A Method for the Synthesis of Phenanthridine Derivatives by an Application of the Stieglitz Rearrangement

Abstract

2. The constants of three specimens of oleic acid, prepared by slight modifications of the pro- COLUMBUS, OHIORECEIVED OCTOBER 8, 1936 1. A simplified procedure for preparing oleic cedure, are described. acid of high purity is described.

The Chemistry of Fluorene and its Derivatives.

“…It seems to us that this reaction is influenced by the labile nature of the hydrogen in the 9-position, because when this hydrogen was replaced by a relatively large group, such as phenyl or naphthyl, the compound reacted normally with ammonia to give the 9-substituted primary amine. Thus Pinck and Hilbert (231) readily prepared 9-phenyl-9-aminofluorene and 9-a-naphthyl-9-aminofluorene by this reaction. The secondary amine could be formed by using an excess of ammonia in a steel bomb at 180°C.…”

“…Other reactions of this type have also been studied (25,30,191,197,275,276,277,278). Fluorene derivatives in which one of the hydrogen atoms on the 9-carbon atom is replaced by an alkyl or aromatic radical and the other hydrogen atom by chlorine or bromine may be synthesized easily by the action of the Grignard reagent on fluorenone followed by treatment with the phos- phorus or hydrogen halide (231,259). Hydriodic acid reduces the hydroxyl group and (CeH^CHR is obtained.…”

“…Recently Pinck and Hilbert (231) have published the results of an investigation into the application of the Stieglitz rearrangement (233). In an A-substituted 9-aminofluorene, stabilization can be attained by undergoing two types of rearrangement.…”

“…Their rearrangement was accomplished in an anhydrous pyridine11 solution of the chloroamine with excess dry sodium methylate. Similarly 9-a-naphthylphenanthridine was also prepared by the thermal decomposition of 9-a-naphthyl-9-fiuoreneazide (231).…”

“…From a consideration of valency angles and interatomic distances a model is produced that would result in considerable strain if a planar formula is assumed (231).…”