75273-64-2Relevant academic research and scientific papers
Preparation and Reactions of Novel Cyclic β-Oxosulphonium Salts obtained by the Acid-induced Cycisation of 1-Diazo-ω-phenylthio-2-alkanones
Flowers, William T.,Freitas, Ana M.,Holt, Geoffrey,Purkiss, Stuart C.
, p. 1119 - 1124 (2007/10/02)
With perchloric acid, the diazo-ketones PhSnCOCHN2 (1a)-(1d) give the corresponding cyclic β-oxosulphonium salts (2a)-(2d); the p-chlorophenyl analogue of (2d) was similarly prepared.The salts (2a), (2c), and (2d) react with triphenylphosphine at C(2) to give the acyclic phosphonium salts (3a), (3c), and (3d) and, analogously, with potassium O-ethyl dithiocarbonate to give the corresponding acyclic O-ethyl dithiocarbonates (3f), (3g), and (3h).All the reactions of the salt (2b) with nucleophiles gave either 1-phenylthiobut-3-en-2-one (11) or products of its Michael addition.Salts (2c) and (2d) with sodium methoxide in methanol provide, respectively, methyl ω-phenylthio-butanoate and -pentanoate in a process that involves the loss of a methylene group.These and other reactions are considered to proceed via ylide intermediates; the intermediate derived by the deprotonation of (2d) being isolated, whereas that from (2c) rearranged to give 3-phenylthiocyclopentanone.
REACTIONS OF α-DIAZO KETONES. IV. S-5 PARTICIPATION AND β-ELIMINATION IN THE ACETOLYSIS OF 4-ARYLTHIO- AND 4-ARALKYLTHIO-1-DIAZO-2-BUTANONES
Rosnati, Vittorio,Saba, Antonio
, p. 211 - 214 (2007/10/02)
The acetolyses of α-diazo ketones 2a-d, bearing a thioether group on the β'-carbon have been studied in neat AcOH and in the presence of acetate.All these reactions lead to products arising from the 1,4-shift of the thioether group, normal substitution being only a secondary pathway, particularly in the case of 2d, which almost exclusively undergoes fragmentation to benzhydryl acetate and 3-oxotetrahydrothiophene.The mechanisms involved are discussed.
