Abstract
Trimethyl orthoacetate, orthopropionate or orthobenzoate in contrast to orthoformiate do not undergo a three component condensation with anilines and cyclic sixmembered active methylene compounds to the corresponding N-substituted aminomethylene derivatives; they do react, however, with five membered ring compounds. The reaction proceeds smoothly with primary aliphatic or aromatic amines, whilst secondary amines give no or only low yields. In comparison to other synthetic routes to β,β-diacyl-enamines the condensation described has the following advantages: a) The products thus obtained have previously often required a two step procedure, b) the only reaction product besides the aminoalky lidene derivative is an alkohol, c) the usually mild conditions allow the preparation of compounds so far not available by employing more drastic alternative methods.
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Literatur
DeWolfe, R., Orthocarboxylic Acid Derivatives, S. 190 New York-London: Academic Press. 1970.
Snyder, H. R., Jones, R. E., J. Amer. Chem. Soc.68, 1253 (1946);
Fischer, H. Deutsch. Pat. 834. 104 (17. 3. 1952, Hoechst AG); Chem. Abstr.50, 402f (1956)
Whitehead, C. W., Traverso, J. J., J. Amer. Chem. Soc.75, 671 (1953).
Zacharias, G., Wolfbeis, O. S., Junek, H., Mh. Chem.105, 1283 (1974)
Wolfbeis, O. S., Ziegler, E., Z. Naturforsch.31b, 514 (1976)
Ollinger, P., Wolfbeis, O. S., Junek, H., Mh. Chem.106, 963 (1975)
Wolfbeis, O. S., Ziegler, E., Z. Naturforsch.32b, 1077 (1977).
Fungizide:Iwataki, I., Shibuya, M., Nakada, A., Mizuno, M., (Nippon Soda Co.), Japan Kokai 78-101336 (4. 9. 1978). Chem. Abstr.90, 96852 (1979)
Herbizide:Rebstock, T. L., Sell, H. M., J. Amer. Chem. Soc.74, 274 (1952)Grohe, K., Frohberger, P. E., Scheinpflug, H. DOS 2.248.819 (11. 4. 1974). Chem. Abstr.81, 25186 (1979).
Yuki, H., (Yoshitomi Pharmaceut. Ind. Ltd.) Japan Kokai 73-28465 (14. 4. 1973); Chem. Abstr.78, 159418 z (1973);
Sterling Drug Inc., Brit. Pat. 1. 147.759 (10. 4. 1969); Chem. Abstr.71, 70125 (1969).
DePuy, C. H., Zaweski, E. F., J. Amer. Chem. Soc.81, 4920 (1959).
Eaton, P. E., Lin K., J. Amer. Chem. Soc.87, 2025 (1965).
Wären Ha' bzw. Hb' exoständig, so würden sie mit Ha bzw. Hb mit ca. 4. Hz koppeln:LaRochette, R. W., Trost, B. M., J. Chem. Soc. Chem. Comm.1970, 1353;Eaton, P. E., Lin, K., J. Amer. Chem. Soc.87, 2052 (1965).
Seitz, G., Braun, H., Arch. Pharm. (Weinheim)309, 34 (1976).
DissertationWolfbeis, O. S., Univ. Graz, 1972.
Henning, H. G., Thurner, J. W., Z. Chem.18, 256 (1978).
Wolfbeis, O. S., Junek, H., Z. Naturforsch.34 b, 283 (1979).
Gelin, S., Hartmann, D., J. Heterocyclic Chem.13, 521 (1976);
Chantegrel, B., J. Chem. Research (S)1977, 127; (M)1977, 1482.
Brit. Pat. 585.089 (30. 1. 1947), Erf.H. J. Barber, Slack, R., Stickings, Ch. E., Elliott , D. F., Attenburrow, J., (May & Baker Ltd. und Glaxo Labs., Ltd.); Chem. Abstr.41, 3822 a (1947).
Cornforth, J. W., Chemistry of Penicillin (Clarke, H. T., Johnson, J. R., Robinson, R., Hrsg.), S. 688 ff und 748 ff. Princeton: Princeton University Press. 1949.
Cornforth, J. W., in Heterocyclic Compounds (Elderfield, R. C., Hrsg.), Band 5, S. 361 ff. New York: J. Wiley 1957. Wegen der Bedeutung von 4-Aminomethylenderivaten der 5(4H)-oxazolidone in der Penicillinchemie gibt es über sie eine ziemlich umfangreiche Literatur.
Imperial Chem. Ind. Erf.Davies, J. S. H., Jones, W. G. M., Brit. Pat. 583.190 (11. Dez. 1946); Chem. Abstr.41, 3491 (1947).
Zur geometrischen Isomerie von 4-Yliden-5(4H)-oxazolonen siehe:Rao. Y. S., Filler, R., Synthesis1975, 749.
Dains, F. B., Griffin, E. L., J. Amer. Chem. Soc.35, 959 (1913).
Maquestiau, A., van Haverbeke, Y., Muller, R. N., J. Heterocyclic Chem.12, 27 (1975).
Die Verbindungen sind von Bedeutung bei der Synthese von photographischen Sensibilisatoren: Lit.22–24.
Kodak Ltd., (Erf.Knott, E. B.), Brit. Pat. 614.471 (16. Dez. 1948); Chem. Abstr.43, 8692 f (1949).
Eastman Kodak Comp. (Erf.Knott, E. B.), US-Pat. 2.515.878 (18. Juli 1950); Chem. Abstr.44, 8953 h (1950).
Ogata, T., Tauno, R., Nishida, K., Repts. Sci. Research Inst. (Japan)28, 259 (1952); Chem. Abstr.47, 5284 c (1953).
Freyer, W., Tomaschewski, G., J. Prakt. Chem.319, 905 (1977).
Zenno, H., J. Pharm. Soc. Jap.73, 1063 (1953).
Zur Stereochemie dieser Verbindungen siehe:Maquestiau, A., van Haverbeke, Y., Vanovervelt, J. C., Bull. Soc. Chim. Belg.84, 741 (1975).
Behringer, H., Weissauer, H., Chem. Ber.85, 774 (1952).
Kornet, M. J., Thio, A. P., Thorstenson, J. H., J. Pharm. Sci.66, 1022 (1977).
Andreani, A., Bonazzi, D., Cavrini, V., Gatti, R., Giavanninetti, G., Rambaldi, M., Franchi, L., Nanetti, A., Guarda, M. A., Farmazia Ed. Sci.33, 754 (1978).
Beim 2-Indanon wurde sie hingegen beschrieben:Wolfbeis, O. S., Zacharias, G., Junek, H., Mh. Chem.106, 1207 (1975).
Wolfbeis, O. S., unpublizierte Versuche.
Konotsune, T., Kawakubo, K., Yanai, T., in Advances in Pesticide Science, (Geissbühler, H., Hrsg.), Teil 2, S. 94–98, Oxford: Pergamon Press. 1979.
Rappoport, Z., Topo, A., J. Chem. Soc. Perkin I,1975, 863.
Chu, J. H., Murty, B. S. R., Fedar, L., J. Amer. Chem. Soc.98, 3632 (1976).
Schulz, D., Helv. Chim. Acta58, 1207 (1975).
Ridi, M., Checchi, S., Gazz. Chim. Ital.83, 36 (1953).
Uray, G., Wolfbeis, O. S., Junek, H., J. Mol. Struct.54, 77 (1979).
Freyer, W., J. prakt. Chem.319, 911 (1977)
Freyer, W., Radeglia, R., Mh. Chem.109, 1093 (1978).
Knippel, M., Knippel, E., Michalik, M., Kelling, H., Kristen, H., J. Chem.15, 402 (1975).
Kvitko, I. Y., Kurkorskaya, L. N., Khoozeva, R. V., Eltsor, A. V., Khim. Geterotsikl. Soedin.1978, 1677.
Filira, F., Acampora, M., Giormani, V., Rothstein, M., D'Angeli, F. Gazz. Chim. Ital.107, 479 (1977).
v. Dobeneck, H., Prietzel, H. Z. Physiol. Chem.299, 214 (1955).
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5. Mitt.:Wolfbeis, O. S., Junek, H., Mh. Chem.110, 1387 (1979).
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Wolfbeis, O.S. Eine effiziente Synthese von Aminoalkylidenderivaten fünfringcyclischer methylenaktiver Verbindungen. Monatshefte für Chemie 112, 369–383 (1981). https://doi.org/10.1007/BF00900767
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DOI: https://doi.org/10.1007/BF00900767