Synthesis 2008(14): 2303-2306  
DOI: 10.1055/s-2008-1067145
PSP
© Georg Thieme Verlag Stuttgart ˙ New York

2,5-Dihydroxyterephthalates, 2,5-Dichloro-1,4-benzoquinone-3,6-dicarbox­ylates, and Polymorphic 2,5-Dichloro-3,6-dihydroxyterephthalates

Lukas Hintermann, Keisuke Suzuki*
Department of Chemistry, Tokyo Institute of Technology, 2-12-1 O-okayama, Meguro-ku, Tokyo 152-8551, Japan
Fax: +81(3)57342788; e-Mail: [email protected];
Further Information

Publication History

Received 7 May 2008
Publication Date:
18 June 2008 (online)

Abstract

Reaction of 2,5-dihydroxycyclohexa-1,4-diene-1,4-dicarboxylates with one equivalent of N-chlorosuccinimide cleanly gives 2,5-dihydroxyterephthalates; reaction with four equivalents of N-chlorosuccinimide gives 2,5-dichloro-1,4-benzoquinone-3,6-dicarboxylates instead. The latter compounds react with sodium dithionite to give 2,5-dichloro-3,6-dihydroxyterephthalates, which will find use in the study of polymorphic phase changes.

    References

  • 2a Modern Arene Chemistry   Astruc D. Wiley-VCH; Weinheim: 2002. 
  • 2b Hintermann L. Nachr. Chem.  2005,  53:  776 
  • 3 Succinylsuccinate (or: succinylosuccinate) is a trivial name for esters of 2,5-dioxocyclohexane-1,4-dicarboxylic acid (or, in the more stable enol form: 1,4-dihydroxycyclohexa-1,4-diene dicarboxylic acids), obtained by the condensation of two molecules of succinic esters, compare: Nielsen AT. Carpenter WR. Org. Synth. Coll. Vol. V   John Wiley & Sons; London: 1973.  p.288 
  • With Br2:
  • 4a Herrmann F. Justus Liebigs Ann. Chem.  1882,  211:  306 
  • 4b Bagrov FV. Bagrov DF. Russ. J. Org. Chem.  1994,  30:  637 
  • With MnO2:
  • 4c Padias AB. Hall HK. J. Org. Chem.  1985,  50:  5417 
  • 4d Itami K. Palmgren A. Thorarensen A. Bäckvall J.-E. J. Org. Chem.  1998,  63:  6466 
  • 5 Hantzsch A. Zeckendorf A. Ber. Dtsch. Chem. Ges.  1887,  20:  1308 
  • 6a Liebermann H. Lewin G. Gruhn A. Gottesmann E. Lisser D. Schonda K. Justus Liebigs Ann. Chem.  1934,  513:  156 
  • 6b Neidlein R. Throm S. Arch. Pharm. (Weinheim, Ger.)  1980,  313:  572 
  • 7a von der Crone J, and Pugin A. inventors; US  3,130,195.  1964
  • 7b Jaffe EE. inventors; US  3,124,582.  1964
  • Compare:
  • 7c Imai M, Ikuta H, Akahori H, Hasegawa K, Asano M, and Tsujimoto M. inventors; JP  57185237.  1982
  • 7d Altiparmakian R. Helv. Chim. Acta  1978,  61:  1146 
  • 8 Hantzsch A. Ber. Dtsch. Chem. Ges.  1915,  48:  797 
  • 9a Curtin DY. Byrn SR. J. Am. Chem. Soc.  1969,  91:  1865 
  • 9b Curtin DY. Byrn SR. J. Am. Chem. Soc.  1969,  91:  6102 
  • 9c Swiatkiewicz J. Prasad PN. J. Am. Chem. Soc.  1982,  104:  6913 
  • 9d Strohmeier M. Orendt AM. Alderman DW. Grant DM. J. Am. Chem. Soc.  2001,  123:  1713 
  • 10a Byrn SR. Curtin DY. Paul IC. J. Am. Chem. Soc.  1972,  94:  890 
  • 10b Yang Q.-C. Richardson MF. Dunitz JD. J. Am. Chem. Soc.  1985,  107:  5535 
  • 10c Yang Q.-C. Richardson MF. Dunitz JD. Acta Crystallogr., Sect. B.  1989,  45:  312 
  • 10d Richardson MF. Yang Q.-C. Novotny-Bregger E. Dunitz JD. Acta Crystallogr., Sect. B  1990,  46:  653 
  • 11a Yatsenko AV. J. Mol. Model.  2003,  9:  207 
  • 11b Swerts B. Van Droogenbroeck J. Peeters A. Van Alsenoy C. J. Phys. Chem. A  2002,  106:  4245 
  • 11c Peeters A. Lenstra ATH. Van Doren VE. Van Alsenoy C. THEOCHEM  2001,  546:  25 
  • 11d Peeters A. Lenstra ATH. Van Doren VE. Van Alsenoy C. THEOCHEM  2001,  546:  17 
  • 11e Ceolin R. Toscani S. Agafonov V. Dugue J. J. Solid State Chem.  1992,  98:  366 
  • 12a Asano M, Hasegawa K, Akahori H, and Tsujimoto M. inventors; EP  55,847.  1982
  • 12b Morishima S, Wariishi K, Shibata M, and Ishida T. inventors; EP  820,057.  1998
  • Thermal transesterification of β-oxo esters (in the absence of a catalyst) is an old reaction:
  • 13a Peters T. Justus Liebigs Ann. Chem.  1890,  257:  353 
  • 13b Cohn P. Monatsh. Chem.  1900,  21:  200 
  • 13c Bader AR. Cummings LO. Vogel HA. J. Am. Chem. Soc.  1951,  73:  4195 
  • 13d Witzeman JS. Tetrahedron Lett.  1990,  31:  1401 
  • 14 Sinnreich J. Batzer H. Helv. Chim. Acta  1979,  62:  1682 
  • 15a Taber DF. Amedio JC. Patel YK. J. Org. Chem.  1985,  50:  3618 
  • 15b Christoffers J. Önal N. Eur. J. Org. Chem.  2000,  1633 
  • 16 Grandmougin E. J. Prakt. Chem.  1907,  76:  124 
  • 17 This pseudo-polymorphism is analogous to that described for the bromo analogue of 4b, for which X-ray crystal structures of both the solvent-free substance and a solvate are reported: Näther C. Nagel N. Bock H. Seitz W. Havlas Z. Acta Crystallogr., Sect. B.  1996,  52:  697 
1

Current address: L. Hintermann, Institute of Organic Chemistry, RWTH, Aachen, Germany.