63418-53-1Relevant academic research and scientific papers
Copper-catalyzed oxidative desulfurization-oxygenation of thiocarbonyl compounds using molecular oxygen: An efficient method for the preparation of oxygen isotopically labeled carbonyl compounds
Shibahara, Fumitoshi,Suenami, Aiko,Yoshida, Atsunori,Murai, Toshiaki
, p. 2354 - 2356 (2008/02/09)
A novel copper-catalyzed oxidative desulfurization reaction of thiocarbonyl compounds, using molecular oxygen as an oxidant and leading to formation of carbonyl compounds, has been developed, and the utility of the process is demonstrated by its application to the preparation of a carbonyl-18O labeled sialic acid derivative. The Royal Society of Chemistry.
Kinetics and mechanism of the aminolysis of aryl propanedithioates in acetonitrile
Hyuck Keun Oh,Sun Kyung Kim,Hai Whang Lee,Lee
, p. 313 - 317 (2007/10/03)
The kinetics and mechanism of the aminolysis of aryl proanedithioates with benzylamines are investigated in acetonitrile at - 35.0 °C. A large magnitude of the Hammett (ρx and ρz) and Broensted (βx and βz) coefficients and exceptionally large cross-interaction constant ρxz(= 3.5) are consistent with a stepwise mechanism in which leaving group expulsion from an intermediate, T±, is the rate-determining step. The faster rates observed for dithio esters (I1) than for thio esters (I), and the validity of the reactivity-selectivity principle (RSP) are also in line with the mechanism proposed. The kH/kD values (= 1.0-1.8) determined with deuterated benzylamines (XC6H4CH2ND2) and the activation parameters, ΔH≠(?8 kcal mol-1) and ΔS≠(= -16 to -23 e.u.), suggest that proton transfer occurs concurrently with leaving group departure in the transition state.
A New Route to N-Monosubstituted Thioamides Utilizing Phosphoramidothionates as Reagents for the Thioamidation of Carboxylic Acids
DeBruin, Kenneth E.,Boros, Eric E.
, p. 6091 - 6098 (2007/10/02)
Several N-monosubstituted thioamides have been synthesized from the corresponding carboxylic acid chlorides and primary amines by a new procedure.The procedure utilizes a commercially available and inexpensive organophosphorus reagent (dimethyl chlorothiophosphate) to derivatize the amine, form the carboxamide bond, and accomplish the thionation of the carbonyl by an intramolecular rearrangement.The phosphoryl group is then cleaved from the resulting thiocarbonyl phosphoryl mixed imide by a simple hydrolysis.Thioamides (RCSNHR') containing a variety of functionality(R= simple alkyl, phenyl, bulky alkyl, cycloalkylalkyl, α,β-unsaturated, and alkyl with remote keto, ester, or amide carbonyl groups; R'= methyl, benzyl, allyl) have been prepared by this method in generally high overall yields (50-80 percent).Competing thionation of remote carbonyl groups or epimerization of a chiral center containing a proton α to a ketone group was not observed.
