1114-20-1Relevant articles and documents
Rates of Bromination of Dimethyl Fumarate and of Dimethyl Acetylenedicarboxylate
Wolf, Susan A.,Ganguly, Soma,Berliner, Ernst
, p. 1053 - 1055 (1985)
Rates of bromination of dimethyl fumarate and of dimethyl acetylenedicarboxylate were determined in 50percent aqueous acetic acid in the presence of varying amounts of sodium bromide.In the presence of bromide ions both substrates are believed to react by the termolecular AdE3 mechanism, and the acetylenic substrate reacts faster than the olefin.The acetylene also reacts faster in the reaction which involves a bimolecular attack by bromine (AdE2).Usually olefins react considerably faster than acetylenes in halogenation, and possible reasons for the reversal of the relative rates observed here are discussed.
Unlocking acyclic π–bond rich structure space with tetraethynylethylene–tetravinylethylene hybrids
Horvath, Kelsey L.,Magann, Nicholas L.,Sowden, Madison J.,Gardiner, Michael G.,Sherburn, Michael S.
, p. 19746 - 19753 (2019)
Literature reports describe tetraethynylethylene (TEE) as unstable but tetravinylethylene (TVE) as stable. The stabilities of these two known compounds are reinvestigated, along with those of five unprecedented TEE-TVE hybrid compounds. The five new C10 hydrocarbons possess a core, tetrasubstituted C=C bond carrying all possible combinations of vinyl and ethynyl groups. A unified strategy is described for their synthesis, whereupon cross-conjugated ketones are dibromo-olefinated then cross-coupled. Due to an incorrect but nonetheless widely held belief that acyclic π-bond rich hydrocarbons are inherently unstable, a standardized set of robustness tests is introduced. Whereas only TVE survives storage in neat form, all seven hydrocarbons are remarkably robust in dilute solution, generally surviving exposure to moderate heat, light, air, and acid. The first X-ray crystal structure of TEE is reported. Subgroups of hybrids based upon conformational preferences are identified through electronic absorption spectra and associated computational studies. These new acyclic π-bond rich systems have extensive, untapped potential for the production of stable, conjugated carbon-rich materials.
A domino copper-catalyzed C-N and C-O cross-coupling for the conversion of primary amides into oxazoles
Schuh, Kerstin,Glorius, Frank
, p. 2297 - 2306 (2008/02/13)
A variety of oxazoles can efficiently be prepared, in a single step and in good yield, from primary amides and 1,2-dihaloalkenes using copper-catalysis. This new method allows the regioselective formation of a range of substituted oxazoles. The required 1,2-dihaloalkenes can prepared by simple treatment of alkynes with elemental bromine or iodine. Georg Thieme Verlag Stuttgart.
Synthesis of Chiral Esters of Acetylenedicarboxylic Acid
Charlton, James L.,Chee, Gaiklean
, p. 6243 - 6246 (2007/10/02)
A general method for the preparation of acetylenedicarboxylic acid esters has been investigated and several esters have been prepared in excellent yield.The bis-(methyl (S)-lactyl), bis-(methyl (R)-mandelyl), and bis-menthyl esters were prepared, as well as achiral diaryl and dialkyl esters.The esters were synthesized from the corresponding dibromofumarates by 2,3-dibromo elimination using zinc or zinc amalgam in THF at room temperature or at reflux.The dibromofumarates were prepared by the esterification of dibromofumaryl chloride with the corresponding alcohols.
