Ammonium amides

The third mechanism starts with addition of the AT-allylamine 103 to the cumulated acceptor system of an allene carbonester 108 (Acc=CHC02Me) to form an intermediate iV-allyl ammonium amide enolate 109 (allene carbonester Claisen rearrangement). The anion stabilizing group is exclusively placed... 

The effect of hydrophobicity of some ionic liquids was explored (119) in a recent example of a condensation synthesis involving a quaternary ammonium amide. The water produced was continuously removed from the reaction mixture, producing a much higher yield than had previously been possible for this reaction in other media. 

Varner, J.E., Bulen, W.A., Vanccko, S., and Burrell, R.C. 1953. Determination of ammonium, amide, nitrile and nitrate nitrogen in plant extracts. Anal. Chem. 25 11528-1529. 

Another approach for organocatalytic C-H functionalization of heteroaromatic W-oxides has been reported by using in situ generated ammonium amides and C-nucleophiles (Scheme 29), which are introduced into heteroaromatics through a sequence of the addition and elimination steps to give a-substituted azines under metal-free reaction conditions. 

Scheme 30 C-H functionalization of benzothiazole catalyzed by in situ generated ammonium amide...

It is worth noting that ammonium amides, generated in situ from a mixture of aminosilanes and ammonium fluorides, have recently been employed as bases for organocatalytic deprotonative C-H functionalization of heteroaromatics under mild conditions (Scheme 30) [71]. 

Scheme 33 Heterobiaryl synthesis using ammonium amide catalyst...

The nucleophilic attack of the carbonyl group of an amide under hydrolyzing conditions is a very nice example of medium-assisted reaction (Menger and Fei, 1994). Long-chain ammonium amides could be hydrolyzed... 

Although quaternary onium bromides and chlorides as phase-transfer catalysts are generally beUeved to require base additives for phase-transfer reactions of active methylene and methine compounds, which were discussed above, we have recently discovered an hitherto unknown base-free neutral phase-transfer reaction system in asymmetric conjugate additions (Scheme 14.5) [23]. The reactions were efficiently promoted by chiral bifunctional ammonium bromide (S)-7 under neutral conditions with water-rich biphasic solvent. The role of hydroxy groups in the bifunctional catalyst was clearly shown in the transition-state model of the reaction based on the single-crystal X-ray structure of ammonium amide [23b] and nitro-nate [23c]. 

An ammonium betaine of type (R)-16 could be considered as an intramolecular version of ammonium phenoxide. The potential of chiral ammonium betaine (R)-16 as Brpnsted base catalyst has been demonstrated in asymmetric Mamiich reactions (Scheme 14.9) [6b, 32]. The basic phenoxide anion is responsible for abstraction of the active methine proton of a nucleophile 18 and thus gives the corresponding chiral ammonium enolate. Subsequent stereoselective bond formation with imine 17 afforded ammonium amide that can be rapidly protonated by the in situ formed phenolic hydrogen to regenerate the ammonium betaine (R)-16. 

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. 

Liquid ammonia, like water, is only a poor conductor of electricity. Ammonium salts dissolved in water behave as acids giving the ion NH4, whilst amides which give the ion NHj behave as bases. Thus the reaction ... 

Ammonium salt of any acid Acid amides Acid nitriles Imides of dibasic acids... 

Section i6. Ammonium salts, amides, imides, and nitriles, (c/. Tables XI, XII, pp. 543 545)... 

Amides (except urea and thiourea), imides and nitriles, after the above alkaline hydrolysis, give derivatives similarly to those from the alkaline solution obtained from ammonium salts (p. 360). (A) If the original compound is aromatic, acidification of the cold solution deposits the crystalline acid. (B) The cold solution, when carefully neutralised (p. 332) and treated with benzylthiuronium chloride, deposits the thiuromum salt. 

The reaction commences at about 120° the carbamic acid formed decomposes immediately into carbon dioxide and ammonia. The latter may form the ammonium salt with unreacted acid the ammonium salt also reacts with urea at temperatures above 120° to yield the amide ... 

When an alkyl aryl ketone is heated with yellow ammonium polysulphide solution at an elevated temperature, an aryl substituted aliphatic acid amide is foimed the product actually isolated is the amide of the ci-aryl carboxylic acid together with a smaller amount of the corresponding ammonium salt of the oarboxylio acid. Thus acetophenone affords phenylacetamide (50 per cent.) and ammonium phenylacetate (13 per cent.) ... 

The conversion of a carbonyl compound by ammonium polysulphide solution into an amide with the same number of carbon atoms is known as the Willgerodt reaction. The procedure has been improved by the addition of about 40 per cent, of dioxan or of pyridine to increase the mutual solubility of the ketone and aqueous ammonium polysulphide the requisite temperature is lowered to about and the yield is generally better. 

The enyne system in the amines 828=88-8 8-882 can be reversed by potassium amide in liquid ammonia. Addition of the enyne amines to an equivalent amount of this reagent gives the potassium acetylides, K-8e8-88=88-8R2, from which the ynene" amines can be obtained in excellent yields by addition of solid ammonium chloride. 

Terminal alkynes are only reduced in the presence of proton donors, e.g. ammonium sulfate, because the acetylide anion does not take up further electrons. If, however, an internal C—C triple bond is to be hydrogenated without any reduction of terminal, it is advisable to add sodium amide to the alkyne solution Hrst. On catalytic hydrogenation the less hindered triple bonds are reduced first (N.A. Dobson, 1955, 1961). 

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