IV-Haloamides

Scheme 4. Synthesis of 4-substituted y-lactones by photolysis of iV-haloamides [13]...

The principal product from irradiation of quinoline-2-carbonitrile in propan-2-ol-aqueous HCl is the radical-derived dimer (225). The factors influencing the photoaddition of iV-haloamides to alkenes have been examined/ and full details... 

There are related procedures involving iV-haloamides which lead to lactones via iminolactone intermediates. ... 

The first intermediates of the Hofmann reaction are A -haloamides e.g. 1), which are subsequently converted to alkaline salts e.g. 2). Both intermediates can be isolated under carefully controlled conditions. Kinetic evidence on both the substituent and isotope effects in the Hofmann rearrangement of various IV-halobenzamides (1) in an aqueous sodium hydroxide solution strongly support a concerted mechanism, involving the bridged anion (3), shown in Scheme 6. 

Chlorination of Alkenes and Alkynes. The haloamidation of olefins was carried out hy reaction of IV-haloimides (X = Cl, Br) with nitriles in the presence of Lewis acids. It was presumed that the reaction involves nucleophilic attack of nitrile on the halonium ion followed by hydrolysis of the products (eq 38). ... 

Carbonylation Reactions. A three-component palladium-catalyzed amidocarbonylation reaction provides IV-acylamino acids from aromatic and aliphatic aldehydes or acetals with amides under elevated CO pressure (60 bar) in the presence of PdBr2, PPhs, LiBr, an acid additive (typically H2SO4), and iV-methyl-2-pyrrolidone. Mechanistically, the palladium-catalyzed amidocarbonylation reaction is proposed to proceed through the in situ formation of an a-haloamide and Pd(0) species, which can undergo oxidative addition, followed by CO insertion, and lastly hydrolysis of the acyl palladium complex to afford the product and regenerate the catalyst (eq 45). 

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