Abstract
A study was carried out on the use of Pt/Al2O2 catalysts in the synthesis of pyrazines via the dehydrogenation of piperazines, dehydrodeamination of diamines, and dehydrocyclocondensation of N-hydroxyalkyldiamines. In contrast to the current hypothesis of the intermediate formation of piperazine in the latter two reactions, evidence was found that these reactions proceed through initial dehydrogenation and the dehydrogenated intermediate then undergoes cyclization. Polyalkylpyrazines, formed by the alkylotion of the pyrazine ring by hydrogenolysis products, are the major side-products in all the reactions studied. Pyrazines may be obtained in high yield and satisfactory selectivity by selecting suitable modifiers, which enhance the dehydrogenation activity of the catalyst and suppress the hydrogenolysis of the C-N bond.
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G. W. H. Cheeseman and E. S. C. Wertiuk, in: Advances in Heterocyclic Chemistry, Vol. 14 (1972), p. 104.
G. B. Barlin, in: A. Weissberger, The Chemistry of Heterocyclic Compounds, Interscience Publ., Vol. 41 (1982), p. 8.
J. K. Dixon, US Patent No. 2,580,221; Chem. Abstr., 46, 6673 (1952).
M. Cenker and G. E. Baxter, US Patent No. 3,005,820; Chem. Abstr., 56, 7335d (1952).
K. Satoh, Japanese Patent No. 7656479; Chem. Abstr., 86, 29872 (1977).
M. Inoue, S. Enomoto, and J. Imamura, J. Pharm. Soc. Jpn., 95, No. 7, 852 (1975).
A. A. Anderson, S. P. Yurel', and M. V. Shimanskaya, USSR Inventor's Certificate No. 523,898; Byull. Izobret., No. 92 (1976).
G. V. Isagulyants, K. M. Gitis, V. A. Myasnikov, and G. E. Neumoeva, Izv. Akad. Nauk SSSR, Ser. Khim., No. 7, 1483 (1990).
A. A. Anderson, S. P. Yurel', and M. V. Shimanskaya, Izv. Akad. Nauk LatvSSR, No. 6, 683 (1968).
M. Haftendorn, H. G. Hauthal, R. Kloss, and P. Trautmann, German Democratic Republic Patent No. 141,522; Chem. Abstr., 94, 156969 (1981).
K. Sato, US Patent No. 4,097,478; Chem. Abstr., 88, 170196 (1978).
L. Forni, PCT Int. WO 88/00189; Chem. Abstr., 108, 188920 (1988).
G. T. Fedolyak, L. A. Krichevskii, and A. D. Kagarlitskii, Izv. Akad. Nauk KazSSR, Ser. Khim., No. 5, 50 (1989).
S. Yasuda and T. Niwa, Japanese Patent 74101391; Chem. Abstr., 82, 140181 (1975).
J. Sanwaka, Japanese Patent No. 80122769; Chem. Abstr., 94, 103430k (1981).
Korea Research Institute of Chemical Technology, Japanese Patent No. 01203370; Chem. Abstr., 111, 214508 (1989).
J. Okada, N. Nakamoto, and K. Hayakawa, J. Pharm. Soc. Jpn., 93, 1468 (1973).
W. K. Langdon, W. Levis, D. R. Jackson, M. Ceker, and C. E. Baxter, Ind. Eng. Chem., 56, 76 (1964).
S. Shimizu, T. Niwa, and T. Shoji, Japanese Patent No. 63162678, Chem. Abstr., 110, 23915 (1989).
N. R. Bursian, S. V. Kogan, V. Sh. Gruver, and P. N. Borutskii, Promoted Platinum Catalysts and the Isomerization and Dehydrogenation of Paraffin Hydrocarbons. A Review [in Russian], TSNIITÉNeftekhim, Moscow (1981).
G. V. Isagulyants, M. I. Rozengart, and Yu. G. Dubinskii, Catalytic Aromatization of Aliphatic Hydrocarbons [in Russian], Nauka, Moscow (1983), p. 86.
G. N. Maslyanskii and R. N. Shapiro, Catalytic Gasoline Reforming [in Russian], Khimiya, Leningrad (1985).
N. R. Bursian, S. B. Kogan, G. I. Semenov, and É. A. Levitskaya, Kinet. Katal., 15, 1608 (1974).
A. P. Tyupaev, E. A. Timofeeva, and G. V. Isagulyants, Izv. Akad. Nauk SSSR, Ser. Khim., No. 9, 2089 (1982).
M. V. Shimanskaya, Ya. F. Oshis, and A. A. Anderson, Advances in Heterogeneous Catalysis in Heterocyclic Chemistry [in Russian], Zinatne, Riga (1984), p. 50.
A. A. Anderson, S. P. Yurel', and M. V. Shimanskaya, Izv. Akad. Nauk LatvSSR, No. 1, 47 (1971).
H. F. Pfann, US Patent No. 2,427,473; Chem. Abstr. 42, 623 (1948).
E. Lorg and R. S. Bagby, US Patent No. 3,056,787; Chem. Abstr., 59, 1661 (1963).
F. Marshall and R. L. Mayhew, US Patent No. 3,112,317; Chem. Abstr, 60, 8044 (1964).
M. B. Kluev and M. L. Khidekel', Usp. Khim., 59, No. 1, 28 (1980).
J. H. Sinfelt, Adv. Catal., 23, 110 (1973).
B. Gates, J. Katzer, and G. Shuit, Chemistry of Catalytic Processes [Russian translation], Mir, Moscow (1981), p. 336.
L. Forni and P. Pollesei, J. Catalysis, 130, 403 (1991).
J. R. Kingsley, D. Pablgiren, and J. C. Hemminger, Surface Sci., 139, Nos. 2–3, 417 (1984).
G. Ya. Kondrat'eva and Yu. S. Dol'skaya, USSR Inventor's Certificate No. 320,494; Byul. Izobr., No. 34, 70 (1977).
P. Weiss, Catalysis: Polyfunctional Catalysis and Complex Reactions [Russian translation], Mir, Moscow (1965), p. 49.
Yu. A. Stakheev, A. A. Yuffa, E. S. Shpiro, G. V. Antoshin, A. A. Slinkin, É. A. Fedorovskaya, and Kh. M. Minachev, Kinetika i Kataliz, 25, No. 3, 750 (1984).
S. Enomoto, T. Kamiyama, and N. Mitsui, Japanese Patent No. 7924878; Chem. Abstr., 91, 57055 (1979).
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Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1516–1525, November, 1993.
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Gitis, K.M., Neumoeva, G.E. & Isagulyants, G.V. Pt/Al2O3 catalysts in the synthesis of nitrogen heterocycles. Catalytic synthesis of pyrazines. Chem Heterocycl Compd 29, 1308–1315 (1993). https://doi.org/10.1007/BF00532031
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DOI: https://doi.org/10.1007/BF00532031