Acid Amides and Nitriles

According to the investigations of Baillie and Tafel,3 the reduction of acid amides in sulphuric-acid solution at lead cathodes leads to amines, as shown in the equation  

Benzamide yields only a little benzylamine benzaldhyde, which probably contained benzyl alcohol, was also formed. In a similar manner 

The p-nitro-substitution products of o-toluenesulphcnamide are said to behave similarly. 

Just as amines are easily obtained by reduction of nitriles with sodium amalgam or sodium and alcohol, so this reaction can be carried out electrolytically (p. 121). 

Benzonitrile.—Ahrens,2 by electrolytic reduction of this substance in dilute sulphuric acid at a platinum cathode, obtained benzylamine in like manner, 

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Alkylation of Aldehydes, Esters, Carboxylic Acids, Amides, and Nitriles... 

DichIoro-2-(trichloromethyl)imidazo[4,5-i ]pyrazine (238) was converted into the 2-carboxylic acid ethyl ester (239) by treatment with silver nitrate in ethanol (80JHC381). The ester was converted into the acid, amide and nitrile (240). 

Not only esters but also acids, amides, and nitriles can react with nucleophiles, the latter leading to an imino group rather than a carbonyl (Scheme 4.21). 

A soln. of methyl vinyl ketone and p-toluenesulfonyl iodide in dichloromethane stirred for ca. 1 day at room temp. - 3-iodo-4-(/ -tolylsulfonyl)butan-2-one (Y 87%), in dichloromethane treated slowly with a soln. of NEt, in the same solvent at 0° with stirring, and worked up after 1 h at room temp. - (E)-4-(/>-tolylsulfonyl)but-3-en-2-one (Y 95%). F.e. (incl. aldehyde, ester, acid, amide and nitrile analogs), also with in 5/m-generated / -toluenesulfonyl iodide (from Na-/ -toluenesulfinate and L), s. C. Najera et al., J. Chem. Soc. Perkin Trans. I 1988, 1029-32. 

Addition reactions of carbanions derived from esters, carboxylic acids, amides, and nitriles... 

The lower members of other homologous series of oxygen compounds— the acids, aldehydes, ketones, anhydrides, ethers and esters—have approximately the same limits of solubility as the alcohols and substitution and branching of the carbon chain has a similar influence. For the amines (primary, secondary and tertiary), the limit of solubility is about C whilst for the amides and nitriles it is about C4. 

Acid chlorides and bromides, allyl halides, a-halo-ketones, esters, amides and nitriles react at 25° within 3 minutes. Vinyl and aryl halides are inert. 

Carboxylic acids and derivatives (including amides and nitriles). 

This chapter concerns the preparation and reactions of acyl chlorides acid anhydrides thioesters esters amides and nitriles These com pounds are generally classified as carboxylic acid derivatives and their nomenclature is based on that of carboxylic acids... 

Esters, amides, and nitriles are not readily hydrolyzed under neutral conditions, but they are hydrolyzed by aqueous acid. 

The influence of other groups in a pyridine or similar ring system is more difficult to assess because no kinetic data are available. The deactivating effect of the bromine atom in the 2-position is greater than that in the 3-position, while 2,6-dibromopyridine is very slow to react with dimethyl sulfate. Esters, amides, and nitriles of nicotinic and isonicotinic acids undergo fairly easy quaternization at about... 

The acids can be esterified or converted to acid chlorides and hence to amides and nitriles [107] Scheme XXIII ... 

A number of 4-pyrimidinecarboxylic acids of the general formula (XVI) and their esters, amides and nitriles are claimed to possess cardiovascular, hypotensive, and spasmolytic properties [214]. Other biological activities and medicinal uses of 5-halo-substituted orotic acids, as well as those of uracil-6-sulphonic acid and related compounds, have been discussed in Part I of this review [215]. 

If the reduction has been carried out in ether, the ether layer is separated after the acidification with dilute hydrochloric or sulfuric acid. Sometimes, especially when not very pure lithium aluminum hydride has been used, a gray voluminous emulsion is formed between the organic and aqueous layers. Suction filtration of this emulsion over a fairly large Buchner funnel is often helpful. In other instances, especially in the reductions of amides and nitriles when amines are the products, decomposition with alkalis is in order. With certain amounts of sodium hydroxide of proper concentration a granular by-product - sodium aluminate - may be separated without problems [121],... 

The third group of target molecules comprises chiral carboxylic acid and their derivatives esters, amides and nitriles. Enantiomerically pure esters are prepared in an analogous manner to the enantiomerically pure alcohols discussed earlier [i.e. by esterase- or lipase-catalyzed hydrolysis or (trans)esterification]. However, these reactions are not very interesting in the present context of cascade reactions. Amides can be produced by enantioselective ammoniolysis of esters or even the... 

The suffixes -oic acid, -al, -amide and -nitrile are used to name acyclic compounds having one or two characteristic groups. Locants are not necessary, as these groups must be at the end of a chain. The suffixes -carboxylic acid, -carbaldehyde, -carboxamide and -carbonitrile are used when more than two groups are attached to chains or one or more groups are attached to cycles. 

The carboxylic acids of triazoles are readily decarboxylated on heating but are otherwise stable. Esters, amides, nitriles, and hydrazides react normally. This is illustrated in Scheme 18 for the amide and nitrile functions (88JMC330). 

R.A. Reck, J. Am. Oil Chem. Soc. 56, 796A-801A (1979) . .Nitrogen Derivatives of Fatty Acids (Amides, Diamides, Nitriles, Primary Amines, and Oxides)". 

Carboxylic acids are prepared hy the hydrolysis of acid chlorides and acid anhydrides, and acid- or hase-catalysed hydrolysis (see Section 5.6.1) of esters, primary amides and nitriles (see Section 5.6.1). 

Monolayers are best formed from water-insoluble molecules. This is expressed well by the title of Gaines s classic book Insoluble Monolayers at Liquid-Gas Interfaces [104]. Carboxylic acids (7-13 in Table 1, for example), sulfates, quaternary ammonium salts, alcohols, amides, and nitriles with carbon chains of 12 or longer meet this requirement well. Similarly, well-behaved monolayers have been formed from naturally occurring phospholipids (14-17 in Table 1, for example), as well as from their synthetic analogs (18,19 in Table 1, for example). More recently, polymerizable surfactants (1-4, 20, 21 in Table 1, for example) [55, 68, 72, 121], preformed polymers [68, 70, 72,122-127], liquid crystalline polymers [128], buckyballs [129, 130], gramicidin [131], and even silica beads [132] have been demonstrated to undergo monolayer formation on aqueous solutions. 

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