1483-64-3Relevant articles and documents
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Gilman,Bailie
, p. 267 (1943)
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Electrochemical Reduction of 1,1-Diaryl-substituted Ethenes in Dimethylformamide
Fruianu, Michelina,Marchetti, Mauro,Melloni, Giovanni,Sanna, Gavino,Seeber, Renato
, p. 2039 - 2044 (2007/10/02)
The cathodic behaviour of 1,1-diaryl-substituted ethenes (Ar)PhC=CH2 (where Ar=phenyl-, 2-naphthyl-, 2-pyridyl-, 2-thienyl-, 2-furyl-) at a Hg cathode in N,N-dimethylformamide (DMF) and 0.1 mol dm-3 tetraethylammonium tetrafluoroborate (TEAF), was investigated by cyclic voltammetry and controlled potential electrolysis experiments.In cyclic voltammetry, at a potential scan rate of 0.2 V s-1, all substrates showed an irreversible reduction peak p,c) between -2.27 and -2.54 V vs. saturated calomel electrode (SCE)>.Controlled potential coulometries indicated that the apparent charge number of the process involved ranges from 1 to 2.The reduction products were characterised as (Ar)PhCH-Me (1-aryl-1-phenylethanes) and (Ar)PhCH-2-CHPh(Ar) (1,4-diaryl-1,4-diphenylbutanes).The charge number of the process and the ratio between the two different reduction products depended strongly on the structure and concentration of the substrate.Exhaustive electrolyses performed in the presence of variable amounts of D2O or in DMF allowed us to suggest that two distinct pathways are involved in the reduction process, leading to the monomeric and dimeric product, respectively.Hypotheses on the nature of the two reduction mechanisms are discussed.
Carbanion Rearrangements by Intramolecular 1,ω Proton Shifts, IV. The Reaction of ω,ω-Diphenylalkyllithium Compounds: Proof for an Intramolecular Transmetallation Reaction by Crossover Experiments Using Isotopic Labelled Starting Material
Maercker, Adalbert,Passlack, Michael
, p. 710 - 723 (2007/10/02)
3,3-Diphenylpropyllithium (2) and 2-(9-fluorenyl)ethyllithium (43) do not show a 1,3 proton shift but splitt off ethylene.On the other hand 4,4-diphenylbutyllithium (19) in diethyl ether can be forced to rearrange to 1,1-diphenylbutyllithium (18) by the addition of THF.The half reaction time for this 1,4 proton shift was found to be about 4 minutes.Proof for the intramolecular character of this transmetallation reaction was obtained by crossover experiments with specifically deuterated starting material.The 1,5 proton shift with 5,5-diphenylpentyllithium (12) occurs considerably slower than the 1,4 shift with 4,4-diphenylbutyllithium (19).The rearrangement also takes place in pure diethyl ether although with a half reaction time of about 2 days.Only 3-(9-fluorenyl)propyllithium (41) in diethyl ether spontaneously shows rearrangement already at -30 deg C, whereby 9-propyl-9-fluorenyllithium (42) is formed by a 1,4 proton shift.A 1,ω phenyl migration according to Grovenstein-Zimmerman in no case could be observed.