Hydroquinone

Hydroquinone
IUPAC name Benzene-1,4-diol
Other names Hydroquinone Idrochinone Quinol/1-4 dihydroxy benzene/1-4 hydroxy benzene
Identifiers
CAS number	123-31-9 Y
ChemSpider	764 Y
UNII	XV74C1N1AE Y
KEGG	D00073 Y
ChEBI	CHEBI:17594 Y
ChEMBL	CHEMBL537 Y
RTECS number	MX3500000
Jmol-3D images	Image 1
SMILES c1cc(ccc1O)O
InChI InChI=1S/C6H6O2/c7-5-1-2-6(8)4-3-5/h1-4,7-8H Y Key: QIGBRXMKCJKVMJ-UHFFFAOYSA-N Y InChI=1/C6H6O2/c7-5-1-2-6(8)4-3-5/h1-4,7-8H Key: QIGBRXMKCJKVMJ-UHFFFAOYAX
Properties
Molecular formula	C6H6O2
Molar mass	110.11 g mol−1
Appearance	white solid
Density	1.3 g cm−3, solid
Melting point	172 °C, 445 K, 342 °F
Boiling point	287 °C, 560 K, 549 °F
Solubility in water	5.9 g/100 mL (15 °C)
Structure
Dipole moment	0 D
Hazards
EU classification	Harmful (Xn) Carc. Cat. 3 Muta. Cat. 3 Dangerous for the environment (N)
R-phrases	R22 R40 R41 R43 R50 R68
S-phrases	(S2) S26 S36/37/39 S61
NFPA 704	1 2 0
Flash point	165 °C
Related compounds
Related benzenediols	Pyrocatechol Resorcinol
Related compounds	1,4-benzoquinone
Y (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

Hydroquinone, also benzene-1,4-diol or quinol, is an aromatic organic compound that is a type of phenol, having the chemical formula C₆H₄(OH)₂. Its chemical structure, shown in the table at right, has two hydroxyl groups bonded to a benzene ring in a para position. It is a white granular solid. Substituted derivatives of this parent compound are also referred to as hydroquinones.

Production

Hydroquinone is produced industrially by three routes, two of which are dominant.^[1] Similar to the cumene process in reaction mechanism, the most widely used route involves the dialkylation of benzene with propene to give 1,4-diisopropylbenzene. This compound reacts with air to afford the bis(hydroperoxide), which is structurally similar to cumene hydroperoxide and rearranges to give acetone and hydroquininone in acid. A second route involves hydroxylation of phenol. The conversion uses hydrogen peroxide and affords a mixture of hydroquinone and catechol:

C₆H₅OH + H₂O₂ → C₆H₄(OH)₂ + H₂O

The third method, practiced only in China, is the oxidation of aniline by manganese dioxide followed by reduction of the resulting 1,4-benzoquinone. The process is conducted batchwise and generates a substantial waste stream.

Reactions

In term of the reactivity of its O-H groups, hydroquinone resembles other phenols, being weakly acidic. The resulting conjugate base undergoes easy O-alkylation to give mono- and diethers. Similarly, hydroquinone is highly susceptible to ring substitution by Friedel-Crafts reactions such as alkylation. This reaction is exploited en route to popular antioxidants such as 2-tert-butyl- 4-methoxyphenol ("BHA"). The useful dye quinizarin is produced by diacylation of hydroquinone with phthalic anhydride^[1]

Redox

Hydroquinone undergoes oxidation under mild conditions to give benzoquinone. This process can be reversed. Some naturally occurring hydroquinone derivatives exhibit this sort of reactivity, one example being coenzyme Q. Industrially this reaction is exploited both with hydroquinone itself but more often with its derivatives where one OH has been replaced by an amine.

Amination

An important reaction is the conversion of hydroquinone to the mono- and diamino derivatives. Methylaminophenol, used in photography, is produced in this way:^[1]

C₆H₄(OH)₂ + CH₃NH₂ → C₆H₄(OH)(N(H)CH₃) + H₂O

Similarly diamines, useful in the rubber industry as antiozone agents, are produced similarly from aniline:

C₆H₄(OH)₂ + 2 C₆H₅NH₂ → C₆H₄(N(H)CH₆H₅)₂ + 2 H₂O

Uses

Hydroquinone has a variety of uses principally associated with its action as a reducing agent which is soluble in water. It is a major component in most photographic developers for film and paper where, with the compound Metol, it reduces silver halides to elemental silver.

There are a variety of other uses associated with its reducing power. As a polymerization inhibitor, hydroquinone prevents polymerization of acrylic acid, methyl methacrylate, and other monomers that are susceptible to radical-initiated polymerization. This application exploits the antioxidant properties of hydroquinone.

Hydroquinone can undergo mild oxidation to convert to the compound parabenzoquinone, C₆H₄O₂, often called p-quinone or simply quinone. Reduction of quinone reverses this reaction back to hydroquinone. Some biochemical compounds in nature have this sort of hydroquinone or quinone section in their structures, such as Coenzyme Q, and can undergo similar redox interconversions.

Hydroquinone can lose an H⁺ from both to form a diphenolate ion. The disodium diphenolate salt of hydroquinone is used as an alternating comonomer unit in the production of the polymer PEEK.

Skin depigmentation

In human medicine, hydroquinone is used as a topical application in skin whitening to reduce the color of skin as it does not have the same predisposition to cause dermatitis as metol does. This use is banned in some countries, including the member states of the European Union under Directive 76/768/EEC:1976.^[2][3]

In 2006, the United States Food and Drug Administration revoked its previous approval of hydroquinone and proposed a ban on all over-the-counter preparations.^[4] The FDA stated that hydroquinone cannot be ruled out as a potential carcinogen. This conclusion was reached based on the extent of absorption in humans and the incidence of neoplasms in rats in several studies where adult rats were found to have increased rates of tumours, including thyroid follicular cell hyperplasias, anisokaryosis, mononuclear cell leukemia, hepatocellular adenomas and renal tubule cell ademonas. The Campaign for Safe Cosmetics has also highlighted concerns.^[5]

Numerous studies have revealed that hydroquinone can cause exogenous ochronosis, a disfiguring disease in which blue-black pigments are deposited onto the skin, if taken orally; however, skin preparations containing the ingredient are administered topically. The FDA has classified hydroquinone currently as a safe product, as currently used.^[4][6]

While using hydroquinone as lightening agent can be effective with proper use, it can also cause skin sensitivity. Using a daily sunscreen with a high PPD (persistent pigment darkening) rating reduces the risk of further damage. Hydroquinone is sometimes combined with alpha hydroxy acids that exfoliate the skin to quicken the lightening process. In the United States, topical treatments usually contain up to 2% in hydroquinone. Otherwise, higher concentrations (up to 4%) should be prescribed and used with caution.

Natural occurrences

Hydroquinones are one of the two primary reagents in the defensive glands of bombardier beetles, along with hydrogen peroxide (and perhaps other compounds, depending on the species), which collect in a reservoir. The reservoir opens through a muscle-controlled valve onto a thick-walled reaction chamber. This chamber is lined with cells that secrete catalases and peroxidases. When the contents of the reservoir are forced into the reaction chamber, the catalases and peroxidases rapidly break down the hydrogen peroxide and catalyze the oxidation of the hydroquinones into p-quinones. These reactions release free oxygen and generate enough heat to bring the mixture to the boiling point and vaporize about a fifth of it, producing a hot spray from the beetle's abdomen.^[7]

Farnesyl hydroquinone derivatives are the principal irritants exuded by the poodle-dog bush, which can cause severe contact dermatitis in humans.

Hydroquinone is thought to be the active toxin in Agaricus hondensis mushrooms.^[8]

See also

• Pyrocatechol
• Resorcinol
• Photographic developer
• Semiquinone

References

1. ^ ^{a b c} Phillip M. Hudnall "Hydroquinone" in Ullmann's Encyclopedia of Industrial Chemistry 2002, Wiley-VCH, Weinheim. 2005 Wiley-VCH, Weinheim. doi:10.1002/14356007.a13_499.
2. ^ 76/768/EEC:1976 Council Directive 76/768/EEC of 27 July 1976 on the approximation of the laws of the Member States relating to cosmetic products : http://eur-lex.europa.eu/LexUriServ/LexUriServ.do?uri=CELEX:31976L0768:EN:HTML
3. ^ Example of a product recall in Ireland
4. ^ ^{a b} United States Food and Drug Administration (2006). Skin Bleaching Drug Products for Over-the-Counter Product Use; Proposed Rule (Report). 1978N-0065. http://www.fda.gov/OHRMS/DOCKETS/98fr/78n-0065-npr0003.pdf. 
5. ^ Campaign For Safe Cosmetics - Hydroquinone
6. ^ Olumide, YM; Akinkugbe, AO; Altraide, D; Mohammed, T; Ahamefule, N; Ayanlowo, S; Onyekonwu, C; Essen, N (April 2008). "Complications of chronic use of skin lightening cosmetics". International Journal of Dermatology 47 (4): 344–53. doi:10.1111/j.1365-4632.2008.02719.x. PMID 18377596. 
7. ^ Organic Chemistry, Solomon and Fryhle, 10th edition, Wiley Publishing, 2010.
8. ^ Joval, E; Kroeger, P; N (April 1996). "Hydroquinone: the toxic compound of Agaricus hondensis.". Planta Medica 62 (2): 185. doi:10.1055/s-2006-957852. PMID 17252436. 

External links

• International Chemical Safety Card 0166
• NIOSH Pocket Guide to Chemical Hazards
• IARC Monograph: "Hydroquinone"
• IUPAC Nomenclature of Organic Chemistry (online version of the "Blue Book")