-nitroaniline as a matrix.
2
ОCH2), 4.55 d (2Н, ОCH2, JНH 11.03), 7.37–7.90 m
(4H, Ph), 10.41 s (1H, CH=О). 31Р NMR spectrum
[(CD3)2CO]: δР –14.60 ppm. Mass spectrum (MALDI-
TOF), m/z : 613. Found P, %: 11.04. C12H15O5P.
Calculated P, %: 11.46.
ACKNOWLEDGMENTS
This work was financially supported by the Russian
Foundation for Basic Research (grant no 12-03-
00204).
1,4-Bis[2-(5,5-dimethyl-2-oxo-1,3,2-dioxaphos-
phorinyloxy)benzal]-1,4-diaminobutane (IVа). To a
mixture of 0.55 g of aldehyde III and 0.80 g of
anhydrous magnesium sulfate in 5 ml of anhydrous
chloroform was added dropwise 0.09 g of 1,4-butane-
diamine. After 1 day, magnesium sulfate hydrate was
separated. The solvent was removed in a vacuum, and
the residue crystallized on standing. Yield 0.17 g
(28%), yellow powder, mp 108–111°C. IR spectrum
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 1 2013