Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
권호 표지

Selective Reduction with Lithium Borohydride. Reaction of Lithium Borohydride with Selected Organic Compounds Containing Representative Functional Groups

수소화붕소리튬에 의한 선택환원. 수소화붕소리튬과 대표적 유기화합물과의 반응

  • Nung Min Yoon (Department of Chemistry, College of Science and Engineering) ;
  • Jin Soon Cha (Department of Chemistry, College of Science and Engineering)
  • 윤능민 (서강대학교 이공대학 화학과) ;
  • 차진순 (서강대학교 이공대학 화학과)
  • Published : 1977.04.30
Download PDF
⟨ Previous Next ⟩

Abstract

The approximate rates and stoichiometries of the reaction of lithium borohydride, with fifty two selected organic compounds containing representative functional groups under the standard condition (tetrahydrofuran, $0^{\circ}$), were studied.Among the active hydrogen compounds,primary alcohols and compounds containing an acidic proton liberated hydrogen relatively fast, but secondary and tertiary alcohols very sluggishly. All the carbonyl compounds examined were reduced rapidly within one hour. Especially, among the ${\alpha}{\beta}$-unsaturated carbonyl compounds tested, the aldehydes consumed one hydride cleanly, however the cyclic ketones consumed more than one hydride even at $-20^{\circ}$. Carboxylic acids were reduced very slowly, showing about 60% reduction in 6 days at $25^{\circ}$, however acyl chlorides reduced immediately within 30 minutes. On the other hand, the reductions of cyclic anhydrides proceeded moderately to the hydroxy acid stage, however the further reductions were very slow. Aromatic and aliphatic esters, with exception of the relatively moderate reduction of acetate, were reduced very slowly, however lactones were reduced at a moderate rate. Epoxides reacted slowly, but amides and nitriles as well as the nitro compounds were all inert to this reagent. And cyclohexanone oxime and phenyl isocyanate were reduced very sluggishly. Last of all, all sulfur compounds studied were inert to this hydride.

수소화붕소리튬-테트라히드로푸란용액의 환원특성에 대한 계통적인 연구가 52가지의 대표적인 작용기를 가진 유기화합물을 가지고 표준조건($0^{\circ}$, 테트라히드로 푸란)에서 대략의 반응속도 및 정량 관계를 알아봄으로서 이루어 졌다.

Keywords

References

  1. J. Amer. Chem. Soc. v.75 H. I. Schlesinger;H. C. Brown;R. H. Hoekstra;L. R. Rapp
  2. J. Amer. Chem. Soc. v.69 A. E. FinHolt;A. C. Bond, Jr.;H. I. Schlesinger
  3. J. Amer Chem. Soc. v.80 H. C. Brown;R. F. McFarlin
  4. Israel J. Chem. v.1 H. C. Brown;P. M. Weissman
  5. J. Amer. Chem. Soc. v.87 H. C. Brown;P. M. Weissman
  6. J. Amer. Chem. Soc. v.87 H. C. Brown;P. M. Weissman
  7. J. Amer. Chem. Soc. v.92 H. C. Brown;P Heim;N. M. Yoon
  8. Reduction With Complex Metal Hydride N. G. Gaylord
  9. Borane in Organic Chemistry H. C. Brown
  10. Reduction R. L. Augustine
  11. Newer Method of Preparative Organic Chemistry v.4 E. Schenker;W. Foerst(ed.)
  12. J. Amer. Chem. Soc. v.62 H. I. Schlesinger;H. C. Brown
  13. J. Amer. Chem. Soc. v.75 H. I. Schlesinger;H. C. Brown
  14. Chem. Abst. v.45 H. I. Schlesinger;H. C. Brown
  15. U. S. Pat. 2,545,633 H. I. Schlesinger;H. C. Brown
  16. J. Amer. Chem. Soc. v.75 H. I. Schlesinger;H. C. Brown
  17. U. S. Pat. 2,461,661 H. I. Schlesinger;H. C. Brown
  18. J. Amer. Chem. Soc. v.77 H. C. Brown;E. J. Mead;B. C. Subbarao
  19. J. Amer. Chem. Soc. v.75 H. I. Schlesinger;H. C. Brown;E. K. Hyde
  20. J. Amer. Chem. Soc. v.88 H. C. Brown;P. M. Weissman;N. M. Yoon
  21. J. Amer. Chem. Soc. v.98 E. C. Ashby;J. R. Boone
  22. J. Amer. Chem. Soc. v.71 R. F. Nystrom;S. W. Chaikin;W. G. Brown
  23. J. Korean Chem. Soc. v.19 N. M. Yoon;H. J. Lee;J. S. Chung;J. Kang
  24. J. Org. Chem. v.41 H. C. Brown;S. Krishnamurtby;N. M. Yoon
  25. J. Amer. Chem. Soc. v.88 H. C. Brown;N. M. Yoon
  26. J. Amer. Chem. Soc. v.76 R. Fuchs;C. A. Vanderwerf
  27. J. Org. Chem. v.28 A. T. Bottini;V. Dev;M. Stewart
  28. M. S. Thesis, Sogang University D. H. Kim
  29. J. Org. Chem. v.26 J. M. Stewart
  30. J. Korean Chem. Soc. v.20 N. M. Soon;H. J. Lee;H. K. Kim;J. Kang