Transition Metal Catalyzed the Double Hydrohydroxymethylation of Carbonyl Compounds by a Carbon Monoxide-Water System

전이금속촉매-일산화탄소-물계에 의한 카르보닐화합물의 이중 히드로히드록시메틸화 반응

  • Sang Chul Shim (Department of Industrial Chemistry, Kyungpook National University) ;
  • Kyung Eun Min (Department of Industrial Chemistry, Kyungpook National University) ;
  • Keun Tae Huh (Department of Industrial Chemistry, Kyungpook National University)
  • 심상철 (경북대학교 공과대학 공업화학과) ;
  • 민경은 (경북대학교 공과대학 공업화학과) ;
  • 허근태 (경북대학교 공과대학 공업화학과)
  • Published : 1986.02.20

Abstract

Dialdehydes such as adipaldehyde, glutaraldehyde, and succinaldehyde were readily reduced to give their corresponding 1,6-hexanediol, 1,5-pentanediol, and 1,4-butanediol in good yields in the presence of catalytic amount of hexarhodium hexadecacarbonyl or iron pentacarbonyl in water and methoxyethanol or ethanol at 180$^{\circ}C$ for 4 hr under carbon monoxide atmosphere. Under the same reaction conditions, diketones such as 2,5-hexanedione, 2,4-pentanedione, and 2,3-butanedione afforded their corresponding 2,5-hexanediol, 2,4-pentanediol and 2,3-butanediol in moderate yields. For double hydrohydroxymethylation of dialdehydes or diketones, rhodium or iron carbonyl complexes are more effective than others. Particularly, benzoquinone gave hydroquinone quantitatively.

Keywords

References

  1. Chem. Lett. T. Kitamura;T. Joh;N. Hagihara
  2. Bull. Chem. Soc. Jpn. v.49 Y. Watanabe;S.C. Shim;T. Mitsudo;M. Yamashita;Y. Takegami
  3. Chem. Lett. Y. Watanabe;Y. Shimizu;K. Takatsuki;Y. Takegami
  4. Tetrahedron Lett. S.C. Shim;S. Antebi;H. Alper
  5. J. Org. Chem. v.50 S.C. Shim;S. Antebi;H. Alper
  6. J. Kor. Chem. Soc. v.23 H.S. Kim;S. C. Shim
  7. 27th Symposium on Organometallic Chemistry v.B105 S. Mura. hashi;K. Ito;T. Maeda
  8. Inorg. Chem. v.18 D.J. Darensberg;M.Y. Darensberg;N. Walker;J.A. Froelich;H.L. Barros
  9. Tetrahedron Lett. S.C. Shim;K.N. Choi
  10. Chem. Lett. T. Okano;K. Fujiwara;H. Konishi;J. Kiji
  11. European Patent, EP 0146291 A1 S.C. Shim;H. Alper;D.J.H. Smith
  12. J. Am. Chem. Soc. v.100 R.B. King;C.C. Frazier;R.M. Hanes;A.D. King
  13. J. Am. Chem. Soc. v.103 A.D. King, Jr.;R.B. King;D.B. Yang
  14. Chem. Lett. Y. Sugi;A. Matsuda;K. Bando;K. Murata
  15. Tetrahedron Lett. A.F.M. Iqbal
  16. J. Am. Chem. Soc. v.72 J. Fakstorp;D. Raleigh;L.E. Shniepp
  17. Tetrahedron S.C. Shim;K.T. Huh;W.H. Park
  18. Bull. Chem. Soc. Jpn v.49 Y. Watanabe;S. C. Shim;T. Mitsudo;M. Yamashita;Y. Takegami
  19. J. Am. Chem. Soc. v.99 H. Kang;C.H. Mauldrin;T. CCle;W. Siegeir;K. Cann;R. Pettit
  20. J. Am. Chem. Soc. v.71 J. English, Jr.;G.W. Barber
  21. J. Chem. Soc. Perken II P.M. Hardy;A.C. Nicholls;H.N. Rydon
  22. J. Am. Chem. Soc. v.101 C. Ungermann;V. Landis;S.A. Moya;H. Cohen;H. Walker;R. G. Pearson;R.G. Rinker;P.C. Ford
  23. J. Am. Chem. Soc. v.68 L.C. Keagle;W. H. Hartung
  24. J. Am. Chem. Soc. v.99 R.M. Laine;R.G. Rinker;P.C. Ford
  25. J. Am. Chem. Soc. v.71 P. Krumholz;H.M. Stettiner
  26. J. Am. Chem. Soc. v.99 C-H. Cheng;D.E. Hendrikson;R. Eisenberg
  27. Dissertation, Kyoto University S.C. Shim