New tetradentate ligands in the series of phosphorus containing bisazomethines

Full text of DOI:10.1134/S1070363213070293

ISSN 1070-3632, Russian Journal of General Chemistry, 2013, Vol. 83, No. 7, pp. 1461–1462. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © R.Kh. Bagautdinova, A.R. Burilov, M.A. Pudovik, 2013, published in Zhurnal Obshchei Khimii, 2013, Vol. 83, No. 7, pp. 1215–
1216.
LETTERS
TO THE EDITOR
New Tetradentate Ligands in the Series
of Phosphorus Containing Bisazomethines
R. Kh. Bagautdinova, A. R. Burilov, and M. A. Pudovik
Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Centre,
Russian Academy of Sciences, ul. Arbuzova 8, Kazan, Tatarstan, 420088 Russia
e-mail: pudovik@iopc.ru
Received February 14, 2013
DOI: 10.1134/S1070363213070293
Metal complexes based on hydroxyl-containing methines which are not found in the literature can
diimines are known to exhibit catalytic properties be effective tetradentate ligands. We obtained O-
in various chemical processes [1–6]. Some metal thiophosphorylated salicylic aldehyde III by
complexes possess high fungicidal, antibacterial, reaction of salicylaldehyde with 2-chloro-2-
antimicrobial and antitumor activity [7–12]. We thioxo-5,5-dimethyl-1,3,2-dioxaphosphorinane II
believe that O,O-di(thio)phosphorylated bisazo-
in the presence of triethylamine.
CHO
CHO
O
Me
Me
Et3N
S
+
P(S)Cl
.
Et3N HCl
Me
Me
O
O
O
OH
O
P
I
II
III
1,3,2-Dioxaphosphorinane III reacts readily
with aliphatic and aromatic diamines to form the 1,3,2-dioxaphosphorinane (III). To a mixture of
2-Thioxo-2-(2-formylphenoxy)-5,5-dimethyl-
1.71 g of aldehyde I and 1.45 g of triethylamine in
30 ml of anhydrous benzene was added dropwise
a solution of 2.81 g chlorothiophosphate II in
10 ml of benzene. The reaction mixture was
refluxed for 62 h. After cooling, triethylamine
hydro-chloride was separated, and the solvent was
re-moved. The residue was purified by column
chromatography (silica gel, methylene chloride–
ethanol, 40:1). Yield 1.51 g (38%), mp 81–83°C.
IR spectrum, ν, cm–1: 825 (P=S), 1602 (Ph), 1694
desired bisazomethines IVa–IVc.
2 III
H2N
+
R
NH2
_2 H2O
H
C
H
C
R
N
N
O
P
O
1
Me
Me
O
O
Me
Me
(C=O). H NMR spectrum, (CDCl3), δ, ppm (J,
O
P
S
S
Hz): 0.95 s (3H, CH3), 1.32 s (3H, CH3), 4.11–4.20 m
(2H, OCH2), 4.58–4.62 m (2H, OCH2), 7.39–7.91 m
O
IVа_IVc
3
(2H, CHАr), 7.61 t (1H, CHАr, JHH 7.74), 7.92 d (1H,
3
CHАr, JHH 8.68), 10.36 s (1H, CHO). 31P NMR
R = (CH2)2 (a), p-С6Н4 (b); (1R,2R)-(–)-1,2-diaminocyclo-
hexane (c).
spectrum, (CDCl3): δP 54.27 ppm. Mass spectrum
(MALDI-TOF), m/z: 287 [М + H]+. Found, %: С
1461

1462
BAGAUTDINOVA et al.
The IR spectra were recorded on a Vector-22
Bruker spectrometer in the range of 400–3600 cm–1
50.55; Н 5.29; P 10.91; S 11.08. С12Н15O4PS. Cal-
culated, %: С 50.35; Н 5.24; P 10.84; S 11.19.
1
(KBr). The H NMR spectra were taken on an Avance
Bis[2-(5,5-dimethyl-2-thioxo-1,3,2-dioxaphos-
phorinyloxy)benzal]ethanediamine (IVa). To a
solution of 0.56 g of aldehyde III in 10 ml ethanol
600 instrument operating at 600.13 MHz using the
residual proton signals of the deuterated solvent
(CDCl3) as internal reference. The 31P NMR spectra
was added 0.06 g of ethylene diamine. The were registered on a Bruker MSL-400 Fourier spec-
trometer (100.62 MHz). Mass spectra (MALDI-TOF)
were recorded on a Ultraflex III TOF/TOF Bruker
instrument (matrix – p-nitroaniline).
reaction mixture was refluxed for 0.4 h. After 12 h
the solvent was removed, and to the residue was
added 5 ml of diethyl ether. The formed pre-
cipitate was separated and washed with ethanol.
Yield 0.55 g (95%), mp 129–132°С. IR spectrum, ν,
cm–1: 1604 (С6Н4), 1639 (C=N). 1H NMR spectrum,
[(CD3)2C=O)], δ, ppm: 0.99 s (6H, CH3), 1.34 s (6H,
CH3), 4.08–4.16 m (2H, CH2N), 4.12–4.21 m (2H,
CH2N), 4.40–4.44 m (4H, CH2O), 4.59–4.63 m (4H,
CH2O), 7.40–7.93 m (8H, C6H4), 8.87 s (СH=N). 31P
NMR spectrum, [(CD3)2C=O)]: δP 54.41 ppm. Found,
%: P 10.44; S 10.71. С26Н34N2O6P2S2. Calculated, %:
P 10.38; S 10.75.
ACKNOWLEDGMENTS
This work was financially supported by the Russian
Foundation for Basic Research (grant no. 12-03-
00204).
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Bis[2-(5,5-dimethyl-2-thioxo-1,3,2-dioxaphos-
phorinyloxy)benzal]-1,4-diaminobenzene (IVb)
was obtained similarly from 0.37 g of aldehyde
III and 0.07 g of 1,4-diaminobenzene in 10 ml of
ethanol. Yield 0.33 g (79%), mp 258–262°С. IR
1
spectrum, ν, cm–1: 1600 (С6Н4), 1614 (C=N). H
NMR spectrum, (CDCl3), δ, ppm: 0.96 s (6H, CH3),
1.33 s (6H, CH3), 4.04–4.14 m (4H, CH2O), 4.28–4.37
m (4H, CH2O), 7.14–7.95 m (12H, C6H4), 9.36 s
31
(CH=N). P NMR spectrum, (CDCl3): δP 55.50 ppm.
Mass spectrum (MALDI-TOF), m/z: 645 [М + H]+.
Found, %: P 9.18; S 9.88. С30Н34N2O6P2S2. Cal-
culated, %: P 9.61; S 9.95.
Bis[2-(5,5-dimethyl-2-thioxo-1,3,2-dioxaphos-
phorinyloxy)benzal]-1,2-diaminocyclohexane
(IVb) was obtained similarly from 0.35 g of alde-
hyde III and 0.07 g of (1R,2R)-(–)-1,2-diamino-
cyclohexane in 10 ml of ethanol. Yield 0.33 g (83%),
mp 80–83°С, [α]D20 7.0 (c 0.76 CH3CN). IR spectrum,
1
ν, cm–1: 1604 (С6Н4), 1638 (C=N). H NMR spec-
trum, (CDCl3), δ, ppm: 0.89 s (6H, CH3), 1.28 s (6H,
CH3), 1.51–1.87 m [8Н, (СН2)4], 3.48–3.50 m (СН2N),
3.96–4.06 m (4H, CH2O), 4.16–4.25 m (4H, CH2O),
7.13–7.64 m (8H, C6H4), 8.56 s (CH=N). 31P NMR spec-
trum, (CDCl3): δP 54.50 ppm. Mass spectrum (MALDI-
TOF), m/z: 651 [М + H]+. Found, %: P 9.41; S 9.87.
С30Н40N2O6P2S2. Calculated, %: P 9.52; S 9.86.
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 7 2013