10394-60-2Relevant academic research and scientific papers
Kinetic studies of the homogeneous coupling reaction between electrochemically generated aromatic radical anions and alkyl radicals
Pedersen, Steen Uttrup,Lund, Torben,Daasbjerg, Kim,Pop, Mihaela,Fussing, Ingrid,Lund, Henning
, p. 657 - 671 (2007/10/03)
Radicals produced via the indirect reduction of alkyl halides by aromatic radical anions are likely to couple fast with the mediator. In the presence of activated olefins or good hydrogen atom donors the fate of the alkyl radicals might be changed. In this study rate constants for the coupling reaction (2) between primary, secondary and tertiary alkyl radicals and some aromatic radical anions were measured via the competition with addition of the radical to styrene or ethyl cinnamate, or via the competition with hydrogen atom transfer from thiophenol or 2-methyl-2-propanethiol to the alkyl radical. It is shown that for all the alkyl radicals and aromatic radical anions investigated so far the rate constant for coupling is close to 1 × 109 M-1 s-1. Acta Chemica Scandinavica 1998.
Use of Magnesium Anthracene * 3 THF in Synthesis: Generation of Grignard Compounds and Other Reactions with Organic Halides
Bogdanovic, Borislav,Janke, Nikolaus,Kinzelmann, Hans-Georg
, p. 1507 - 1515 (2007/10/02)
The course (a), (b), (c) (Scheme 1) of the reaction of magnesium anthracene * 3 THF (1) with organic halides (RX) is dependent on the nature of RX.With alkyl halides in THF 1 reacts as a nucleophile, whereby primary as well as secondary alkyl halides produce dialkyldihydroanthracenes (4-4'') and tertiary alkyl halides yield primarily monoalkyl-substituted dihydroanthracenes (2, 2').With bromo- and iodobenzene in THF 1 reacts predominantly as a radical with H atom abstraction from the solvent affording benzene and 9.The formation of Grignard compounds (5) and anthracene (6), originating from primary and secondary alkyl and aryl halides and 1 in toluene or ether at elevated temperatures, is not caused by the reaction of 1 but by the "active magnesium" (Mg*) formed by decomposition of 1 in these solvents.In contrast, allyl, propargyl, and benzyl halides react with 1 independently of the solvent under mild conditions to produce 5 and 6.Allyl- and the difficultly accessible allenylmagnesium chloride can be prepared in THF at -78 and 0 deg C, respectively, from the corresponding halides and ordinary Mg powder via catalytic amounts of 1.
