102580-68-7Relevant academic research and scientific papers
Photoredox Reaction of 2-Mercaptothiazolinium Salts with Silyl Enol Ethers
Zemtsov, Artem A.,Ashirbaev, Salavat S.,Levin, Vitalij V.,Kokorekin, Vladimir A.,Korlyukov, Alexander A.,Dilman, Alexander D.
, (2019)
A method for the generation of free radicals from thiazolinium salts upon photocatalytic reduction is described. The thiazolinium salts are generated by treatment with methyl triflate of 2-mercaptothiazolines, which can be readily obtained from alkyl bromides and tosylates via a nucleophilic substitution reaction or by hydrothiolation of alkenes. Silyl enol ethers were used to trap the radicals, furnishing ketones after successive single-electron oxidation and elimination of the silyl cation.
A STUDY OF THE NORRISH TYPE II REACTION IN THE SOLID STATE
Scheffer, John R.,Trotter, James,Omkaram, Nalamasu,Evans, Stephen V.,Ariel, Sara
, p. 169 - 196 (2007/10/02)
The solid state photochemistry of six α-cycloalkyl-p-chloroacetophenone derivatives (cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, exo-2-norbornyl and 1-adamantyl) is reported.All six undergo smooth type II photochemistry in the crystalline phase.The cyclization-to-cleavage ratios and the cis-to-trans cyclobutanol ratios are tabulated for each ketone, and the results are compared with the corresponding data from the solution photolyses.In general, the solid state medium was found to exert a relatively small effect on the product ratios.The γ-hydrogen atom to carbonyl oxygen abstraction distances, as well as the angular relationships between these two atoms, were determined from the X-ray crystal structure data for each ketone.The data showed that (1) six atom abstraction geometries other than chairlike can be accommodated, (2) abstraction can occur over distances much longer than previously supposed (up to 3.10 Angstroem), and (3) there is no strict requirement that the hydrogen undergoing abstraction be in the plane of the carbonyl oxygen n-orbital.Attempts were made to correlate the solid state structural data with the rate constants for hydrogen atom abstraction as determined in solution from Stern-Volmer quenching plots.The lack of any such correlation is interpreted as indicating a significant contribution to reaction in solution from non-minimum energy ketone conformations.
