Chemical Sciences: A Manual for CSIR-UGC National Eligibility Test for Lectureship and JRF/Named Reactions/Lossen Rearrangement

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The Lossen rearrangement is the conversion of a hydroxamic acid (1) to an isocyanate (3) via the formation of an O-acyl, sulfonyl, or phosphoryl intermediate hydroxamic acid O-derivative (2) and then conversion to its conjugate base. Here, 4-Toluenesulfonyl chloride is used to form a sulfonyl O-derivative of hydroxamic acid. [1] [2]

The Lossen rearrangement

The isocyanate can be used further to generate ureas in the presence of amines (4) or generate amines in the presence of H2O (5).

IsocyanateGOES.png

Reaction Mechanism[edit]

The mechanism below begins with an O-acylated hydroxamic acid derivative that is treated with base to form an isocyanate that generates an amine and CO2 gas in the presence of H2O. The hydroxamic acid acid derivative is first converted to its conjugate base by abstraction of a hydrogen by a base. Spontaneous rearrangement kicks off a carboxylate anion to produce the isocyanate intermediate. The isocyanate in the presence H2O hydrolyzes and then decarboxylation via abastraction of a hydrogen by a base generates an amine and CO2 gas.

LossenRearangmentCHEMDRAW.jpg


Several reviews have been published. [3] [4] [5]


Hydroxamic acids are commonly synthesized from their corresponding esters.[6]

References[edit]

  1. Lossen, W. Ann. 1872, 161, 347.
  2. Lossen, W. Ann. 1874, 175, 271 & 313.
  3. Yale, H. L. Chem. Rev. 1943, 33, 209. (Review)
  4. Bauer, L.; Exner, O. Angew. Chem. Int. Ed. Engl. 1974, 13, 376. (Review)
  5. Shiori, T. Comp. Org. Syn. 1991, 6, 821-825. (Review)
  6. Hauser, C. R.; Renfrow, Jr., W. B. [[w:Organic Syntheses|]], Coll. Vol. 2, p.67 (1943); Vol. 19, p.15 (1939). (Article)