Journal of Physical Organic Chemistry

Cover image for Vol. 25 Issue 4

April 2012

Volume 25, Issue 4

Pages i–iii, 271–360

  1. Issue Information

    1. Top of page
    2. Issue Information
    3. Early Excellence Profiles
    4. Research Articles
    1. Issue Information (pages i–iii)

      Version of Record online: 27 MAR 2012 | DOI: 10.1002/poc.2947

  2. Early Excellence Profiles

    1. Top of page
    2. Issue Information
    3. Early Excellence Profiles
    4. Research Articles
  3. Research Articles

    1. Top of page
    2. Issue Information
    3. Early Excellence Profiles
    4. Research Articles
    1. Efficient additives to improve the catalytic effects of ferric(III) chloride on the reaction of N-vinylcarbazole: hydroquinone for methanolysis, hydrogen peroxide for cyclobutanation respectively (pages 272–277)

      Li-Qiang Liu, Dong-Qing Sun and Jing-Kui Yang

      Version of Record online: 26 JUL 2011 | DOI: 10.1002/poc.1892

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      Hydroquinone(HQ) combined with FeCl3 can reduce the methanolysis time of N-vinylcarbazole(NVC) in CH3OH from 9 hours to 1 hour, the addition of H2O2 successfully made the FeCl3 catalytic cyclobutanization of NVC in the yield from zero up to 33%.

    2. Theoretical analysis on geometries and electronic structures of antiaromatic pentalene and its N-substituted derivatives: monomer, oligomers and polymer (pages 278–286)

      Binyao Liu, Wei Shen, Xiaohua Xie, Lidan Deng and Ming Li

      Version of Record online: 4 AUG 2011 | DOI: 10.1002/poc.1907

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      The electronic structures of anti-aromatic pentalene and its nitrogen-containing heterocyclic analogs were computed DFT at the B3LYP/6-31G(d) level of theory. All monomers were singlet ground states, their respective dimers, trimers, and polymers are triplet ground states (with the exception of PP2 and II). The aromaticity/antiaromaticity and band structures of these molecules were analyzed. It predicted that polymers of CPP and CI with small band gaps could be potential conductors.

    3. Difference between 1H NMR signals of primary amide protons as a simple spectral index of the amide intramolecular hydrogen bond strength (pages 287–295)

      Nikolay Yu. Gorobets, Sergey A. Yermolayev, Thomas Gurley, Andrey A. Gurinov, Peter M. Tolstoy, Ilya G. Shenderovich and Nicholas E. Leadbeater

      Version of Record online: 4 AUG 2011 | DOI: 10.1002/poc.1910

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      The origins of the amide proton signals nonequivalence are discussed. The value Δδ(H) = δ(Hb) − δ(Ha) is suggested as a simple comparative spectral index of the intramolecular hydrogen bond strength in these and similar compounds. The effect of the intramolecular H-bond on the reactivity of the amide group towards electrophiles is studied.

    4. Towards mechanisms of bimolecular nucleophilic reactions in solution—probing the variation of the activation parameters in the reactions of aromatic compounds (pages 296–308)

      Vladislav M. Vlasov

      Version of Record online: 2 AUG 2011 | DOI: 10.1002/poc.1912

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      ΔH = δΔHσ + ΔH0; δΔH = δΔHext + δΔHint; δΔHint = (−0.3 ± 0.2) − (6.0 ± 0.1) ρ (r = 0.994, s = 1.7, n = 82) where ρ = ρ(k1). The charge development in the transition state (k1) in SN2, SNAr, SNV, and AdN and acyl-transfer reactions is mainly governed by the internal part of the activation enthalpy change, δΔHint. The deviations of the equation give a possibility to elucidate a change of TS structure or reaction mechanism.

    5. Effect of irradiation on ethyl 2-amino-4,5,6,7-tetrahydrobenzo[b]thiophene-3-carboxylate: an ESR study (pages 309–313)

      Ayhan Usta, Mehmet Birey, Nursen Sari, Aliye Altundas and Dilek Nartop

      Version of Record online: 25 AUG 2011 | DOI: 10.1002/poc.1915

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      Single crystals of ethyl 2-amino-4,5,6,7-tetrahydrobenzo[b]thiophene-3-carboxylate synthesized by Gewald method were irradiated for 72 h at 298K by using 60Co gamma source with dose speed of 0.864 k Gy/h. After irradiation, ESR measurements were carried out to study radiation induced radicals in the temperature range from 120 to 450K.

    6. Synthesis of and structure–property relationships in zinc complexes of bis-metaphenylene semiquinone biradical species (pages 314–321)

      Joseph C. Sloop, David A. Shultz, Tashni Coote, Benjamin Shepler, Ubie Sullivan, Jeff W. Kampf and Paul D. Boyle

      Version of Record online: 22 AUG 2011 | DOI: 10.1002/poc.1917

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      We report the synthesis of three new bis(ZnII(SQ)TpCum,Me) complexes containing the bis-metaphenylene coupling fragment. Using electron paramagnetic resonance, ab initio computations and superconducting quantum interference device magnetometry we show how spin-density is affected by the bis-metaphenylene system substituents.

    7. Chemical reactivity of lithium-doped fullerenes (pages 322–326)

      Pablo A. Denis

      Version of Record online: 16 AUG 2011 | DOI: 10.1002/poc.1918

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      Lithium doping significantly increases the free radical addition energies to fullerenes.

    8. The substituent effect on the UV energy of 4,4′-disubstituted benzylideneanilines (pages 327–333)

      Guanfan Chen, Chenzhong Cao, Bingtao Lu and Bin Sheng

      Version of Record online: 24 AUG 2011 | DOI: 10.1002/poc.1919

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      For 4, 4′-disubstituted benzylideneanilines with an imine bridging group (C = N), the substituent effect on their UV energy is different from that on UV energy of substituent stilbenes with a bridge group (C = C). It is not only related to the σCCex, but also associated with the σp. And it was found that the Δσ2 is a better parameter than the σXY to scale the substituent cross-interaction effect on the UV wavenumbers of XBAY molecules.

    9. Theoretical studies of the structural, electronic and optical properties of carbazole-based compounds (pages 334–342)

      Lei-Jiao Li, Fu-Quan Bai and Hong-Xing Zhang

      Version of Record online: 18 AUG 2011 | DOI: 10.1002/poc.1920

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      In different carbazole-linked functional groups, (1) enlarging the π-conjugated area, the corresponding spectra for these compounds red shifted markedly; (2) by introducing the electron-donor such as carbazole, the spectra blue shifted slightly; (3) compared with diphenylamine derivative, the spectra for these compounds are hardly influenced by introducing an electron-acceptor or heterocyclic substitution.

    10. Kinetic studies of the reaction of phenacyl bromide derivatives with sulfur nucleophiles (pages 343–350)

      Gamal Abdel-Nasser Gohar, Sherine Nabil Khattab, Omaima Osman Farahat and Hosam Hassan Khalil

      Version of Record online: 25 AUG 2011 | DOI: 10.1002/poc.1921

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      Kinetic studies of the reaction of phenacyl bromide derivatives with sulfur nucleophiles

      The reaction of the substituted phenacyl bromides with thioglycolic acid and thiophenol in methanol underwent the nucleophilic substitution SN2 mechanism. The reaction was found to proceed by a concerted mechanism. Kinetic data and structure-reactivity relationships are consistent with this concept.

    11. Computational study of the proton affinity and basicity of structurally diverse α1-adrenoceptor ligands (pages 351–360)

      C. Matijssen, G. K. Kinsella, G. W. Watson and I. Rozas

      Version of Record online: 25 OCT 2011 | DOI: 10.1002/poc.1940

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      A conformational analysis of 26 agonist/antagonist of α1-adrenoceptor was carried out previous to the computation at DFT level of their proton affinity, basicity (using PCM aqueous solvation) and their corresponding pKa.