72572-09-9Relevant academic research and scientific papers
Single-electron Transfer-initiated Thermal Reactions of Arylmethyl Halides. Part 8. The Reaction of 2-Halogeno-NN-dimethyl-2,2-diphenylacetamides with Sodium Methoxide in 2,2-Dimethoxypropane. The Effects of Added Acetone, Temperature Elevation, and of the Nature of the Halogen. Refin...
Lempert, Karoly,Simig, Gyula,Tamas, Jozsef,Toth, Gabor
, p. 1927 - 1936 (2007/10/02)
In addition to the previously isolated products (1c) and (2a), trimeric (2b) and oligomeric products (2c) were shown to result from the title reaction.The reactions leading to all these products are initiated by single-electron transfer (SET) to the halogenoacetamides (1a and b).The operation of chain processes is established (Scheme 4).Acetone enolate is shown to be a more effective single-electron donor towards compound (1a) than methoxide.In the absence of acetone enolate SN reactions with methoxide compete with SET-initiated reactions of compound (1a) at room temperature.Temperature elevation favours SET over SN reactions.The mechanism of trimer (2b) and oligomer (2c) formation is discussed and, in addition to the radical recombination mechanism, the carbanionic mechanism of dimer (2a) formation is established.The chloro derivative (1b) is shown to be less reactive in the title reaction than the bromo analogue (1a).
SINGLE ELECTRON TRANSFER INITIATED THERMAL REACTIONS OF ARYLMETHYL HALIDES, VII. THERMALLY GENERATED (DIMETHYLCARBAMOYL)DIPHENYLMETHYL RADICALS. SOME REACTIONS OF IMPORTANCE FOR THE REFINEMENT OF THE MECHANISM OF SINGLE ELECTRON TRANSFER INITIATED REACTIONS OF 2-HALO-N,N-DIMETHYL-2,2-...
Lempert, Karoly,Simig, Gyula,Tamas, Jozsef
, p. 313 - 322 (2007/10/02)
The previously suggested scheme describing the formation of the thermolysis products 1c, 1d and 2 of N,N-dimethyl-2,2-diphenyl-2-(phenylazo)acetamide (1b) has been refined on the basis of deuterium tracer studies and the results of thermolysis experiments with compound 1b, carried out in 2,2-dimethoxypropane in the presence of sodium methoxide and acetone.The deuteration studies have revealed the ambident reactivity of (N,N-dimethylcarbamoyl)diphenylmethyl radicals(3) in hydrogen abstraction reactions, as a result of which the 1,4-cyclohexadiene 6 (and/or the isomeric 1,3-cyclohexadiene) derivatives may be formed, in addition to the fully aromatic isomer 1c, as the primary products of these reactions.
THE MECHANISM OF THE REACTION OF 2-BROMO-N,N-DIMETHYL-2,2-DIPHENYLACETAMIDE AND SODIUM METHOXIDE IN 2,2-DIMETHOXYPROPANE. A METHOD FOR ESTABLISHING THE RADICAL-ANION RADICAL CHAIN MECHANISM
Simig, Gy.,Lempert, K.
, p. 375 - 382 (2007/10/02)
Thermolysis of N,N-dimethyl-2,2-diphenyl-2-phenylazoacetamide (1f) in the presence of sodium methoxide in 2,2-dimethoxypropane furnishes N,N-dimethyl-2,2-diphenylacetamide (1e), the dimeric product 3 and 2-hydroxymethyl-2,2-diphenylacetamide (1g).An analysis of this result leads to the conclusion that the title reaction (which yields compounds 1e and 3) is a radical-anion radical chain process.
