61248-63-3Relevant academic research and scientific papers
Molecular Dynamics Simulations of the Initial-State Predict Product Distributions of Dediazoniation of Aryldiazonium in Binary Solvents
Cruz, Gustavo N.,Lima, Filipe S.,Dias, Luís G.,El Seoud, Omar A.,Horinek, Dominik,Chaimovich, Hernan,Cuccovia, Iolanda M.
, p. 8637 - 8642 (2015/09/15)
The dediazoniation of aryldiazonium salts in mixed solvents proceeds by a borderline SN1 and SN2 pathway, and product distribution should be proportional to the composition of the solvation shell of the carbon attached to the -N2 group (ipso carbon). The rates of dediazoniation of 2,4,6-trimethylbenzenediazonium in water, methanol, ethanol, propanol, and acetonitrile were similar, but measured product distributions were noticeably dependent on the nature of the water/cosolvent mixture. Here we demonstrated that solvent distribution in the first solvation shell of the ipso carbon, calculated from classical molecular dynamics simulations, is equal to the measured product distribution. Furthermore, we showed that regardless of the charge distribution of the initial state, i.e., whether the positive charge is smeared over the molecule or localized on phenyl moiety, the solvent distribution around the reaction center is nearly the same.
A New Rearrangement of Alkoxybenzyl Anions
Bates, Robert B.,Siahaan, Teruna J.,Suvannachut, Kessara
, p. 1328 - 1334 (2007/10/02)
Alkyl groups migrate from oxygen to carbon in alkyl aryl ethers which have been metalated in benzylic positions. 2,6-Dimethylanisole provides a variety of 2,6-dialkylphenols and their ethers in 45-80percent yields.Rearrangement products are obtained in 10-30percent yields from other dimethylanisoles and from methylanisoles.The reactions appear to proceed, like Wittig rearrangements, by homolytic cleavage of the alkyl-oxygen bond followed by recombination of the resulting radical pair in a different way.The rearrangements can be avoided by using methyl ethers and working at or below room temperature.
Regio- and Stereoselectivity in Rearrangements of Bicyclic N,N-Ylides
Fennhoff, Gerhard,Heesing, Albert
, p. 1153 - 1160 (2007/10/02)
Under the influence of strong bases both 2-amino-2-azoniabicyclohept-5-enes and -oct-5-enes rearrange.Insertion of the exocyclic nitrogen products and systems, respectively.Correct stereochemistry at the ammonium atom is necessary for this 2,3-shift. - Keywords: N,N-Ylides; Azabicycles; Rearrangement
