ISSN 1070-4272, Russian Journal of Applied Chemistry, 2006, Vol. 79, No. 10, pp. 1726!1728. + Pleiades Publishing, Inc., 2006.
Original Russian Text + O.V. Bakbardina, I.Yu. Pukhnyarskaya, M.A. Gazalieva, S.D. Fazylov, E.M. Makarov, 2006, published in Zhurnal Prikladnoi
Khimii, 2006, Vol. 79, No. 10, pp. 1744 !1746.
Synthesis and Fungicidal Activity of S-Amino Derivatives
of O-Alkyldithiocarbonic Acids
O. V. Bakbardina, I. Yu. Pukhnyarskaya, M. A. Gazalieva,
S. D. Fazylov, and E. M. Makarov
Institute of Organic Synthesis and Coal Chemistry of the Republic of Kazakhstan,
Limited Liability Company, Karaganda, Kazakhstan
Research Institute of Plant Protection, Almaty, Kazakhstan
Received November 2, 2005
Abstract-S-Amino derivatives of O-alkyldithiocarbonic acid were prepared by oxidative condensation
of certain alkaloids with sodium xanthates. Some of the compounds synthesized exhibit fungicidal activity.
Alkali metal xanthates are widely used as additives
to lubricating oils , flotation agents for dressing of
various mineral ores , and complexing agents .
Their effect on the central nervous system and on re-
dox processes in a human body has been examined .
The properties of numerous sodium xanthate de-
rivatives showing promise for development of new
pesticides have been studied . However, no data
are available on the compounds derived from sodium
xanthates and natural alkaloids anabasine and cytisine,
whose insecticidal and fungicidal properties are well
Therefore, we studied the oxidative condensation
of cytisine and anabasine with a series of sodium
The oxidative condensation of sodium xanthates,
prepared according to , with cytisine and anabasine
was performed in an aqueous solution in the presence
(in 20% KI solution) by the scheme
where R = C
CH (c), C
To determine the optimal reaction conditions, we
examined the influence of temperature on the yield of
the target products. With compound Ia as an example,
we performed a series of experiments at temperatures
varied in the range 03 80oC.
We found that the highest yield of Ia, 86%, is
attained at 40oC. At lower temperatures, sodium xan-
thates are oxidized too slowly, and the yield of Ia
decreases to 12%; at higher temperatures (603 80oC),
the products form an intractable tar. As for the influ-
ence exerted by the structure of the alkyl substituent
in sodium xanthates, the yields of the target prod-
ucts decrease with an increase in its size and with its
3 > (CH
The yields of the anabasine derivatives are consid-
erably lower than those of the cytisine derivatives.
This trend may be due to the presence of a bulky pyr-
idyl fragment with a conjugated system in the a-posi-
tion of the piperidine ring in anabasine. As shown
in , the anabasine molecule can exist in the form
of two stable equatorial conformers produced by rota-
tion of the pyridyl and piperidyl substituents about
the C3C bond linking the two rings. At a certain steric
orientation of the pyridyl fragment, its p-electron
system can interact with the lone electron pair of
the piperidyl nitrogen atom, thus decreasing the re-
activity of the anabasine molecule.