33426-67-4Relevant academic research and scientific papers
Competing Pathways in O-Arylations with Diaryliodonium Salts: Mechanistic Insights
Stridfeldt, Elin,Lindstedt, Erik,Reitti, Marcus,Blid, Jan,Norrby, Per-Ola,Olofsson, Berit
, p. 13249 - 13258 (2017/09/12)
A mechanistic study of arylations of aliphatic alcohols and hydroxide with diaryliodonium salts, to give alkyl aryl ethers and diaryl ethers, has been performed using experimental techniques and DFT calculations. Aryne intermediates have been trapped, and additives to avoid by-product formation originating from arynes have been found. An alcohol oxidation pathway was observed in parallel to arylation; this is suggested to proceed by an intramolecular mechanism. Product formation pathways via ligand coupling and arynes have been compared, and 4-coordinated transition states were found to be favored in reactions with alcohols. Furthermore, a novel, direct nucleophilic substitution pathway has been identified in reactions with electron-deficient diaryliodonium salts.
An efficient copper-catalyzed etherification of aryl halides
Huang, Jinkun,Chen, Ying,Chan, Johann,Ronk, Mike L.,Larsen, Robert D.,Faul, Margaret M.
experimental part, p. 1419 - 1422 (2011/07/30)
An efficient and mild copper-catalyzed ether formation from aryl halides and aliphatic alcohols has been developed. The key to the successful coupling is the use of lithium alkoxide, directly or in situ generated by lithium tert-butoxide, and the corresponding alcohol as solvent. Georg Thieme Verlag Stuttgart - New York.
Selectivity engineering of phase transfer catalyzed alkylation of 2′-hydroxyacetophenone: Enhancement in rates and selectivity by creation of a third liquid phase
Yadav, Ganapati D.,Desai, Neesha M.
, p. 749 - 756 (2012/12/26)
Enhancements in rate of reaction and selectivity of the desired product in biphasic reactions are achieved by creating a third liquid phase, under appropriate conditions, where the third liquid phase is the locale of the main reaction, having a dramatic effect on product distribution in complex chemical reactions. Thus, in the case of phase transfer catalysis (PTC), conversion of liquid-liquid (L-L) PTC into liquid-liquid-liquid (L-L-L) PTC is of considerable techno-commercial interest resulting in waste minimization which is a major theme of green chemistry. Etherification of 2′-hydroxyacetophenone with 1-bromopentane, under traditional liquid-liquid phase transfer catalysis, results in loss of catalyst. However, the transformation of two liquid phases into three liquid phases (L-L-L) PTC leads enhancement in rates by orders of magnitude, with 100% conversion of the limiting reactant 1-bromopentane and 100% selectivity to 2′-pentyloxyacetophenone. This strategy eliminates separation problems and results in high reaction rates reducing the total reaction time. Moreover, the catalyst-rich third phase is recycled more than 7 times without loss in activity. The kinetics of the reaction are studied in great detail. There is a substantial reduction in activation energy under L-L-L PTC vis-a-vis L-L PTC, where the locale of the reaction is shifted from the organic phase to the third phase.
