43003-47-0

Upstream product

• 95646-46-1 1-(2-Acetylamino-2-phenyl-ethyl)perhydroazepin 
• 111-49-9 hexamethylene imine 
• 21572-32-7 2-chloro-1-phenyl-ethanone oxime 
• 344302-45-0 (E/Z)-1-(2-hydroximino-2-phenylethyl)perhydroazepine 
• 42564-24-9 2-Phenyl-5,6,7,8,9,9a-hexahydro-3H-imidazo<1,2-a>azepin-1-oxid 
• 876149-83-6 1-hydroxy-2-phenyl-perhydroimidazo[1,2-a]azepine 
• 876149-78-9 2-phenyl-2,3,6,7,8,9-hexahydro-5H-imidazo[1,2-a]azepin-1-oxide 
• 95646-35-8 1-(2-Amino-2-phenyl-ethyl)perhydroazepin 

Downstream Products

• 95646-51-8 1-(2-Phenyl-octahydro-imidazo[1,2-a]azepin-1-yl)-ethanone 
• 95646-34-7 2-phenyl-perhydroimidazo[1,2-a]azepine 

Relevant academic research and scientific papers

Hydroxylamine function as neighboring group with dehydrogenations

The β-amino-hydroxylamines 5a-d are prepared of the α-amino-oximes 1a-d with borane-dimethylsulfide. With mercury-EDTA, 5a-d react to (E/Z)-oxime-lactams 3a-d and benzaldoxime 7. Additionally 5b,c give the bicyclic amidine-N-oxides 8b,c, which slowly hydrolyze to the hydroxylamine-lactams 9b,c. These are easily oxidized to (E/Z)-3b,c. Postulated as intermediates in the mercury-assisted reduction of 5, the cyclic hydroxylamines 10a-d are available from the nitrones 4a-d with LiAlH 4. From 10a-d with mercury-EDTA the same products are obtained as from 5a-d but without 7. Only the pyrrolidine 10a forms besides (E/Z)-3a the nitrone 4a. Thin-layer chromatography shows that the pure isomers of 3a-d in solution isomerize, contrary to the amine-oximes 1a-d. The configuration of the oxime-lactams depends on the manner of preparation. With mercury-EDTA, 1b,c yield 3b,c with retention of the configuration, while the oximation of phenacyl-lactams 13b,c give rise to (E/Z)-mixtures of 3b,c. The condensed imidazoles 12 result from the nitrones 4a-d and the dihydrooxadiazines 2a,d on treatment with hydrogen chloride.

Dehydrogenation of cyclic tertiary amines with neighbouring of enantiomeric nucleophiles

For stereochemical investigation of their dehydrogenation, the enantiomers of the aminoalcohols 1, 2, and 3 were prepared from optically active sources, while the enantiomers of the diamines 8 and 9 were available by resolution of the racemates. The pure antipodes of 1, 2, and 3 reacted with mercury(II)-EDTA by a twofold dehydrogenation via intermediate participation of the neighbouring alcoholic group to the optically active lactams 5, 6, and 7 under complete retention of configuration. In the same manner the diamines 8 and 9 generated by four electron withdrawal the cycloamidines 10 and 11.

Neighbour Group Participation with Reductions and Hydride Abstractions - Part 2

The reduction of N-(2-aminoalkyl)lactams with diisobutylaluminium hydride and the hydride ion abstraction of the corresponding diamines give under neighbour group participation the fused aminals.