Phenol

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This article is about the molecule. For the class of chemicals containing a phenol group, see Phenols.

Phenol

IUPAC name[hide] Phenol Other names[hide] Carbolic Acid, Benzenol, Phenylic Acid, Hydroxybenzene, Phenic acid Identifiers CAS number PubChem ChemSpider 108-95-2 996 971

UNII DrugBank KEGG ChEBI ChEMBL RTECS number ATC code Jmol-3D images

339NCG44TV DB03255 D06536 CHEBI:15882 CHEMBL14060 SJ3325000 C05BB05,D08AE03, N01BX03, R02AA19 Image 1 SMILES

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InChI
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Properties Molecular formula Molar mass Appearance Density Melting point Boiling point Solubility in water Acidity (pKa) C6H6O 94.11 g mol1 transparent crystalline solid 1.07 g/cm3 40.5 C, 314 K, 105 F 181.7 C, 455 K, 359 F 8.3 g/100 mL (20 C) 9.95 (in water), 29.1 (in acetonitrile)[2] max Dipole moment 270.75 nm[1] 1.7 D Hazards GHS pictograms

[3]

GHS hazard statements GHS precautionary statements EU classification

H301, H311, H314, H331, H341, H373[3] P261, P280, P301+310, P305+351+338,P310[3]

Toxic (T) Muta. Cat. 3 Corrosive (C)

R-phrases S-phrases NFPA 704

R23/R24/R25-R34-R48/R20/R21/R22-R68 (S1/2)-S24/S25-S26-S28-S36/S37/S39-S45

2 3 0
COR
Flash point 79 C Related compounds Related compounds Benzenethiol (verify) (what is: / ?)

Except where noted otherwise, data are given for materials in theirstandard state (at 25 C, 100 kPa) Infobox references

Phenol, also known as carbolic acid and phenic acid, is an organic compound with the chemical formula C6H5OH. It is a white crystallinesolid at room temperature. The molecule consists of a phenyl (-C6H5), bonded to a hydroxyl (-OH) group. It is produced on a large scale (about 7 billion kg/year) as a precursor to many materials and useful compounds.[4] It is only mildly acidic but requires careful handling due to its propensity to cause burns. Phenol was first extracted from coal tar, and its major uses involve its conversion to plastics or related materials. Phenols are key for building polycarbonates, epoxies, Bakelite, nylon, detergents and a large collection of drugs, herbicides and pharmaceuticals. See also: Bisphenol A
Contents
[hide]

1 Properties 1.1 Acidity 1.1.1 Phenoxide anion 1.1.2 Tautomerism

1.2 Reactions

2 Production 3 Uses 3.1 Niche uses

4 History 4.1 Second World War

5 Occurrence 6 Biodegradation 7 Toxicity 8 Phenols 9 See also 10 References 11 External links

[edit]Properties
Phenol is appreciably soluble in water, with about 8.3 g dissolving in 100 mL (0.88 M). The sodium salt of phenol, sodium phenoxide, is far more water soluble.

[edit]Acidity
It is slightly acidic: the phenol molecules have weak tendencies to lose the H+ ion from the hydroxyl group, resulting in the highly water-soluble phenolate anion C6H5O (also called phenoxide).[5] Compared to aliphatic alcohols, phenol is about 1 million times more acidic, although it is still considered a weak acid. It reacts completely with aqueous NaOH to lose H+, whereas most alcohols react only partially. Phenols are less acidic than carboxylic acids, and even carbonic acid. One explanation for the increased acidity over alcohols is resonance stabilization of the phenoxide anion by the aromatic ring. In this way, the negative charge on oxygen is shared by the ortho and para carbon atoms.[6] In another explanation, increased acidity is the result of orbital overlap between the oxygen's lone pairs and the aromatic system.[7] In a third, the dominant effect is the induction from the sp2 hybridised carbons; the comparatively more powerful inductive withdrawal of electron density that is provided by the sp 2 system compared to an sp3system allows for great stabilization of the oxyanion. In making this conclusion, one can examine the pKa of the enol of acetone, which is 19.0, in comparison to phenol with a pKa of 10.0.[8]However, this similarity of acidities of phenol and acetone enol is not observed in the gas phase, and is because the difference of solvation energies of the deprotonated acetone enol and phenoxide almost exactly offsets the experimentally observed gas phase acidity difference. It has recently been shown that only about 1/3 of the increased acidity of phenol is due to inductive effects, with resonance accounting for the rest.[9]

[edit]Phenoxide anion
Phenol can be deprotonated with moderate base such as triethylamine, forming the nucleophilic phenoxide anion or phenolate anion, which is highly water-soluble.

Resonance structures of the phenoxide anion

The phenoxide anion has a similar nucleophilicity to free amines, with the further advantage that its conjugate acid (neutral phenol) does not become entirely deactivated as a nucleophileeven in moderately acidic conditions. Phenols are sometimes used in peptide synthesis to "activate" carboxylic acids or esters to form activated esters. Phenolate esters are far more stable than acid anhydrides or acyl halides but are sufficiently reactive under mild conditions to facilitate the formation of amide bonds. Phenoxides are enolates stabilised by aromaticity. Under normal circumstances, phenoxide is more reactive at the oxygen position, but the oxygen position is a "hard" nucleophile whereas the alpha-carbon positions tend to be "soft".[10]

[edit]Tautomerism

Phenol-cyclohexadienone tautomerism

Phenol exhibits keto-enol tautomerism with its unstable keto tautomer cyclohexadienone, but only a tiny fraction of phenol exists as the keto form. The equilibrium constant for enolisation is approximately 1013, meaning that only one in every ten trillion molecules is in the keto form at any moment.[11] The small amount of stabilisation gained by exchanging a C=C bond for a C=O bond is more than offset by the large destabilisation resulting from the loss of aromaticity. Phenol therefore exists entirely in the enol form. [12]

[edit]Reactions

Neutral phenol substructure "shape". An image of a computed electrostatic surface of neutral phenol, showing neutral regions in green, electronegative areas in orange-red, and the electropositive phenolic proton in blue.

Phenol is highly reactive toward electrophilic aromatic substitution as the oxygen atom's pi electrons donate electron density into the ring. By this general approach, many groups can be appended to the ring, via halogenation, acylation,sulfonation, and other processes. However, phenol's ring is so strongly activated second only to aniline - that bromination or chlorination of phenol leads to substitution on all carbons ortho and para to the hydroxy group, not only on one carbon.

[edit]Production
Because of phenol's commercial importance, many methods have been developed for its production. The dominant current route, accounting for 95% of production (2003), involves the partial oxidation of cumene (isopropylbenzene) via the Hock rearrangement:[4] C6H5CH(CH3)2 + O2 C6H5OH + (CH3)2CO Compared to most other processes, the cumene-hydroperoxide process uses relatively mild synthesis conditions, and relatively inexpensive raw materials. However, to operate economically, there must be demand for both phenol, and the acetone by-product. An early commercial route, developed by Bayer and Monsanto in the early 1900's, begins with the reaction of strong base withbenzenesulfonate[13]: C6H5SO3H + 2 NaOH C6H5OH + Na2SO3 + H2O Other methods under consideration involve: hydrolysis of chlorobenzene, using base or steam (Raschig-Hooker process)[14]:

C6H5Cl + H2O C6H5OH + HCl direct oxidation of benzene with nitrous oxide, a potentially "green" process:

C6H6 + N2O C6H5OH + N2 oxidation of toluene, as developed by Dow Chemical:

C6H5CH3 + 2 O2 C6H5OH + CO2 + H2O In the Lummus Process, the oxidation of toluene to benzoic acid is conducted separately. Phenol is also recoverable byproduct of coal pyrolysis[14].

[edit]Uses
The major uses of phenol, consuming two thirds of its production, involve its conversion to plastics or related materials. Condensation with acetone givesbisphenol-A, a key precursor to polycarbonates and epoxide resins. Condensation of phenol, alkylphenols, or diphenols with formaldehyde gives phenolic resins, a famous example of which

is Bakelite. Hydrogenation of phenol gives cyclohexanone, a precursor to nylon. Nonionic detergents are produced by alkylation of phenol to give the alkylphenols, e.g., nonylphenol, which are then subjected to ethoxylation.[4] Phenol is also a versatile precursor to a large collection of drugs, most notably aspirin but also many herbicides and pharmaceuticals. Phenol is also used as an oral anesthetic/analgesic, commonly used to temporarily treat pharyngitis.

[edit]Niche

uses

Phenol is so inexpensive that it attracts many small-scale uses. It once was widely used as an antiseptic, especially as Carbolic soap, from the early 1900s through the 1970s. It is a component of industrial paint strippers used in the aviation industry for the removal of epoxy, polyurethane and other chemically resistant coatings.[15] Phenol derivatives are also used in the preparation of cosmetics including sunscreens,[16] hair dyes, and skin lightening preparations.[17]

[edit]History
Phenol was discovered in 1834, when it was first extracted from coal tar by Friedlieb Ferdinand Runge, which remained the primary source until the development of the petrochemical industry. The antiseptic properties of phenol were used by Sir Joseph Lister (18271912) in his pioneering technique of antiseptic surgery, although the skin irritation caused by continual exposure to phenol eventually led to the substitution of aseptic (germ-free) techniques in surgery. Lister decided that the wounds themselves had to be thoroughly cleaned. He then covered the wounds with a piece of rag or lint[18] covered in phenol, or carbolic acid as he called it. It is also the active ingredient in some oral analgesics such as Chloraseptic spray as well as Carmex. Phenol was also the main ingredient of the Carbolic Smoke Ball, an ineffective device marketed in London in the 19th century as protecting the user against influenza and other ailments, and the subject of a famous law case.

[edit]Second

World War

Injections of phenol have occasionally been used as a means of execution. In particular, phenol and cyanide injections were used as a means of individual execution by the Nazis during the Second World War.[19] Originally used by the Nazis in 1939 as part of Action T4, phenol,[20] inexpensive, easy to make and quickly lethal, became the injectable toxin of choice as part of Nazi Germany's "euthanasia" program.[20][19][21] Although Zyklon-B pellets, invented by Gerhard Lenz, were used in the gas chambers to exterminate large groups of people, the Nazis learned that

extermination of smaller groups was more economical via injection of each victim, one at a time, with phenol. Phenol injections were given to thousands of people in concentration camps, especially at Auschwitz-Birkenau. Approximately one gram is enough to cause death.[22] Injections were administered by medical doctors, their assistants, or sometimes prisoner doctors; such injections were originally givenintravenously, more commonly in the arm, but injection directly into the heart, so as to induce nearly instant death, was later adopted.[23] One of the best known inmates to be executed with a phenol injection in Auschwitz was St. Maximilian Kolbe, a Catholic priest who volunteered to undergo three weeks of starvation and dehydration in the place of another inmate.[23]

[edit]Occurrence
Phenol is a measurable component in the aroma and taste of the distinctive Islay scotch whisky,[24] generally ~30, but up to 100[25] ppm.

[edit]Biodegradation
Cryptanaerobacter phenolicus is a bacterium species that produces benzoate from phenol via 4-hydroxybenzoate.[26] Rhodococcus phenolicus is a bacterium species able to degrade phenol as sole carbon sources.[27]

[edit]Toxicity
Phenol and its vapors are corrosive to the eyes, the skin, and the respiratory tract.[28] Repeated or prolonged skin contact with phenol may cause dermatitis, or even second and third-degree burns due to phenol's caustic and defatting properties.[29] Inhalation of phenol vapor may cause lung edema.[28] The substance may cause harmful effects on the central nervous system and heart, resulting indysrhythmia, seizures, and coma.[30] The kidneys may be affected as well. Exposure may result in death and the effects may be delayed. Long-term or repeated exposure of the substance may have harmful effects on the liver and kidneys."[31] There is no evidence to believe that phenol causes cancer in humans.[32] Besides its hydrophobic effects, another mechanism for the toxicity of phenol may be the formation of phenoxyl radicals.[33] Chemical burns from skin exposures can be decontaminated by washing with polyethylene glycol,[34] isopropyl alcohol,[35] or perhaps even copious amounts of water.[36] Removal of contaminated clothing is required, as well as immediate hospital treatment for large splashes. This is particularly important if the phenol is mixed with chloroform (a commonly-used mixture in molecular biology forDNA & RNA purification from proteins).

[edit]Phenols
Main article: Phenols The word phenol is also used to refer to any compound that contains a sixmembered aromatic ring, bonded directly to a hydroxyl group (-OH). Thus, phenols are a class of organic compounds of which the phenol discussed in this article is the simplest member.

[edit]See

also

Bamberger rearrangement Claisen rearrangement Cresols Fries rearrangement Polyphenol

[edit]References
^ http://omlc.ogi.edu/spectra/PhotochemCAD/html/phenol.html ^ Ktt, A.; Movchun, V.; Rodima, T.; Dansauer, T.; Rusanov, E. B.; Leito, I.; Kaljurand, I.; Koppel, J.; Pihl, V.; Koppel, I.; Ovsjannikov, G.; Toom, L.; Mishima, M.; Medebielle, M.; Lork, E.; Rschenthaler, G.-V.; Koppel, I. A.; Kolomeitsev, A. A. Pentakis(trifluoromethyl)phenyl, a Sterically Crowded and Electron-withdrawing Group: Synthesis and Acidity of Pentakis(trifluoromethyl)benzene, -toluene, phenol, and -aniline. J. Org. Chem. 2008, 73, 2607-2620. DOI: 10.1021/jo702513w ^ ^
a b c a b c

Online Sigma Catalogue , accessdate: June 16, 2011. Manfred Weber, Markus Weber, Michael Kleine-Boymann "Phenol" in

Ullmann's Encyclopedia of Industrial Chemistry 2004, WileyVCH.doi:10.1002/14356007.a19_299.pub2. ^ Smith, Michael B.; March, Jerry (2007), Advanced Organic Chemistry: Reactions, Mechanisms, and Structure (6th ed.), New York: Wiley-Interscience, ISBN 0-47172091-7 ^ Organic Chemistry 2nd Ed. John McMurry ISBN 0534079687 ^ "The Acidity of Phenol". ChemGuide. Jim Clark. Retrieved 2007-08-05. ^ For further reading on the fine points of this topic, see David A. Evans's explanation. ^ Pedro J. Silva (2009). "Inductive and Resonance Effects on the Acidities of Phenol, Enols, and Carbonyl -Hydrogens.". J. Org. Chem. 74 (2): 914

916. doi:10.1021/jo8018736.PMID 19053615.(Solvation effects on the relative acidities of acetaldehyde enol and phenol described in the Supporting Information) ^ David Y. Curtin and Allan R. Stein (1966). "2,6,6-Trimethyl-2,4Cyclohexadione.". Organic Syntheses 46: 115. ^ Capponi, Marco; Gut, Ivo G.; Hellrung, Bruno; Persy, Gaby; Wirz, Jakob (1999). "Ketonization equilibria of phenol in aqueous solution". Can. J. Chem. 77: 605 613.doi:10.1139/cjc-77-5-6-605. ^ Clayden, Jonathan; Greeves, Nick; Warren, Stuart; Wothers, Peter (2001). Organic Chemistry (1st ed.). Oxford University Press. p. 531. ISBN 978-019-850346-0. ^ Wittcoff, H.A., Reuben, B.G. Industrial Organic Chemicals in Perspective. Part One: Raw Materials and Manufacture. Wiley-Interscience, New York. 1980. ^
a b

Franck, H.-G., Stadelhofer, J.W. Industrial Aromatic Chemistry. Springer-

Verlag, New York. 1988. pp. 148-155. ^ "CH207 Aircraft paintstripper, phenolic, acid". Callington. 14 October 2009. Retrieved 27 August 2011. ^ A. Svobodov*, J. Psotov, and D. Walterov (2003). "Natural Phenolics in the Prevention of UV-Induced Skin Damage. A Review". Biomed. Papers 147 (2): 137 145. ^ DeSelms, R. H.; UV-Active Phenol Ester Compounds; Enigen Science Publishing: Washington, DC, 2008. ^ Lister, Joseph (1867). "Antiseptic Principle Of The Practice Of Surgery". ^ ^
a b a b

The Experiments by Peter Tyson. NOVA The Nazi Doctors, Chapter 14, Killing with Syringes: Phenol Injections. By Dr.

Robert Jay Lifton ^ Euthanasia Program: Holocaust Encyclopedia ^ "Phenol: Hazards and Precautions". University of Connecticut, USA. Retrieved 2011-12-02. ^
a b

"Killing through phenol injection". Auschwitz - FINAL STATION

EXTERMINATION. Johannes Kepler University, Linz, Austria. Retrieved 2006-0929. ^ "Peat, Phenol and PPM, by Dr P. Brossard" (PDF). Retrieved 2008-05-27. ^ "Ardbeg "Supernova" Islay Single Malt Whisky". ^ Cryptanaerobacter phenolicus gen. nov., sp. nov., an anaerobe that transforms phenol into benzoate via 4-hydroxybenzoate. Pierre Juteau, Valrie Ct, MarieFrance Duckett, Rjean Beaudet, Franois Lpine, Richard Villemur and Jean-Guy

Bisaillon, IJSEM, January 2005, vol. 55, no. 1, pages 245250, doi:10.1099/ijs.0.02914-0 ^ Rhodococcus phenolicus sp. nov., a novel bioprocessor isolated actinomycete with the ability to degrade chlorobenzene, dichlorobenzene and phenol as sole carbon sources. Rehfuss M and Urban J, Syst. Appl. Microbiol. (2005), 28, pages 695-701 (Erratum: Syst. Appl. Microbiol. (2006) 29, page 182), PubMed, doi:10.1016/j.syapm.2005.05.011 ^
a b

Budavari, S, ed (1996). The Merck Index: An Encyclopedia of Chemical,

Drugs, and Biologicals. Whitehouse Station, NJ: Merck. ^ Lin TM, Lee SS, Lai CS, Lin SD (June 2006). "Phenol burn".Burns: Journal of the International Society for Burn Injuries 32(4): 517 21. doi:10.1016/j.burns.2005.12.016.PMID 16621299. ^ Warner, MA; Harper, JV (1985). "Cardiac dysrhythmias associated with chemical peeling with phenol".Anesthesiology 62 (3): 3667. doi:10.1097/00000542198503000-00030. PMID 2579602. ^ World Health Organization/International Labour Organization: International Chemical Safety Cards,http://www.inchem.org/documents/icsc/icsc/eics0070.htm ^ U.S. Department of Health and Human Services. "How can phenol affect my health?". Toxicological Profile for Phenol: 24. ^ Hanscha, Corwin; McKarnsb, Susan C; Smith, Carr J; Doolittle, David J (June 15, 2000). "Comparative QSAR evidence for a free-radical mechanism of phenolinduced toxicity". Chemico-Biological Interactions 127 (1): 61 72.doi:10.1016/S0009-2797(00)00171-X. PMID 10903419. ^ Brown, VKH; Box, VL; Simpson, BJ (1975). "Decontamination procedures for skin exposed to phenolic substances".Archives of Environmental Health 30 (1): 1 6.PMID 1109265. ^ Hunter, DM; Timerding, BL; Leonard, RB; McCalmont, TH; Schwartz, E (1992). "Effects of isopropyl alcohol, ethanol, and polyethylene glycol/industrial methylated spirits in the treatment of acute phenol burns". Annals of Emergency Medicine 21 (11): 13037. doi:10.1016/S0196-0644(05)81891-8. ^ Pullin, TG; Pinkerton, MN; Johnson, RV; Kilian, DJ (1978). "Decontamination of the skin of swine following phenol exposure: a comparison of the relative efficacy of water versus polyethylene glycol/industrial methylated spirits". Toxicol Appl Pharmacol 43 (1): 199206. doi:10.1016/S0041-008X(78)80044-1. PMID 625760.

[edit]External

links

Look up phenol in Wiktionary, the free dictionary.

International Chemical Safety Card 0070 Phenol Material Safety Data Sheet National Pollutant Inventory: Phenol Fact Sheet NIOSH Pocket Guide to Chemical Hazards IARC Monograph: "Phenol" Arcane Radio Trivia outlines competing uses for Phenol circa 1915