1702-41-6Relevant articles and documents
Reactions of benzyltriphenylphosphonium salts under photoredox catalysis
Boldt, Andrew M.,Dickinson, Sidney I.,Ramirez, Jonathan R.,Benz-Weeden, Anna M.,Wilson, David S.,Stevenson, Susan M.
supporting information, p. 7810 - 7815 (2021/09/28)
The development of benzyltriphenylphosphonium salts as alkyl radical precursors using photoredox catalysis is described. Depending on substituents, the benzylic radicals may couple to form C-C bonds or abstract a hydrogen atom to form C-H bonds. A natural product, brittonin A, was also synthesized using this method.
Kinetic Study of the Substitution Reactions of Triphenylphosphine with Chlorobenzyl Chlorides, Dimethylbenzyl Chloride, and Methylbenzyl Bromides in Various Two-Phase Organic Solvent/Water Media
Shieh, Ruey-Lone,Lin, Ruey-Lih,Hwang, Jiann-Jyh,Jwo, Jing-Jer
, p. 517 - 523 (2007/10/03)
The kinetics of the substitution reactions of triphenylphosphine (TP) with chlorobenzyl chlorides (CBC), 2,5-dimethylbenzyl chloride (DMBC), and methylbenzyl bromides (MBB) in aprotic organic solvent was studied under the extraction by water. The effects of water, agitation, organic solvent, reactant, and temperature were investigated. These reactions take place via the SN2 mechanism and exhibit large and negative entropy of activation. The order of relative activity of solvents is CHCl3 > CH2Cl2 >> C6H6. In CHCl3, the order of relative reactivity of benzyl chloride (BC), benzyl bromide (BB), CBC, DMBC, and MBB toward reaction with TP is 2-MBB > 4-MBB > 3-MBB > BB > DMBC > BC > 2-CBC > 4-CBC > 3-CBC. These reactions produce quantitatively benzyltriphenylphosphonium salts, which are useful for synthesizing Z-form isomers of stilbenes via the two-phase Wittig reaction.
Spatial Structure of 4n? Helicene Dianions
Frim, R.,Goldblum, A.,Rabinovitz, M.
, p. 267 - 274 (2007/10/02)
Helicene dianions, e.g. phenanthrene derivatives, once believed to be non-helical, maintain their chirality as 4n? dianions.Phenanthrene 5, as well as substituted phenanthrene derivatives, undergo a two-electron reduction to form the respective 4n? dianion e.g. 52-/2Li+.Phenanthrene derivatives substituted at the 4- and 5-positions (bay substituents) e.g. 6-11, which are helical, afford stable dianions.These dianions are also prepared by a two-electron reduction of the (4n+2)? electron hydrocarbons and show, in their 1H NMR spectra, a quench of the paratropicity compared to 52- as well as a line shape dependence on their twist angle.The quench of paratropicity was also observed in the closely related charged helicenes derived from the benzochrysene system, i.e. anions 122- and 132-.The twist angles were calculated by MMX and MNDO calculations for the neutral systems, i.e., 5-11, and by MNDO for the dianions.MNDO calculations also included the preferred location of the counter cation.A dynamic NMR spectroscopic study proves experimentally the helicity of anion 112- thus shedding light on the behaviour of this novel class of dianions.