Oxime

An oxime is one in a class of chemical compounds with the general formula R₁R₂C N O H, where R₁ is an organic side chain and R₂ is either hydrogen, forming an aldoxime, or another organic group, forming a ketoxime.

Oximes can be formed by the action of hydroxylamine on aldehydes or ketones.

The term oxime dates to the 19th century, a condensation of the words oxygen and imide.

Oximes exists as two stereoisomers: a syn isomer and an anti isomer. Aldoximes, except for aromatic aldoximes, exist only as a syn isomer, while ketoximes can be separated almost completely and obtained as a syn isomer and an anti isomer.

organic synthesis

Oximes can be synthesized by condensation of an aldehyde or a ketone with hydroxylamine. The condensation of aldehydes with hydroxylamine gives aldoxime, and ketoxime is produced from ketones and hydroxylamine. Generally, oximes are colorless crystals and do not dissolve into water easily. Therefore, oxime is used for the identification of ketone or aldehyde.

Oximes can also be obtained from reaction of nitrites such as isoamyl nitrite with compounds containing an acidic hydrogen atom. Examples are the reaction of ethyl acetoacetate and sodium nitrite in acetic acid Organic Syntheses, Coll. Vol. 2, p.202 (1943); Vol. 15, p.17 (1935). [Article] Organic Syntheses, Coll. Vol. 3, p.513 (1955); Vol. 21, p.67 (1941) [Article]. , the reaction of methyl ethyl ketone with ethyl nitrite in hydrochloric acid Organic Syntheses, Coll. Vol. 2, p.204 (1943); Vol. 10, p.22 (1930) [Article]. and a similar reaction with propiophenone Organic Syntheses, Coll. Vol. 2, p.363 (1943); Vol. 16, p.44 (1936). [Article], the reaction of phenacyl chloride Organic Syntheses, Coll. Vol. 3, p.191 (1955); Vol. 24, p.25 (1944) [Article]., the reaction of malononitrile with sodium nitrite in acetic acid Organic Syntheses, Coll. Vol. 5, p.32 (1973); Vol. 48, p.1 (1968) [Article]..

A conceptually related reaction is the Japp-Klingemann reaction.

Organic reactions

The hydrolysis of oximes proceeds easily by heating in the presence of various inorganic acids, and the oximes decompose into the corresponding ketones or aldehydes, and hydroxylamines. The reduction of oximes by sodium amalgam or hydrogenation produces amines. The reduction of aldoximes gives both primary amines and secondary amines.

Generally oximes can be changed to the corresponding amide derivatives by treatment with various acids. This reaction is called Beckmann rearrangement. In this reaction, a hydroxyl group is exchanged with the group that is in the anti position of the hydroxyl group. The amide derivatives that are obtained by Beckmann rearrangement can be transformed into a carboxylic acid and an amine by hydrolysis. Beckmann rearrangement is used for the industrial synthesis of caprolactam, which is the material used to make nylon-6.

References

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