Smiles rearrangement

The Smiles rearrangement is an organic-chemical reaction and belongs to the rearrangement reactions . It is named after Samuel Smiles , who described it in 1931.

It is an intramolecular, nucleophilic aromatic substitution. The group X here can be a sulfone , sulfide , ether or other electron-withdrawing substituent. Group Y must be a strong nucleophile such as phenol oxygen, amine nitrogen, or sulfur. As with other nucleophilic substitutions on aromatics, this must be activated by additional electron-withdrawing groups in the ortho or para position to the X group.

A variant of the Smiles rearrangement is known as the Truce Smiles rearrangement . Here the nucleophile Y is so strong that the aromatic does not have to contain any other activating groups. Organolithium compounds serve as nucleophiles here.

The reaction uses the ortho -sulfone group to generate the anion through an ortho -metallation as a nucleophile.

A similar rearrangement reaction is known as the Chapman rearrangement .

Individual evidence

^ AA Levy, HC Rains and S. Smiles, J. Chem. Soc. 1931, 3264.
^ WE Truce, WJ Ray, OL Norman, and DB Eickemeyer: In 'Rearrangements of Aryl Sulfones. I. The Metalation and Rearrangement of Mesityl Phenyl Sulfone ' J. Am. Chem. Soc. 1958 , 80 , 3625 - 3629 doi : 10.1021 / ja01547a038 .
↑ AW Chapman: In CCLXIX. - Imino-aryl ethers. Part III. The molecular rearrangement of N-phenylbenziminophenyl ether J. Chem. Soc. , Transactions, 1925 , 127 , 1992-1998.

Web links

Masahiro Mizuno and Mitsuhisa Yamano: A new practical One-Pot Conversion of Phenols to Anilines: 6-Amino-3,4-Dihydro-1 (2H) -Naphthalenone In: Organic Syntheses . 84, 2007, pp. 325-333, doi : 10.15227 / orgsyn.084.0325 ( PDF ).

[1] AA Levy, HC Rains and S. Smiles, J. Chem. Soc. 1931, 3264.

[2] WE Truce, WJ Ray, OL Norman, and DB Eickemeyer: In 'Rearrangements of Aryl Sulfones. I. The Metalation and Rearrangement of Mesityl Phenyl Sulfone ' J. Am. Chem. Soc. 1958 , 80 , 3625 - 3629 doi : 10.1021 / ja01547a038 .

[3] AW Chapman: In CCLXIX. - Imino-aryl ethers. Part III. The molecular rearrangement of N-phenylbenziminophenyl ether J. Chem. Soc. , Transactions, 1925 , 127 , 1992-1998.