22802-40-0Relevant articles and documents
Ortho-selective nucleophilic addition of primary amines to silylbenzynes: Synthesis of 2-silylanilines
Ikawa, Takashi,Nishiyama, Tsuyoshi,Shigeta, Takashi,Mohri, Shinya,Morita, Shinsuke,Takayanagi, Sho-Ichi,Terauchi, Yuki,Morikawa, Yuki,Takagi, Akira,Ishikawa, Yoshinobu,Fujii, Satoshi,Kita, Yasuyuki,Akai, Shuji
supporting information; experimental part, p. 5674 - 5677 (2011/08/06)
Cause and effect: The first ortho-selective nucleophilic addition reaction of amines to 3-substituted benzynes has been achieved. Despite a large trimethylsilyl substituent, primary amines attack the C2 position of 3-silylbenzynes to produce 2-silylanilines (see scheme). This outcome is likely to result from the inductive electron-donating effect of the silyl group, which overrides its steric repulsion with the approaching amines. Copyright
Halogenation using quaternary ammonium polyhalides. XX. Bromination of phenols with polymer-bound benzyltrimethylammonium tribromide
Kakinami,Suenaga,Yamaguchi,Okamoto,Kajigaeshi
, p. 3373 - 3375 (2007/10/02)
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ipso Halogenation. II. Bromination of phenols, isomerisation and disproportionation of bromophenols, and dione-phenol rearrangement of bromodienones
Fischer, Alfred,Henderson, George Narayanan
, p. 1045 - 1052 (2007/10/02)
Bromination of p-cresol, bromo-p-cresol, 3,4-dimethylphenol, and mesitol in trifluoromethanesulfonic acid gices as the main product the bromo derivative with bromine meta to hydroxyl, a result attributed to the intermediate formation of a bromodienone and its rearrangement.Phenols does not give m-bromophenol in trifluoromethanesulfonic acid. 4-Bromo-2,4,6-trimethylcyclohexa-2,5-dienone rearranges to 3-bromomesitol in trifluoromethanesulfonic acid and, similarly, 2,4,6-tribromo-4-methylcyclohexa-2,5-dienone rearranges to 3-bromomesitol in trifluoromethanesulfonic acid and, similarly, 2,4,6-tribromo-4-methylcyclohexa-2,5-dienone rearranges to 2,3,6-tribromo-4-methylphenol.Under appropriate conditions debromination of bromodienones is competitive with rearrangement.Tetramethylammonium bromide in trifluoromethanesulfonic acid is an effective reagent for isomerization and disproportionation of bromophenols.Tetramethylammonium iodide in trifluoromethanesulfonic acid is an effective reagent for selective debromination of bromophenols at the ortho and para position.