Nitrile

A nitrile is any cyanides.

Nitriles sometimes release the highly toxic CN⁻ cyanide ion. See the article on cyanide for a discussion of biological effects and toxicity.

History

Théophile-Jules Pelouze synthesized propionitrile in 1834.

Synthesis of nitriles

Nitriles can be prepared in organic synthesis by the following methods:

Two intermediates in this reaction are amide phosphate adduct B.

amides (von Braun amide degradation)
sulfuryl chloride
sodium sulfate.

In one study ^[3] an aromatic or aliphatic aldehyde is reacted with hydroxylamine and microwave irradiation through an intermediate aldoxime.

reaction of metal cyanides with aldehydes in the cyanohydrin reaction
from aryl carboxylic acids (Letts nitrile synthesis)
aromatic nitriles from Sandmeyer reaction
from hydrocyanation
A commercial source for the cyanide group is diethylaluminum cyanide Et₂AlCN which can be prepared from Kuwajima Taxol total synthesis
cyanide ions facilitate the coupling of dibromides. Reaction of α,α'-dibromo cyclobutane:^[6]

In the so-called Franchimont Reaction (A. P. N. Franchimont, 1872) an α-bromocarboxylic acid is dimerized after hydrolysis of the cyanogroup and decarboxylation ^[7]

Reactions of nitriles

Nitrile groups in organic compounds can undergo various reactions when subject to certain reactants or conditions. A nitrile group can be hydrolyzed, reduced, or ejected from a molecule as a cyanide ion.

In carboxylic acid, the alkali hydrolysis forms a carboxylate.
In Stephen aldehyde synthesis
A nitrile is an nucleophilic addition reactions:
- with an Blaise reaction
- and with alcohols in the Pinner reaction.
- likewise, the reaction of the creatine ^[8]
In reductive decyanation the nitrile group is replaced by a proton ^[9]. An effective decyanation is by a dissolving metal reduction with lithium aluminium hydride.
Nitriles self-react in presence of base in the nucleophilic addition
In alkynes in carbocyanation:^[10]

References

^ David T. Mowry (1948). "The Preparation of Nitriles". Chem. Rev. 42 (2): 189 - 283. doi:10.1021/cr60132a001.
^ Chun-Wei Kuo, Jia-Liang Zhu, Jen-Dar Wu, Cheng-Ming Chu, Ching-Fa Yao and Kak-Shan Shia (2007). "A convenient new procedure for converting primary amides into nitriles". Chem. Commun. 2007: 301 - 303. doi:10.1039/b614061k.
^ Sharwan K, Dewan, Ravinder Singh, and Anil Kumar (2006). "One pot synthesis of nitriles from aldehydes and hydroxylamine hydrochloride using sodium sulphate (anhyd) and sodium bicarbonate in dry media under microwave irradiation" (open access). Arkivoc: (ii) 41-44.
^ W. Nagata and M. Yoshioka (1988). "Diethylaluminum cyanide". Org. Synth.; Coll. Vol. 6: 436.
^ W. Nagata, M. Yoshioka, and M. Murakami (1988). "PREPARATION OF CYANO COMPOUNDS USING ALKYLALUMINUM INTERMEDIATES: 1-CYANO-6-METHOXY-3,4-DIHYDRONAPHTHALENE". Org. Synth.; Coll. Vol. 6: 307.
^ Reynold C. Fuson, Oscar R. Kreimeier, and Gilbert L. Nimmo (1930). "RING CLOSURES IN THE CYCLOBUTANE SERIES. II. CYCLIZATION OF α,α′-DIBROMO-ADIPIC ESTERS". J. Am. Chem. Soc. 52 (10): 4074 - 4076. doi:10.1021/ja01373a046.
^ http://www.drugfuture.com/OrganicNameReactions/ONR143.htm
^ Smith, Andri L.; Tan, Paula (2006). "Creatine Synthesis: An Undergraduate Organic Chemistry Laboratory Experiment". J. Chem. Educ. 83: 1654.
^ The reductive decyanation reaction: chemical methods and synthetic applications Jean-Marc Mattalia, Caroline Marchi-Delapierre, Hassan Hazimeh, and Michel Chanon Arkivoc (AL-1755FR) pp 90-118 2006 Article
^ Yoshiaki Nakao, Akira Yada, Shiro Ebata, and Tamejiro Hiyama (2007). "A Dramatic Effect of Lewis-Acid Catalysts on Nickel-Catalyzed Carbocyanation of Alkynes" (Communication). J. Am. Chem. Soc. 129 (9): 2428 - 2429. doi:10.1021/ja067364x.

v • d • e Thiol

Categories: Nitriles

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Nitrile

History

Synthesis of nitriles

Reactions of nitriles

See also

References