Russian Journal of Applied Chemistry, 2009, Vol. 82, No. 2, pp. 276−281.
Pleiades Publishing, Ltd., 2009.
Original Russian Text
V.M. Chernyshev, A.V. Chernysheva, V.A. Taranushich, 2009, published in Zhurnal Prikladnoi Khimii, 2009, Vol. 82, No. 2,
AND INDUSTRIAL ORGANIC CHEMISTRY
Optimization of the Synthesis of 5-Amino-1,2,4-triazol-3-ylacetic
Acid and Bis(5-amino-1,2,4-triazol-3-yl)methane
V. M. Chernyshev, A. V. Chernysheva, and V. A. Taranushich
South-Russian State Technical University, Novocherkassk, Rostov oblast, Russia
Received June 3, 2008
Abstract—The influence of the molar ratio and concentration of the reactants and of the temperature and time
of the synthesis on the yield of malonic acid guanylhydrazides in the reaction of aminoguanidine with malonic
acid in acidic aqueous solutions was examined, and improved procedures for preparing 5-amino-1,2,4-triazol-3-
ylacetic acid and bis(5-amino-1,2,4-triazol-3-yl)methane were suggested.
5-Amino-1,2,4-triazol-3-ylacetic acid I is a typical
representative of aminoazolecarboxylic acids, which are
extensively studied because of their capability to form
heteroaromatic oligoamides and affect gene expression
[1–4]. Compound I can be used for preparing antibiotics
[5, 6] and biologically active  and energy-rich 
substances. However, in contrast to its commercially
produced homolog, 5-amino-1,2,4-triazole-3-carboxylic
acid, acid I is yet relatively difﬁ cultly available. Two
procedures for preparing this compound have been
described in the literature: reaction of aminoguanidine
hydrocarbonate II with ethoxycarbonylethyl acetimidate
hydrochloride in acetic acid  and reaction of II with
malonic acid (MA) in aqueous solution [10, 11]. The latter
procedure is more attractive because of the availability
of the starting substances.
According to this procedure, ﬁ rst hydrocarbonate II is
dissolved in an aqueous solution of MA to obtain a solution
of aminoguanidine malonate III. On heating, salt III in
solution is converted to malonic acid guanylhydrazide
(GH) which, in turn, is converted without isolation to
target product I by heating with an alkali, followed by
acidiﬁ cation of the reaction mixture (Scheme 1).
It should be noted that, in synthesis of I, formation of
a second product, bis(5-amino-1,2,4-triazol-3-yl)methane
IV, could be expected because of comparable reactivity