Russian Journal of Applied Chemistry, 2012, Vol. 85, No. 2, pp. 256−260.
Pleiades Publishing, Ltd., 2012.
Original Russian Text © E.I. Markova, M.Kh. Mamedov, S.R. Raﬁ eva, N.F. Dzhanibekov, 2012, published in Zhurnal Prikladnoi Khimii, 2012, Vol. 85, No. 2,
AND INDUSTRIAL ORGANIC CHEMISTRY
Synthesis of Nitrogen-containing Metal Dithiophosphates
E. I. Markova, M. Kh. Mamedov, S. R. Raﬁ eva, and N. F. Dzhanibekov
Mamedaliev Institute of Petrochemical Processes, National Academy of Sciences of Azerbaijan, Baku, Azerbaijan
e-mail: email@example.com; firstname.lastname@example.org
Received August 13, 2010
Abstract—Problems associated with synthesis of metal complexes and salts of dithiophosphates containing
phosphorus, sulfur, and nitrogen heteroatoms and a sterically hindered hydroxy group in their molecule are
A particular place among chemical compounds
serving as additives to oils, fuels, and polymeric
materials is occupied by alkyl aryl dithiophosphates
containing various functional groups and variable-
valence metals in their molecules.
The reason is that these compounds are highly
efﬁ cient and polyfunctional and can serve as antioxidant
and aniticorrosive additives to oils and thermo- and
photostabilizers, as well as quenchers for polymeric
It is known that the efﬁ ciency and polyfunctionality
of organic metal dithiophosphates depend not only on
the nature of a metal contained in the complex, but also
on functional groups in the chemical structure of the
ligand environment of the central metal atom [5–7].
Stabilizing additives must contain various
functional groups in their molecules, e.g., shielded
hydroxy groups and P, S, and N heteroatoms acting
by various mechanisms. Appropriate combination of
these groups gives rise to synergism and enhances the
polyfunctionality of the inﬂ uence exerted by compounds
of this kind.
For this purpose, we synthesized in this study
organic compounds having in their molecules shielded
hydroxy groups, heteroatoms (of phosphorus, sulfur,
and nitrogen), and variable-valence metals.
We ﬁ rst synthesized amino methyl derivatives
(Mannich bases) by the reaction of 2,6-di-tert-
butylphenol, formaldehyde, and mono- and
diethylamines (Scheme 1).
The reaction was performed in benzene at 70–85°C
in the course of 2.0–2.5 h . The analytical and
physicochemical characteristics of Mannich bases are
listed in Table 1. The compounds obtained were used
in the phosphosulfuration reaction with P
occurred by Scheme 2.