organic chemistry Organic chemistry is a subdiscipline within chemistry involving the science, scientific study of the structure, properties, and reactions of organic compounds and organic matter, organic materials, i.e., matter in its various forms that contain ...

, alkyl nitrites are a group of

organic compound Some chemical authorities define an organic compound as a chemical compound that contains a carbon–hydrogen or carbon–carbon bond; others consider an organic compound to be any chemical compound that contains carbon. For example, carbon-co ...

s based upon the

molecular structure Molecular geometry is the three-dimensional arrangement of the atoms that constitute a molecule. It includes the general shape of the molecule as well as bond lengths, bond angles, torsional angles and any other geometrical parameters that det ...

, where R represents an

alkyl group In organic chemistry, an alkyl group is an alkane missing one hydrogen. The term ''alkyl'' is intentionally unspecific to include many possible substitutions. An acyclic alkyl has the general formula of . A cycloalkyl group is derived from a cy ...

. Formally they are alkyl

ester In chemistry, an ester is a compound derived from an acid (either organic or inorganic) in which the hydrogen atom (H) of at least one acidic hydroxyl group () of that acid is replaced by an organyl group (R). These compounds contain a distin ...

s of

nitrous acid Nitrous acid (molecular formula ) is a weak and monoprotic acid known only in solution, in the gas phase, and in the form of nitrite () salts. It was discovered by Carl Wilhelm Scheele, who called it " phlogisticated acid of niter". Nitrous ac ...

. They are distinct from

nitro compound In organic chemistry, nitro compounds are organic compounds that contain one or more nitro functional groups (). The nitro group is one of the most common explosophores (functional group that makes a compound explosive) used globally. The nit ...

s (). The first few members of the series are volatile liquids;

methyl nitrite Methyl nitrite is an organic compound with the chemical formula . It is a gas, and is the simplest alkyl nitrite. Structure At room temperature, methyl nitrite exists as a mixture of ''cis'' and ''trans'' conformers. The ''cis'' conformer i ...

and ethyl nitrite are gaseous at room temperature and pressure. The compounds have a distinctive fruity odor. Another frequently encountered nitrite is

amyl nitrite Amyl nitrite is a chemical compound with the formula C5H11ONO. A variety of isomers are known, but they all feature an amyl group attached to the nitrite functional group. The alkyl group (the amyl in this case) is unreactive and the chemical ...

(3-methylbutyl nitrite). Alkyl nitrites were initially, and largely still are, used as

medication Medication (also called medicament, medicine, pharmaceutical drug, medicinal product, medicinal drug or simply drug) is a drug used to medical diagnosis, diagnose, cure, treat, or preventive medicine, prevent disease. Drug therapy (pharmaco ...

s and

chemical reagent In chemistry, a reagent ( ) or analytical reagent is a substance or compound added to a system to cause a chemical reaction, or test if one occurs. The terms ''reactant'' and ''reagent'' are often used interchangeably, but reactant specifies a ...

s, a practice which began in the late 19th century. In their use as medicine, they are often inhaled for relief of

angina Angina, also known as angina pectoris, is chest pain or pressure, usually caused by insufficient blood flow to the heart muscle (myocardium). It is most commonly a symptom of coronary artery disease. Angina is typically the result of parti ...

and other heart-related symptoms of disease. However, when referred to as "''

poppers Poppers are recreational drugs belonging to the alkyl nitrite family of chemical compounds. When fumes from these substances are inhaled, they act as potent vasodilators, producing mild euphoria, warmth, and dizziness. Most effects have a r ...

''", alkyl nitrites represent

recreational drug Recreational drug use is the use of one or more psychoactive drugs to induce an altered state of consciousness, either for pleasure or for some other casual purpose or pastime. When a psychoactive drug enters the user's body, it induces an Sub ...

Synthesis and properties

Organic nitrites are prepared from

alcohol Alcohol may refer to: Common uses * Alcohol (chemistry), a class of compounds * Ethanol, one of several alcohols, commonly known as alcohol in everyday life ** Alcohol (drug), intoxicant found in alcoholic beverages ** Alcoholic beverage, an alco ...

s and

sodium nitrite Sodium nitrite is an inorganic compound with the chemical formula . It is a white to slightly yellowish crystalline powder that is very soluble in water and is hygroscopic. From an industrial perspective, it is the most important nitrite sa ...

sulfuric acid Sulfuric acid (American spelling and the preferred IUPAC name) or sulphuric acid (English in the Commonwealth of Nations, Commonwealth spelling), known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen, ...

solution Solution may refer to: * Solution (chemistry), a mixture where one substance is dissolved in another * Solution (equation), in mathematics ** Numerical solution, in numerical analysis, approximate solutions within specified error bounds * Solu ...

. They decompose slowly on standing, the decomposition products being

oxide An oxide () is a chemical compound containing at least one oxygen atom and one other element in its chemical formula. "Oxide" itself is the dianion (anion bearing a net charge of −2) of oxygen, an O2− ion with oxygen in the oxidation st ...

s of

nitrogen Nitrogen is a chemical element; it has Symbol (chemistry), symbol N and atomic number 7. Nitrogen is a Nonmetal (chemistry), nonmetal and the lightest member of pnictogen, group 15 of the periodic table, often called the Pnictogen, pnictogens. ...

water Water is an inorganic compound with the chemical formula . It is a transparent, tasteless, odorless, and Color of water, nearly colorless chemical substance. It is the main constituent of Earth's hydrosphere and the fluids of all known liv ...

, the alcohol, and

polymerization In polymer chemistry, polymerization (American English), or polymerisation (British English), is a process of reacting monomer molecules together in a chemical reaction to form polymer chains or three-dimensional networks. There are many fo ...

products of the

aldehyde In organic chemistry, an aldehyde () (lat. ''al''cohol ''dehyd''rogenatum, dehydrogenated alcohol) is an organic compound containing a functional group with the structure . The functional group itself (without the "R" side chain) can be referred ...

. They are also prone to undergo homolytic cleavage to form alkyl radicals, the nitrite C–O bond being very weak (on the order of 40–50 kcal ⋅ mol⁻¹). Alkyl nitrites are generally weak nitrosating agents, but nitrosate amines in the presence of a nucleophile catalyst.

Reactions

* ''tert''-Butyl nitrite has been shown to be an effective reagent for the selective nitration of

phenols In organic chemistry, phenols, sometimes called phenolics, are a class of chemical compounds consisting of one or more hydroxyl groups (− O H) bonded directly to an aromatic hydrocarbon group. The simplest is phenol, . Phenolic compounds ar ...

and aryl sulfonamides * ''n''-Butyl nitrite and

ammonia Ammonia is an inorganic chemical compound of nitrogen and hydrogen with the chemical formula, formula . A Binary compounds of hydrogen, stable binary hydride and the simplest pnictogen hydride, ammonia is a colourless gas with a distinctive pu ...

convert phenylhydroxylamine to its

nitrosamine Nitrosamines (or more formally ''N''-nitrosamines) are organic compounds produced by industrial processes. The chemical structure is , where R is usually an alkyl group. Nitrosamines have a nitroso group () that are "probable human carcinogens", ...

derivative cupferron. Likewise

pyrrolidine Pyrrolidine, also known as tetrahydropyrrole, is an organic compound with the molecular formula (CH2)4NH. It is a cyclic secondary amine, also classified as a saturated heterocycle. It is a colourless liquid that is miscible with water and most ...

is a substrate for ethyl nitrite. * Alkyl nitrites are also used in the formation of

oxime In organic chemistry, an oxime is an organic compound belonging to the imines, with the general Chemical formula, formula , where R is an organic Side chain, side-chain and R' may be hydrogen, forming an aldoxime, or another organic functional g ...

s with the stronger carbon acids and acid or base catalysis for example in the reaction of 2-butanone, ethyl nitrite and

hydrochloric acid Hydrochloric acid, also known as muriatic acid or spirits of salt, is an aqueous solution of hydrogen chloride (HCl). It is a colorless solution with a distinctive pungency, pungent smell. It is classified as a acid strength, strong acid. It is ...

forming the oxime, the similar reaction with phenacyl chloride, or the reaction of phenylacetonitrile with

and

sodium hydroxide Sodium hydroxide, also known as lye and caustic soda, is an inorganic compound with the formula . It is a white solid ionic compound consisting of sodium cations and hydroxide anions . Sodium hydroxide is a highly corrosive base (chemistry), ...

. An isolated but classic example of the use of alkyl nitrites can be found in Woodward and Doering's quinine total synthesis:''The Total Synthesis of Quinine'' R. B. Woodward and W. E. Doering J. Am. Chem. Soc.; 1945; 67(5) pp 860 - 874; : QuinineNitriteReaction

for which they proposed this

reaction mechanism In chemistry, a reaction mechanism is the step by step sequence of elementary reactions by which overall chemical reaction occurs. A chemical mechanism is a theoretical conjecture that tries to describe in detail what takes place at each stage ...

: :

References

External links

*
Alkyl nitrite synthesis, with a distinct blue layer of dinitrogen trioxide from decomposition
{{DEFAULTSORT:Alkyl Nitrites Functional groups