Naphthalene
Naphthalene
Naphthalene
History
In electrophilic aromatic substitution reactions, naphthalene reacts more readily than benzene. For example,
chlorination and bromination of naphthalene proceeds
without a catalyst to give 1-chloronaphthalene and 1bromonaphthalene. Likewise, whereas both benzene and
naphthalene can be alkylated using FriedelCrafts reactions, naphthalene can also be easily alkylated by reaction
with alkenes or alcohols, using sulfuric or phosphoric acid
catalysts.
In terms of regiochemistry, electrophiles attack occurs at
the alpha position. The selectivity for alpha over beta
substitution can be rationalized in terms of the resonance structures of the intermediate: for the alpha substitution intermediate, seven resonance structures can be
drawn, of which four preserve an aromatic ring. For
beta substitution, the intermediate has only six resonance structures, and only two of these are aromatic.
Sulfonation, however, gives a mixture of the alpha
product 1-naphthalenesulfonic acid and thebetaproduct 2-naphthalenesulfonic acid, with the ratio dependent
on reaction conditions. The 1-isomer forms predominantly at 25 C, and the 2-isomer at 160 C. Sulfonation
to give the 1- and 2-sulfonic acid occurs readily:
H
2SO
4+C
10H
8C
10H
7SO
3H + H
2O
1
PRODUCTION
Further sulfonation occurs to give di-, tri-, and tetrasul- practice, distillation of coal tar yields an oil containing
fonic acids.
about 50% naphthalene, along with twelve other aromatic
compounds. This oil, after being washed with aqueous
sodium hydroxide to remove acidic components (chiey
2.2 Lithiation
various phenols), and with sulfuric acid to remove basic
components, undergoes fractional distillation to isolate
Analogous to the synthesis of phenyllithium is the con- naphthalene. The crude naphthalene resulting from this
version of 1-bromonaphthalene to 1-lithionaphthalene, a process is about 95% naphthalene by weight. The chief
lithium-halogen exchange:
impurities are the sulfur-containing aromatic compound
benzothiophene (< 2%), indane (0.2%), indene (< 2%),
and methylnaphthalene (< 2%). Petroleum-derived naphC10 H7 Br + BuLi C10 H7 Li + BuBr
thalene is usually purer than that derived from coal tar.
The resulting lithionaphthalene undergoes a second lithi- Where required, crude naphthalene can be further puriation, in contrast to the behavior of phenyllithium. These ed by recrystallization from any of a variety of solvents,
1,8-dilithio derivatives are precursors to a host of peri- resulting in 99% naphthalene by weight, referred to as 80
C (melting point). Approximately 1.3M tons are pronaphthalene derivatives.* [18]
duced annually.* [19]
2.3
With alkali metals, naphthalene forms the dark bluegreen radical anion salts such as sodium naphthalenide,
Na* +C10 H8 * -. The naphthalenide salts are strong reducing agents.
Naphthalene can be hydrogenated under high pressure in the presence of metal catalysts to give 1,2,3,4tetrahydronaphthalene(C
10H
12), also known as tetralin. Further hydrogenation yields
3.1 Other sources and occurrences
decahydronaphthalene or decalin (C
10H
18).
Aside from coal tar, trace amounts of naphthalene are
produced by magnolias and certain species of deer, as
Oxidation with O
2 in the presence of a vanadium catalyst gives phthalic well as the Formosan subterranean termite, possibly
produced by the termite as a repellant against ants,
anhydride:
poisonous fungi and nematode worms.* [20] Some
strains of the endophytic fungus Muscodor albus proC10 H8 + 4.5 O2 C6 H4 (CO)2 O + 2 CO2 +
duce naphthalene among a range of volatile organic com2 H2 O
pounds, while Muscodor vitigenus produces naphthalene
almost exclusively.* [21]
This reaction is the basis of the main use of naphthalene.
Naphthalene has been found in meteorites: n C
Oxidation can also be eected using conventional stoi10H
chiometric chromate or permanganate reagents.
7SO
3H + n CH
2=O SO
3 Production
3HC
10H
Most naphthalene is derived from coal tar. From the 7(CH
1960s until the 1990s, signicant amounts of naphtha- 2C
lene were also produced from heavy petroleum fractions 10H
during petroleum rening, but today petroleum-derived 7SO
naphthalene represents only a minor component of naph- 3H)
n+nH
thalene production.
2O
Naphthalene is the most abundant single component of
coal tar. Although the composition of coal tar varies
Neutralization step (naphthalene sulfonic acid conwith the coal from which it is produced, typical coal
densate plus sodium hydroxide):
tar is about 10% naphthalene by weight. In industrial
4.2
Niche applications
3.2
Naphthalene
medium
in
the
Uses
Naphthalene is used mainly as a precursor to other chemicals. The single largest use of naphthalene is the industrial
production of phthalic anhydride, although more phthalic
anhydride is made from o-xylene. Many azo dyes are produced from naphthalene. The insecticide 1-naphthyl-Nmethylcarbamate (carbaryl). Other useful agrichemicals
include naphthoxyacetic acids.
OH
O
OH
NH2
4.1
Many naphthalenesulfonic acids and sulfonates are useful. Alkyl naphthalene sulfonate are surfactants, The
aminonaphthalenesulfonic acids, naphthalenes substituted with amines and sulfonic acids, are intermediates
in the preparation of many synthetic dyes. The hydrogenated naphthalenes tetrahydronaphthalene (tetralin)
and decahydronaphthalene (decalin) are used as lowvolatility solvents. Naphthalene sulfonic acids are also
used in the synthesis of 1-naphthol and 2-naphthol, pre-
REFERENCES
6 See also
5
Health eects
Camphor
Dialin, Tetralin, Octalin, Decalin
List of interstellar and circumstellar molecules
Mothballs
1-Naphthol, 2-Naphthol
Sodium naphthalenide
Wagner-Jauregg reaction (classic naphthalene synthesis)
7 References
[1] Ambient Water Quality Criteria for Naphthalene
(PDF). United States Environmental Protection Agency.
Retrieved 2014-06-21.
[2] Lide, David R., ed. (2009). CRC Handbook of Chemistry
and Physics (90th ed.). Boca Raton, Florida: CRC Press.
ISBN 978-1-4200-9084-0.
[3] Anatolievich, Kiper Ruslan.naphthalene. chemister.ru.
Retrieved 2014-06-21.
[24] Hoover, Rachel (February 21, 2014).Need to Track Organic Nano-Particles Across the Universe? NASA's Got
an App for That. NASA. Retrieved February 22, 2014.
[25] Mothballs in Space. Astrobiology Magazine. Retrieved
December 25, 2008.
[26] K. Komatsua; Y. Murataa; N. Sugitaa; K. Takeuchib;
T.S.M. Wan (1993).Use of naphthalene as a solvent for
selective formation of the 1:1 DielsAlder adduct of C60
with anthracene. Tetrahedron Letters. 34 (52): 8473
8476. doi:10.1016/S0040-4039(00)61362-X.
[27] M.A. Filatov; A.V. Cheprakov (2011).The synthesis of
new tetrabenzo- and tetranaphthoporphyrins via the addition reactions of 4,7-dihydroisoindole. Tetrahedron. 67
(19): 35593566. doi:10.1016/j.tet.2011.01.052.
[28] Summary of Possum Repellent Study. Archived from
the original on September 28, 2013.
[29]Removing a possums from your roof, NSW
Department of the Environment and Heritage,
http://www.environment.nsw.gov.au/animals/
RemovingAPossumFromYourRoof.htm
[30] Santucci K, Shah B (Jan 2000). Association of naphthalene with acute hemolytic anemia. Acad Emerg Med.
7 (1): 427. PMID 10894241.
[31] MedlinePlus Encyclopedia Naphthalene poisoning
[32] NTP Technical Reports 410 and 500. NTP Technical
Reports 410 and 500, available from NTP: Long-Term Abstracts & Reports. Archived from the original on October
24, 2004. Retrieved March 6, 2005.
[33] IARC Monographs on the Evaluation of Carcinogenic
Risks to Humans. Monographs on the Evaluation of
Carcinogenic Risks to Humans, Some Traditional Herbal
Medicines, Some Mycotoxins, Naphthalene and Styrene,
Vol. 82 (2002) (p. 367). Retrieved December 25, 2008.
[34] Proposition 65, Oce of Environmental Health Hazard
Assessment
[35] Scientists May Have Solved Mystery Of Carcinogenic
Mothballs, Physorg.com, June 20, 2006.
External links
NaphthaleneNational Pesticide Information Center
NaphthaleneEPA Air Toxics Web Site
Naphthalene (PIM 363) mostly on toxicity of
naphthalene
Naphthalene CDC NIOSH Pocket Guide to
Chemical Hazards
Naphthalene in the Pesticide Properties DataBase
(PPDB)
EXTERNAL LINKS
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9.3
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