ABSTRACT:
J.Phys.Chem.A 2000, 104: 3 557 - 561
Detection of Transient Intermediates in the Photochemical Reaction of Hydrogen Peroxide with Dimethyl sulfoxide by Time-Resolved EPR Techniques
Formation of peroxycarboximidic acid (1) is not rate-determining in the reaction of nitrile with alkaline hydrogen peroxide to form amide and oxygen; the yield of amide based on H2O2 varies from 20 to 60%.When dimethyl sulfoxide (DMSO), a reactive substrate, is added, the rate is independent of (DMSO) and governed in turn by a rate-determining addition of HOO- to nitrile.This reaction gives a reliable á-value of kHOO-/kHO-, which is 10000 for benzonitrile.A facile conversion of nitrile to amide may be achieved by the reaction in the presence of DMSO, unacco mpanied by side reactions such as the epoxyamide formation from á,â-unsaturated nitrile.Kinetics and product analysis suggest that a predominant reaction is not a non-radical oxidation of H2O2 with 1 but a radical decomposition of H2O2 which is induced by the homolysis of anion of 1 (1A).No singlet oxygen could be trapped chemically.The reaction of superoxide ion, O2-., with acetonitrile is shown to be analogous to that of HOO-; the decomposition of O2-. is fast in the presence of MeCN and DMSO in benzene, affording acetamide and dimethyl sulfone.
I'm thinking that you could take a nitrile, and using the above synthesis convert this to an amide in high yeilds, and follow that with a reduction or Hofmann rearrangement to yeild an amine.
It's an idea anyway. I guess i'm just waiting for someone to shoot me down or tell me that someone has been there and done that and got a t-shirt.
Flip
Conclusion /nm./: the place where you got tired of thinking.
