ISSN 1070-4272, Russian Journal of Applied Chemistry, 2014, Vol. 87, No. 5, pp. 585−590. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © V.R. Akhmetova, G.R. Anpilogova, G.R. Khabibullina, N.S. Akhmadiev, A.G. Ibragimov, 2014, published in Zhurnal Prikladnoi Khimii,
2014, Vol. 87, No. 5, pp. 595
AND ION EXCHANGE PROCESSES
One-Pot Synthesis of Bis-1,5,3-dithiazepanes
and Their Sorption Properties Toward
Silver(I) and Palladium(II)
V. R. Akhmetova
, G. R. Anpilogova
, G. R. Khabibullina
N. S. Akhmadiev
, and A. G. Ibragimov
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences, pr. Oktyabrya 141, Ufa, 450075 Russia
Institute of Organic Chemistry, Ufa Scientiﬁ c Centre, Russian Academy of Sciences, pr. Oktyabrya 71, Ufa, 450054 Russia
Received February 10, 2014
Abstract—The possibility of one-pot synthesis of bis-1,5,3-dithiazepanes by multicomponent condensation of
Cl, hydrazine, and 1,2-ethylenediamine) with formaldehyde and 1,2-ethanedithiol was described.
Their sorption properties relative to Ag(I) and Pd(II) were studied by a static method. It was shown that at room
temperature bis-1,5,3-dithiazepanes recovered with high efﬁ ciency silver(I) and palladium(II) from nitrate solutions
and hydrochloric acid solutions, respectively.
Saturated sulfur and nitrogen-containing heterocy-
clic compounds as polydentate ligands are of interest
as complexing sorbents and extractants of soft ions of
platinum metals: gold, silver, and mercury [1, 2]. A one-
pot cyclothiomethylation of amines is rational and ef-
ﬁ cient method for the synthesis of sulfur- and nitrogen-
containing heterocycles [3, 4]. It is noted that the in-
tensive development of one-pot strategies of synthesis
of heterocycles based on the use of multicomponent
reactions of three or more molecules is consistent with
the principles of green chemistry in terms of minimizing
the number of steps and, correspondingly, reducing the
amount of side products.
Previously it was shown that 1,2-bis(1,3,5-dithiazine-
5-yl)ethane synthesized by condensation of ethylene
diamine with formaldehyde and H
S  is an effective
sorbent of silver(I), palladium(II), and mercury(II) .
It was suggested that new types of binuclear satu-
rated S,N-heterocycles also exhibit a high sorption ac-
tivity relative to noble metal ions. There is procedure
of one-pot synthesis of 1,5,3-dithiazepane, which based
on multicomponent reaction of amines with formalde-
hyde and 1,2-dithiol [7, 8]. Bis-1,5,3-dithiazepanes:
3-ylmethyl)sulfanyl]ethylsulﬁ de (I) and bis(1,5,3-di-
thiazepane-3-yl) (II), were recently synthesized by re-
action of CH
O and 1,2-ethanedithiol with NH
 in the aqueous medium (Scheme1). In
this study the one-pot synthesis of 1,2-bis(1,5,3-dithiaz-
epane-3-yl)ethane (III) was ﬁ rst carried out by conden-
sation of 1,2-ethylenediamine with CH
O and 1,2-eth-
anedithiol at room temperature.
The purpose of the study is examination of the
sorption properties of bis-1,5,3-dithiazepanes I–III with
respect to silver(I) and palladium(II).
Commercially available original compounds of
purity at least 95% were used for the synthesis of bis-
azepan-3-ylmethyl)sulfanyl]ethylsulﬁ de (I) was
prepared according to the procedure described in .