Alkyl nitrites

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This article is about alkyl nitrites as a laboratory reagent. For their use in medicine and
as a recreational drug, see Poppers.

Alkyl nitrites are a group of chemical compounds based upon the molecular

structure R-ONO. Formally they are alkyl esters of nitrous acid. They are distinct
from nitro compounds (R-NO2).
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 medications and chemical
reagents, a practice which began in the late 19th century. In their use as medicine, they
are often inhaled for relief of angina and other heart-related symptoms of disease.
However, when referred to as "poppers", alkyl nitrites represent recreational drugs.

Contents

 1Synthesis and properties

 2Reactions
 3Medical use
o 3.1Antidote to cyanide poisoning
 4References
 5External links

Synthesis and properties[edit]

Addiction experts in psychiatry, chemistry, pharmacology, forensic science, epidemiology, and the police and
legal services engaged in delphic analysis regarding 20 popular recreational drugs. Alkyl nitrites were ranked
20th social and physical harm, and 18th in dependence. [1]

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.[2] 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[edit]
 tert-Butyl nitrite has been shown to be an effective
reagent for the selective nitration
of phenols[3] and aryl sulfonamides[4]
 n-Butyl
nitrite and ammonia convert phenylhydroxylamine to
its nitrosamine derivative cupferron.[5] Likewise pyrroli
dine is a substrate for ethyl nitrite.[6]
 Alkyl nitrites are also used in the formation
of oximes with the stronger carbon acids and acid or
base catalysis for example in the reaction of 2-
butanone, ethyl nitrite and hydrochloric acid forming
the oxime,[7] the similar reaction with phenacyl
chloride,[8] or the reaction
of phenylacetonitrile with methyl nitrite and sodium
hydroxide.[9]
An isolated but classic example of the use of alkyl nitrites can be found in Woodward
and Doering's quinine total synthesis:[10]
for which they proposed this reaction mechanism:

Medical use[edit]
Antidote to cyanide poisoning[edit]
Amyl nitrite is used medically as an antidote to cyanide
poisoning,[11] The light alkyl nitrites cause the formation
of methemoglobin wherein, as an effective antidote to
cyanide poisoning, the methemoglobin combines with
the cyanide to form nontoxic cyanmethemoglobin.[citation
needed]
 First responders typically carry a cyanide poison kit
containing amyl nitrite.

References[edit]
1. ^ Nutt, D; King, LA; Saulsbury, W; Blakemore, C (24
March 2007). "Development of a rational scale to
assess the harm of drugs of potential
misuse".  Lancet.  369  (9566): 1047–
53.  doi:10.1016/s0140-6736(07)60464-4.  PMID  173
82831. S2CID  5903121.
2. ^ 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
 3. ^ Chemoselective Nitration of Phenols with tert-Butyl
Nitrite in Solution and on Solid Support Organic
Letters, Coll. Vol 11, p.4172-4175 (2009)
4. ^ Chemoselective Nitration of Aromatic
Sulfonamides with tert-Butyl Nitrite  Chemical
Communications, doi:10.1039/C2CC37481A
5. ^ Cupferron Organic Syntheses, Coll. Vol. 1, p.177
(1941); Vol. 4, p.19 (1925) Link
6. ^ 2-Pyrrolidinemethanol, α,α-diphenyl-, (±)- Organic
Syntheses, Coll. Vol. 6, p.542 (1988); Vol. 58, p.113
(1978) Link
7. ^ Dimethylglyoxime Organic Syntheses, Coll. Vol. 2,
p.204 (1943); Vol. 10, p.22 (1930) Link
8. ^ Glyoxylyl chloride, phenyl-, oxime Organic
Syntheses, Coll. Vol. 3, p.191 (1955); Vol. 24, p.25
(1944) Link
9. ^ [Benzeneacetonitrile, α-(1,1-
dimethylethoxy)carbonylcarbonyl]oxy]imino]-] Organi
c Syntheses, Coll. Vol. 6, p.199 (1988); Vol. 59, p.95
(1979) Link
10. ^ 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
11. ^ "Amyl Nitrite". Medsafe. New Zealand Medicines
and Medical Devices Safety Authority. 2000-05-18.
Archived from  the original on 2006-11-11.
Retrieved 2007-03-15.

External links[edit]
  Media related to Alkyl nitrites at Wikimedia
Commons
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Nitroalkene
From Wikipedia, the free encyclopedia
Jump to navigationJump to search
A nitroalkene, or nitro olefin, is a functional group combining the functionality of its
constituent parts, an alkene and nitro group, while displaying its own chemical
properties through alkene activation, making the functional group useful in specialty
reactions such as the Michael reaction or Diels-Alder additions.[1]

Synthesis[edit]
Nitroalkenes are synthesized by various means, notable examples include:

 Nitroaldol reactions such as the Henry reaction:[1][2][3][4]

  Nitration of an alkene with nitryl iodide
generated in-situ from silver nitrite and
elemental iodine:[5]

 Direct nitration of alkenes with nitric oxide and

an aluminum oxide catalyst in acidic conditions:[6]

 Direct nitration of alkenes with Clayfen (Iron(III)

nitrate supported on Montmorillonite clay):[7]

 Dehydration of nitro-alcohols:[8]

Reactions[edit]
Nitroalkenes are useful intermediates for various chemical
functionalities.

 A nitroalkene behaving as a Michael acceptor in

the synthesis of Lycoricidine:[1][9]
 Nitroalkene acting as an
activated dienophile toward butadiene in a Diels-
Alder cycloaddition:[1][10]

 The synthesis of pyrrole derivatives via

the Barton–Zard reaction:[11]

 Pericyclic reaction of a nitroalkene yielding

an indole:[12]

 Partial hydrogenation to an alkene baring

a hydroxylamine functional group:[13]

 Reduction to primary amines:[13][14]
  Asymmetric Stetter reaction:[15]

References[edit]
1. ^ Jump up to:        Furniss, Brian; Hannaford, Antony; Smith,
a b c d

Peter & Tatchell, Austin (1996).  Vogel's Textbook of

Practical Organic Chemistry 5th Ed. London: Longman
Science & Technical. pp. 635, 768, 1035–1036, &
1121.  ISBN  9780582462366.
2. ^ Ballini, Roberto; Castagnani, Roberto; Petrini, Marino
(1992). "Chemoselective synthesis of functionalized
conjugated nitroalkenes". The Journal of Organic
Chemistry.  57  (7): 2160–
2162.  doi:10.1021/jo00033a045.
3. ^ Worrall, David E. (1929). "Nitrostyrene". Org. Synth. 9:
66.  doi:10.15227/orgsyn.009.0066.
4. ^ Chandrasekhar, S.; Shrinidhi, A. (2014). "Useful
Extensions of the Henry Reaction: Expeditious Routes to
Nitroalkanes and Nitroalkenes in Aqueous
Media".  Synthetic Communications. 44 (20): 3008–
3018.  doi:10.1080/00397911.2014.926373.  S2CID 9843
9096.
5. ^ Waldman, Steve; Monte, Aaron, Monte; Bracey, Ann &
Nichols, David (1996). "One-pot Claisen
rearrangement/O-methylation/alkene isomerization in the
synthesis of ortho-methoxylated
phenylisopropylamines". Tetrahedron Letters.  37  (44):
7889–7892.  doi:10.1016/0040-4039(96)01807-2.
 6. ^ Mukaiyama, T.; Hata E. & Yamada, T. (1995).
"Convenient and Simple Preparation of Nitroolefins
Nitration of Olefins with Nitric Oxide". Chemistry
Letters.  24  (7): 505–506.  doi:10.1246/cl.1995.505.
7. ^ Varma, Rajender; Naicker, Kannan; Liesen, Per
(1998). "Selective nitration of styrenes with clayfen and
clayan: A solvent-free synthesis of β-
nitrostyrenes".  Tetrahedron Letters. 39 (23): 3977–
3980.  doi:10.1016/S0040-4039(98)00740-0.
8. ^ Ranganathan, Darshan; Rao, Bhushan; Ranganathan,
Subramania; Mehrotra, Ashok & Iyengar, Radha (1980).
"Nitroethylene: a stable, clean, and reactive agent for
organic synthesis".  The Journal of Organic
Chemistry.  45  (7): 1185–
1189.  doi:10.1021/jo01295a003.
9. ^ Jubert, Carole & Knochel, Paul (1992). "Preparation of
polyfunctional nitro olefins and nitroalkanes using the
copper-zinc reagents RCu(CN)ZnI". The Journal of
Organic Chemistry.  57  (20): 5431–
5438.  doi:10.1021/jo00046a027.
10. ^ Noboru Ono; Hideyoshi Miyake; Akio Kamimura &
Aritsune, Kaji (1987). "Regioselective Diels–Alder
reactions. The nitro group as a regiochemical control
element".  Perkin Transactions. 1: 1929–
1935.  doi:10.1039/P19870001929.
11. ^ Jie Jack Li (2013).  Heterocyclic Chemistry in Drug
Discovery. New York:
Wiley. ISBN 9781118354421. pp.43-4
12. ^ Novellino, Luisa; d'Ischia, Marco & Prota, Giuseppe
(1999). "Expedient Synthesis of 5,6-Dihydroxyindole and
Derivatives via an Improved Zn(II)-Assisted 2,β-
Dinitrostyrene Approach". Synthesis. 1999 (5): 793–
796.  doi:10.1055/s-1999-3469.
13. ^ Jump up to:a b Masahiko Kohno; Shigehiro Sasao & Shun-
Ichi Murahashi (1990). "Synthesis of Phenethylamines by
Hydrogenation of β-Nitrostyrenes".  Bulletin of the
Chemical Society of Japan.  63  (4): 1252–
1254.  doi:10.1246/bcsj.63.1252.
14. ^ Koch, Werner & Reichert, Benno (1935). "Über die
katalytische Hydrierung substituierter ω-
Nitrostyrole". Archiv der Pharmazie. 273 (18–20): 265–
274.  doi:10.1002/ardp.19352731802.  S2CID 95731916.
15. ^ DiRocco, D. A.; Oberg, K. M.; Dalton, D. M.; Rovis, T.
(2009).  "Catalytic Asymmetric Intermolecular Stetter
Reaction of Heterocyclic Aldehydes with Nitroalkenes:
Backbone Fluorination Improves Selectivity". Journal of
the American Chemical Society. 131 (31): 10872–
10874. doi:10.1021/ja904375q. PMC  2747345.  PMID  19
722669.

Categories: 
 Alkene derivatives
 Nitro compounds
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