Phosphorus-containing bisazomethines based on terephthalic aldehyde as tetradentate ligand of new type

Full text of DOI:10.1134/S1070363214060334

ISSN 1070-3632, Russian Journal of General Chemistry, 2014, Vol. 84, No. 6, pp. 1249–1250. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © R.Kh. Bagautdinova, A.P. Vanichkina, E.M. Pudovik, A.R. Burilov, M.A. Pudovik, 2014, published in Zhurnal Obshchei Khimii,
2014, Vol. 84, No. 6, pp. 1049–1050.
LETTERS
TO THE EDITOR
Phosphorus-containing Bisazomethines Based on Terephthalic
Aldehyde as Tetradentate Ligand of New Type
R. Kh. Bagautdinovaa, A. P. Vanichkinaa, E. M. Pudovikb, A. R. Burilova, and M. A. Pudovika
a Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center of the Russian Academy of Sciences,
ul. Akademika Arbuzova 8, Kazan, Tatarstan, 420088 Russia
e-mail: pudovik@iopc.ru
b Kazan (Volga) Federal University, Kazan, Tatarstan, Russia
Received April 10, 2014
Keywords: terephthalic aldehydes, bisazomethines, phosphorylation
DOI: 10.1134/S1070363214060334
Recently, hydroxyl-containing bisazomethines and
complexes based on them attract a great interest. A
wide range of metals including biogenic Zn(II), Cu(II),
Cd(II), Co(II), Ni(II), Fe(III), Pd(II), Zr(IV), U(II) was
used to obtain metal complexes catalyzing enantio-
selective epoxidation of unsubstituted olefins [1, 2],
selective ortho-hydroxylation of phenols [3], epoxida-
tion of styrene [4], oxidation of styrene to carbonyl
compounds under the action of hydrogen peroxide [5],
oxidation of alcohols to carbonyl compounds [6],
oxidation of organic sulfides to sulfoxides [7],
heterogeneous hydrogenation of alkenes and alkynes
[8], butadiene polymerization [9]. Some of metal
complexes showed high fungicidal, antibacterial,
antimicrobial, anticancer activity [10–15].
ligands for metal complexes. We performed phospho-
rylation of diimine I with P(V) acid chlorides IIa–IIc
in the presence of a base to obtain diphosphorylated
derivatives IIIa–IIIc. The latter are promising tetra-
dentate ligands. Compounds IIIa–IIIc are crystalline
substances. Their composition and structure were
proved by elemental analysis, mass spectrometry, IR,
1H and 31P NMR spectroscopy methods (Scheme 1).
1,2-Phenylenebis(methanylidene)bis(azanylidene)-
bis(2,1-phenylene) bis(diphenylphosphinate) (IIIa).
To a suspension of 0.30 g of diimine I and 0.2 g of
triethylamine in 10 mL of anhydrous benzene was
added dropwise a solution of 0.45 g of diphenyl-
chlorophosphine oxide in 5 mL of benzene. After 12 h,
the precipitated triethylamine hydrochloride was se-
parated, and the solvent was removed. To the residue
was added 20 mL of hexane, and then the precipitate
At the same time there are no data on the O-
phosphorylated bisazomethines, which can be used as
Scheme 1.
HC
CH
HC
CH
N
N
N
N
Et3N
+ R2P(X)Cl
HO
O
OH
O
P(X)R2
P(X)R2
I
IIа−IIc
IIIа−IIIc
R = Ph, X=O (а); R = Ph, X = S (b); R = OPh, X = O (c).
1249

1250
BAGAUTDINOVA et al.
was separated. Yield 0.48 g (71%), mp 201–204°C. 1H
NMR spectrum (CDCl3), δ, ppm: 6.50–8.07 m (32H,
Ph), 8.44 s (2H, CH=N). 31P NMR spectrum (CDCl3):
δР 30.81 ppm. Mass spectrum (MALDI-TOF): m/z
716. Found P, %: 9.06. C44H34N2O4P2. Calculated P,
%: 8.86.
ACKNOWLEDGMENTS
This work was supported by the Russian Founda-
tion for Basic Research (grant no. 12-03-00204).
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was added 10 mL of ethanol, and the precipitate was
separated. Yield 0.47 g (66%), mp 176–179°C. IR
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 6 2014