Nierenstein reaction
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The Nierenstein reaction is an organic reaction describing the conversion of an acid chloride into an haloketone with diazomethane.[1][2]
[edit] Reaction mechanism
Like the related Arndt-Eistert reaction, this reactions proceeds through a diazoketone intermediate (5). The loss of nitrogen to gives the desired haloketone (2).
The synthesis of benzyl chloromethyl ketone from phenylacetyl chloride [3] in fact requires the addition of HCl gas to the diazoketone intermediate for it to succeed. The unassisted reaction failed.
[edit] Scope
One original 1924 Nierenstein reaction:[4]
and a reaction starting from benzoyl bromide going haywire with formation of the dioxane dimer:[5]
[edit] References
- ^ Clibbens, D.; Nierenstein, M. J. Chem. Soc. 1915, 107, 1491.
- ^ Bachman, W. E.; Struve, W. S. Org. React. 1942, 1, 38. (Review)
- ^ McPhee, W. D; Klingsberg, E. Organic Syntheses, Coll. Vol. 3, p.119 (1955); Vol. 26, p.13 (1946). (Article)
- ^ THE ACTION OF DIAZOMETHANE ON SOME AROMATIC ACYL CHLORIDES II. SYNTHESIS OF FISETOL M. Nierenstein, D. G. Wang, and J. C. Warr J. Am. Chem. Soc.; 1924; 46(11) pp 2551 - 2555. (DOI:10.1021/ja01676a028)
- ^ THE ACTION OF DIAZOMETHANE ON SOME AROMATIC ACYL CHLORIDES. III. THE MECHANISM OF THE REACTION H. H. Lewis, M. Nierenstein, and Enid M. Rich J. Am. Chem. Soc.; 1925; 47(6) pp 1728 - 1732. (DOI:10.1021/ja01683a036)
