Various mechanisms of the formation of naphthalene and its substituted derivatives have been investigated by ab initio G3(MP2,CC)∕B3LYP∕6-311G∗∗ calculations of potential energy surfaces for the reactions of one and two C(2)H additions to styrene combined with RRKM calculations of product branching ratios under single-collision conditions. The results show that for the C(2)H + styrene reaction,...

physical-organic chemistry communities. Toluene portrays the simplest representative of an alkyl-substituted benzene molecule with the methyl group enhancing the reactivity toward radical and electrophile aromatic substitution compared to benzene. It is further considered as a crucial building block to form methyl-substituted polycyclic aromatic hydrocarbons (PAHs) such as 1and 2-methylnaphthal...

Florian Pevny, Emmanuel Di Piazza, Lucie Norel, Malte Drescher, Rainer F. Winter,* and St ephane Rigaut* Institut f€ ur Anorganische Chemie der Universit€ at Regensburg, Universit€ atsstrasse 31, D-93040 Regensburg, Germany, Fachbereich Chemie der Universit€ at Konstanz, Universit€ atsstrasse 10, D-78453 Konstanz, Germany, and UMR 6226 CNRS-Universit e de Rennes 1, Sciences Chimiques de Rennes,...

The donor–acceptor ability of frustrated Lewis pairs (FLPs) has led to widespread applications in organic synthesis. Single electron transfer from a donor base an acceptor acid can generate radical pair (FRP) depending on the substrate and energy required (thermal or photochemical) promote FLP into FRP system. Herein, we report Csp3–Csp cross-coupling reaction aryl esters with terminal alkynes ...

Recent theoretical research employing a continuum solvent model predicted that radical centers would enhance the acidity (RED-shift) of certain proton-donor molecules. Microhydration studies employing a DFT method are reported here with the aim of establishing the effect of the solvent micro-structure on the acidity of radicals with and without RED-shifts. Microhydration cluster structures were...

The crossed molecular beam experiment of the deuterated ethynyl radical (C(2)D; X(2)Sigma(+)) with benzene [C(6)H(6)(X(1)A(1g))] and its fully deuterated analog [C(6)D(6)(X(1)A(1g))] was conducted at a collision energy of 58.1 kJ mol(-1). Our experimental data suggest the formation of the phenylacetylene-d(6) via indirect reactive scattering dynamics through a long-lived reaction intermediate; ...

The work presented here investigates the dynamics of the photodissociation of ethyl ethynyl ether at 193.3 nm with photofragment translational spectroscopy and laser-induced fluorescence. The data from two crossed laser-molecular beam apparatuses, one with vacuum ultraviolet photoionization detection and one with electron bombardment detection, showed that only cleavage of the C–O bond to form ...

Cyclic C 5 H ( c -C H), the radical formed by substituting an ethynyl group CCH for hydrogen atom in 3 radical, has been detected first time space. The species is isomer of well-known linear l and ?6 kcal mol ?1 less stable. A total 17 rotational transitions were TMC-1 within 31.0–50.3 GHz range using Yebes 40m radio telescope. We derive a column density (9.0 ± 0.9) × 10 cm ?2 H. Additionally, ...

In this theoretical research, the mechanism of the C2H + C2H2 reaction is studied by high-level quantum-chemical methods and kinetics of the reaction is investigated by statistical rate theories. High-level electronic structure calculation methods including M06-2X, CCSD(T), CBS-Q and G4 methods are employed to explore the doublet potential energy surface of the reaction and compute the molecula...

We investigated the potential of 4'-C-substituted nucleosides for the treatment of HIV-1 and HBV. Of the nucleosides we prepared, several 4'-C-ethynyl-2'-deoxypurine nucleosides showed the most potent anti-HIV activity. However, two candidates, 4'-C-ethynyl-2'-deoxyguanosine and 9-(2-deoxy-4-C-ethynyl-beta-D-ribo-pentofuranosyl)-2,6-diaminopurine, were very toxic during in vivo study. On the ot...