The Preparation of Aromatic Amines with Sodium Amide in Liquid Ammonia

Solvent Influence on Rates and Mechanisms

“…Ionization of the M = C1 is predicted by both schemes. The entering amide displaces a hydrogen atom ortho to the halogen atom; also ether solutions of aryl halides were attacked by lithium dialkylamides [503]. An amide group replaces another atom or group, for example, a halogen atom in a molecule, in both ammonolysis and amination which are thus synonymous.…”

Design and Synthesis of a Series of Truncated Neplanocin Fleximers

“…This method seemed promising since one of the examples utilized 2-chloropyridine, which was successfully converted in a 96% yield [28], but it too proved to be unsuccessful. Use of NaNH 2 in ammonia was also tried but the conditions proved to be too harsh and decomposition ensued [43]. Another approach involved converting the chloro group using hydrazine followed by reduction.…”

The Chemistry of the Alkali Amides.

“…61, 914 (1939). 63) Overhoff, J., and Hackmann, J. T.: German patent 742,225; Chem. Abstracts 40, 434 (1946).…”

“…Massie (582) has treated 1-bromonaphthalene with lithium didodecylamide and obtained 2-didodecylaminonaphthalene (42 per cent). A number of o-and p-halogenated aryl alkyl ethers (63,339,341,342), o-halogenated aryl alkyl sulfides (344, 574), o-halophenols (341), and o-h&lo-N,Ndialkylanilines (343) have been treated with lithium amide, sodium amide, potassium amide, lithium diethylamide, and W-lithiopiperidine to give products in which the halogen atom has been eliminated and an amino or substituted amino group has been introduced into the ring in a position meta to the ether, thioether, phenolic, or N, V-dialkylamino function. When either o-or m-chlorobenzotrifluoride is treated with sodium amide in liquid ammonia, m-aminobenzotrifluoride is obtained (64).…”

“…These workers have proposed the following course for these reactions: Compound I is converted to anion III, which undergoes intramolecular nucleophilic substitution to give IV, which in turn isomerizes to II. While in the base-induced Stieglitz rearrangement (829) of tritylhaloamines the main reaction product is benzophenoneanil (V), Ayres and Hauser (38) have found that the reaction of N-trityl-O-benzylhydroxylamine with potassium amide gives less than 3 per cent of V. Instead, triphenylmethane (60)(61)(62)(63)(64)(65) per cent) and benzaldoxime (25-37 per cent) are obtained. Bergstrom (80) has observed that potassium amide reacts with potassium nitrate according to the following equation.…”