Synthese d'imines cycliques non-stabilisees par reactions gaz-solide sous vide et thermolyse-eclair (1,2)

doi:10.1016/S0040-4020(01)86146-9

Tetrahedron

Volume 44, Issue 14, 1988, Pages 4447-4455

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Abstract

Unstabilized cyclic imines $1$ – $4$ were synthetized in gram-scale by vacuum dehydrochlorination of N-chlorocycloamines. Azirine $5$ was prepared by flash vacuum thermolysis of the corresponding vinylazide $19$ . All the new compounds were characterized at low temperature by ¹H, ¹³C NMR and IR spectroscopy.

Résumé

Références (37)

U. Schmidt et al.F.E. Scully
J. Org. Chem.
(1980)
S.J. Danishevsky et al.
J. Org. Chem.
(1986)
Y. Nomura et al.
Chem. Lett.
(1977)
S. Wawzonek et al.
J. Org. Chem.
(1953)
J.C. Guillemin et al.
J. Am. Chem. Soc.
(1981)
J.C. Guillemin et al.
J. Chem. Soc., Chem. Commun.
(1983)
M.C. Lasne et al.
Tetrahedron Lett.
(1984)
R. Dammel et al.
Chem. Phys. Lett.
(1983)
d)iiLes imines cycliques présentées dans ce travail ont été caractérisées par spectroscopie photoélectronique ; leur...
D.H.R. Barton et al.
(1979)
G.A. Kraus et al.
J. Org. Chem.
(1981)
A.B. Levy et al.
J. Am. Chem. Soc.
(1971)
A. Hassner et al.
J. Org. Chem.
(1974)
G. Szeimies et al.J. Harnisch et al.
Chem. Ber.
(1979)
R.G. Kostyanovsky et al.
Org. Mass. Spectrom.
(1972)
T.S. Cantrell
J. Org. Chem.
(1977)

P. de Mayo et al.

J. Chem. Soc. Chem. Commun.

(1980)

K.E. Wilzbach et al.

J. Am. Chem. Soc.

(1970)

J.C. Guillemin et al.

Synthesis

(1985)

B. Witkop

J. Am. Chem. Soc.

(1956)

R. Bonnet et al.

J. Org. Chem.

(1959)

A. Hassner et al.

J. Am. Chem. Soc.

(1973)

B. Yang et al.

J. Chem. Soc., Chem. Commun.

(1976)

H. Böhme et al.

Chem. Ber.

(1979)

V. Eisner et al.

Chem. Rev.

(1972)

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Synthese d'imines cycliques non-stabilisees par reactions gaz-solide sous vide et thermolyse-eclair (1,2)

Abstract

Résumé

J. Org. Chem.

J. Org. Chem.

Chem. Lett.

J. Org. Chem.

J. Am. Chem. Soc.

J. Chem. Soc., Chem. Commun.

Tetrahedron Lett.

Chem. Phys. Lett.

J. Org. Chem.

J. Am. Chem. Soc.

J. Org. Chem.

Chem. Ber.

Org. Mass. Spectrom.

J. Org. Chem.

J. Chem. Soc. Chem. Commun.

J. Am. Chem. Soc.

Synthesis

J. Am. Chem. Soc.

J. Org. Chem.

J. Am. Chem. Soc.

J. Chem. Soc., Chem. Commun.

Chem. Ber.

Chem. Rev.