Phosphorus-containing azomethines based on salicylaldehyde and thiosemicarbazide

Full text of DOI:10.1134/S1070363213100307

ISSN 1070-3632, Russian Journal of General Chemistry, 2013, Vol. 83, No. 10, pp. 1963–1964. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © R.Kh. Bagautdinova, A.R. Burilov, A.B. Dobrynin, M.A. Pudovik, 2013, published in Zhurnal Obshchei Khimii, 2013, Vol. 83,
No. 10, pp. 1757–1758.
LETTERS
TO THE EDITOR
Phosphorus-Containing Azomethines
Based on Salicylaldehyde and Thiosemicarbazide
R. Kh. Bagautdinova, A. R. Burilov, A. B. Dobrynin, 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 June 17, 2013
DOI: 10.1134/S1070363213100307
Recently, azomethines derived from aromatic
aldehydes and thiosemicarbazide and their metal
complex compounds with a wide range of metal salts
were intensively studied. Some thiosemicarbazones of
aromatic aldehydes possess melanin inhibitory [1] and
high antibacterial activity [2]. They can be used as
inhibitors of carbon steel in salt water [3], inhibitors of
decomposition of cumene hydroperoxide [4] and as
components of the high-sensitive copper membranes
[5]. Their nickel complexes are effective catalysts for
C–C coupling [6]. Some of the copper and nickel
complexes showed antibacterial [2], and palladium
complexes anti-malarial and anti-tumor properties [7].
Also they are catalysts in the cyclopropanation reac-
tions of unactivated olefins [8].
In our opinion, thiosemicarbazones containing
thiophosphoryl, thiocarbonyl, and azomethine moieties
can serve as effective tridentate ligands. Synthesis of
compounds of this type was performed using thio-
phosphorylated salicylaldehyde derivatives. The latter
were prepared by reacting salicylaldehyde with di-
phenylchlorothiophosphinate or 2-chloro-1,3,2-dioxa-
phosphorinane in the presence of a base.
S
S
S
CHO
CH=NNHCNH2
CHO
OH
R
R
H2NNHCNH2
B
S
S
Cl
+
P
R
R
R
−H2O
O
O
P
P
R
Iа, Ib
IIа, IIb
IIIа, IIIb
R = Ph (а); R = OCH2CMe2CH2O (b).
double P=S bond: ∠S2AP2AO9AC10A 63.7(4)°,
∠S2BP2BO9BC10B 53.8(3)°. Phosphorus atom has a tetra-
gonal configuration, the six-membered heterocyclic
ring was in a chair conformation. A crystal contains a
water molecule.
Compounds IIa and IIb are crystalline substances,
the structure of which was confirmed by a complex of
physical methods. Heating of a mixture of IIa or IIb
with thiosemicarbazide in ethanol for 12 h results in
the desired product, azomethines IIIa or IIIb. Struc-
ture and composition of the latter were confirmed by
Diphenyl 2-formylphenoxythiophosphinate (IIa).
To a solution of 1.27 g of salicylaldehyde and 1.05 g
of triethylamine in 20 mL of anhydrous benzene was
added with stirring 2.63 g of diphenylchlorothiophos-
phinate. After 12 h the precipitated triethylamine
hydrochloride was filtered off. The solvent was
removed, and the residue was washed with diethyl
1
the IR, H and 31P NMR spectroscopy, mass spectro-
metry, X-ray diffraction and elemental analysis.
According to XRD data, compound IIIb crys-
tallizes in the space group P21/n. In the unit cell there
are two independent molecules, which differ from each
other by reversing the phenyl moiety relative to the
1963

1964
BAGAUTDINOVA et al.
ether. Yield 2.13 g (61%), mp 98–100°C. IR spectrum
4.10–4.19 m (2Н, ОCH2), 4.51–4.55 m (2H, ОCH2),
7.26–7.48 m (4H, Ph), 8.48 s (1H, РhCH). 31Р NMR
spectrum [(CD3)2CO]: δР 54.10 ppm. Mass spectrum,
m/z: 359. Found, %: P 8.33; S 17.40. C13H18N3O3PS2.
Calculated, %: P 8.62; S 17.84.
1
(KBr), ν, cm–1: 1599 (Ph), 1692 (C=O). H NMR
spectrum [(CD3)2CO], δ, ppm: 7.52–8.15 m (14H, Ph),
10.33 s (1H, РhCH). 31P NMR spectrum [(CD3)2CO]:
δР 85.26 ppm. Mass spectrum, m/z: 338. Found, %: P
9.27; S 9.21. C19H15O2PS. Calculated, %: P 9.16; S
9.48.
The IR spectra were recorded on a Bruker Vector-
22 spectrometer in the range of 400–3600 cm–1 from
1
2-Thioxo-2-(2-formylphenoxy)-5,5-dimethyl-1,3,2-
dioxaphosphorinane (IIb). To a mixture of 1.71 g of
aldehyde I and 1.45 g of triethylamine in 30 mL of an-
hydrous benzene was added dropwise a solution of
2.81 g chlorothiophosphinate II in 10 mL of benzene.
After 12 h the precipitated triethylamine hydrochloride
was filtered off. The solvent was removed, the residue
was purified by column chromatography (silica gel,
eluent a methylene chloride–ethanol mixture, 40:1).
Yield 1.51 g (38%), mp 81–83°C. IR spectrum (KBr),
KBr pellets. H NMR spectra were registered on an
Avance 600 instrument operating at 600.13 MHz
relative to the residual proton signals of the deuterated
solvents (CDCl3). 31P NMR spectra were taken on a
Bruker MSL-400 FT-NMR spectrometer (100.62 MHz).
Mass spectrum MALDI-TOF was obtained on a Ultra-
flex III TOF/TOF Bruker instrument (p-nitroaniline
matrix). Electron impact mass spectra were recorded
on a DFS Thermo Electron Corporation instrument
(ionizing electron energy 70 eV, ion source tem-
perature 280°C, direct input of the sample into the
source, evaporator temperature varied from 50 to 350°C).
1
ν, cm–1: 825 (P=S), 1602 (Ph), 1694 (C=O). H NMR
spectrum (CDCl3), δ, ppm (J, Hz): 0.95 s (3H, CH3),
1.32 s (3H, CH3), 4.08 m (2H, OCH2), 4.32–4.42 m
(2H, OCH2), 7.30–7.48 m (2H, CHAr), 7.61 t (1H,
CHAr, 3JHH 7.74), 7.92 d (1H, CHAr, 3JHH 8.68), 10.36 s
(1H, CHO). 31Р NMR spectrum (CDCl3): δP 54.27
ppm. Mass spectrum (MALDI-TOF), m/z: 287 [М +
H]+. Found, %: С 50.55; Н 5.29; P 10.91; S 11.08.
С12Н15O4PS. Calculated, %: С 50.35; Н 5.24; P 10.84;
S 11.19.
ACKNOWLEDGMENTS
This work was financially supported by the Russian
Foundation for Basic Research (grant no. 12-03-00204).
REFERENCES
1. Lee, Ki-Cheul, Thanigaimalai, Pillaiyar, Sharma, Vinay K.,
Kim, Min-Seok, Roh, Eunmiri, Hwang, Bang-Yeon,
Kim, Youngsoo, and Jung, Sang-Hun, Bioorg. Med.
Chem. Lett., 2010, vol. 20, no. 22, p. 6794.
2. Joseph, Jisha, Mary, N.L., and Sidambaram, Raja,
Synthesis and Reactivity in Inorganic, Metal-Organic
and Nano-Metal Chemistry, 2010, vol. 40, no. 10,
p. 930.
2-Diphenylthiophosphinyloxybenzalthio-semi-
carbazide (IIIa ). A mixture of 0.25 g of aldehyde I,
0.07 g of thiosemicarbazide and 5 mL of anhydrous
ethanol was heated at reflux for 6 h. After cooling the
precipitate was separated. Yield 0.25 g (83%), mp
198–201°C. IR spectrum (KBr), ν, cm–1: 1598 (Ph),
3. Samide, A. and Tutunaru, B., J. Environ. Sci. Health
(A), 2011, vol. 46, no. 14, p. 1713.
1
1603 (C=N), 3109, 3164, 3250, 3342 (NH2). H NMR
4. Lyavinets, O.S. and Andriichuk, Yu.M., Kataliz i
Neftekhimiya, 2010, no. 18, p. 27.
5. Ganjali, M.R., Ghafarloo, A., Faridbod, F., and Norouzi, P.,
spectrum (CDCl3), δ, ppm: 7.05–8.1 m (14H, Ph), 8.49
s (1H, РhCH). 31Р NMR spectrum [(CD3)2CO]: δР
83.35 ppm. Mass spectrum, m/z: 412. Found, %: P
7.42; S 15.38. C20H18N3OPS2. Calculated, %: P 7.53; S
15.59.
Int. J. Electrochem. Sci., 2012, vol. 7, no. 4, p. 3706.
6. Datta, S., Seth Dipravath, K., Gangopadhyay, S.,
Karmakar, P., and Bhattacharya, S., Inorg. Chim. Acta,
2012, vol. 392, p. 118.
7. Chellan, P., Shunmoogam, G., Nelusha, H., Gut, J.,
Rosenthal, P.J., Lategan, C., Smith, P.J., Chibale, K.,
and Smith, G.S., Europ. J. Inorg. Chem., 2010, no. 22,
p. 3520.
2-Thioxo-1,3,2-dioxaphosphorinyloxybenzalthio-
semicarbazide (IIIb). A mixture of 0.32 g of aldehyde
II, 0.1 g of thiosemicarbazide in 5 mL of ethanol was
heated at reflux for 0.5 h. After cooling the precipitate
was separated. Yield 0.32 g (80%), mp 209–212°C. IR
spectrum (KBr), ν, cm–1: 1600 (Ph), 1603 (C=N),
8. Youssef Nabil, S., El-Seidy, A.M.A, Schiavoni, M.,
Castano, B., Ragaini, F., Gallo, E., and Caselli, A.,
J. Organomet. Chem., 2012, vol. 714, p. 94.
1
3162, 3266, 3376, 3411 (NH2). H NMR spectrum
(CDCl3), δ, ppm: 0.99 s (3Н, CH3), 1.33 s (3Н, CH3),
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 10 2013