Synthesis of thiophosphoryl-containing bisazomethines

Full text of DOI:10.1134/S1070363213040312

ISSN 1070-3632, Russian Journal of General Chemistry, 2013, Vol. 83, No. 4, pp. 779–780. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © R.Kh. Bagautdinova, I.R. Knyazeva, Yu.V. Voronina, A.R. Burilov, M.A. Pudovik, 2013, published in Zhurnal Obshchei Khimii,
2013, Vol. 83, No. 4, pp. 699–700.
LETTERS
TO THE EDITOR
Synthesis of Thiophosphoryl-Containing Bisazomethines
R. Kh. Bagautdinova, I. R. Knyazeva, Yu. V. Voronina, A. R. Burilov, and M. A. Pudovik
Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Centre,
Russian Academy of Sciences,ul. Akademika Arbuzova 8, Kazan, Tatarstan, 420088 Russia
e-mail: pudovik@iopc.knc.ru
Received November 19, 2012
DOI: 10.1134/S1070363213040312
In recent years, the metal complex compounds
based on the hydroxyl containing diimines and a wide
range of the metal salts attracted much interest. The
metal complexes of this type show the catalytic
activity in various chemical processes [1–6]. Some
metal complexes have a high fungicidal, antibacterial,
antimicrobial [7–11], and anti-cancer activity [12].
O,O-Diphosphorylated bisazomethines are of some
interest as the effective tetradentate ligands. The data
on these compounds are scarce. The reaction of O-
thiophosphorylated salicylaldehyde with diamines is
the simplest approach to the synthesis of compounds of
this type. The phosphorylated aldehyde III was
obtained in high yield by a sequential reaction of
salicylaldehyde with sodium hydride and 2-chloro-2-
thioxo-5,5-dimethyl-1,3,2-dioxaphosphorinane II.
CHO
S
CHO
OH
CHO
ONa
Me
Me
O
O
NaH
Me
Me
+
P(S)Cl
O
O
O
−NaCl
−H2
P
III
I
II
According to the XRD data, the bond and torsion
angles in the molecule of III lie within the values
range characteristic of each type of linking. The tetra-
coordinated phosphorus atom is part of the six-
membered ring, which is in a chair conformation. In
the crystal of compound III there are no any
significant intermolecular interactions.
II in the presence of a base. However, in this case
aldehyde III was obtained in a lower yield.
Et3N
III
I + II
−Et3N HCl
The reaction of aldehyde III with hydrazine results
in the tetradentate ligand IV containing a combination
of two azomethine and two thiophosphoryl fragments.
Another method for the synthesis of compound III
is the reaction of salicylaldehyde I with acid chloride
H
C
H
C
N
N
2III + H2N NH2
−2H2O
O
O
Me
Me
Me
Me
O
O
O
O
P
S
S
P
IV
dropwise a solution of 4.87 g of 2-hydroxybenz-
aldehyde I in 35 ml of THF. The mixture was stirred
for 1 h at 20°C. After adding a solution of 8.0 g of
2-Thioxo-2-(2-formylphenoxy)-5,5-dimethyl-1,3,2-
dioxaphosphorinane (III). a. To a suspension of 0.96 g
of sodium hydride in 70 ml of THF at 10°C was added
779

780
BAGAUTDINOVA et al.
1
chlorothiophosphate II in 100 ml of THF, the mixture
was heated with stirring under nitrogen atmosphere (24 h,
65°C). After cooling, the precipitate was separated,
and the solvent was removed. The residue was purified
by the column chromatography on a silica gel (n-
hexane–diethyl ether, 1:1). Yield 8.9 g (78%), white
crystals, mp 82–83°C. IR spectrum, ν, cm–1: 825
KBr pellets. The Н NMR spectra were registered on
an Avance 600 spectrometer in CDC13 operating at
600.13 MHz. The 31P NMR spectra were recorded on a
Bruker MSL-400 Fourier spectrometer (100.62 MHz).
The mass spectra (MALDI-TOF) were obtained on a
Ultraflex III TOF/TOF Bruker instrument (p-nitro-
aniline matrix). The X-ray diffraction analysis was
carried out on a Bruker SMART Apex II diffrac-
tometer (graphite monochromator, λМоKα 0.71073 Å).
1
(P=S), 1602 (Ph), 1694 (C=O). Н NMR spectrum,
(СDCl3), δН, ppm (J, Hz): 0.95 s (3H, CH3), 1.32 s
(3H, CH3), 4.08 m (2H, OCH2), 4.37 m (2H, OCH2),
7.35 m (2H, CHAr), 7.61 t (1H, CHAr, 3JHH 7.7), 7.92 d
ACKNOWLEDGMENTS
3
(1H, CHAr, JHH 8.6), 10.36 s (1H, CHO). 31Р NMR
This work was financially supported by the Russian
Foundation for Basic Research (grant no. 12-03-00204).
spectrum, (СDCl3): δР 54.22 ppm. Mass spectrum
(MALDI-TOF), m/z: 287 [М + H]+. Found, %: С
50.45; Н 5.21; P 10.87; S 11.11. С12Н15O4PS.
Calculated, %: С 50.35; Н 5.24; P 10.84; S 11.19.
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b. To a mixture of 1.71 g of aldehyde I and 1.45 g
of triethylamine in 30 ml of anhydrous benzene was
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1
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2
2
d (2H, OCH2, JHH 10.9), 4.11 d (2H, OCH2, JHH
10.9), 4.27 d (2H, OCH2, 2JHH 6.9), 4.29 d (2H, OCH2,
2JHH 6.9), 7.44 m (8H, CHar), 8.04 s (2H, CH=N). 31Р
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The IR spectra were recorded on a Bruker Vector-
22 spectrometer in the range of 400–3600 cm–1 from
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 4 2013