Norrish reaction

A Norrish reaction in organic chemistry is a photochemical reaction taking place with ketones and aldehydes. Such reactions are subdivided into Norrish type I reactions and Norrish type II reactions. The reaction is named after Ronald George Wreyford Norrish. While of limited synthetic utility these reactions are important in the photo-oxidation of polymers such as polyolefins, polyesters, certain polycarbonates and polyketones. The Norrish type I reaction is the photochemical cleavage or homolysis of aldehydes and ketones into two free radical intermediates (α-scission). The carbonyl group accepts a photon and is excited to a photochemical singlet state. Through intersystem crossing the triplet state can be obtained. On cleavage of the α-carbon bond from either state, two radical fragments are obtained. The size and nature of these fragments depends upon the stability of the generated radicals; for instance, the cleavage of 2-butanone largely yields ethyl radicals in favor of less stable methyl radicals. Several secondary reaction modes are open to these fragments depending on the exact molecular structure. The fragments can simply recombine to the original carbonyl compound, with racemisation at the α-carbon. The acyl radical can lose a molecule of carbon monoxide, forming a new carbon radical at the other α-carbon, followed by formation of a new carbon–carbon bond between the radicals. The ultimate effect is simple extraction of the carbonyl unit from the carbon chain. The rate and yield of this product depends upon the bond-dissociation energy of the ketone's α substituents. Typically the more α substituted a ketone is, the more likely the reaction will yield products in this way. The abstraction of an α-proton from the carbonyl fragment may form a ketene and an alkane. The abstraction of a β-proton from the alkyl fragment may form an aldehyde and an alkene. The synthetic utility of this reaction type is limited, for instance it often is a side reaction in the Paternò–Büchi reaction.