A nitrile is any organic compound which has a -C≡N functional group. An organic compound is any member of a large class of Chemical compounds whose Molecules contain Carbon. Carbon (kɑɹbən is a Chemical element with the symbol C and its Atomic number is 6 Nitrogen (ˈnaɪtɹəʤɪn is a Chemical element that has the symbol N and Atomic number 7 and Atomic weight 14 In Organic chemistry, functional groups are specific groups of Atoms within Molecules that are responsible for the characteristic Chemical reactions 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. Carbon (kɑɹbən is a Chemical element with the symbol C and its Atomic number is 6 Nitrogen (ˈnaɪtɹəʤɪn is a Chemical element that has the symbol N and Atomic number 7 and Atomic weight 14 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⁻. A cyanide is any Chemical compound that contains the cyano group (C≡N which consists of a Carbon Atom triple-bonded to a 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. A cyanide is any Chemical compound that contains the cyano group (C≡N which consists of a Carbon Atom triple-bonded to a

Nitriles sometimes release the highly toxic CN⁻ cyanide ion. See the article on cyanide for a discussion of biological effects and toxicity. A cyanide is any Chemical compound that contains the cyano group (C≡N which consists of a Carbon Atom triple-bonded to a

Contents 1 History 2 Synthesis of nitriles 3 Reactions of nitriles 4 Organic cyanamides 5 See also 6 External links 7 References

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. Formic acid (systematically called methanoic acid) is the simplest Carboxylic acid. Hydrogen cyanide is a Chemical compound with Chemical formula HCN Carl Wilhelm Scheele (9 December 1742 &ndash 21 May 1786 was a German - Swedish pharmaceutical chemist born in Stralsund, Western Pomerania, ^[1] In 1811 J. L. Gay-Lussac was able to prepare the very toxic and volatile pure acid. Joseph Louis Gay-Lussac (also Louis Joseph Gay-Lussac, December 6, 1778 – May 9, 1850) was a French chemist 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 or chemical properties where determined nor a structure was suggested. Friedrich Wöhler (31 July 1800 - 23 September 1882 was a German Chemist, best-known for his synthesis of Urea, but also the first to isolate several Justus von Liebig ( May 12, 1803 &ndash April 18, 1873) was a German Chemist Théophile-Jules Pelouze synthesized propionitrile in 1834 suggesting it to be an ether of propionic alcohle and hydrocyanic acid. Théophile-Jules Pelouze (also known as Jules Pelouze, Théophile Pelouze, Theo Pelouze, or TJ Pelouze, February 26, 1807 Propionitrile, or ethyl cyanide, is a low-molecular weight Nitrile with the molecular formula C2H5CN ^[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. Benzonitrile is the Chemical compound with the formula C6H5CN abbreviated PhCN This Aromatic Organic compound is Hermann von Fehling ( 9 June 1812 - 1 July 1885) was a German Chemist, famous as the developer of Fehling's solution He determined the structure by comparing it to the already known synthesis of hydrogen cyanide by heating ammonium formiate to his results. Formate or methanoate is the ion CHOO&minus ( Formic acid minus one Hydrogen ion) He coined the name nitrile for the newfound substance, which became the name for the compound group. ^[3]

Synthesis of nitriles

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

• Nucleophilic aliphatic substitution reactions of alkyl halides with metal cyanides in the Kolbe nitrile synthesis. Organic synthesis is a special branch of Chemical synthesis and is concerned with the construction of Organic compounds via Organic reactions Organic In organic and Inorganic chemistry, nucleophilic substitution is a fundamental class of Substitution reaction in which an "electron rich" The haloalkanes (also known as halogenoalkanes or alkyl halides) are a group of Chemical compounds consisting of Alkanes such as Methane A cyanide is any Chemical compound that contains the cyano group (C≡N which consists of a Carbon Atom triple-bonded to a The Kolbe nitrile synthesis is a method for the preparation of alkyl nitriles by reaction of the corresponding alkylhalide with a metal Cyanide. Aryl nitriles are prepared in the Rosenmund-von Braun synthesis. The Rosenmund-von Braun synthesis is an Organic reaction in which an Aryl Halide reacts with Cuprous cyanide to an Aryl Nitrile
• dehydration of primary amides. In Chemistry, a dehydration reaction is usually defined as a chemical reaction that involves the loss of water from the reacting molecule In Chemistry, an amide is one of three kinds of Compounds (sometimes called acid amide the organic Functional group characterized Many reagents are available, the combination of ethyl dichlorophosphate and DBU just one of them in this conversion of benzamide to benzonitrile:^[4]

Two intermediates in this reaction are amide tautomer A and its phosphate adduct B. Benzamide is an off-white solid with the chemical formula of C6H5CONH2 Benzonitrile is the Chemical compound with the formula C6H5CN abbreviated PhCN This Aromatic Organic compound is Tautomers are Organic compounds that are interconvertible by a Chemical reaction called tautomerization. An organophosphate (sometimes abbreviated OP) is the general name for Esters of Phosphoric acid.

• dehydration of secondary amides (von Braun amide degradation)
• dehydration of aldoximes with triethylamine/sulfur dioxide, zeolites, or sulfuryl chloride
• One-pot synthesis of aldehyde with hydroxylamine and sodium sulfate. In Chemistry, a dehydration reaction is usually defined as a chemical reaction that involves the loss of water from the reacting molecule In Chemistry, an amide is one of three kinds of Compounds (sometimes called acid amide the organic Functional group characterized The von Braun amide degradation is the Chemical reaction of a monosubstituted Amide with Phosphorus pentachloride to give a Nitrile and an organo In Chemistry, a dehydration reaction is usually defined as a chemical reaction that involves the loss of water from the reacting molecule oxime is one in a class of Chemical compounds with the general formula R1R2 C[[nitrogen N]] O[[hydrogen H]] where R1 is an Triethylamine is the Chemical compound with the formula N(CH2CH33 commonly abbreviated Et 3N Zeolites (Greek zein, "to boil" lithos, "a stone" are hydrated Aluminosilicate Minerals and have a micro-porous structure Sulfuryl chloride is SO2Cl2 a compound composed of Sulfur, Oxygen, and Chlorine. In Chemistry a one-pot synthesis is a strategy to improve the efficiency of a Chemical reaction whereby a Reactant is subjected to successive chemical reactions An aldehyde is an organic compound containing a terminal Carbonyl group. Hydroxylamine is a reactive chemical with formula NH2OH It can be considered a hybrid of Ammonia and Water due to parallels it shares Sodium sulfate is the Sodium salt of Sulfuric acid

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. As a general term a substance is said to be anhydrous if it contains no Water. A dry media reaction or solid-state reaction or solventless reaction is a Chemical reaction system in the absence of a Solvent. Microwave chemistry is the science of applying Microwave irradiation to chemical reactions.

• reaction of metal cyanides with aldehydes in the cyanohydrin reaction
• from aryl carboxylic acids (Letts nitrile synthesis)
• aromatic nitriles from diazonium compounds in the Sandmeyer reaction
• from alkenes and alkynes in hydrocyanation
• A commercial source for the cyanide group is diethylaluminum cyanide Et₂AlCN which can be prepared from triethylaluminium and HCN ^[6]. A Cyanohydrin reaction is an organic chemical reaction by an Aldehyde or Ketone with a Cyanide Anion or a Nitrile to form In the context of organic molecules aryl refers to any Functional group or Substituent derived from a Simple aromatic ring, may it be Phenyl Carboxylic acids are Organic acids characterized by the presence of a Carboxyl group, which has the formula -C(=OOH usually written -COOH or -CO2H The Letts nitrile synthesis is the Chemical reaction of aromatic Carboxylic acids with Metal Thiocyanates to form Nitriles Diazonium compounds or diazonium salts are a group of Organic compounds sharing a common Functional group with the characteristic structure of R-N2+ The Sandmeyer reaction is a Chemical reaction used to synthesize Aryl Halides from aryl Diazonium salts It is named after the Swiss chemist In Organic chemistry, an alkene, olefin, or olefine is an unsaturated Chemical compound containing at least one Carbon Alkynes are Hydrocarbons that have at least one Triple bond between two Carbon atoms with the formula CnH2n-2. Hydrocyanation is most fundamentally the process whereby H+ and &ndashCN Ions are added to a molecular substrate Triethylaluminium or TEA is a volatile Organometallic compound which is used in various chemical processing and as an ignitor for jet and rocket It has been used in nucleophilic addition to ketones. In Organic chemistry, a nucleophilic addition reaction is an Addition reaction where in a Chemical compound a π bond is removed by the creation A ketone (pronounced as key tone) is either the Functional group characterized by a Carbonyl group (O=C linked to two other Carbon atoms or ^[7] For an example of its use see: Kuwajima Taxol total synthesis
• cyanide ions facilitate the coupling of dibromides. The Kuwajima Taxol total synthesis by the group of Isao Kuwajima of the Tokyo Institute of Technology is one of several efforts in Taxol total synthesis published Reaction of α,α'-dibromo adipic acid with sodium cyanide in ethanol yields the cyano cyclobutane:^[8]

In the so-called Franchimont Reaction (A. Adipic acid ( IUPAC Systematic name: hexanedioic acid) is a di Carboxylic acid. Sodium cyanide is the Inorganic compound with the formula NaCN Cyclobutane, C4H8 with a molecular mass of 56107g/mol is a four Carbon Alkane in which all the Carbon Atoms are arranged 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]}

Reactions of nitriles

Nitrile groups in organic compounds can undergo various reactions when subject to certain reactants or conditions. Decarboxylation is any Chemical reaction in which a Carboxyl group (-COOH is split off from a compound as Carbon dioxide (CO2 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 RCO2H. Hydrolysis is a Chemical reaction during which one or more water molecules are split into hydrogen and hydroxide ions which may go on to participate in further reactions 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•10–5 M–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 [V. Yu. Kukushkin, A. J. L. Pombeiro, Metal-mediated and metal-catalyzed hydrolysis of nitriles (a review), Inorg. Chim. Acta, 358 (2005) 1–21].
• In organic reduction the nitrile is reduced by reacting it with hydrogen with a nickel catalyst; an amine is formed in this reaction. Organic reductions or organic oxidations or organic redox reactions are Redox reactions that take place with Organic compounds In Organic Hydrogen (ˈhaɪdrədʒən is the Chemical element with Atomic number 1 Nickel (ˈnɪkəl is a metallic Chemical element with the symbol Ni and Atomic number 28 Catalysis is the process in which the rate of a Chemical reaction is increased by means of a Chemical substance known as a catalyst Amines are Organic compounds and Functional groups that contain a basic Nitrogen Atom with a Lone pair. 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:
  • with an organozinc compound in the Blaise reaction
  • and with alcohols in the Pinner reaction. Stephen aldehyde synthesis, a Named reaction in chemistry was invented by Henry Stephen ( OBE / MBE) In Chemistry, an electrophile (literally electron-lover) is a Reagent attracted to Electrons that participates in a chemical reaction by accepting In Organic chemistry, a nucleophilic addition reaction is an Addition reaction where in a Chemical compound a π bond is removed by the creation Organozinc compounds in Organic chemistry contain Carbon to Zinc Chemical bonds Organozinc chemistry is the science of organozinc The Blaise reaction is an Organic reaction that forms a β-ketoester from the reaction of Zinc metal with a α-bromoester and a Nitrile. In Chemistry, an alcohol is any Organic compound in which a Hydroxyl group ( - O[[hydrogen H]]) is bound to a Carbon The Pinner reaction (after Adolf Pinner) is an Organic reaction of a Nitrile with an Alcohol under Acid Catalysis for instance
  • likewise, the reaction of the amine sarcosine with cyanamide yields creatine ^[12]
• Nitriles react in Friedel-Crafts acylation in the Houben-Hoesch reaction to ketones
• In reductive decyanation the nitrile group is replaced by a proton ^[13]. Amines are Organic compounds and Functional groups that contain a basic Nitrogen Atom with a Lone pair. Sarcosine is the N- Methyl derivative of Glycine. It is a natural Amino acid found in muscles and other body tissues Cyanamide ( C[[Nitrogen N]]2 H 2 is an Amide of Cyanogen, a white crystalline compound Creatine is Nitrogenous Organic acid that occurs naturally in Vertebrates and helps to supply energy to Muscle and nerve cells The Hösch reaction (also known as the Hoesch reaction or Houben-Hoesch reaction) is an Organic reaction in which a Nitrile reacts with an An effective decyanation is by a dissolving metal reduction with HMPA and potassium metal in tert-butyl alcohol. A one-electron reduction in Organic chemistry involves the transfer of an electron from a Metal to an organic substrate. Hexamethylphosphoramide (abbreviated HMPA is a colorless organic liquid with the formula 3PO Potassium (pəˈtæsiəm is a Chemical element. It has the symbol K (kalium from qalīy Atomic number 19 and Atomic mass 39 tert -Butanol, or 2-methyl-2-propanol (colourless liquid or white solid depending on the ambient temperature is the simplest Tertiary alcohol. α-Amino-nitriles can be decyanated with lithium aluminium hydride. Lithium aluminium hydride ( Li[[Aluminium Al]] H4) commonly abbreviated to LAH, is a Reducing agent used in Organic synthesis
• 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:^[14]

Organic cyanamides

Cyanamides are N-cyano compounds with general structure R1R2N-CN and related to the inorganic parent cyanamide. The Thorpe reaction is a Chemical reaction described as a self-condensation of Aliphatic Nitriles catalyzed by base to form Enamines In Organic chemistry, a nucleophilic addition reaction is an Addition reaction where in a Chemical compound a π bond is removed by the creation Organometallic chemistry is the study of Chemical compounds containing bonds between Carbon and a Metal. Alkynes are Hydrocarbons that have at least one Triple bond between two Carbon atoms with the formula CnH2n-2. Cyanamide ( C[[Nitrogen N]]2 H 2 is an Amide of Cyanogen, a white crystalline compound For an example see: von Braun reaction. The Von Braun reaction is an Organic reaction in which a Tertiary amine reacts with Cyanogen bromide to an organocyanamide.

See also

• Category:Nitriles
• For the polymer used to make safety gloves, see Nitrile rubber. A polymer is a large Molecule ( Macromolecule) composed of repeating Structural units typically connected by Covalent Chemical bonds Nitrile rubber or Buna-N, is a Synthetic rubber Copolymer of Acrylonitrile (ACN and Butadiene.
• Thorpe reaction

External links

• International Union of Pure and Applied Chemistry. The Thorpe reaction is a Chemical reaction described as a self-condensation of Aliphatic Nitriles catalyzed by base to form Enamines The International Union of Pure and Applied Chemistry ( IUPAC) (aɪjuːpæk or ay-yoo-pec) is an international Non-governmental organization "nitrile". Compendium of Chemical Terminology Internet edition. Compendium of Chemical Terminology (ISBN 0-86542-684-8 is a book published by IUPAC containing internationally accepted definitions for terms in Chemistry.
• International Union of Pure and Applied Chemistry. The International Union of Pure and Applied Chemistry ( IUPAC) (aɪjuːpæk or ay-yoo-pec) is an international Non-governmental organization "cyanide". Compendium of Chemical Terminology Internet edition. Compendium of Chemical Terminology (ISBN 0-86542-684-8 is a book published by IUPAC containing internationally accepted definitions for terms in Chemistry.

References

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