Amide, sodium reaction with ammonium salts

By analogy, ammonium salts should behave as acids in liquid ammonia, since they produce the cation NH4 (the solvo-cation ), and soluble inorganic amides (for example KNHj, ionic) should act as bases. This idea is borne out by experiment ammonium salts in liquid ammonia react with certain metals and hydrogen is given off. The neutralisation of an ionic amide solution by a solution of an ammonium salt in liquid ammonia can be carried out and followed by an indicator or by the change in the potential of an electrode, just like the reaction of sodium hydroxide with hydrochloric acid in water. The only notable difference is that the salt formed in liquid ammonia is usually insoluble and therefore precipitates. 

The heterocycles react directly with alkali metals or undergo exchange reactions with, for example, sodium amide and hydride, n-butyllithium and thallium ethoxide, to form the TV-heteroaryl salts. The salts of the alkali metals exist as solvent separated ion-pairs or as contact ion-pairs (71JOC3091), as do the quaternary ammonium salts, whereas the salts of the heavier metals are generally considered to have a high N—metal covalent character. These characteristics, which can be modified by a change in the polarity of the solvent, control the reactions of the heteroaryl anions. 

A vigorously stirred suspension of 0.2 to 1 mole of sodium amide in 200 ml of xylene, in which were dissolved 0.1 mole of a,a-diphenyl-7-hexamethyleneimino butyronitrile was boiled for 12 hours. Thereupon the excess of sodium amide was decomposed with water and the xylene layer was separated, washed with water and extracted with hydrochloric acid. This acidic extract was made strongly alkaline with concentrated lye and the separated base was extracted with ether. After drying, the ether was evaporated and the l,l-diphenyl-3-hexamethyleneimino propane distilled in vacuo. The boiling point was 170-174°C/1 mm, the refractive index nD20 = 1.56 36, and the density d420 = 1.009. From the oil obtained several acid additions and quaternary ammonium salts can be obtained by reaction with acids containing a non-toxic anion or esters thereof. The hydrochloric acid salt, for instance, melts at 189-192°C, the methiodide at 174-177°C under decomposition. 

A hydrotrope is a compound that helps other compounds normally not very soluble in water to dissolve in water.) The one used was (2.26). Pyrolysis of the carbamate (obtained in 90-96% yield) would lead to the isocyanate. This type of reaction can also be carried out in 95% yield using TV-bromosuccinimide and sodium methoxide in methanol or with bromine and sodium hydroxide.67 This suggests the possibility of generating the bromine or iodine during the reaction by electrolysis of sodium bromide or sodium iodide so that no waste salts result. The starting amides can be made by heating the ammonium salts of the acids. This... 

On the other hand, A-tosylated aza-crowns were formed in good yields (50-94%) from the reaction of the bis-sulfonamides with dibromides or di-tosylates in aqueous alkali-toluene or benzene mixtures in the presence of quaternary ammonium salt phase-transfer catalysts. Some cyclizations did not depend on alkali concentration, but for the tri- or tetraaza-crowns, 50% alkali solutions were preferred. In the synthesis of A,jV -ditosyldiaza-18-crown-6 via the interaction of the bis-sulfonamide with a dibromide, dichloride, diiodide, or ditosylate using 50% aqueous sodium hydroxide-toluene or benzene solution in the phase-transfer reaction, the cyclization rate varied according to the leaving group, Br > OTs > I > Cl. In dilute alkaline solution (7.5%), the diiodide was more reactive than the ditosylate. This could be a result of the greater activity of water in the solution so that hydrolysis of the tosylate is more rapid and, therefore, there would be less tosylate to react with the amide (Bogatskii et al., 1984 Lukyanenko et al., 1987, 1988). 

Violent reaction with reducing agents, amines, ammonia, ammonium salts, combustible materials, oxidizable materials, sodium carbonate. Incompatible with sulfuric acid, caustics, alkanolamines, amides, organic anhydrides, isocyanates, vinyl acetate, alkylene oxides, epichlorohydrin. May increase the explosive sensitivity of nitromethane. 

Definite sulfimide sulfonic acids are formed from S03 adducts and sulf-amide in a melt the pyrid nium salt of the sulfamide disulfonic acid, H0(02SNH)2—S03H was obtained. The analogous reaction with imido-sulfamide results in the dipyridinium salt of trisulfimide sulfonic acid H0(02SNH)3—S03H. Besides the pyridinium salts, several potassium, ammonium and sodium salts were prepared (92a). 

Identification of Amides.—The reaction of primary amides which is of the most importance in their identification, is that which takes place when they are heated with alkalies. If a substance has been found to contain nitrogen, it should first be tested to determine whether it is an amine, a salt of an amine, or an ammonium salt. Amines or ammonia will be set free from their salts when they are treated with a cold solution of sodium hydroxide. If no reaction takes place the substance should be... 

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