Alkyl nitrites

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Alkyl nitrites are chemical compounds of structure R-ONO. Formally they are alkyl esters of nitrous acid.

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.

Synthesis

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]

Reactions

An isolated but classic example of the use of alkyl nitrites can be found in Woodward's and Doering's quinine total synthesis [7]:

Key step in quinine total synthesis by Woodward / Doering

for which they proposed this reaction mechanism:

Reaction mechanism for ring opening

References

  1. 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
  2. Cupferron Organic Syntheses, Coll. Vol. 1, p.177 (1941); Vol. 4, p.19 (1925) Link
  3. 2-Pyrrolidinemethanol, α,α-diphenyl-, (±)- Organic Syntheses, Coll. Vol. 6, p.542 (1988); Vol. 58, p.113 (1978) Link
  4. Dimethylglyoxime Organic Syntheses, Coll. Vol. 2, p.204 (1943); Vol. 10, p.22 (1930) Link
  5. Glyoxylyl chloride, phenyl-, oxime Organic Syntheses, Coll. Vol. 3, p.191 (1955); Vol. 24, p.25 (1944) Link
  6. Benzeneacetonitrile, α-[[[(1,1-dimethylethoxy)carbonyl]]carbonyl]oxy]imino] Organic Syntheses, Coll. Vol. 6, p.199 (1988); Vol. 59, p.95 (1979) Link
  7. The Total Synthesis of Quinine R. B. Woodward and W. E. Doering J. Am. Chem. Soc.; 1945; 67(5) pp 860 - 874; doi:10.1021/ja01221a051

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