Carboxylic acid amides and nitriles

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

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

Reduction of azides. Alkyi and aryi azides are reduced to primary amines by the combination of 1,3-propanedithiol and triethylamine (equation 1). The method is highly selective, and does not affect double or triple bonds, nitro, nitrile, carboxylic acid, amide, and ester groups. ... 

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). 

Subst. carboxylic acid amides from nitriles and ethylene derivatives Ethylene derivatives from, snbst. carboxylic acid amides... 

Controlled hydrolysis of a-acylaminonitriles Carboxylic acids and carboxylic acid amides from nitriles... 

The earlier studies and the competition experiments [5b] with equivalent molar, enal, or enone 9-BBN (3-5% excess) reveal that enals or enones are selectively reduced to allylic alcohols (Eq. 25.9) in the presence of other organic functional groups such as nitro, halogen, epoxide, carboxylic acid, amide, ester, nitrile, sulfide, disulfide, sulfoxide, sulfone, tosylate, azo, etc. 

Nitriles from carboxylic acid amides and thioamides... 

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... 

The synthesis of nitriles from halides is valuable in medicinal chemistry because nitriles are flexible building blocks readily converted into carboxylic acids, amides, amines, or a variety of heterocycles, e. g. thiazoles, oxazolidones, triazoles, and tetrazoles. The importance of the tetrazole group in medicinal chemistry is easily understood if we consider that it is the most commonly used bioisostere of the carboxyl group. 

Addition of HCN to acetone to form the cyanohydrin is still the main route to methyl methacrylate. Hydrocyanins can be converted to amino acids as well. The nitrile group can be easily converted to amines, carboxylic acids, amides, etc. Addition to aldehydes and activated alkenes can be done with simple base, but addition to unactivated alkenes requires a transition metal catalyst. The methods of HCN addition have been discussed by Brown [2],... 

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). 

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). 

Carboxylic acid derivatives are compounds that possess an acyl group (R—C=0) linked to an electronegative atom, e.g. —Cl, —CO2 R, —OR or —NH2. They can be converted to carboxylic acids via simple acidic or basic hydrolysis. The important acid derivatives are acid chlorides, acid anhydrides, esters and amides. Usually nitriles are also considered as carboxylic acid derivatives. Although nitriles are not directly carboxylic acid derivatives, they are conveniently hydrolysed to carboxylic acids by acid or base catalysts. Moreover, nitriles can be easily prepared through dehydration of amides, which are carboxylic acid derivatives. 

Amides are the least reactive of the carboxylic acid derivatives, and undergo acid or base hydrolysis to produce the parent carboxylic acids, and reduction to appropriate amines (see Section 4.3.10). They can also be dehydrated to nitriles, most commonly with boiling acetic anhydride, (AcO)20, sulphonyl chloride (SOCI2) or phosphoms oxychloride (POCI3) (see Section 4.3.18). Amines (with one less carbon) are prepared from amides by the treatment of halides (Br2 or CI2) in aqueous NaOH or KOH. This reaction is known as Hofmann rearrangement (see Section 4.3.10). 

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. 

Tertiary benzylic nitriles are useful synthetic intermediates, and have been used for the preparation of amidines,2 lactones,3 primary amines,4 5 pyridines,6 aldehydes,78 carboxylic acids,9 and esters.10,11 The general synthetic pathway to this class of compounds relies on the displacement of an activated benzylic alcohol or benzylic halide with a cyanide source followed by double alkylation under basic conditions. For instance, 2-(2-methoxyphenyl)-2-methylpropionitrile has been prepared by methylation of (2-methoxyphenyl)acetonitrile using sodium amide and iodomethane.12 In the course of the preparation of a drug candidate,13 the submitters discovered that the nucleophilic aromatic substitution of aryl fluorides with the anion of a secondary nitrile is an effective method for the preparation of these compounds.14 The reaction was studied using isobutyronitrile and 2-fluoroanisole. The submitters first showed that KHMDS was the superior base for the process when carried out in either THF or toluene (Table I). For example, they found that the preparation of 2-(2-methoxyphenyl)-2-methylpropionitrile could be accomplished h... 

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