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Carbonitrile)
This article is about the group of organic compounds. For the polymer used for making safety gloves, see
Nitrile rubber.
The structure of the nitrile group
A nitrile is any organic compound which has a -C≡N functional group. The -C≡N functional group is called a nitrile group. In the -CN group, the carbon atom and the nitrogen atom are triple bonded together. The prefix cyano is used in chemical nomenclature to indicate the presence of a nitrile group in a molecule. A cyanide ion is a negative ion with the formula CN−. The -CN group is sometimes, less properly, referred to as a cyanide group or cyano group and compounds with them are sometimes referred to as cyanides.
Nitriles sometimes release the highly toxic CN− cyanide ion. See the article on cyanide for a discussion of biological effects and toxicity.
[edit] History
The first compound of the homolog row of nitriles, the nitrile of formic acid, hydrogen cyanide was first synthesized by K.W. Scheele in 1782.[1] In 1811 J. L. Gay-Lussac was able to prepare the very toxic and volatile pure acid. The nitrile of benzoic acids was first prepared by Friedrich Wohler and Justus von Liebig, but due to minimal yield of the synthesis neither physical nor chemical properties were determined nor a structure suggested. Théophile-Jules Pelouze synthesized propionitrile in 1834 suggesting it to be an ether of propionic alcohol and hydrocyanic acid.[2] The synthesis of benzonitrile by Hermann Fehling in 1844, by heating ammonium benzoate, was the first method yielding enough of the substance for chemical research. He determined the structure by comparing it to the already known synthesis of hydrogen cyanide by heating ammonium formiate to his results. He coined the name nitrile for the newfound substance, which became the name for the compound group. [3]
[edit] Synthesis of nitriles
Nitriles can be prepared in organic synthesis by the following methods:
- Two intermediates in this reaction are amide tautomer A and its phosphate adduct B.
- In one study [5] an aromatic or aliphatic aldehyde is reacted with hydroxylamine and anhydrous sodium sulfate in a dry media reaction for a very small amount of time under microwave irradiation through an intermediate aldoxime.
- In the so-called Franchimont Reaction (A. P. N. Franchimont, 1872) an α-bromocarboxylic acid is dimerized after hydrolysis of the cyanogroup and decarboxylation [9]
- Aromatic nitriles can be prepared from base hydrolysis of trichloromethyl aryl ketimines (RC(CCl3)=NH) in the Houben-Fischer synthesis [10] [11]
[edit] 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.
- The hydrolysis of nitriles RCN proceeds in the distinct steps under acid or base treatment to achieve carboxamides RC(=O)NH2 and then carboxylic acids RCOOH. The hydrolysis of nitriles is generally considered to be one of the best methods for the preparation of carboxylic acids. However, these base or acid catalyzed reactions have certain limitations and/or disadvantages for preparation of amides. The general restriction is that the final neutralization of either base or acid leads to an extensive salt formation with inconvenient product contamination and pollution effects. Particular limitations are as follows: (i) The base catalyzed reactions. The kinetic studies allowed the estimate of relative rates for the hydration at each step of the reaction and, as a typical example, the second-order rate constants for hydroxide-ion catalyzed hydrolysis of acetonitrile and acetamide are 1.6×10–6 and 7.4×10–5M–1s–1, respectively. Comparison of these two values indicates that the second step of the hydrolysis for the base-catalyzed reaction is faster than the first one, and the reaction should proceed to the final hydration product (the carboxylate salt) rather than stopping at the amide stage. This implies that amides prepared in the conventional metal-free base-catalyzed reaction should be contaminated with carboxylic acids and they can be isolated in only moderate yields. (ii) The acid catalyzed reactions. Application of strong acidic solutions requires a careful control of the temperature and of the ratio of reagents in order to avoid the formation of polymers, which is promoted by the exothermic character of the hydrolysis. [12]
- In organic reduction the nitrile is reduced by reacting it with hydrogen with a nickel catalyst; an amine is formed in this reaction. Reduction to the imine followed by hydrolysis to the aldehyde takes place in the Stephen aldehyde synthesis
- A nitrile is an electrophile at the carbon atom in a nucleophilic addition reactions:
- Nitriles react in Friedel-Crafts acylation in the Houben-Hoesch reaction to ketones
- In reductive decyanation the nitrile group is replaced by a proton [14]. An effective decyanation is by a dissolving metal reduction with HMPA and potassium metal in tert-butyl alcohol. α-Amino-nitriles can be decyanated with lithium aluminium hydride.
- Nitriles self-react in presence of base in the Thorpe reaction in a nucleophilic addition
- In organometallic chemistry nitriles are known to add to alkynes in carbocyanation:[15]
[edit] Organic cyanamides
Cyanamides are N-cyano compounds with general structure R1R2N-CN and related to the inorganic parent cyanamide. For an example see: von Braun reaction.
[edit] See also
[edit] References
- ^ David T. Mowry (1948). "The Preparation of Nitriles". Chemical reviews 42 (2): 189–283. doi:10.1021/cr60132a001, http://pubs.acs.org/cgi-bin/abstract.cgi/chreay/1942/42/i02/f-pdf/f_cr60132a001.pdf.
- ^ J. Pelouze (1834). "Notiz über einen neuen Cyanäther". Annalen der Chemie und Pharmacie 10 (2): 249. doi:10.1002/jlac.18340100302.
- ^ Hermann Fehling (1844). "Ueber die Zersetzung des benzoësauren Ammoniaks durch die Wärme". Annalen der Chemie und Pharmacie 49 (1): 91–97. doi:10.1002/jlac.18440490106.
- ^ 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 sulfate (anhyd) and sodium bicarbonate in dry media under microwave irradiation" (open access). Arkivoc: (ii) 41–44, http://www.arkat-usa.org/ark/journal/2006/I02_General/1646/05-1646D%20as%20published%20mainmanuscript.pdf.
- ^ 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.
- ^ Franchimont Reaction
- ^ Über eine neue Methode zur Darstellung cyclischer Nitrile durch katalytischen Abbau (I. Mitteil.) (p 2464-2472) J. Houben, Walter Fischer Berichte der deutschen chemischen Gesellschaft (A and B Series) Volume 63, Issue 9 , Pages 2464 - 2472 doi:10.1002/cber.19300630920
- ^ http://www.drugfuture.com/OrganicNameReactions/ONR197.htm Merck & Co., Inc., Whitehouse Station
- ^ V. Yu. Kukushkin, A. J. L. Pombeiro, Metal-mediated and metal-catalyzed hydrolysis of nitriles (a review), Inorg. Chim. Acta, 358 (2005) 1–21
- ^ Smith, Andri L.; Tan, Paula (2006). "Creatine Synthesis: An Undergraduate Organic Chemistry Laboratory Experiment". J. Chem. Educ. 83: 1654, http://jchemed.chem.wisc.edu/Journal/Issues/2006/Nov/abs1654.html.
- ^ 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.
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