Novel polycyclic heterocycles. X. Synthesis of 3‐amino derivatives derived from 1,2‐dihydro‐l 1 (trifluoromethyl)‐3 H ,7 H ‐quino [8,1‐ cd ][ 1,5]benzoxazepin‐3‐one

The reactions of the tetracyclic ketone, 1,2‐dihydro‐11‐(trifluoromethyl)‐3 H ,7 H ‐quino[8,1‐ cd ] [1,5]benzoxazepin‐3‐one ( 1 ) with pyrrolidine, piperazine, N ‐methylpiperazine, and dimethyl‐amine gave the enamines 2, 13, 11 , and 4 . These were reduced with sodium borohydride to the corresponding 3‐amino derivatives 3, 14, 12 , and 5 . The 3‐(2‐hydroxyethylpiperazino) derivative ( 8 ) was obtained from the 3‐chloro compound ( 7 ); 7 was prepared from the carbinol ( 6 ). The 3‐NH 2 derivative ( 10 ) was obtained by reduction of the oxime ( 9 ). In 3, 5, 6, 7, 8, 10, 12 , and 14 , the ‐OCH 2 protons were non‐equivalent, since in the pmr spectrum of each of these compounds there was seen a symmetrical, perturbed AB quartet, with a common JAB of 12 cps, that must be attributed to geminal interproton coupling. This phenomenon had not previously been observed with 1, 9 , or the enamines, since in their pmr spectra, the ‐OCH 2 protons had invariably been seen as singlets.