Russian Journal of Applied Chemistry, 2011, Vol. 84, No. 2, pp. 225−229.
Pleiades Publishing, Ltd., 2011.
Original Russian Text © V.R. Akhmetova, N.N. Murzakova, G.R. Khabibullina, N.F. Galimzyanova. Okhremchuk, 2011, published in Zhurnal Prikladnoi
Khimii, 2011, Vol. 84, No. 2, pp. 229−233.
AND INDUSTRIAL ORGANIC CHEMISTRY
Synthesis of N- and N,N'-Coordinated Derivatives
and Their Fungicidal Activity
V. R. Akhmetova
, N. N. Murzakova
, G. R. Khabibullina
and N. F. Galimzyanova
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences, Ufa, Bashkortostan, Russia
Institute of Biology, Ufa Scientiﬁ c Center, Russian Academy of Sciences, Ufa, Bashkortostan, Russia
Received May 6, 2010
Abstract—Possibility of obtaining water-soluble N- and N,N'-coordinated adducts by reacting 3,7-dithia-1,5-
diazabicyclo[3.3.0]octane with methyl iodide and Brønsted (HCl, HBr) and Lewis (AlCl
) acids was examined. The
fungicidal activity of 3,7-dithia-1,5-diazabicyclo[3.3.0]octane and its water-soluble adducts with hydrobromide and
methyl iodide against a number of microscopic fungi affecting cultivated plants and various materials was studied.
Compounds of the thiadiazole series are used as
fungicides in medicine and agriculture [1–3]. Previously,
single-reactor methods for synthesis of 3,7-dithia-
1,5-diazabicyclo[3.3.0]octanes (1) and (2) in which
thiadiazolidine rings are conjugated at the N–N bond
have been developed [4–6]. Compounds 1 and 2 are of
interest as promising fungicides. However, it is known
that practical application of substances exhibiting
a fungicidal activity preferably requires water-soluble
where R = (1) H and (2) CH
In order to obtain water-soluble derivatives of
the bicycle 1, we studied reactions of quaternization
of a nitrogen atom in bicyclane 1 via coordination
binding of lone pairs (LP) with electrophilic agents.
A calculation (AIM) and an experimental (XRD)
analyses of the stereoelectronic effect in the N–C–S
system of compound 1 demonstrated that the electron
density accumulates to a greater extent at the LP of
the nitrogen atom antiperiplanarly to the S–C bond
. Consequently, reactions with electrophilic agents
will occur with a higher probability at a nitrogen atom
in compound 1: speciﬁ cally, at the more nucleophilic
center of the molecule.
As expected, the interaction of 1 with an equimolar
amount of methyl iodide occurs selectively at a single
nitrogen atom to give adduct 3. A similar behavior is
observed in interaction with AlCl
adduct 4 is formed in 85% yield. Raising the amount of
the electrophilic agents (HCl, HBr, and AlCl
in the reaction with 1 gives N,N'-coordinated adducts
5–7 (see scheme).
The yields of adducts 3–7, melting points, and
H NMR and elemental analysis data are listed in
It should be noted that, because of the high
conformational lability of the rings, methylene protons
have an averaged value and appear as singlets in
H NMR spectra of N,N'-adducts 5–7, as also in those of