264910-19-2Relevant academic research and scientific papers
The role of ion-molecule pairs in solvolysis reactions. Nucleophilic addition of water to a tertiary allylic carbocation
Jia, Zhi Sheng,Ottosson, Henrik,Zeng, Xiaofeng,Thibblin, Alf
, p. 182 - 187 (2002)
The acid-catalyzed solvolysis of 2-methoxy-2-phenyl-3-butene (1-OMe) in 9.09 vol % acetonitrile in water provides 2-hydroxy-2-phenyl-3-butene (1-OH) as the predominant product under kinetic control along with the rearranged alcohol 1-hydroxy-3-phenyl-2-butene (2-OH) and a small amount of the rearranged ether 2-OMe. The more stable isomer 2-OH is the predominant product after long reaction time, Keq = [2-OH]eq/[1-OH]eq = 16. The ether 2-OMe reacts to give 2-OH and a trace of 1-OH. Solvolysis of 1-OMe in 18O-labeled water/acetonitrile shows complete incorporation of 18O in the product 1-OH, confirming that the reaction involves cleavage of the carbon-oxygen bond to the allylic carbon. A completely solvent-equilibrated allylic carbocation is not formed since the solvolysis of the corresponding chloride 1-chloro-3-phenyl-2-butene (2-C1) yields a larger fraction of 1-OH. This may be attributed to a shielding effect from the chloride leaving group. Quantum chemical calculations of the geometry and charge distribution show that the cation should rather be described as a vinyl-substituted benzyl cation than as an allyl cation, which is in accord with its higher reactivity at the tertiary carbon.
Use of cis-dichloro[(S)-α-methylbenzylamine](ethylene)Pt(II) as a chiral derivatizing agent for the determination by 195Pt-NMR of the enantiomeric composition of unsaturated ethers or alcohols having a quaternary chiral carbon atom
Uccello-Barretta, Gloria,Bernardini, Raffaella,Lazzaroni, Raffaello,Salvadori, Piero
, p. 174 - 178 (2007/10/03)
cis-Dichloro[(S)-α-methylbenzylamine](ethylene)platinum(II) is an efficient chiral derivatizing agent for the determination, by 195Pt-NMR spectroscopy, of the enantiomeric composition of unsaturated ethers and alcohols having a quaternary chiral carbon atom.
