18152-31-3Relevant articles and documents
Rhodium-catalyzed codimerization of n-butenes with allylic halides
Behr, Arno,Bayrak, Zeynep,Peitz, Stephan,Maschmeyer, Dietrich,Stochniol, Guido
, p. 68 - 71 (2014/04/03)
This paper describes the codimerization of n-butenes with allylic halides such as cinnamyl chloride and crotyl chloride. The highly active catalyst RhCl3·3H2O was investigated, resulting 70% yield of codimers with cinnamyl chloride and 1-butene. Furthermore, the reaction is dependent on the molar ratio of allylic chloride to RhCl3· 3H2O ratio, where a ratio of 75:1 is optimal at a catalyst concentration of 2 mol%. Additionally allylic compounds such as cinnamyl chloride lead to higher yields of the codimer than other short chained allylic chlorides. So the codimerization of an allylic compound with 1-butene represents a simple method to produce short chained dienes at very mild reaction conditions.
Evidence for a free radical mechanism in the decomposition of bis(but-2-enyl)tellurium
Stevenson, John,Bell, William,Ferry, Joseph,Cole-Hamilton, David J.,Hails, Janet E.
, p. 141 - 145 (2007/10/02)
Reactions of basic aqueous solution of Na2Te with MeCH=CHCH2Br or CH2=CHCHMeCl give ZZ-, ZE- and EE(MeCH=CHCH2)2.This is interpreted in terms of a mechanism involving attack of Na2Te on the 2-butenyl cation formed from the allyl halide under the basic reaction conditions.The rate of reaction to give the E-configuration is ca. 3 times that to form the Z.Decomposition of (MeCH=CHCH2)2Te in the liquid or gas phases gives all possible products arising from dimerization of the allyl group.This is interpreted in terms of homolytic fission of the Te-C bond followed by coupling of the allyl radicals formed, particularly as no compounds containing CH2-CHCHMeTe are recovered after partial pyrolysis.The products can be fitted to a purely statistical model in which the reactivity ratio of the primary to secondary allyl is ca. 0.63:0.37.The statistical fit is taken to indicate that mechanism other than that involving homolytic fission and free radical coupling play a negligible part.
SPECIFIC ALLYLIC-ALLYLIC COUPLING PROCEDURES EFFECTED BY LIGAND-INDUCED ELIMINATION FROM DI(ALLYLIC)PALLADIUM SPECIES
Goliaszewski, Alan,Schwartz, Jeffrey
, p. 5779 - 5790 (2007/10/02)
Bis(allylic)palladium complexes can be induced to undergo reductive elimination by replacement of phosphine ligands in the system with ?-acidic ligands.The product 1,5-dienes, formed in high yield, are predominantly the 'head-to-head' coupled isomers.The bis(allylic)palladium intermediates may be formed by addition of an allylic Grignard or trialkyl(allylic)tin reagent to an(η3-allyl)palladium chloride complex, or by 1,3-diene condensation.The latter process leads to cyclodimerization, 'unusual' for palladium catalysed reactions.
