Inorganic chemistry,alkyl nitrites are a group oforganic compounds based upon themolecular structureR−O−N=O, where R represents analkyl group. Formally they are alkylesters ofnitrous acid. They are distinct fromnitro compounds (R−NO₂).

The first few members of the series arevolatile liquids;methyl nitrite andethyl nitrite are gaseous at room temperature and pressure. The compounds have a distinctive fruity odor. Another frequently encountered nitrite isamyl nitrite (3-methylbutyl nitrite).

Alkyl nitrites were initially, and largely still are, used asmedications andchemical reagents, a practice which began in the late 19th century. In their use as medicine, they are often inhaled for relief ofangina and other heart-related symptoms of disease. However, when referred to as "poppers", alkyl nitrites representrecreational drugs.

Organic nitrites are prepared fromalcohols andsodium nitrite insulfuric acidsolution. They decompose slowly on standing, the decomposition products beingoxides ofnitrogen,water, the alcohol, andpolymerization products of thealdehyde.^[1] 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).^{[citation needed]} Alkyl nitrites are generally weaknitrosating agents, but nitrosate amines in the presence of a nucleophile catalyst.^[2]

• tert-Butyl nitrite has been shown to be an effective reagent for the selective nitration ofphenols^[3] andaryl sulfonamides^[4]
• n-Butyl nitrite andammonia convertphenylhydroxylamine to itsnitrosamine derivativecupferron.^[5] Likewisepyrrolidine is a substrate for ethyl nitrite.^[6]
• Alkyl nitrites are also used in the formation ofoximes with the strongercarbon acids and acid or base catalysis for example in the reaction of2-butanone,ethyl nitrite andhydrochloric acid forming the oxime,^[7] the similar reaction withphenacyl chloride,^[8] or the reaction ofphenylacetonitrile withmethyl nitrite andsodium hydroxide.^[9]

An isolated but classic example of the use of alkyl nitrites can be found in Woodward and Doering'squinine total synthesis:^[10]

for which they proposed thisreaction mechanism:

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• Alkyl nitrite synthesis, with a distinct blue layer of dinitrogen trioxide from decomposition

• Alkyl nitrites
• Functional groups

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