Zirconyl(IV) chloride: a novel and efficient reagent for the rapid synthesis of 1,5-benzodiazepines under solvent-free conditions

doi:10.1070/MC2006v016n02ABEH002171

Mendeleev Communications

Volume 16, Issue 2, 2006, Pages 113-115

https://doi.org/10.1070/MC2006v016n02ABEH002171 Get rights and content

o-Phenylenediamines undergo rapid condensation with ketones having hydrogens at the α-position in the presence of 10 mol% zirconyl(IV) chloride under extremely mild reaction conditions to afford the corresponding 1,5-benzodiazepines in excellent yields with high selectivity. This method works well for both electron-rich as well as electron-deficient o-phenylenediamines.

References (10)

H. Schutz
Benzodiazepines
(1982)
J.K. LandquistR.I. Fryer
L.O. Randall et al.
R. C. Haris and J. M. Straley. US Patent 1537757, 1968 (Chem. Abstr., 1970, 73,...
J. R. De Baun, F. M. Pallos and D. R. Baker, US Patent 3978227, 1976 (Chem. Abstr., 1977, 86,...
M.C. Aversa et al.
Synthesis
(1986)
M. Essaber et al.
Synth. Commun.
(1998)
A.M. El-Sayed et al.
Synth. Commun.
(1999)
A. Chimirri et al.
J. Heterocycl. Chem.
(1990)

There are more references available in the full text version of this article.

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Zirconyl(IV) chloride: a novel and efficient reagent for the rapid synthesis of 1,5-benzodiazepines under solvent-free conditions

Benzodiazepines

Synthesis

Synth. Commun.

Synth. Commun.

J. Heterocycl. Chem.