THERMODYNAMIC AND KINETIC ASPECTS OF THE REACTION OF AMINOGUANIDINE
1817
catalyzed reactions of carboxylic acids with the amine,
but the role of a nucleophile in this process is played
by the protonated, rather than neutral form of aminogua-
nidine. This fact allows synthesis of guanylhydrazides in
fairly acidic media providing high reaction rate.
REFERENCES
1. Chipen, G.I. and Grinshtein, V.Ya., Izv. Akad. Nauk
Latv. SSR, Ser. Khim., 1965, no. 2, pp. 204–208.
2. USSR Inventor’s Certificate, no. 3 204 967.
3. Kofman, T.P., Uvarova, T.A., and Kartseva, G.Yu.,
Fig. 3. Temperature dependence of the logarithms of the rate
Zh. Org. Khim., 1995, vol. 31, no. 2, pp. 271–275.
constants of the (1) forward (k1) and (2) reverse (k' ) reac-
–1
4. US Patent 2 744 116.
5. US Patent 5 990 084.
6. US Patent 6 831 177.
7. Chernyshev, V.M., Chernysheva, A.V., and Taranu-
shich, V.A., Zh. Prikl. Khim., 2006, vol. 79, no. 5,
pp. 792–795.
tions.
The linear dependence of the logarithms of the rate
constants k1 and k' on the reciprocal temperature
(Fig. 3) allows calculation of the parameters of the Ar-
rhenius equation k = Aexp(–Ea/RT):
–1
8. US Patent 7 150 782.
9. US Patent 7 294 211.
Rate constant
А
Ea, kJ mol–1
42.1 ± 3.0
69.6 ± 3.5
10. Barmin, M.I., Kartavykh, V.P., Korolev, E.A., et al.,
k1
9.93 ± 0.1 × 104
3.33 ± 0.48 × 108
Zh. Obshch. Khim., 2001, vol. 71, no. 4, pp. 557–566.
k'
–1
11. Dervan, P.B., Bioorg. Med. Chem., 2001, vol. 9, no. 9,
pp. 2215–2235.
Notably, the activation energy of hydrolysis of
malonic acid guanylhydrazide is close to Ea of hy-
drolysis of hydroxamic acids [21] and of carboxylic
acid amides and polyamides [22–24] under the condi-
tions of acid catalysis (66–90 kJ mol–1), which occur
by the same mechanism. Thus, the kinetic data are consis-
tent with the suggested mechanism of reaction (5).
12. Brown, R.S., Bennet, A.J., and Slebocka-Tilk, H., Acc.
Chem. Res., 1992, vol. 25, no. 11, pp. 481–488.
13. Aman, A.M. and Brown, R.S., J. Am. Chem. Soc., 1999,
vol. 121, no. 19, pp. 4598–4607.
14. Bender, M.R., Chem. Rev., 1960, vol. 60, no. 1, pp. 53–113.
15. Dneprovskii, A.S. and Temnikova, T.I., Teoreticheskie
osnovy organicheskoi khimii (Theoretical Principles of
Organic Chemistry), Leningrad: Khimiya, 1991.
The thermodynamic and kinetic data we obtained
can be used for development of an improved procedure
for preparing 5-amino-1,2,4-triazol-3-ylacetic acid II
and bis(5-amino-1,2,4-triazol-3-yl)methane III.
16. Houben–Weyl, Methoden der organischen Chemie,
vol. 2: Analytische Methoden, Stuttgart: Georg Thieme,
1953.
17. Koskinen, M., Mutikainen, I., Tilus, P., et al., Monatsh.
Chem., 1997, vol. 128, nos. 8–9, pp. 767–775.
18. Bharatam, P.V., Iqbal, P., Malde, A., and Tiwari, R., J. Phys.
Chem. A, 2004, vol. 108, no. 47, pp. 10509–10517.
CONCLUSIONS
19. Albert, A. and Serjeant, E., Ionization Constants of Acids and
Bases. A Laboratory Manual, New York: Wiley, 1962.
20. Lebedev, N.N., Manakov, M.N., and Shvets, V.F., Te-
oriya tekhnologicheskikh protsessov osnovnogo organi-
cheskogo i neftekhimicheskogo sinteza (Theory of Proc-
esses of Basic Organic and Petrochemical Synthesis),
Moscow: Khimiya, 1975.
(1) The reaction of aminoguanidine with malonic
acid in acidic aqueous solutions yields not only
guanylhydrazide, but also diguanylhydrazide of malo-
nic acid. In the temperature range 50–71°C, both reac-
tions are reversible and exothermic. The equilibrium
constant of formation of malonic acid guanylhydrazide
is, on the average, seven times that of formation of
malonic acid diguanylhydrazide.
21. Chung, D.Y. and Lee, E.H., J. Ind. Eng. Chem., 2006,
vol. 12, no. 8, pp. 962–966.
22. Williams, A., J. Am. Chem. Soc., 1976, vol. 98, no. 18,
(2) A kinetic model was suggested for the formation
of malonic acid guanylhydrazide, which adequately
describes the experimental data in the range pH 0.5–
1.3. The reaction of aminoguanidine with malonic
acid follows the mechanism characteristic of acid-
pp. 5645–5651.
23. Zahn, D., J. Phys. Chem. B, 2003, vol. 107, no. 44,
pp. 12 303–12 306.
24. Meyer, A., Jones, N., Lin, Y., and Kranbuehl, D., Mac-
romolecules, 2002, vol. 35, no. 7, pp. 2784–2798.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 81 No. 10 2008