1990 Fiscal Year Final Research Report Summary

Direct Conversion Reaction of Toluenes to Conjugated-Trienes and Their Applications

Research Project

Project/Area Number	01571160
Research Category	Grant-in-Aid for General Scientific Research (C)
Allocation Type	Single-year Grants
Research Field	Chemical pharmacy
Research Institution	Nagoya City University
Principal Investigator	SATO Yoshiro Nagoya City University Pharmaceutical Sciences Professor, 薬学部, 教授
Project Period (FY)	1989 – 1990
Keywords	Ylide / Ammonium Salt / Sigmatropic Rearrangement / Sommelet-Hauser Rearrangement / Stevens Rearrangement / Conjugated-Triene / Organosilicon Compound / Amine
Research Abstract	When trialkylbenzylammonium salts were treated with a strong base such as sodium amide in liquid ammonia, benzylammonium N-ylides intermediates are initially formed which subsequently rearrange to 6-aminomethyl-5-methylene-1,3-cyclohexadenes (conjugated trienes) via a [2,3] sigmatropic pathway. However, isolation of the trienes was difficult because they were quickly aromatized to 2-methylbenzylamines (Sommelet-Hauser rearrangement). N-Methylide formation reaction in non-basic mediums was revealed as a result of fluoride-ion induced desilylation reaction of N- (trimethylsilyl) methylammonium salts with cesium fluoride in dimethylformamide or hexamethylphosphoramide at room temperature in our laboratory. In this reaction condition, some conjugated triene compounds which were rearrangement products of benzylammonium N-methylides, were stable enough to isolate at room temperature and applied for DielsーAlder reaction to give polycyclic amines.

(6 results)