High Campbell Reaction

The Hoch Campbell reaction (also Hoch Campbell aziridine synthesis ) is a name reaction in organic chemistry , which was first described in 1934 by Joseph Hoch and expanded by Kenneth N. Campbell in the early 1940s. The reaction produces aziridines from oximes with the help of a Grignard compound .

Overview reaction

In the Hoch-Campbell reaction, an oxime (R ¹ and R ² = organic radicals) react with an excess of a Grignard compound (X = Cl , Br , I ; R ³ = organic radical) and subsequent hydrolysis to form an aziridine. As a solvent z. B. toluene or THF , the solvent having an influence on whether only a main product or different isomers of the product are formed.

Reaction mechanism

The addition of a Grignard reagent to give the oxime 1 leading to deprotonation of the oxime to give the compound 2 . Compound 3 is formed with another equivalent of the Grignard compound . With the elimination of O (MgX) ₂ , the unstable nitrene 4 is formed , which cyclizes to compound 5 . By adding a further equivalent of the Grignard compound, an aziridine magnesium halide 6 is initially formed , which is then worked up to aziridine 7 by hydrolysis .

Sample reaction

In the example of the Hoch-Campbell reaction shown below in the oxime, a phenyl group is used for the radical R ¹ and only a hydrogen atom is used for R ² , and ethyl magnesium bromide is used as the Grignard compound . The hydrolysis is carried out using an aqueous ammonium chloride solution. 2-Ethyl-2-phenylaziridine is formed as a product.

Individual evidence

^ Joseph Hoch: Action des organomagnésiens sur les cétoximes . In: Comptes rendus de l'Académie des sciences . No. 198 , 1934, pp. 1865 .
↑ Kenneth N. Campbell, James F. McKenna: The Action of Grignard Reagents on Oximes I. The Action of Phenylmagnesoum Bromide on Mixed Ketoximes . In: J. Org. Chem. Band 4 , no. 2 , 1939, pp. 198-205 , doi : 10.1021 / jo01214a012 .
↑ Kenneth N. Campbell, Barbara Knapp Campbell, Elmer Paul Chaput: The Reaction of Grignard Reagents with Oximes. II. The Action of Aryl Grignard Reagents with Mixed Ketoximes. In: J. Org. Chem. Band 8 , no. 1 , 1943, p. 99-102 , doi : 10.1021 / jo01189a015 .
^ ^A ^b ^c ^d Zerong Wang: Hoch-Campbell Reaction . In: Comprehensive Organic Name Reactions and Reagents . John Wiley & Sons, Inc., Hoboken, NJ, USA 2010, ISBN 978-0-470-63885-9 , pp. 1434-1437 , doi : 10.1002 / 9780470638859.conrr320 .
^ Jie Jack Li: Name Reactions in Heterocyclic Chemistry . In: Comprehensive Name Reactions . tape 3 . John Wiley & Sons, 2004, ISBN 0-471-70414-8 , pp. 22-23 .

[1] Joseph Hoch: Action des organomagnésiens sur les cétoximes . In: Comptes rendus de l'Académie des sciences . No. 198 , 1934, pp. 1865 .

[2] Kenneth N. Campbell, James F. McKenna: The Action of Grignard Reagents on Oximes I. The Action of Phenylmagnesoum Bromide on Mixed Ketoximes . In: J. Org. Chem. Band 4 , no. 2 , 1939, pp. 198-205 , doi : 10.1021 / jo01214a012 .

[3] Kenneth N. Campbell, Barbara Knapp Campbell, Elmer Paul Chaput: The Reaction of Grignard Reagents with Oximes. II. The Action of Aryl Grignard Reagents with Mixed Ketoximes. In: J. Org. Chem. Band 8 , no. 1 , 1943, p. 99-102 , doi : 10.1021 / jo01189a015 .

[:0-4] A ^b ^c ^d Zerong Wang: Hoch-Campbell Reaction . In: Comprehensive Organic Name Reactions and Reagents . John Wiley & Sons, Inc., Hoboken, NJ, USA 2010, ISBN 978-0-470-63885-9 , pp. 1434-1437 , doi : 10.1002 / 9780470638859.conrr320 .

[:1-5] Jie Jack Li: Name Reactions in Heterocyclic Chemistry . In: Comprehensive Name Reactions . tape 3 . John Wiley & Sons, 2004, ISBN 0-471-70414-8 , pp. 22-23 .