105371-72-0Relevant articles and documents
Metallation reactions. XXI. Metallation of alkyl (alkylthio) benzenes by superbases versus organolithium compounds
Cabiddu, Salvatore,Fattuoni, Claudia,Floris, Costantino,Melis, Stefana,Serci, Alessandro
, p. 6037 - 6048 (2007/10/02)
The metallation regiochemistry of alkyl(alkylthio)benzenes with butyllithium or with the superbasic mixture of butyllithium with potassium tert-butoxide is described. The reaction pattern depends on the substrate and the reagent. Butyllithium monometallates the thiomethylic carbon of methyl (methylthio) benzenes and bimetallates the thiomethylic and the annular carbon ortho to the thioethereal group. With superbases the metallation occurs at the thiomethylic and methylic carbon. Metallation with butyllithium of the higher homologs substitutes exclusively the hydrogen ortho to the thioalkylic group, while the superbases attack also the carbon atom alpha to the thioalkyl substituent.
Reaction of 4-Bromo-1,2-dimethylbenzene with Various Nucleophiles via Aryne Reaction
Biehl, Edward R.,Razzuk, Aziz,Jovanovic, Misa V.,Khanapure, Subhash P.
, p. 5157 - 5160 (2007/10/02)
4-Bromo-1,2-dimethylbenzene (4a) reacts with a variety of amines, mercaptans, and nitriles under aryne-forming conditions to yield predominantly 4-substituted 1,2-dimethylbenzenes and minor quantities of 3-substituted 1,2-dimethylbenzenes.The product distributions from these reactions are heavily in favor of the 4-substituted isomer since it is formed exclusively from the symmetric 4,5-dimethylbenzyne intermediate (6) and partly from the unsymmetric 3,4-dimethylbenzyne intermediate (5).
