Grignard reagents reaction with acyl halides

Decomposition of azo compounds and peroxides provides the alkoxyamine by the nitroxide-trapping of the primary radicals [29]. The radicals produced by hydrogen abstraction with oxy radicals are also trapped by the nitroxide [242, 243]. In the photoreaction, alkoxyamines were isolated with high yields [244]. The reactions of Grignard reagents with nitroxides [215] and the coupling reaction of sodium nitroxides with bromo compounds [234,235] are also used. The hydrolysis of 56 followed by the reaction with acyl or alkyl halides afforded alkoxyamines with various functional groups,63 (Eq. 68) [245-251] ... 

The reactions of Grignard reagents with different types of carbonyl groups yield a number of important functional groups. For example, reaction with formaldehyde yields 1° alcohols with higher aldehydes, 2° alcohols with ketones, 3° alcohols with esters, 3° alcohols with acyl halides, ketones with N,N-dialkylformamides, aldehydes and with carbon dioxide, carboxylic acids. 

Acid halides are among the most reactive of carboxylic acid derivatives and can be converted into many other kinds of compounds by nucleophilic acyl substitution mechanisms. The halogen can be replaced by -OH to yield an acid, by —OCOR to yield an anhydride, by -OR to yield an ester, or by -NH2 to yield an amide. In addition, the reduction of an acid halide yields a primary alcohol, and reaction with a Grignard reagent yields a tertiary alcohol. Although the reactions we ll be discussing in this section are illustrated only for acid chlorides, similar processes take place with other acid halides. 

Acylated glycosyl thiocyanates are made by treatment of acylated glycopyranosyl halides with potassium thiocyanate.30 Reaction at —40° with a Grignard reagent affords alkyl or aryl 1-thioglycosides.54... 

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