Sample records for 1,4-diazines

  1. Synthesis of quinoxalines or quinolin-8-amines from N-propargyl aniline derivatives employing tin and indium chlorides.


    Aichhorn, Stefan; Himmelsbach, Markus; Schöfberger, Wolfgang


    Pyrazino compounds such as quinoxalines are 1,4-diazines with widespread occurrence in nature. Quinolin-8-amines are isomerically related and valuable scaffolds in organic synthesis. Herein, we present intramolecular main group metal Lewis acid catalyzed formal hydroamination as well as hydroarylation methodology using mono-propargylated aromatic ortho-diamines. The annulations can be conducted utilizing equal aerobic conditions with either stannic chloride or indium(iii) chloride and represent primary examples for main group metal catalyzed 6-exo-dig and 6-endo-dig, respectively, cyclizations in such settings. Both types of reactions can also be utilized in a one-pot manner starting from ortho-nitro N-propargyl anilines using stoichiometric amounts SnCl2·2H2O or In powder. Mechanistic considerations are presented regarding the substituent-depending regioselectivity.

  2. C-H bond strengths and acidities in aromatic systems: effects of nitrogen incorporation in mono-, di-, and triazines.


    Wren, Scott W; Vogelhuber, Kristen M; Garver, John M; Kato, Shuji; Sheps, Leonid; Bierbaum, Veronica M; Lineberger, W Carl


    The negative ion chemistry of five azine molecules has been investigated using the combined experimental techniques of negative ion photoelectron spectroscopy to obtain electron affinities (EA) and tandem flowing afterglow-selected ion tube (FA-SIFT) mass spectrometry to obtain deprotonation enthalpies (Δ(acid)H(298)). The measured Δ(acid)H(298) for the most acidic site of each azine species is combined with the EA of the corresponding radical in a thermochemical cycle to determine the corresponding C-H bond dissociation energy (BDE). The site-specific C-H BDE values of pyridine, 1,2-diazine, 1,3-diazine, 1,4-diazine, and 1,3,5-triazine are 110.4 ± 2.0, 111.3 ± 0.7, 113.4 ± 0.7, 107.5 ± 0.4, and 107.8 ± 0.7 kcal mol(-1), respectively. The application of complementary experimental methods, along with quantum chemical calculations, to a series of nitrogen-substituted azines sheds light on the influence of nitrogen atom substitution on the strength of C-H bonds in six-membered rings.


    SciTech Connect

    Wang, Zhe-Chen; Cole, Callie A.; Bierbaum, Veronica M.; Snow, Theodore P.


    Studies of interstellar chemistry have grown in number and complexity by both observations and laboratory measurements, and nitrogen-containing aromatics have been implicated as important interstellar molecules. In this paper, the gas-phase collision induced dissociation (CID) processes of protonated pyridazine (1,2-diazine), pyrimidine (1,3-diazine), and pyrazine (1,4-diazine) cations (C{sub 4}H{sub 5}N{sub 2} {sup +}) are investigated in detail both experimentally and theoretically. The major neutral loss for all three CID processes is HCN, leading to the formation of C{sub 3}H{sub 4}N{sup +} isomers; our density functional theory (DFT) calculations support and elucidate our experimental results. The formation of C{sub 3}H{sub 4}N{sup +} isomers from the reaction of abundant interstellar acrylonitrile (CH{sub 2}CHCN) and H{sup +}is also studied employing DFT calculations. Our results lead to a novel mechanism for interstellar protonated diazine formation from the consecutive reactions of CH{sub 2}CHCN+ H{sup +} + HCN. Moreover, our results motivate the continuing search for interstellar C{sub 3}H{sub 4}N{sup +} isomers as well as polycyclic aromatic N-containing hydrocarbons (PANHs)

  4. Quantum symmetry and photoreactivity of azabenzenes

    SciTech Connect

    Chesko, James David Mark


    The fundamental processes associated with a photochemical reaction are described with reference to experimental properties of azabenzenes. Consideration of both excitation and relaxation processes led to presentation of the symmetry propagator, a unifying principle which maps system fluctuations (perturbations acting on an initial state) with dissipations (transitions to different states), thus directing the energy flow along competing reactive and nonreactive pathways. A coherent picture of relaxation processes including chemical reactions was constructed with the aid of spectroscopic data. Pyrazine (1,4 diazine) possesses vibronically active modes which provide an efficient mechanism for internal conversion to the first excited singlet state, where other promoting modes of the correct symmetry induce both intersystem crossing to the triplet manifold, isomerization through diaza-benzvalene, and chemical reactions through cycloreversion of dewar pyrazine to yield HCN plus an azete. At higher energies simple H atom loss and internal conversion become more predominant, leading to ring opening followed by elimination of methylene nitrile and ground state reaction products. Efficiency of chemical transformations as dissipation mechanisms versus competing fluorescence, phosphorescence and radiationless relaxation was mapped from near ultraviolet to far ultraviolet by photodissociation quantum yields into reaction channels characterized by molecular beam photofragment translational spectroscopy. A reaction path model for azabenzene photochemistry was presented and tested against experiment. Presence of undiscovered channels in other azabenzene systems was predicted and verified. The dominant process, HCN elimination, was resolved into three distinct channels. Both molecular and atomic hydrogen elimination was observed, the former with significant vibrational excitation. Small yields of isomerization products, acetylene and N2, were also observed.

  5. Effects of static vs. tidal hydrology on pollutant transformation in wetland sediments.


    Catallo, W James; Junk, Thomas


    This work addressed effects of hydrology on biogeochemical processes relevant to pollutant chemical transformation in wetland sediments. Microcosms were designed to impose three hydrologic conditions on salt marsh sediments: (i) drained-oxidized redox potenial (Eh); (ii) flooded-reduced Eh and, (iii) diurnal tide-oscillating Eh. The test chemicals were N- and/or S-heterocycles (NSHs) including quinoxaline (1,4-benzodiazine), 2-methylquinoxaline(2-methyl-1,4-benzodiazine), 2,3-dimethylquinoxalinen (2,3-dimethyl-1,4-benzodiazine), phenazine (2,3,5,6-dibenzo-1,4-diazine), acridine (2,3,5,6-dibenzopyridine), dibenzothiophene (2,3,5-dibenzothiophene), phenothiazine (dibenzo-1,4-thiazine), and phenanthridine (2,3-benzoisoquinoline). Biogeochemical processes reflected the hydrologic conditions in ways analogous to field settings, e.g., Eh characteristics were drastically different: static (flooded and drained) systems had reduced (mu = -428 mV +/- 57) and oxidized (mu = +73 mV +/- 32) values, respectively, with no evidence of periodic variation while the tidal systems exhibited regularly oscillating Eh (amplitudes 40-250 mV). Sediment trace gases also corresponded to the Eh, with the major species detected being CO2 and H2O (drained, tidal) vs. CO2 + H2O + sulfides + methane (flooded). The NSH transformation rates were different in each hydrologic regime and decreased as follows: tidal > or = drained > flooded. These results indicated that there were subtle differences in NSH processing in drained and tidal systems, but both of these systems transformed NSHs faster and to lower levels than flooded sediments. These data suggest that in situ remediation options that preserve wetland integrity and tidal hydrology can be as or more effective than static conditions that obtain in approaches such as impoundment and excavation-upland placement.

  6. En route to controlled catalytic CVD synthesis of densely packed and vertically aligned nitrogen-doped carbon nanotube arrays

    PubMed Central

    Pattinson, Sebastian W; Geiser, Valérie; Shaffer, Milo S P


    Summary The catalytic chemical vapour deposition (c-CVD) technique was applied in the synthesis of vertically aligned arrays of nitrogen-doped carbon nanotubes (N-CNTs). A mixture of toluene (main carbon source), pyrazine (1,4-diazine, nitrogen source) and ferrocene (catalyst precursor) was used as the injection feedstock. To optimize conditions for growing the most dense and aligned N-CNT arrays, we investigated the influence of key parameters, i.e., growth temperature (660, 760 and 860 °C), composition of the feedstock and time of growth, on morphology and properties of N-CNTs. The presence of nitrogen species in the hot zone of the quartz reactor decreased the growth rate of N-CNTs down to about one twentieth compared to the growth rate of multi-wall CNTs (MWCNTs). As revealed by electron microscopy studies (SEM, TEM), the individual N-CNTs (half as thick as MWCNTs) grown under the optimal conditions were characterized by a superior straightness of the outer walls, which translated into a high alignment of dense nanotube arrays, i.e., 5 × 108 nanotubes per mm2 (100 times more than for MWCNTs grown in the absence of nitrogen precursor). In turn, the internal crystallographic order of the N-CNTs was found to be of a ‘bamboo’-like or ‘membrane’-like (multi-compartmental structure) morphology. The nitrogen content in the nanotube products, which ranged from 0.0 to 3.0 wt %, was controlled through the concentration of pyrazine in the feedstock. Moreover, as revealed by Raman/FT-IR spectroscopy, the incorporation of nitrogen atoms into the nanotube walls was found to be proportional to the number of deviations from the sp2-hybridisation of graphene C-atoms. As studied by XRD, the temperature and the [pyrazine]/[ferrocene] ratio in the feedstock affected the composition of the catalyst particles, and hence changed the growth mechanism of individual N-CNTs into a ‘mixed base-and-tip’ (primarily of the base-type) type as compared to the purely