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Synthetic Communications
An International Journal for Rapid Communication of Synthetic Organic Chemistry
Volume 10, 1980 - Issue 3
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Original Articles

A Non-Organometallic Method for the Synthesis of Methyl Ketones from Acyl Chlorides

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Pages 221-224 | Published online: 05 Dec 2006

References

  • Hart , D. W. and Schwartz , J. 1974 . J. Am. Chem. Soc. , 96 : 811 For Mg, Zn and Cd organometallics, see D. A. Shirley, Org. Reactions 8 28 (1954); for recent uses of other organometallics, see,D. B. Carr and J. Schwartz, J. Am. Chem. Soc. 101 3521 (1979)
  • Taylor , E. C. , Hawks , G. H. III and McKillop , A. 1968 . J. Am. Chem. Soc. , 90 : 2421
  • Posner , G. H. , Brunelle , D. J. and Sinoway , L. 1974 . Synthesis , : 662
  • Frainnet , E. , Calas , R. and Gerval , P. 1965 . Compt. rend. C , 261 : 1329 T. H. Chan, E. Chang and E. Vinokur, Tetrahedron Lett. 1970 1137; J. P. Pillot, J. Dunogues and R. Calas, Tetrahedron Lett. 1976 1871; G. A. Olah, T-L. Ho, G. K. S. Prakash and B. G. B. Gupta, Synthesis 1977 677
  • Cahiez , G. , Masuda , A. , Bernard , D. and Normant , J. F. 1977 . Synthesis , : 130
  • Kurts , A. L. , Beletskaya , I. P. , Savchenko , I. A. and Reutov , O. A. 1969 . J. Organomet. Chem. , 17 : 21
  • Pittman , C. U. Jr. and Hanes , R. M. 1977 . J. Org. Chem. , 42 : 1194
  • Negishi , E. , Chiu , K. and Yosida , T. 1975 . J. Org. Chem. , 40 : 1676
  • Kosugi , M. , Shimizu , Y. and Migita , T. 1977 . Chem. Lett. , : 1423 For the use of enamines, see E. E. Garcia and R. I. Fryer, J. Heteroc. Chem. 11 219 (1974)
  • Oikawa , Y. , Sugano , K. and Yonemitsu , O. 1978 . J. Org. Chem. , 43 : 2087
  • Davidson , D. and Bernhardt , S. A. 1948 . J. Am. Chem. Soc. , 70 : 3426
  • The product ketones 3 were identified and characterised by direct comparison with authentic materials and/or the usual physical methods
  • Isolated overall yield from RCOCl; the formation of 2 is almost quantitative2
  • Benzoic acid (87%), cinnamic acid (55%) and 3-methyl-2-butenoic acid (71%), respectively, was also isolated. The respective acyl Meldrum's acids were formed quantitatively but hydrolysis is apparently occurring here at the acyl carbon atom
  • The isolated acyl Meldrum's acids 2, obtained as described2 from RCOCl, 1 and pyridine (2 eq's) in CH2Cl2 at 0° (1 h) and r.t. (1 h), and used without purification, are refluxed in AcOH-H2O (1:2) until TLC indicates complete consumption of starting material (2–4 h). The mixture is then diluted with water, extracted twice with petr. ether (40–60°) and the combined extracts washed with dil. NaHCO3 soln. and dried. The removal of solvent then gives the ketones 2 which in most cases are > 95% pure by NMR and TLC
  • Reaction with 4 eq's of 1.

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