Issue 12, 2012

Solid-state photochemistry of crystalline pyrazolines: reliable generation and reactivity control of 1,3-biradicals and their potential for the green chemistry synthesis of substituted cyclopropanes

Abstract

To expand on the limited number of examples that exist in the literature for the solid-state photodenitrogenation of azoalkanes, a series of crystalline 7-alkyl-2,3,7-triazabicyclo[3.3.0]oct-2-ene-6,8-diones with varying 4,4-substituents were prepared. Their photochemical behavior in solution and in the solid state was dependent on the 4,4-substitution of the 1-pyrazoline ring, with unsubstituted pyrazoline 12 giving a mixture of products both in solution and in the solid state. Diphenyl substituted pyrazolines 13 denitrogenate spontaneously in solution but require light exposure to react quantitatively in the solid state. t-Butyl-phenyl substituted pyrazolines 14 were shown to denitrogenate both chemo- and diastereoselectively in solution and in the solid state to yield a single product in quantitative yield.

Graphical abstract: Solid-state photochemistry of crystalline pyrazolines: reliable generation and reactivity control of 1,3-biradicals and their potential for the green chemistry synthesis of substituted cyclopropanes

Article information

Article type
Paper
Submitted
24 Jul 2012
Accepted
16 Aug 2012
First published
16 Aug 2012

Photochem. Photobiol. Sci., 2012,11, 1929-1937

Solid-state photochemistry of crystalline pyrazolines: reliable generation and reactivity control of 1,3-biradicals and their potential for the green chemistry synthesis of substituted cyclopropanes

S. Shiraki, C. S. Vogelsberg and M. A. Garcia-Garibay, Photochem. Photobiol. Sci., 2012, 11, 1929 DOI: 10.1039/C2PP25263E

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