Photochemistry of organic geminal diiodides

Abstract

The following were isolated by preparative gas chromatography from the irradiations described in Table VII.2,6-Dimethyl-8-iodo-2-octene (citronellyl iodide) (32) had spectral properties in agreement with those previously published.14 cis -3,7-Dimethyl-l-iodo-l,6-octadiene (33c) was obtained as a colorless liquid: IR

Carbene Complexes of Nonmetals

“…In the case of a quaternary β-carbon atom, rearrangement was observed (Me 3 CϪCHI 2 Ǟ Me 2 CϭCHMe). [150,152] Photoexcited 1,1-dihaloalkanes do not undergo intermolecular cyclopropanation reactions, and intramolecular cyclopropanation is only a minor process with 8,8-diiodo-2,6-dimethyl-2-octene (93). [150] The products indicate that haloalkyl radicals 81 and haloalkyl Scheme 22.…”

One- vs Two-Photon Processes in the Photochemistry of 1,n-Dihaloalkanes

“…On the other hand, irradiation of 1,1-diiodo-2,2-dimethylpropane ( 4 ) affords 1-iodo-2,2-dimethylpropane ( 5 ) in cyclohexane, 1,1-dimethoxy-2,2-dimethylpropane ( 6 ) in methanol, and 2-methyl-2-butene ( 7 ) in 1,2-dichloroethane (Scheme ). , While product 5 could be explained through the intermediacy of an α-iodo radical, the formation of 6 and 7 could involve a iodocationic intermediate. However, attempts to achieve cyclopropanation of olefins failed.…”

Solvent-Dependent Photochemistry of 2,2,2-Tribromoethyl-(2′-phenylacetate)

“…These products were attributed to an electron transfer process in the geminal radical pair, which in favorable cases predominates over cage escape. In the case of bromides, the general trend was to observe mixtures of products resulting from radical as well as cation formation. − …”