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Original Articles

RING FLATTENING IN THIANTHRENE SULFONIUM BIS(CARBOMETHOXY)METHYLIDES

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Pages 63-66 | Received 01 Aug 1992, Accepted 10 Sep 1992, Published online: 23 Sep 2006

References

  • Ternay , A. L. Jr. and Lam , W. W. Phosphorous, Sulfur and Silicon in press, and references cited herein;
  • Kluba , M. , Harwood , J. , Casey , P. K. and Ternay , A. L. Jr. 1985 . J. Heterocyclic Chem. , 22 : 1261 ;
  • Ternay , A. L. Jr. , Baack , J. C. , Chu , S. S. C. , Napoleone , V. , Martin , G. and Alfaro , C. 1982 . J. Heterocyclic Chem. , 19 : 833
  • A flattened central ring leads to geometrics between a' and e' and with an intermediate rotation rate.
  • 50.3 MHz; CDCl3; 25°C.
  • Galloy , J. , Watson , W. H. , Craig , D. , Guidry , C. , Morgan , M. , McKellar , R. , Ternay , A. L. Jr. and Martin , G. 1983 . J. Heterocyclic Chem. , 20 : 399 In addition to Reference 1, see:.
  • Oki , M. and Yamada , Y. 1988 . Bull. Chem. Soc. Jpn. , 61 : 1181 For a related discussion of sulfonium salts see:.
  • Oki , M. 1985 . Applications of Dynamic NMR Spectroscopy to Organic Chemistry 407 Florida : VCH . The free energy of activation (δG‡) were obtained using the Eyring equation, ΔGc‡ = 4.575 Tc |9.972 + log10(Tc/Δvmax)|. ΔGc‡ = free energy of activation in cal mol−1; Tc = temperature of coalescence; Δvmax = maximum chemical shift difference (Hz) at very slow exchange:, p.
  • Gutowsky , H. S. and Holm , C. H. 1956 . J. Chem. Phys. 25 1228;
  • Gutowsky , H. S. and Saika , A. 1953 . J. Chem. Phys. 21 1688;
  • Gutowsky , H. S. , McCall , D. W. and Slichter , C. P. 1953 . J. Chem. Phys. 21 279;
  • Bloch , F. 1946 . Phys. Rev. 70 460.
  • Using the NMCXCH program provided by Nicolet Magnetics.
  • Ternay , A. L. Jr. and McKellar , R. Tc ≈ 310 K, ΔGc‡ ≈ = 15 Kcal mol−1, manuscript in preparation.
  • Ternay , A. L. 1981 . IUPAC Organic Sulfur Chemistry Edited by: Freidlina , R. Kh. 175 – 188 . New York : Pergamon Press . The X-ray structure of 2-chlorothioxanthone reveals an angle of fold of 173.5°:, in,pp.
  • 3.37 and 3.80 δ (200 MHz/CDCl3/25°C).
  • In general, it appears that gem-disubstituted systems are flattened relative to their less-substituted analogs.
  • Reactions were conducted under nitrogen. Melting points are uncorrected and chemical shifts referenced to internal TMS. TLC's were on silica gel with chloroform eluent and iodine visualization.
  • Some white solid had formed after refluxing for 1 h.
  • The column (length: 4.5 cm; diameter: 2.0 cm) was packed with 15 g of 200–325 mesh silica gel using chloroform.
  • Addition was exothermic and accompanied by various color changes.
  • CAUTION: The quench was quite exothermic and accompanied by significant foaming.
  • Ternay , A. L. Jr. , Ens , L. , Herrmann , J. and Evans , S. 1969 . J. Org. Chem. , 34 : 940 An earlier, different preparation of this compound produced an oil which solidified after several months:. The present scheme affords much improved yields.
  • The melting point was unchanged when the sample was cooled and remelted in a closed capillary tube.
  • Ternay , A. L. Jr. and Lam , W. W. Phosphorous, Sulfur and Silicon in press, and references cited herein;
  • Kluba , M. , Harwood , J. , Casey , P. K. and Ternay , A. L. Jr. 1985 . J. Heterocyclic Chem. , 22 : 1261 ;
  • Ternay , A. L. Jr. , Baack , J. C. , Chu , S. S. C. , Napoleone , V. , Martin , G. and Alfaro , C. 1982 . J. Heterocyclic Chem. , 19 : 833
  • A flattened central ring leads to geometrics between a' and e' and with an intermediate rotation rate.
  • 50.3 MHz; CDCl3; 25°C.
  • Galloy , J. , Watson , W. H. , Craig , D. , Guidry , C. , Morgan , M. , McKellar , R. , Ternay , A. L. Jr. and Martin , G. 1983 . J. Heterocyclic Chem. , 20 : 399 In addition to Reference 1, see:.
  • Oki , M. and Yamada , Y. 1988 . Bull. Chem. Soc. Jpn. , 61 : 1181 For a related discussion of sulfonium salts see:.
  • Oki , M. 1985 . Applications of Dynamic NMR Spectroscopy to Organic Chemistry 407 Florida : VCH . The free energy of activation (δG‡) were obtained using the Eyring equation, ΔGc‡ = 4.575 Tc |9.972 + log10(Tc/Δvmax)|. ΔGc‡ = free energy of activation in cal mol−1; Tc = temperature of coalescence; Δvmax = maximum chemical shift difference (Hz) at very slow exchange:, p.
  • Gutowsky , H. S. and Holm , C. H. 1956 . J. Chem. Phys. 25 1228;
  • Gutowsky , H. S. and Saika , A. 1953 . J. Chem. Phys. 21 1688;
  • Gutowsky , H. S. , McCall , D. W. and Slichter , C. P. 1953 . J. Chem. Phys. 21 279;
  • Bloch , F. 1946 . Phys. Rev. 70 460.
  • Using the NMCXCH program provided by Nicolet Magnetics.
  • Ternay , A. L. Jr. and McKellar , R. Tc ≈ 310 K, ΔGc‡ ≈ = 15 Kcal mol−1, manuscript in preparation.
  • Ternay , A. L. 1981 . IUPAC Organic Sulfur Chemistry Edited by: Freidlina , R. Kh. 175 – 188 . New York : Pergamon Press . The X-ray structure of 2-chlorothioxanthone reveals an angle of fold of 173.5°:, in,pp.
  • 3.37 and 3.80 δ (200 MHz/CDCl3/25°C).
  • In general, it appears that gem-disubstituted systems are flattened relative to their less-substituted analogs.
  • Reactions were conducted under nitrogen. Melting points are uncorrected and chemical shifts referenced to internal TMS. TLC's were on silica gel with chloroform eluent and iodine visualization.
  • Some white solid had formed after refluxing for 1 h.
  • The column (length: 4.5 cm; diameter: 2.0 cm) was packed with 15 g of 200–325 mesh silica gel using chloroform.
  • Addition was exothermic and accompanied by various color changes.
  • CAUTION: The quench was quite exothermic and accompanied by significant foaming.
  • Ternay , A. L. Jr. , Ens , L. , Herrmann , J. and Evans , S. 1969 . J. Org. Chem. , 34 : 940 An earlier, different preparation of this compound produced an oil which solidified after several months:. The present scheme affords much improved yields.
  • The melting point was unchanged when the sample was cooled and remelted in a closed capillary tube.

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