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Nitriles

Suffix: Prefix: -nitrile or -onitrile cyano-

Nitriles contain a carbon - nitrogen triple bond (R-CN or R-CN). They are indirectly related to amides (by the loss of H2O from a primary amide), and react chemically similar to carboxylic acids and their derivatives. It should be noted that H-CN is not truly a nitrile and is named hydrogen cyanide.

When a nitrile group is the highest priority functional group present in the molecule, it is named as an alkanenitrile (alkenenitrile, alkynenitrile, ...). Since the -CN must occur at the end of a chain of carbon atoms, the carbon of the nitrile will be carbon 1 in the numbering scheme. Other functional groups are located by this numbering scheme. Since the nitrile group is always at carbon number 1, there is no need to indicate its' location. Examples naming simple nitriles: Compound Name ethanenitrile propanenitrile butanenitrile 2-methylpropanenitrile Line Drawing 3D Model

cyclobutyronitrile * pentanedinitrile ** * note: the -yl is changed to a -yro. ** note: numbers are not needed as the nitriles must be at the ends of the chain.

Examples naming more complex nitriles:

Compound Name 4,4-dimethylpentanenitrile

Line Drawing

2,4-pentadienenitrile

4-amino-3-hydroxy-2-methylhexanenitrile

4-chloro-2-cyclohexenenitrile

2-mercapto-4-oxo-6-heptynenitrile

Nitriles as Substituents: In more complex molecules with higher priority functional groups the nitrile group is named as a cyano- substituent. It is located by numbering the longest chain of carbons (according to the higher priority functional group) and locating the carbon atom to which the -CN group is attached by this numbering scheme. Examples of these structures will be given in the subsequent pages.

Acetonitrile is the chemical compound with formula CH3CN. This colourless liquid is the simplest organic nitrile. It is produced mainly as a byproduct of acrylonitrile manufacture. It is used as a polar aprotic solvent in organic synthesis and in the purification of butadiene.[2] In the laboratory, it is used as a medium-polarity solvent that is miscible with water and has a convenient liquid range. With a dipole moment of 3.92 D[citation needed], acetonitrile dissolves a wide range of ionic and nonpolar compounds (e.g. Wohl-Ziegler reaction) and is useful as a mobile phase in HPLC and LCMS.

Contents
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1 Applications o 1.1 Organic synthesis o 1.2 Ligand in coordination chemistry 2 Production o 2.1 Acetonitrile shortage in 2008–2009 3 Safety o 3.1 Toxicity  3.1.1 Metabolism and excretion 4 References 5 External links

[edit] Applications
Acetonitrile is used mainly as a solvent in the purification of butadiene in refineries. It is widely used in battery applications because of its relatively high dielectric constant and ability to dissolve electrolytes. For similar reasons it is a popular solvent in cyclic voltammetry. Its low viscosity and low chemical reactivity make it a popular choice for liquid chromatography. Acetonitrile plays a significant role as the dominant solvent used in the manufacture of DNA oligonucleotides from monomers. Industrially, it is used as a solvent for the manufacture of pharmaceuticals and photographic film.[3]
[edit] Organic synthesis

Acetonitrile is a common two-carbon building block in organic synthesis[4] of many useful chemicals, including acetophene, thiamine, acetamidine, and α-napthaleneacetic acid.[5] Its reaction with cyanogen chloride affords malononitrile.[2]
[edit] Ligand in coordination chemistry

In inorganic chemistry, acetonitrile is employed as a solvent and often an easily displaceable ligand. For example, PdCl2(CH3CN)2 is prepared by heating a suspension of (polymeric) palladium chloride in acetonitrile:
PdCl2 + 2 CH3CN → PdCl2(CH3CN)2

The CH3CN groups undergo rapid displacement by many other ligands.

[edit] Production
Acetonitrile is a by-product from the manufacture of acrylonitrile.[6] Production trends for acetonitrile thus generally follow those of acrylonitrile. Acetonitrile can also be produced by many other methods, but these are of no commercial importance as of 2002. Illustrative routes are by dehydration of acetamide or by hydrogenation of mixtures of carbon monoxide and ammonia.[7] The main distributors of acetonitrile in the world are: INEOS, Purification Technologies Inc, BioSolve BV, Carlo Erba Reagents, Panreac, J.T. Baker Chemical, VWR, Sigma Aldrich, and Petrolchem Trading Ltd. In 1992, 32.3 million pounds (14,700 t) of acetonitrile were produced in the US.
[edit] Acetonitrile shortage in 2008–2009

Starting in October 2008, the worldwide supply of acetonitrile was low because Chinese production was shut down for the Olympics. Furthermore, a U.S. factory was damaged in Texas during Hurricane Ike.[8] Owing to the global economic slowdown, the production of acrylonitrile that is used in acrylic fibers and acrylonitrile-butadiene-styrene (ABS) resins decreased. Because acetonitrile is a byproduct in the production of acrylonitrile, its production has also decreased.[9] The global shortage of acetonitrile continued through early 2009.
http://en.wikipedia.org/wiki/Acetonitrile

Nitrile
Definition

A nitrile is an organic chemical that contains a cyano functional group (subunit), CN-, in which the carbon and nitrogen atoms have a triple bond i.e. C≡N-. The general chemical formula of a nitrile is RCN, where R is the organic group.

Nitriles can be thought of as organic cyanides, although they are ordinarily much less toxic than simple cyanide salts such as sodium or potassium cyanide (NaCN or KCN).
Additional Information Under the standard chemical naming convention used by chemists

(IUPAC nomenclature), nitriles are named according to these rules: a. Compounds in which the carbon atom of the CN group is attached to an acyclic hydrocarbon fragment are generally named using the suffix nitrile. b. Nitriles in which the -CN group can be thought of as having replaced the -COOH group of a corresponding trivially named carboxylic acid are named by removing "ic acid" or "oic acid" and replacing it with onitrile. c. A nitrile that is an analog of a compound that has "carboxylic acid" as its suffix, is named by subsitituting the suffix carbonitrile

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In addition, the use of cyanide as a suffix is still common, and one nitrile may be known by a variety of different names. Some examples of these are shown below, with the most rigorous IUPAC name for each shown in red:

When there are other functional groups that take naming precedence over the cyanide/nitrile group, the prefix cyano is used. In this example, we have color-coded the parts of the name and the parts of the molecule that correspond to each other:

Nitriles are usually less toxic than cyanide salts, although they may contain some of the latter as impurities. Aliphatic nitriles can be metabolized to the free cyanide ion, making them generally more toxic than arylnitriles which are stable in the body. The cyanide unit occurs in other compounds such as cyanamide (carbodiimide, H2NC≡N), cyanoacetic acid (malonic mononitrile, N≡CH2COOH), potassium ferricyanide (K3[Fe(CN)6]) and potassium ferrocyanide (K4[Fe(CN)6]), however these compounds do not release cyanide and are therefore much less toxic than simple cyanide salts or many nitriles. Nitriles have tremendous industrial importance. For example, through a process called hydrocyanation, HCN reacts with 1,4-butadiene (an alkene) to form adiponitrile (1,4dicyanobutane, hexanedinitrile, tetramethylene cyanide, NC(CH2)4CN), a chemical precursor to hexamethylene diamine (1,6-diaminohexane, H2N(CH2)6NH2), one of the polymers used to make nylon. The wide range of chemical reactivity for nitriles is what makes them so useful, but this same feature means that they are incompatible with many substances (see MSDS relevance below).

Nitriles are also important laboratory and industrial solvents because of their unusual physical properties. For example, nitriles boil much higher than the corresponding hydrocarbon of similar molecular weight; acetonitrile (CH3CN, FW 41 amu) boils at 81 °C whereas propane (CH3CH2CH3, FW 44 amu) boils at -42 °C. This increase can be ascribed to the polar nature (uneven distribution of electron density) of nitriles; the C≡N bond is polarized and intermolecular alignment of these dipoles increases the intermolecular attraction between the solvent molecules. In the drawing below, the lone pair of electrons on the nitrogen atom (present in all nitriles, but normally omitted from simple drawings) is explicitly shown to help the reader understand the polarity of the molecule:

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This polarity makes nitriles terrific aprotic (no easily ionized hydrogen atom) solvents. For example, acetonitrile is completely miscible with water and methanol as well as organic solvents such as diethyl ether, ethyl acetate, and acetone; at the same time it is virtually insoluble in saturated hydrocarbons. This versatility makes it trivially easily to remove acetonitrile from reaction mixtures without resorting to distillation. Its high dielectric constant (38) and dipole moment (3.9 Debye) make acetonitrile ideal for promoting chemical reactions where ionization is involved, as a solvent for inorganic salts (electrolytes), and as a medium for electrochemical studies.
MSDS Relevance Nitriles usually appear on an MSDS in the context of incompatible materials. In general, nitriles are incompatible with acids, bases, amines, oxiranes, and acid anhydrides.

Nitriles can produce other nitriles and highly toxic HCN gas as well as carbon monoxide when burned. You may therefore also see nitriles mentioned as a toxic byproduct of combustion. Although not highly toxic like inorganic cyanides or hydrogen cyanide, nitriles are generally toxic materials and should be used with proper engineering controls and personal protective equipment. As with any hazardous substance, minimize your exposure or potential exposure. Nitrile may also appear on an MSDS as a recommended type of glove, boot, apron or other piece of personal protective equipment. Polymerization of acrylonitrile gives nitrile rubber, a substance with excellent resistance to oils and greases. Nitrile gloves are low cost, have good physical properties, and offer good dexterity. However, they are a poor choice for working with benzene, methylene chloride, trichloroethylene, and many ketones. In this context, the compatibility of the substance with respect to nitrile gaskets, seals or o-rings may also be mentioned.

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