51029-22-2Relevant academic research and scientific papers
Selective opening of ring C in the morphine skeleton by an unexpected cleavage of the C5-C6 bond in cycloadducts of thebaine and acyl nitroso compounds
Sheldrake, Gary N.,Soissons, Nicolas
, p. 789 - 791 (2006)
Acyl nitroso cycloadducts of the alkaloid thebaine undergo an unexpected cleavage of the C5-C6 bond when treated with 2 equiv of samarium(II) iodide in THF to give novel hexahydrobenzazocine products. A proposed mechanism for the transformation involves r
REACTIONS OF TRANSIENT C-NITROSOCARBONYL COMPOUNDS WITH DIENES, MONOOLEFINS, AND NUCLEOPHILES
Corrie, John E.T.,Kirby, Gordon W.,Mackinnon, John W.M.
, p. 883 - 886 (2007/10/02)
Nitrosocarbonylbenzene and nitrosocarbonylmethane, formed as transient intermediates by oxidation of benzo- and aceto-hydroxamic acid, respectively, with tetraethylammonium periodate, are trapped by cyclopentadiene to give the corresponding cycloadducts (5).The adduct (5; R=Ph) dissociates in solution at 80 deg C to reform nitrosocarbonylbenzene, which reacts with thebaine (1) to give (4; R=Ph) and with triphenylphosphine to give phenyl isocyanate.Cycloadducts of nitrosocarbonylbenzene with cyclohexa-1,3-diene (6) and with cyclo-octatetraene (7) have also been prepared.The adduct (3; R=Ph) of nitrosocarbonylbenzene and 9,10-dimethylanthracene, when heated with 1-allyl-3,4-methylenedioxybenzene, oct-1-ene, or 2,5-dimethylhexa-2,4-diene, gives the corresponding 'ene' reaction products of the olefins and nitrosocarbonylbenzene.When heated alone, the adduct (3; R=Ph) gives 9,10-dimethylanthracene, benzoic anhydride, and nitrous oxide.Oxidation of 2,4,6-trimethylbenzohydroxamic acid in the presence of thebaine gives the adduct (4; R=2,4,6-trimethylphenyl).However, 2,4,6-trimethylnitrosocarbonylbenzene is insufficiently stable to be isolated; in the absence of a diene it decomposes to give 2,4,6-trimethylbenzoic anhydride as the major product.
Formation and Dienophilic Reactions of Transient C-Nitrosocarbonyl Compounds
Kirby, Gordon W.,Sweeny, James G.
, p. 3250 - 3254 (2007/10/02)
Oxidation of benzohydroxamic acid with tetraethylammonium periodate in the presence of the conjugated diene thebaine (1) gave the cycloadduct 6β,14β-(N-benzoylepoxyimino)-6,14-dihydrothebaine (2; R = Ph), in high yield.The corresponding N-acetyl derivative (2; R = Me) was prepared similarly using acetoxyhydroxamic acid.Likewise, 2-benzoyl- and 2-acetyl-3,6-dihydro-2H-1,2-oxazine (5; R = Ph) and (5; R = Me) were obtained from buta-1,3-diene, and the N-benzoyl and N-acetyl derivatives of 9,10-epoxyimino-9,10-dihydro-9,10-dimethylanthracene (6; R = PhCO) and (6; R = Ac) from 9,10-dimethylanthracene (DMA).These reactions are believed to involve the formation of nitrosocarbonylbenzene or nitrosocarbonylmethane, representatives of a new class of transient, reactive species.The cycloadduct (6; R = Ac) decomposed in benzene at 60 deg C in the presence of thebaine (1) to give the thebaine adduct (2; R = Me) and DMA.First-order kinetics were observed for the release of DMA, consistent with slow dissociation of the adduct (6; R = Ac) followed by rapid capture of nitrosocarbonylmethane by thebaine.The related adduct (6; R = PhCO) behaved similarly.DMA adducts of the type (6) are valuable in studies on the reactions of nitrosocarbonyl compounds, especially with co-reactants sensitive to oxidation.Thus (6; R = Ac) and 1,3-diphenylisobenzofuran (7) reacted cleanly in benzene at 80 deg C to give the O-acetyloxime (10) of 1,2-dibenzoylbenzene, possibly via the N-acetylnitrone (9) derived from the initially formed cycloadduct (8).
