2971-22-4Relevant articles and documents
The laser-drop method: A new approach to induce multiple photon chemistry with pulsed lasers. Examples involving reactions of diphenylmethyl and cumyloxyl radicals
Banks,Scaiano
, p. 6409 - 6413 (1993)
A new method, described as the laser-drop technique, is presented which allows preparative experiments in laser-induced multiphoton chemistry. The technique shares most of the advantages of the successful laser-jet technique but allows the use of pulsed lasers that are readily available in many laboratories. The laser-drop method has been tested with two photochemical systems. The well-studied diphenylmethyl radical system allows a direct comparison of results from laser-drop, laser-jet, lamp, and two-color two-laser studies. The laser-jet and laser-drop techniques show comparable performance for two-photon processes, but the latter has advantages in reactions of higher order in light intensity. The photolysis of dicumyl peroxide has been used to demonstrate for the first time laser-induced β-cleavage of alkoxyl radicals. Photolysis of dicumyl peroxide in methanol leads to dramatically different product distributions under conditions of lamp and laser-drop photolysis.
Studies on the rearrangement of (trichloromethyl)carbinols to α-chloroacetic acids
Reeve, Wilkins,McKee, James R.,Brown, Robert,Lakshmanan, Sitarama,McKee, Gertrude A.
, p. 485 - 493 (2007/10/02)
Phenyl(trichloromethyl)carbinol undergoes an unimolecular, predominantly intramolecular conversion into potassium α-chlorophenylacetate on stirring with 10percent aqueous potassium hydroxide at 0 deg C for several days.Besides providing an interesting example of a 1-2 chlorine shift, the reaction is of potential importance for the synthesis of α-chloro acids.The study of a variety of (trichloromethyl)carbinols shows the reaction is general for secondary (trichloromethyl)carbinols as well as trichloroethanol.The mechanism of the reaction involves the preliminary formation of an epoxide.Several mechanisms are considered for the conversion of the epoxide to the α-chloroacetate anion, but none accounts for all of the experimental facts.Tertiary carbinols break down at the epoxide stage into a ketone and carbon monoxide.