Naphthalene

Not to be confused with Naphtha, a broad term describing liquid hydrocarbon mixtures.

Naphthalene
IUPAC name bicyclo[4.4.0]deca-1,3,5,7,9-pentene
Other names Tar Camphor, White Tar, Moth Flakes, albocarbon, naphthaline, naphthalin, antimite
Identifiers
CAS number	91-20-3 Y
PubChem	931
ChemSpider	906 Y
UNII	2166IN72UN Y
EC number	202-049-5
KEGG	C00829 Y
ChEBI	CHEBI:16482 N
ChEMBL	CHEMBL16293 Y
RTECS number	QJ0525000
Jmol-3D images	Image 1
SMILES c1ccc2ccccc2c1
InChI InChI=1S/C10H8/c1-2-6-10-8-4-3-7-9(10)5-1/h1-8H Y Key: UFWIBTONFRDIAS-UHFFFAOYSA-N Y InChI=1/C10H8/c1-2-6-10-8-4-3-7-9(10)5-1/h1-8H Key: UFWIBTONFRDIAS-UHFFFAOYAC
Properties
Molecular formula	C10H8
Molar mass	128.17 g mol−1
Appearance	White solid crystals/flakes, strong odor of coal tar
Density	1.14 g/cm³
Melting point	80.26 °C, 353 K, 176 °F
Boiling point	218 °C, 491 K, 424 °F
Solubility in water	Approximately 30 mg/L
Hazards
R-phrases	R22, R40, R50/53
S-phrases	(S2), S36/37, S46, S60, S61
Main hazards	Flammable, sensitizer, possible carcinogen. Dust can form explosive mixtures with air
NFPA 704	2 2 0
Flash point	79–87 °C
Autoignition temperature	525 °C
N (verify) (what is: Y/N?) Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa)
Infobox references

Naphthalene is an organic compound with formula C₁₀H₈. It is a white crystalline solid with a characteristic odor that is detectable at concentrations as low as 0.08 ppm by mass.^[1] As an aromatic hydrocarbon, naphthalene's structure consists of a fused pair of benzene rings. It is best known as the main ingredient of traditional mothballs.

History

In 1819–1820, at least two chemists reported a white solid with a pungent odor derived from the distillation of coal tar. In 1821, John Kidd described many of this substance's properties and the means of its production, and proposed the name naphthaline, as it had been derived from a kind of naphtha (a broad term encompassing any volatile, flammable liquid hydrocarbon mixture, including coal tar).^[2] Naphthaline's chemical formula was determined by Michael Faraday in 1826. The structure of two fused benzene rings was proposed by Emil Erlenmeyer in 1866,^[3] and confirmed by Carl Gräbe three years later.

Structure and reactivity

A naphthalene molecule can be viewed as the fusion of a pair of benzene rings. (In organic chemistry, rings are fused if they share two or more atoms.) As such, naphthalene is classified as a benozenoid polycyclic aromatic hydrocarbon (PAH). There are two sets of equivalent hydrogen atoms: the alpha positions are positions 1, 4, 5, and 8 on the drawing below, and the beta positions are positions 2, 3, 6, and 7.

Unlike benzene, the carbon-carbon bonds in naphthalene are not of the same length. The bonds C1–C2, C3–C4, C5–C6 and C7–C8 are about 1.36 Å (136 pm) in length, whereas the other carbon-carbon bonds are about 1.42 Å (142 pm) long. This difference, which was established by x-ray diffraction^{[citation needed]}, is consistent with the valence bond model of bonding in naphthalene that involves three resonance structures (as shown below); whereas the bonds C1–C2, C3–C4, C5–C6 and C7–C8 are double in two of the three structures, the others are double in only one.

Like benzene, naphthalene can undergo electrophilic aromatic substitution. For many electrophilic aromatic substitution reactions, naphthalene reacts under milder conditions than does benzene. For example, whereas both benzene and naphthalene react with chlorine in the presence of a ferric chloride or aluminium chloride catalyst, naphthalene and chlorine can react to form 1-chloronaphthalene even without a catalyst. Likewise, whereas both benzene and naphthalene can be alkylated using Friedel-Crafts reactions, naphthalene can also be alkylated by reaction with alkenes or alcohols, with sulfuric or phosphoric acid as the catalyst.

Substituted derivatives

Two isomers are possible for mono-substituted naphthalenes, corresponding to substitution at an alpha or beta position. Usually, electrophiles attack 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 the "beta" product 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.

Naphthalene can be hydrogenated under high pressure in the presence metal catalysts to give 1,2,3,4-tetrahydronaphthalene or tetralin (C₁₀H₁₂). Further hydrogenation yields decahydronaphthalene or decalin (C₁₀H₁₈). Oxidation with chromate or permanganate, or catalytic oxidation with O₂ and a vanadium catalyst, gives phthalic acid.

Production

Most naphthalene is derived from coal tar. From the 1960s until the 1990s, significant amounts of naphthalene were also produced from heavy petroleum fractions during petroleum refining, but today petroleum-derived naphthalene represents only a minor component of naphthalene production.

Naphthalene is the most abundant single component of coal tar. Although the composition of coal tar varies with the coal from which it is produced, typical coal tar is about 10% naphthalene by weight. In industrial practice, distillation of coal tar yields an oil containing about 50% naphthalene, along with a variety of other aromatic compounds. This oil, after being washed with aqueous sodium hydroxide to remove acidic components (chiefly various phenols), and with sulfuric acid to remove basic components, undergoes fractional distillation to isolate naphthalene. The crude naphthalene resulting from this process is about 95% naphthalene by weight, often referred to as 78°C (melting point). The chief impurities are the sulfur-containing aromatic compound benzothiophene (<2%), indane (0.2%), indene (<2%), and methylnapthalene (<2%). Petroleum-derived naphthalene is usually purer than that derived from coal tar. Where required, crude naphthalene can be further purified by recrystallization from any of a variety of solvents, resulting in 99% naphthalene by weight, referred to as 80 °C (melting point). Approximately 1M tons are produced annually.^[4]

In North America, coal tar producers are Koppers Inc. and Recochem Inc., and petroleum-derived producer is Advanced Aromatics, L.P.

Natural occurrence

Trace amounts of naphthalene are produced by magnolias and specific types of deer, as well as the Formosan subterranean termite, possibly produced by the termite as a repellant against "ants, poisonous fungi and nematode worms."^[5] Some strains of the endophytic fungus Muscodor albus produce naphthalene among a range of volatile organic compounds, while Muscodor vitigenus produces naphthalene almost exclusively.^[6]

Naphthalene has been found in meteorites. It has also been discovered in the interstellar medium in the direction of the star Cernis 52 in the constellation Perseus.^[7]

Gaseous naphthalene

Recent research at the University of Georgia, led by Dr. Michael Duncan, has shown that protonated cations of naphthalene are the source of part of the spectrum of the Unidentified Interstellar Bands (UIBs). The gaseous naphthalene found in space is different from crystalline form typically used in mothballs in that it has an additional hydrogen atom, with the empirical formula: C₁₀H+
9. The UIBs have been observed by astronomers, and until recently, there has been no solid evidence identifying the compounds responsible for them. The research has recently been publicized as "Mothballs in Space." ^[8]

Uses

As a chemical intermediate

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. Other naphthalene-derived chemicals include alkyl naphthalene sulfonate surfactants, and the insecticide 1-naphthyl-N-methylcarbamate (carbaryl). Naphthalenes substituted with combinations of strongly electron-donating functional groups, such as alcohols and amines, and strongly electron-withdrawing groups, especially sulfonic acids, are intermediates in the preparation of many synthetic dyes. The hydrogenated naphthalenes tetrahydronaphthalene (tetralin) and decahydronaphthalene (decalin) are used as low-volatility solvents. Naphthalene is also used in the synthesis of 2-naphthol, a precursor for various dyestuffs, pigments, rubber processing chemicals and other miscellaneous chemicals and pharmaceuticals.^[4]

Naphthalene sulfonic acids are used in the manufacture of naphthalene sulfonate polymer plasticizers (dispersants), which are used to produce concrete and plasterboard (wallboard or drywall). They are also used as dispersants in synthetic and natural rubbers, and as tanning agents (syntans) in leather industries, agricultural formulations (dispersants for pesticides), dyes and as a dispersant in lead–acid battery plates.

Naphthalene sulfonate polymers are produced by reacting naphthalene with sulfuric acid and then polymerizing with formaldehyde, followed by neutralization with sodium hydroxide or calcium hydroxide. These products are commercially sold in solution (water) or dry powder form.

• Sulfonation Step (sulfuric acid plus naphthalene):

H₂SO₄ + C₁₀H₈ → C₁₀H₇-SO₃H + H₂O

• Polymerization Step (naphthalenesulfonic acid plus formaldehyde):

C₁₀H₇-SO₃H + CH₂-O → C₁₀H₇-SO₃H-(C₁₀H₇-SO₃H)_n + H₂SO₄

• Neutralization Step (naphthalene sulfonic acid condensate plus sodium hydroxide):

C₁₀H₇-SO₃H-(C₁₀H₇-SO₃H)_n + NaOH → C₁₀H₇-SO₃Na-(C₁₀H₇-SO₃Na)_n + H₂O + Na₂SO₄

Wetting agent/surfactant

Alkyl naphthalene sulfonates (ANS) are used in many industrial applications as nondetergent wetting agents that effectively disperse colloidal systems in aqueous media. The major commercial applications are in the agricultural chemical industry, which uses ANS for wettable powder and wettable granular (dry-flowable) formulations, and the textile and fabric industry, which utilizes the wetting and defoaming properties of ANS for bleaching and dyeing operations.

As a fumigant

The most familiar use of naphthalene is as a household fumigant, such as in mothballs although 1,4-dichlorobenzene (or p-dichlorobenzene) is now more widely used. In a sealed container containing naphthalene pellets, naphthalene vapors build up to levels toxic to both the adult and larval forms of many moths that attack textiles. Other fumigant uses of naphthalene include use in soil as a fumigant pesticide, in attic spaces to repel animals and insects, and in museum storage-drawers and cupboards to protect the contents from attack by insect pests.

Niche applications

It is used in pyrotechnic special effects such as the generation of black smoke and simulated explosions. In the past, naphthalene was administered orally to kill parasitic worms in livestock. Naphthalene and its alkyl homologs are the major constituents of creosote. Naphthalene is used in engineering to study heat transfer using mass sublimation.

Health effects

Exposure to large amounts of naphthalene may damage or destroy red blood cells. Humans, in particular children, have developed this condition, known as hemolytic anemia, after ingesting mothballs or deodorant blocks containing naphthalene. Symptoms include fatigue, lack of appetite, restlessness, and pale skin. Exposure to large amounts of naphthalene may cause confusion, nausea, vomiting, diarrhea, blood in the urine, and jaundice (yellow coloration of the skin).^[9]

When the U.S. National Toxicology Program exposed male and female rats and mice to naphthalene vapors on weekdays for two years,^[10] male and female rats exhibited evidence of carcinogenic activity based on increased incidences of adenoma and neuroblastoma of the nose, female mice exhibited some evidence of carcinogenic activity based on increased incidences of alveolar and bronchiolar adenomas of the lung, and male mice exhibited no evidence of carcinogenic activity.

The International Agency for Research on Cancer (IARC)^[11] classifies naphthalene as possibly carcinogenic to humans and animals (Group 2B). The IARC also points out that acute exposure causes cataracts in humans, rats, rabbits, and mice; and that hemolytic anemia, described above, can occur in children and infants after oral or inhalation exposure or after maternal exposure during pregnancy. Under California's Proposition 65, naphthalene is listed as "known to the State to cause cancer".^[12]

Over 400 million people have an inherited condition called glucose-6-phosphate dehydrogenase deficiency. Exposure to naphthalene is more harmful for these people and may cause hemolytic anemia at lower doses.^{[citation needed]}

In China, the use of naphthalene in mothballs is forbidden.^[13] It is due partly to the health effects as well as the wide use of natural camphor as replacement.

See also

• Decalin
• Camphor
• Naphthol
• Classic naphthalene synthesis: the Wagner-Jauregg reaction
• Sodium naphthalenide

External links

• National Pesticide Information Center — Mothballs Case Profile
• Naphthalene — EPA Air Toxics Web Site
• Naphthalene (PIM 363) — mostly on toxicity of naphthalene

References

1. ^ Amoore J E and Hautala E (1983). "Odor as an aid to chemical safety: Odor thresholds compared with threshold limit values and volatiles for 214 industrial chemicals in air and water dilution". J Appl Toxicology 3 (6): 272–290. doi:10.1002/jat.2550030603. 
2. ^ John Kidd (1821). "Observations on Naphthalene, a peculiar substance resembling a concrete essential oil, which is produced during the decomposition of coal tar, by exposure to a red heat". Philosophical Transactions 111: 209–221. doi:10.1098/rstl.1821.0017. 
3. ^ Emil Erlenmeyer (1866). "Studien über die s. g. aromatischen Säuren". Annalen der Chemie und Pharmacie 137 (3): 327–359. doi:10.1002/jlac.18661370309. 
4. ^ ^{a b} Gerd Collin, Hartmut Höke, Helmut Greim "Naphthalene and Hydronaphthalenes"in Ullmann's Encyclopedia of Industrial Chemistry Wiley-VCH, Weinheim, 2003. DOI: 10.1002/14356007.a17_001.pub2. Article Online Posting Date: March 15, 2003.
5. ^ "Termite 'mothball' keep insects at bay". Sci/Tech. BBC News. http://news.bbc.co.uk/1/hi/sci/tech/76115.stm. 
6. ^ Daisy BH, Strobel GA, Castillo U, et al. (November 2002). "Naphthalene, an insect repellent, is produced by Muscodor vitigenus, a novel endophytic fungus". Microbiology (Reading, Engl.) 148 (Pt 11): 3737–41. PMID 12427963. http://mic.sgmjournals.org/cgi/content/abstract/148/11/3737. 
7. ^ "Interstellar Space Molecules That Help Form Basic Life Structures Identified". Science Daily. September 2008. http://www.sciencedaily.com/releases/2008/09/080919075007.htm. 
8. ^ "Mothballs in Space". Astrobiology Magazine. http://www.astrobio.net/pressrelease/3243/mothballs-in-space. Retrieved December 25, 2008. 
9. ^ MedlinePlus Encyclopedia Naphthalene poisoning
10. ^ "NTP Technical Reports 410 and 500". NTP Technical Reports 410 and 500, available from NTP: Long-Term Abstracts & Reports. http://ntp.niehs.nih.gov/INDEX.CFM?OBJECTID=0847DDA0-F261-59BF-FAA04EB1EC032B61. Retrieved March 6, 2005. 
11. ^ "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). http://monographs.iarc.fr/ENG/Monographs/vol82/index.php. Retrieved December 25, 2008. 
12. ^ Proposition 65, Office of Environmental Health Hazard Assessment
13. ^ 国务院经贸办、卫生部关于停止生产和销售萘丸提倡使用樟脑制品的通知（国经贸调（1993）64号） 

• CRC Handbook of Chemistry and Physics 87th edition