Alkyl nitrite
In
The first few members of the series are volatile liquids; methyl nitrite and ethyl nitrite are gaseous at room temperature and pressure. The compounds have a distinctive fruity odor. Another frequently encountered nitrite is amyl nitrite (3-methylbutyl nitrite).
Alkyl nitrites were initially, and largely still are, used as
Synthesis and properties
Organic nitrites are prepared from alcohols and sodium nitrite in sulfuric acid solution. They decompose slowly on standing, the decomposition products being oxides of nitrogen, water, the alcohol, and polymerization products of the aldehyde.[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).
Reactions
- aryl sulfonamides[3]
- n-Butyl nitrite and ammonia convert phenylhydroxylamine to its nitrosamine derivative cupferron.[4] Likewise pyrrolidine is a substrate for ethyl nitrite.[5]
- Alkyl nitrites are also used in the formation of
An isolated but classic example of the use of alkyl nitrites can be found in Woodward and Doering's quinine total synthesis:[9]
for which they proposed this reaction mechanism:
References
- ^ n-butyl nitrite Organic Syntheses, Coll. Vol. 2, p.108 (1943); Vol. 16, p.7 (1936). http://www.orgsynth.org/orgsyn/prep.asp?prep=cv2p0108 Link
- ^ Chemoselective Nitration of Phenols with tert-Butyl Nitrite in Solution and on Solid Support Organic Letters, Coll. Vol 11, p.4172-4175 (2009)
- ^ Cupferron Organic Syntheses, Coll. Vol. 1, p.177 (1941); Vol. 4, p.19 (1925) Link
- ^ 2-Pyrrolidinemethanol, α,α-diphenyl-, (±)- Organic Syntheses, Coll. Vol. 6, p.542 (1988); Vol. 58, p.113 (1978) Link
- ^ Dimethylglyoxime Organic Syntheses, Coll. Vol. 2, p.204 (1943); Vol. 10, p.22 (1930) Link
- ^ Glyoxylyl chloride, phenyl-, oxime Organic Syntheses, Coll. Vol. 3, p.191 (1955); Vol. 24, p.25 (1944) Link
- ^ [Benzeneacetonitrile, α-(1,1-dimethylethoxy)carbonylcarbonyl]oxy]imino]-] Organic Syntheses, Coll. Vol. 6, p.199 (1988); Vol. 59, p.95 (1979) Link
External links
- Media related to Alkyl nitrites at Wikimedia Commons