Reaction with liquid ammonia

Reaction with liquid ammonia at —33°C probably proceeds in a manner similar to that described by Davis and Blanchard it is believed that nitramine (decomposing into N20 and water) and urea (apparently from cyanic acid and ammonia) are formed. 

Esters are prepared by reaction of aldonic acids or lactones with an alcohol in the presence of hydrogen chloride 80 the reaction is slower with 1,4-lactones. Amides are readily formed from lactones by reaction with liquid ammonia followed by evaporation of the solvent.81 D-Gluconamide has also been prepared by treatment of D-glucono-1,5-lactone with concentrated ammonium hydroxide and subsequent precipitation with ethanol.82 A-Substituted aldonamides may be obtained by reaction of the aldono-lactones with ethanolamine, diethanolamine, and related species.83... 

The synthetic scheme often applied for the preparation of 3-aryl-3-(trifluoromethyl)-3//-diazirine nowadays is shown in Scheme 5a [60]. It starts by lithiation of an aryl bromide (38), which subsequently reacts with /V-ftrifluoroacetyl)piperidine 39 (easily prepared from trifluoroacetic anhydride and piperidine) under the formation of trifluoroacetophenone 40. Next, the ketone is converted into the corresponding oxime 41, after which the hydroxyl group is converted into its tosylate (42). Reaction with liquid ammonia (usually under pressure) allows the installment of the diaziridine group (43). Subsequent oxidation with iodine finally results in the diazirine (44). This five-step reaction sequence is especially compatible with acid-labile protective groups, which are often used to protect and/or install functionalities at the R position. 

In conclusion, all results obtained thus far on this reaction show that it is especially the 4-position in the 3-nitro-l,8-naphthyridines which is strongly favored toward the attack of the carbanion of chloromethyl phenyl sulfone. When position 4 is occupied by a substituent no reaction occurs. This behavior is in accordance with the behavior observed in reactions with liquid ammonia and liquid methylamine. 

Caution. Potassium amide is flammable and ignites on contact with moisture. Residues are destroyed by cautious treatment with ethanol or isopropanol. Reactions with liquid ammonia must be done in a hood. 

An unusual base-catalyzed cleavage reaction of the fused spirothiazolidine ring of the hydantoin 122 to 123 occurs by reaction with liquid ammonia.315... 

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