Zusammenfassung
11-Methoxy-18-oxo-3-epialloyohimban-16α-carbonsäueremethylester (IV) wurde nach Methanolyse des Reserpins isoliert. Wir nehmen an, dass derα,β-ungesättigteγ-Oxycarbonsäureester III die gemeinsame Zwischenstufe bei der Bildung von IV und Methyl-Neoreserpat darstellt.
Literatur
W. E. Rosen andJ. M. O'Connor, J. org. Chem.26, 3051 (1961).
W. E. Rosen andH. Sheppard, J. Amer. chem. Soc.83, 4240 (1961).
W. E. Rosen andJ. N. Shoolery, J. Amer. chem. Soc.83, 4816 (1961).
For visible spectra of other saturated ketone dinitrophenylhydrazones seeC. Djerassi andE. Ryan, J. Amer. chem. Soc.71, 1000 (1949).
J. P. Phillips, J. org. Chem.27, 1443 (1962).
Obtained with a Varian Model V-4300-B spectrometer operated at 56.4 me using deuterated chloroform as solvent and tetramethylsilane as internal reference. We are indebted to Dr.J. Lancaster of the Central Research Division, American Cyanamid Co., Stamford (Conn.), for this measurement.
A mechanistically similar isomerization was reported byC. P. Balant andM. Ehrenstein, J. org. Chem.17, 1587 (1952).
P. E. Aldrich, P. A. Diassi, D. F. Dickel, C. M. Dylion, P. D. Hance, C. F. Huebner, B. Korzun, M. E. Kuehne, L. H. Liu, H. B. MacPhillamy, E. W. Robb, D. K. Roychaudhuri, E. Schlittler, A. F. St. André, E. E. van Tamelyn, F. L. Weisenborn, E. Wenkert, andO. Wintersteiner, J. Amer. chem. Soc.81, 2484 (1959).
F. Bohlmann, Ber. dtsch. chem. Ges.91, 2157 (1958).
E. Wenkert andD. K. Roychaudhuri, J. Amer. chem. Soc.78, 6417 (1956).
C-3 equatorial proton signals are observed at 5.67τ in pseudoyohimbine (J. D. Albright, L. A. Mitscher, andL. Goldman, J. org. Chem.28, 38 (1963)) and at 5.56τ in reserpine and methyl reserpate1 c whereas C-3 axial proton signals are observed at higher field.
H. B. MacPhillamy, C. F. Huebner, E. Schlittler, A. F. St. André, andP. R. Ulshafer, J. Amer. chem. Soc.77, 4335 (1955).
E. Wenkert andD. K. Roychaudhuri, J. org. Chem.21, 1315 (1956).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Mitscher, L.A., Paul, J.K. & Goldman, L. Methyl 11-methoxy-18-oxo-3-epialloyohimban-16α-carboxylate, a new keto ester derived from reserpine. Experientia 19, 195–196 (1963). https://doi.org/10.1007/BF02172308
Published:
Issue Date:
DOI: https://doi.org/10.1007/BF02172308