Acid to Nitriles

Cationic palladium-catalyzed addition of arylboronic acids to nitriles for the formation... 

RC N Nitrile CH,C N Acetonitrile or Ethanenitrile -ic or -oic acid to nitrile or add -nitrile to alkane name... 

IsophLhalonitrile (1,3-dicyanoben/ene, 1PN), is a white solid which mells at 161°C and sublimes at 265°C. It is slightly soluble in water but readily dissolves in diinethylfonnamide, jV-inethylpyiToliclinoiie and hot aromatic solvents. IPN undergoes the reactions expected of an aromatic nitrile. It is prepared by vapor-phase ammoxidation of metci- ylcnc. Its principal use is as an intermediate to amines, As a reagent, TPN can be used to convert aromatic acids to nitriles in near quantitative yields. 

Cationic palladium-catalyzed addition of arylboronic acids to nitriles for the formation of benzo[h]furans was reported <06OL5987>, an example of which is illustrated in the following scheme. The palladium-catalyzed cross coupling of alkynes with appropriately substituted aryl iodides for the synthesis of substituted dibenzofurans in moderate to excellent yields was also achieved <06JOC5341>. The benzo[fc]furan core of heliannuls G and H were constructed by a palladium-catalyzed Ji-allyl cyclization reaction <06TL7353>. The palladium-catalyzed oxidative activation of arylcyclopropanes was applied to the synthesis of 2-substituted benzo[Z>]furans <06OL5829>. 

The iodized protein does not exhibit specific binding Often, the incorporated iodine is to blame, but the reagents used for the iodination can also inactivate the protein. For example, chloramine T oxidizes not only 1 but the a-amino group of peptides and amino acids to nitrile. Sensitive phenol derivatives are also destroyed. By the way, these reactions were the basis for the application of chloramine T as a disinfectant during World War I (Dakin et al. 1996). 

Nitriles are considered carboxylic acid derivatives because they are often prepared from acids through the primary amides. Show how you would convert the following carboxylic acids to nitriles. 

Conversion of fatty acids to nitriles, amides and amines. 

SCHEME 1.6 Three routes to cationic derivatives including fatty acid to nitrile to alkyl amine (fop), fatty acid to alkanolamine ester (center), and olefin to alkyl bromide to alkyl dimethyl amine (bottom). 

The in situ generation of carbon nucleophiles via extrusion of CO2 from benzoates cannot only be combined with cross-coupling processes but also with 1,2- and 1,4-addition reactions. An example is the rhodium-catalyzed decarboxylative conjugate addition of activated benzoic acids to acrylic esters or amides developed by Zhao et al. (Scheme 19, right side) [65]. A nice application is the decarboxylative addition of aromatic carboxylic acids to nitriles in the presence of... 

Although a few methods for the direct conversion of acids into nitriles are kno vn, the most popular still proceed via dehydration of the corresponding amides. A new, mild, one-pot method to effect the acid-to-nitrile conversion in high yield involves the use of mixed sulphonic-carboxylic anhydrides (Scheme 23) the method, however, is not applicable to acids containing —NHa, — NHR, —OH, or —SH groups. In a similar vein, a new and efficient one-pot synthesis of nitriles from acid chlorides is mediated by sulphonamide at 120 °C. ... 

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