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

References

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• The product ketones 3 were identified and characterised by direct comparison with authentic materials and/or the usual physical methods
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• Isolated overall yield from RCOCl; the formation of 2 is almost quantitative2
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• 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
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• 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
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• Reaction with 4 eq's of 1.
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