Acid Amide from aldehyde

Carboxylic acid amides from aldehydes and alcohols... 

N-Halogeno-N-sodiosulfonic acid amides Replacement of hydrogen by sulfonylamino groups N-Acylsulfonic acid amides from aldehydes... 

Subst. carboxylic acid amides from aldehydes... 

By analogy with the synthesis of a-hydroxy acids one can envisage a one-pot synthesis of a-hydroxy amides from aldehydes via hydrocyanation and in situ NHase-catalyzed hydrolysis to the amide. Since enantioselective NHases are very rare, the enantioselectivity should be derived from HnL-catalyzed hydrocyanation. The second step has been described for the Rhodococcus erythropolis NHase-catalyzed hydration of (R)-mandelonitrile to give the (R)-amide with retention of enantiopurity [43]. 

The Ugi reaction produces a-amino acid amides from four components (isonitrile, carboxylic acid, aldehyde, and amine) in a one-pot reaction. With glycosylamines and ZnCl2 as promoting Lewis acid, a-amino acid amides are obtained [13,45] with excellent stereoselectivity in these reactions. For example, the galactosylamine 2 gave Ugi product 30 with formic acid as carboxylic component and various aldehydes and isonitriles in high yields and a diastereoselectivity of 19 1 in favor of the D-amino acid amides 30 (Scheme 20). 

Scheme 20.2 Substituted aromatic nitriles as intermediates for aromatic acids, amides, imines, aldehydes and amines. Elaborated from [82a].

A sigruficant use is as a catalyst in a multitude of reactions, such as the formation of acrjdic and methacrjdic acid amides from fatty acid amides (81) of cychc ketones such as 4-phen5icyclopentane-l,2-dione and 2,5-dihydroxy-/)-benzoquinone from benzaldehyde diethji acetal and 2,4-dioxo-5,5-dimethoxy-hexanoic acid methyl ester (82) of dimer aldehydes from propane (83) and for the polymerization of epoxy compounds (84). Mag nesium Kthylate. Magnesium ethoxide [2414-98-4]y Mg(OC2H 2 niol wt 114.4, is an almost white hygroscopic powder density,... 

P-Chloro-a-ketocarboxylic acid amides from dichloroacetic acid amides and aldehydes Darzens condensation... 

Azeotropic water entrainment s. 17, 450 3,4-Dihydro-l,2,4-benzothiadiazine 1,1-dioxides from o-aminosulfonic acid amides and aldehydes... 

As a class of compounds, nitriles have broad commercial utility that includes their use as solvents, feedstocks, pharmaceuticals, catalysts, and pesticides. The versatile reactivity of organonitnles arises both from the reactivity of the C=N bond, and from the abiHty of the cyano substituent to activate adjacent bonds, especially C—H bonds. Nitriles can be used to prepare amines, amides, amidines, carboxyHc acids and esters, aldehydes, ketones, large-ring cycHc ketones, imines, heterocycles, orthoesters, and other compounds. Some of the more common transformations involve hydrolysis or alcoholysis to produce amides, acids and esters, and hydrogenation to produce amines, which are intermediates for the production of polyurethanes and polyamides. An extensive review on hydrogenation of nitriles has been recendy pubHshed (10). 

Tetrahydroharman, m.p. 179-80°, has been prepared by a number of workers by a modification of this reaction, viz., by the interaction of tryptamine (3-)5-aminoethylindole) with acetaldehyde or paraldehyde and Hahn et al. have obtained a series of derivatives of tetrahydronorharman by the use of other aldehydes and a-ketonic acids under biological conditions of pH and temperature, while Asahina and Osada, by the action of aromatic acid chlorides on the same amine, have prepared a series of amides from which the corresponding substituted dihydronorharmans have been made by effecting ring closure with phosphorus pentoxide in xylene solution. 

A -Chloromethylamine attacks ketones in alkaline solution with formation of oxaziranes with cyclohexanone, compound 17 is produced in 50% yield. The reaction with aldehydes with zV-chloromethyl-amine yields predominantly acid amides. However, oxaziranes are also produced here as by-products. From benzaldehyde and A -chloro-methylamine, 2-raethyl-3-phenyloxazirane (15) was obtained in 10% yield. 

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