KINETIC ISOTOPE EFFECTS IN HYDROGEN EXCHANGE
1143
were prepared from the corresponding halo derivatives
by reduction with zinc dust in deutero(tritio)sulfuric
acid. Quinoline-2D(t) was prepared by decarboxyla-
tion of quinaldic acid. Anhydrous liquid ammonia and
deuteroammonia (94 99 at. %) were used.
(Thermal Properties of Ammonia: Handbook),
Moscow: Izd. Standartov, 1978, p. 143.
14. Tupitsyn, I.F., Semenova, N.K., and Avdulov, G.I., in
Radioisotopes in the Physical Sciences and Industry,
Vienna: IAEA, 1962, pp. 255 257.
1
1
1
1
5. Westheimer, F.H., Chem. Rev., 1961, vol. 61, no. 3,
pp. 265 273.
6. Steffa, L.J. and Thornton, E.R., J. Am. Chem. Soc.,
The rates of deuterium and tritium exchange were
measured in solutions containing usually 100 150 mol
of a solvent per mole of an organic compound. The
deuterium concentration was determined with an MI-
1
967, vol. 89, no. 23, pp. 6149 6156.
7. Gold, V. and Grist, S., J. Chem. Soc., Perkin Trans. 2,
972, no. 1, pp. 89 95.
1201 mass spectrometer at an ionizing electron energy
1
of 12 14 eV. The tritium activity was measured using
a scintillation counter with two coaxial photomultipli-
ers operating in the coincidence mode. The scintilla-
tion procedure was used in two versions: (a) samples
of organic compound before and after experiments
were introduced directly into the scintillation solution;
8. Shapiro, I.O., Fizicheskaya khimiya. Sovremennye
problemy (Physical Chemistry. Modern Problems),
Moscow: Khimiya, 1987, pp. 129 164.
9. Lin, A.C., Chang, A.C., Dahlberg, Y., and Kresge, A.J.,
J. Am. Chem. Soc., 1983, vol. 105, no. 16, pp. 5380
1
2
5
386.
(
b) tritium-labeled ammonia was burned over CuO,
0. Aroella, T., Arrowsmith, C.H., Hojatti, M., and
Kresge, A.J., J. Am. Chem. Soc., 1987, vol. 109,
no. 23, pp. 7198 7199.
and the resulting water was dissolved in the scintil-
lator. The measurement conditions were strictly fixed.
The rate constants of deuterium and tritium ex-
change, calculated by a first-order equation, had
stable values in all the systems studied.
21. Kresge, A.J. and Powell, M.F., J. Org. Chem., 1986,
vol. 51, no. 6, pp. 819 822.
22. Argyrou, A. and Washabaugh, N.W., J. Am. Chem.
Soc., 1999, vol. 121, no. 51, pp. 12054 12062.
23. Streitwieser, A., Scannon, P.J., and Niemeyer, K.,
J. Am. Chem. Soc., 1972, vol. 94, no. 22, pp. 7936
7937.
24. Streitwieser, A. and Mares, F., J. Am. Chem. Soc.,
1968, vol. 90, no. 3, pp. 644 648.
25. Stratakis, M., Wang, P.J., and Streitwieser, A., J. Org.
Chem., 1996, vol. 61, no. 9, pp. 3145 3150.
26. Streitwieser, A. and Guibe, B., J. Am. Chem. Soc.,
1978, vol. 100, no. 14, pp. 4523 4534.
REFERENCES
1
2
3
. Malykhin, E.V. and Shteingarts, V.D., Zh. Ross. Khim.
O va, 1999, vol. 43, no. 1, pp. 49 56.
. Huisgen, R., Mack, W., Herbig, K., and Ott, N.,
Chem. Ber., 1960, vol. 93, no. 2, pp. 412 424.
. Hertog, H.J., Pieterse, M.J., and Burman, D., Recl.
Trav. Chim. Pays-Bas, 1963, vol. 82, no. 12,
pp. 1173 1178.
4
5
6
7
8
. Martens, P.J. and Hertog, H.J., Recl. Trav. Chim.
Pays-Bas, 1964, vol. 83, no. 6, pp. 621 630.
. Illuminatti, N., Adv. Heterocycl. Chem., 1965, vol. 4,
pp. 285 314.
. Eigen, M., Angew. Chem. Int. Ed. Engl., 1964, vol. 3,
no. 1, pp. 1 19.
. Washabaugh, M.W. and Jencks, W.P., J. Am. Chem.
Soc., 1989, vol. 111, no. 2, pp. 683 692.
. Shatenshtein, A.I., Yakushin, F.S., and Arshino-
va, M.I., Kinet. Katal., 1964, vol. 5, no. 6, pp. 1000
27. Shapiro, I.O., Ranneva, Yu.I., and Shatenshtein, A.I.,
Zh. Obshch. Khim., 1979, vol. 49, no. 9, pp. 2030
2036.
28. Kane, A.A. and Tupitsyn, I.F., in Khimiya i tekhno-
logiya izotopov (Chemistry and Technology of Iso-
topes), Leningrad: Khimiya, 1967, pp. 232 236.
29. Heterocyclic Compounds, Elderfield, R.C., Ed., New
York: Chapman and Hall, 1950. Translated under the
title Geterotsiklicheskie soedineniya, Moscow: Ino-
strannaya Literatura, 1955, vol. 4, pp. 83 96.
30. Zatsepina, I.F., Kirova, A.V., and Tupitsyn, I.F.,
Reakts. Sposobn. Org. Soedin., 1968, vol. 5, no. 1,
pp. 70 87.
1
007.
9
. Streitwieser, A., Hollyhead, W.B., Pudjaatmaka, A.H.,
and Owens, P.H., J. Am. Chem. Soc., 1971, vol. 93,
no. 20, pp. 5088 5096.
31. Tupitsyn, I.F., Zatsepina, N.N., Kirova, A.V., and
Kapustin, Yu.M., Reakts. Sposobn. Org. Soedin., 1968,
vol. 5, no. 3, pp. 601 611.
1
1
1
0. Thibbin, A., Onicido, I., and Ahlberg, P., Chem.
Scripta, 1982, vol. 19, no. 3, pp. 145 148.
1. Shapiro, I.O., Ranneva, Yu.I., and Shatenshtein, A.I.,
Zh. Org. Khim., 1986, vol. 22, no. 6, pp. 1332 1333.
2. Bell, R.P., The Proton in Chemistry, Ithaca: Cornell
Univ. Press, 1973, 2nd ed. Translated under the title
Proton v khimii, Moscow: Mir, 1974, pp. 291, 297.
3. Teplofizicheskie svoistva ammiaka: Spravochnik
32. Ranneva, Yu.I. and Shatenshtein, A.I., in Korrelya-
tsionnye uravneniya v organicheskoi khimii (Correla-
tion Equations in Organic Chemistry), Tartu: Tartusk.
Gos. Univ., 1962, vol. 1, pp. 136 149.
33. Kamrad, A.G., Reakts. Sposobn. Org. Soedin., 1968,
vol. 5, no. 3, pp. 701 710.
1
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 7 2001