Synthesis of Arylstannanes from Arylamines

Abstract

Arylamines have been converted into aryltrimethylammonium salts, which on reaction with sodium trimethylstannide ( 1 ) in liquid ammonia afford aryltrimethylstannanes by the S RN 1 mechanism. With (4-methoxyphenyl)- ( 2 ), (1-naphthyl)- ( 4 ), phenyl- ( 6 ), (4-acetylphenyl)- ( 8 ), and (4-cyanophenyl)trimethylammonium salts ( 10 ) the substitution products are obtained in good to excellent yields (45−100%). Also, the photostimulated reaction of (2-pyridyl)trimethylammonium iodide ( 12 ) with 1 leads to the substitution product 13 (50%). With (4-chlorophenyl)trimethylammonium iodide ( 14 ) the disubstitution product 19 is obtained in 76% yield. On the other hand, the results obtained in the reaction of (4-bromophenyl)trimethylammonium iodide ( 15 ) with 1 clearly indicate a fast HME reaction in the dark. The ET process (S RN 1) competes, although inefficiently, under irradiation.