Conversion of amide to nitrile

Thenrwlysis of tertiary and secondary alcohols with (caitxjmethoxysulfamoyl) trlethylammoniunn Inner salt 5 to give olefins also conversion of amides to nitriles... 

RCO2H, R OH, 2-chloro-l,3-dimethylimidazolinium chloride, 76-96% yield. The reagent is a powerful dehydrating agent which has a number of other uses such as the conversion of amides to nitriles, acids to anhydrides, etc." ... 

In addition to the reactions mentioned above, boron phosphorous oxide shows catalytic activities for the following reactions alkylations of phenol and 1,2-bcnzenediol with methanol,hydrogen transfer of cyclohexane to cydohexene and methylcyclopentene-1, and conversion of amides to nitriles. The acid sites on... 

The formation of a very electrophilic intermediate 258 from 256 and 257 is proposed (equation 78). The hydroxyl group of the oxime adds to 259, giving a reactive cationic species 260 that rearranges and affords the nitrile 261 (in the case of aldoxime, equation 79), or the amide 262 upon hydrolytic workup (equation 80). The conversion of 260 to the nitrilium ion should occur through a concerted [1,2]-intramolecular shift. This procedure can be applied in the conversion of aldoximes to nitriles. It was observed that the stereochemistry of the ketoximes has little effect on the reaction, this fact being explained by the E-Z isomerization of the oxime isomers under the reaction conditions. 

InCls can be used as an efficient reagent for the conversion of aldoximes to nitriles and ketoximes to amides. Benzaldoxime gives benzonitrile, and benzophenone oxime is converted to the Beckmann rearrangement product, benzanilide, in 95% yield (Scheme 8.135) [179]. Sonication of a mixture of a carbonyl compound, an amine, and diethyl phosphite in fhe presence of a catalytic amount of InCls produces a-aminophosphonate (Scheme 8.136) [180]. 

Conventional conversion of amide, lactam, imide, and urea carbonyl groups into enaminones, enamino esters, or enamino nitriles requires prior activation of the carbonyl groups either by alkylation to imino ethers, followed by reaction with activated methylene groups, or by thiation, e.g. with P2S5, to thiocarbonyl groups followed by alkylation (and possibly also oxidation), and, again, subsequent reac-... 

Although the conversion of an amide to a nitrile may be considered a standard reaction, the conversion of 62 to 63 by treatment with POCI3 represents the synthesis of one of the very few examples of such a nitrile derivative (Equation 25) <2004IZV1257>. 

New polymer-supported reagents for sulfide transfer have been developed to avoid exposure to malodorous and toxic sulfur reagents. Ley et al.15 prepared a stable aminothiophosphate polystyrene resin for the conversion of secondary and tertiary amides to thioamides in high conversion and purity (Table III, entry 11). This procedure is extremely clean and affords the desired product with short reaction times in comparison to Law-esson s reagent. In addition, the aminothiophosphate resin dehydrates primary amides to nitriles. 

The azolides are able to participate in a wide variety of nucleophilic olysis reactions which form aldehydes, ketones, carboxylic acids, esters, amides, thiol esters, hydrazides and anhydrides (Scheme 143). In addition, 1-trifluoroacetylimidazole (252) is a convenient reagent for the conversion of aldoximes into nitriles (Scheme 144) (81601579). 

Sharghi, H., Niknam, K. Conversion of alcohols to amides using alumina-methanesulfonic acid (AMA) in nitrile solvents. Iranian Journal of Chemistry Chemical Engineering 1999,18, 36-39. 

The synthesis of a-homonojirimycin (1) has been carried ont from nojirimycin snlfite (25) (Scheme 4). Conversion of 25 to the nitrile 26, followed by benzoylation, and protection of the NH with TFAA afforded the nitrile 27. Hydrolysis of 27 in 90% TFA fnmished the corresponding amide, whose snbseqnent reaction with N2O4 gave carboxylic acid 28. Reduction of 28 afforded the alcohol 29, which nnderwent removal of the protecting groups to produce 1. 

The amide group of 16 can be converted to a nitrile with acetic anhydride in pyridine at room temperature to give the relatively unstable acid 18. Immediate hydrogenation of the nitrile with platinum oxide furnishes ( S)-4-amino-2-hydroxybutyric acid (19) in 30% overall yield (Scheme 1). Conversion of 18 to the stable benzhydryl ester 20 is accomplished by treatment with diazodiphenylmethane (84% yield) [26]. 

Based on van der Plas N-labeling study with pyrimidines, the following mechanism was deduced for the conversion of 9 to 10. Amide anion attack at the 2-position of pyrimidine 9 produces resonance stabilized anion 13. Fragmentation yields iminoyl bromide 14, which can directly form product (10), or alternatively can eliminate HBr to form nitrile 15, which then proceeds to 10. 

A versatile method for the conversion of aromatic and aliphatic primary amides to nitriles, using dibutyltin oxide as a catalytic neutral dehydrating agent, has been applied in various cases. The reaction temperature is about 110 °C, the reaction time is 12-18 h, and product yields are 70-95% [1145]. A reaction mechanism has been proposed. 

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. ... 

Other dehydration reactions include the conversion of primary amides to nitriles, aldehydes to nitriles (via the hydroxylamine) (eq 13), and carboxylic acids to ketenes (eq 14). ... 

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