Standard Article

The Claisen Rearrangement

  1. D. Stanley Tarbell

Published Online: 15 MAR 2011

DOI: 10.1002/0471264180.or002.01

Organic Reactions

Organic Reactions

How to Cite

Tarbell, D. S. 2011. The Claisen Rearrangement. Organic Reactions. 2:1:1–48.

Author Information

  1. The University of Rochester

Publication History

  1. Published Online: 15 MAR 2011

Chemistry Terms

Choose one or more boxes to highlight terms.

Abstract

Allyl ethers of enols and phenols undergo rearrangement to C-allyl derivatives when heated to sufficiently high temperatures. The reaction, named after its discoverer (Claisen, 1912) was first observed when ethyl O-allylacetonacetate was subjected to distillation at atmospheric pressure in the presence of ammonium chloride. The allyl ethers of phenols rearrange smoothly at temperatures of about 200°C in the absence of catalysts, Allyl ethers of ortho-disubstituted phenols rearrange to the corresponding p-allyphenols. The only known example of para rearrangement accompanied by inversion is the reaction of alpha-ethylallyl 2-carbomethoxy-6-methylphenyl ether. These rearrangements are discussed in detail.

Keywords:

  • Claisen rearrangement;
  • open chain compounds;
  • ally aryl ethers;
  • allylphenols;
  • allyethers;
  • structural requirements;
  • side reactions;
  • experimental conditions