75356-81-9Relevant academic research and scientific papers
ZUR BILDUNGSWEISE VON 1-PHENYLPROPYLLITHIUM AUS BENZYLLITHIUM UND ETHYLEN IN TETRAHYDROFURAN
Maercker, Adalbert,Stoetzel, Reinhard
, p. 1 - 12 (2007/10/02)
3-Phenylpropyllithium primarily formed by the addition of benzyllithium to ethylene in THF does not undergo an intramolecular 1,3-proton shift to 1-phenylpropyllithium.Fast protonation by the solvent takes place instead, yielding n-propylbenzene and new ethylene.An equilibrium is then established between n-propylbenzene and additional benzyllithium, with the formation of toluene and 1-phenylpropyllithium; the equilibrium, however, strongly favours the starting materials (K293=1.1*10-4).As, on the other hand, 1-phenylpropyllithium reacts with ethylene much more rapidly than does benzyllithium, it is removed from the equilibrium and mainly branched secondary products are still obtained.
Carbanion Rearrangements by Intramolecular 1,ω Proton Shifts, III. The Reaction of 2-, 3-, 4-, and 5-Phenylalkyllithium Compounds
Maercker, Adalbert,Passlack, Michael
, p. 540 - 577 (2007/10/02)
Upon addition of THF to a solution of 4-phenylbutyllithium (2) in diethyl ether a rapid intramolecular 1,4 proton shift takes place with the formation of 1-phenylbutyllithium (5).Similarly, although somewhat more slowly, 5-phenylpentyllithium (82) rearranges to 1-phenylpentyllithium (83) via 1,5 proton transfer.The corresponding rearrangements by 1,2 or 1,3 hydrogen shifts, however, starting with 2-phenylethyllithium (1) and 3-phenylpropyllithium (54), respectively, were not detected.With 3-phenylpropyllithium (54) a slow intramolecular 1,5 transfer an ortho proton is observed instead, yielding o-propylphenyllithium (100).The corresponding 1,6 shift with 4-phenylbutyllithium (2) was also detected in a minor amount in addition to the 1,4 proton shift already mentioned.There is no indication, however, for a 1,4 transfer of an ortho proton in 2-phenylethyllithium (1).The reaction products in this case can be exclusively explained by intermolecular transmetallation reactions.All ω-phenylalkyllithium compounds under investigation show interesting side and secondary reactions being rather different in deuterated solvents and in deuteriumfree solvents, respectively, due to the isotope effects.The analysis of the products is accomplished by 1H-NMR spectroscopy and, after derivatization, with the help of a GC-MS-combination.Stereoelectronic reasons are made responsible for the failure of the intramolecular 1,2 and 1,3 proton shift in these systems.
