Sample records for azirines

  1. Photoinduced reactions of both 2-formyl-2H-azirine and isoxazole: A theoretical study based on electronic structure calculations and nonadiabatic dynamics simulations

    Energy Technology Data Exchange (ETDEWEB)

    Cao, Jun, E-mail: [Guizhou Provincial Key Laboratory of Computational Nano-Material Sciences, Guizhou Normal College, Guiyang, Guizhou 550018, China and Key Laboratory of Theoretical and Computational Photochemistry, Ministry of Education, College of Chemistry, Beijing Normal University, Beijing 100875 (China)


    In the present work, the combined electronic structure calculations and dynamics simulations have been performed to explore photocleavages of 2-formyl-2H-azirine and isoxazole in the gas phase and the subsequent rearrangement reactions. The carbonyl n → π{sup *} transition induces a cleavage of the C—N single bond of 2-formyl-2H-azirine to yield β-formylvinylnitrene in open-shell singlet state. However, the n → π{sup *} excitation of the imine chromophore results in a cleavage of the C—C single bond, producing a nitrile ylide intermediate through an internal conversion to the ground state. β-formylvinylnitrene and nitrile ylide with the carbonyl group are easily transformed into 2-formyl-2H-azirine and oxazole, respectively. The N—O bond cleavages on both S{sub 1}({sup 1}ππ{sup *}) and S{sub 2}({sup 1}n{sub N}π{sup *}) of isoxazole are ultrafast processes, and they give products of 2-formyl-2H-azirine, 3-formylketenimine, HCN + CHCHO, and HCO + CHCHN. Both 2H-azirines and ketenimines were suggested to be formed from the triplet vinylnitrenes by intersystem crossing in the previous studies. However, our calculations show that the singlet β-formylvinylnitrene is responsible for the formation of 2-formyl-2H-azirine and 3-formylketenimine, and the singlet vinylnitrenes can play a key role in the photoinduced reactions of both 2H-azirines and isoxazoles.

  2. Annulation Reactions of Donor-Acceptor Cyclopropanes with (1-Azidovinyl)benzene and 3-Phenyl-2H-azirine. (United States)

    Curiel Tejeda, Joanne E; Irwin, Lauren C; Kerr, Michael A


    Under the influence of heat and Lewis acid, donor/acceptor cyclopropanes underwent annulation reactions with (1-azidovinyl)benzene and 3-phenyl-2H-azirine to form an unusual azabicyclic scaffold with an imbedded aziridine. The mechanism of reaction is believed to proceed via a vinyl nitrene intermediate. PMID:27598518

  3. Excited-state dynamics of oxazole: A combined electronic structure calculations and dynamic simulations study (United States)

    Cao, Jun; Xie, Zhi-Zhong; Yu, Xiaodong


    In the present work, the combined electronic structure calculations and surface hopping simulations have been performed to investigate the excited-state decay of the parent oxazole in the gas phase. Our calculations show that the S2 state decay of oxazole is an ultrafast process characterized by the ring-opening and ring-closure of the five-membered oxazole ring, in which the triplet contribution is minor. The ring-opening involves the Osbnd C bond cleavage affording the nitrile ylide and airine intermediates, while the ring-closure gives rise to a bicyclic species through a 2sbnd 5 bond formation. The azirine and bicyclic intermediates in the S0 state are very likely involved in the phototranspositions of oxazoles. This is different from the previous mechanism in which these intermediates in the T1 state have been proposed for these phototranspositions.

  4. The synthesis of (R)- and (S)-[N-methyl-11C]β, β-difluoromethamphetamine for the investigation of the binding mechanism of biogenic amines in vivo

    International Nuclear Information System (INIS)

    In an attempt to elucidate the contribution of the extent of nitrogen protonation on the in vivo binding of methamphetamine in the brain, the enantiomers of [N-methyl-11C]β,β-difluoroamphetamine (4) were prepared for use in positron emission tomography (PET) studies. Thus, the enantiomers of β,β-difluoroamphetamine were prepared from trans-β-methylstyrene, via bromination, conversion into the azirine, fluorination and resolution as the tartrate salts. (R)- and (S)-β,β-difluoroamphetamine (3) were then each labelled with carbon-11 (t1/2=20.4 min) by N-methylation of the corresponding homochiral β,β-difluoroamphetamine with [11C]methyl iodide. The labelled products were each synthesised, purified and formulated in 35 min, starting from [11C]carbon dioxide in 15-16% decay-corrected radiochemical yield, with a radiochemical purity of >99% and specific radioactivity of 50-150 GBq μmol-1 at end of synthesis