Algirdas K. Serelis

The use of model compounds in interpreting the thermal degradation of poly(methy methacrylate)

SummaryMethyl methacrylate oligomers have been synthesised and used as models to probe the effect of groups formed during termination of polymerization on the thermal stability of poly(methyl methacrylate). Oligomers containing a head-to-head linkage were found to be the least thermally stable, degrading at temperatures around 190°C. In comparison, oligomers containing unsaturated end groups degrade at 255°C, while models containing saturated terminal units are relatively stable and only degrade at temperatures in excess of 300°C.

Stereoselectivity in the thermal cycloaddition reactions of tetrafluoroethylene to derivatives of α-(4-ethoxyphenyl)acrylic acid

Abstract Esters of chiral auxiliaries with α-(4-ethoxyphenyl)acrylic acid undergo diastereoselective addition reactions with tetrafluoroethylene at 130°–170° to afford tetrafluorocyclobutanecarboxylic esters. The oxazoline derived from (+)-(1 S ,2 R )-norephedrine and α-(4-ethoxyphenyl)acrylic acid shows negligible stereoselectivity.

The termination mechanism for radical oligomerization of methacrylonitrile

SummaryDecomposition of azobisisobutyronitrile in benzene containing small amounts of methacrylonitrile produces a mixture of oligomers of methacrylonitrile. Analysis by gas chromatography-mass spectrometry indicates that combination is the preponderant (>90%) termination mechanism.

Athelstan L. J. Beckwith and the Flowering of Hex-5-enyl Radical Cyclization Chemistry. The Adelaide Years

Athel Beckwith chose to embark on a career in free radical chemistry at a time when it was largely ignored by all but a small coterie within the broader Organic Chemistry community. Of his many contributions in this area, the mechanistic clarification and exploitation of the cyclization of hex-5-enyl radical-containing systems is undoubtedly the most significant, leading to what is now, in a multitude of variants, a universally-used, powerful, sophisticated, selective, general synthetic methodology. This account revisits and highlights the early studies carried out by the Beckwith group at The University of Adelaide from the late-1960s to 1980, a period when the main breakthroughs in kinetic and mechanistic understanding were made, and the implications for wider synthetic utility in more complex hex-5enyl systems became apparent.

Corrigendum to: Athelstan L. J. Beckwith and the Flowering of Hex-5-enyl Radical Cyclization Chemistry. The Adelaide Years

Athel Beckwith chose to embark on a career in free radical chemistry at a time when it was largely ignored by all but a small coterie within the broader Organic Chemistry community. Of his many contributions in this area, the mechanistic clarification and exploitation of the cyclization of hex-5-enyl radical-containing systems is undoubtedly the most significant, leading to what is now, in a multitude of variants, a universally-used, powerful, sophisticated, selective, general synthetic methodology. This account revisits and highlights the early studies carried out by the Beckwith group at The University of Adelaide from the late-1960s to 1980, a period when the main breakthroughs in kinetic and mechanistic understanding were made, and the implications for wider synthetic utility in more complex hex-5enyl systems became apparent.