Resorcinol

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Resorcinol
Skeletal formula
Ball-and-stick model
Names
Preferred IUPAC name
Benzene-1,3-diol[1]
Other names
Resorcinol[1]
Resorcin
m-Dihydroxybenzene
1,3-Benzenediol
1,3-Dihydroxybenzene
3-Hydroxyphenol
m-Benzenediol
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.003.260
KEGG
UNII
UN number 2876
Properties
C6H6O2
Molar mass 110.1 g/mol
Appearance White solid, turns pink on exposure to air, light, and iron[2]
Odor Faint[2]
Density 1.28 g/cm3, solid
Melting point 110 °C (230 °F; 383 K)
Boiling point 277 °C (531 °F; 550 K)
110 g/100 mL at 20 °C
Vapor pressure 0.0002 mmHg (25°C)[2]
Acidity (pKa) 9.15[3]
-67.26·10−6 cm3/mol
2.07±0.02 D [4]
Pharmacology
D10AX02 (WHO) S01AX06 (WHO)
Hazards
Harmful (Xn)
Dangerous for
the environment (N)
Flash point 127 °C; 261 °F; 400 K [2]
Explosive limits 1.4%-?[2]
US health exposure limits (NIOSH):
PEL (Permissible)
none[2]
REL (Recommended)
TWA 10 ppm (45 mg/m3) ST 20 ppm (90 mg/m3)[2]
IDLH (Immediate danger)
N.D.[2]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☒N verify (what is ☑Y☒N ?)
Infobox references

Resorcinol (or resorcin) is an organic compound with the formula C6H4(OH)2. It is one of three isomeric benzenediols, the 1,3-isomer (or meta-isomer). It is a white, water-soluble solid.[5]

Production[edit]

Resorcinol is produced in several steps from benzene, starting with dialkylation with propylene to give 1,3-diisopropylbenzene. Oxidation and Hock rearrangement of this disubstituted arene gives acetone and resorcinol.[5]

Although of little commercial value, many additional routes exist for resorcinol. It can be produced when any of a large number of resins (e.g., galbanum, asafoetida, etc.) are melted with potassium hydroxide, or by the distillation of Brazilwood extract. It may be prepared synthetically by melting 3-iodophenol, phenol-3-sulfonic acid, or benzene-1,3-disulfonic acid with potassium carbonate; by the action of nitrous acid on 3-aminophenol or on 1,3-diaminobenzene.[6] Many ortho- and para-compounds of the aromatic series (for example, the bromophenols, benzene-para-disulfonic acid) also yield resorcinol on fusion with potassium hydroxide.

Properties[edit]

Resorcinol crystallizes from benzene as colorless needles that are readily soluble in water, alcohol, and ether, but insoluble in chloroform and carbon disulfide.

Reactions[edit]

It reduces Fehling's solution and ammoniacal silver solutions. It does not form a precipitate with lead acetate solution, as does the isomeric pyrocatechol. Iron(III) chloride colors its aqueous solution a dark-violet, and bromine water precipitates tribromoresorcinol. These properties are what give it its use as a colouring agent for certain chromatography experiments.

Sodium amalgam reduces it to dihydroresorcin, which when heated to 150 to 160 °C with concentrated barium hydroxide solution gives γ-acetylbutyric acid

When fused with potassium hydroxide, resorcinol yields phloroglucin, pyrocatechol, and diresorcin. It condenses with acids or acid chlorides, in the presence of dehydrating agents, to oxyketones, e.g., with zinc chloride and glacial acetic acid at 145 °C it yields resacetophenone (HO)2C6H3~CO.CH3.[7] With the anhydrides of dibasic acids, it yields fluoresceins. When heated with calcium chlorideammonia to 200 °C it yields meta-dioxydiphenylamine.[8]

With sodium nitrite it forms a water-soluble blue dye, which is turned red by acids, and is used as an indicator, under the name of lacmoid.[9] It condenses readily with aldehydes, yielding with formaldehyde, on the addition of catalytic hydrochloric acid, methylene diresorcin [(HO)C6H3(O)]2•CH2. Reaction with chloral hydrate in the presence of potassium bisulfate yields the lactone of tetra-oxydiphenyl methane carboxylic acid.[10] In alcoholic solution it condenses with sodium acetoacetate to form 4-methylumbelliferone.[11]

In addition to electrophilic aromatic addition, resorcinol (and other poly-ols) undergo nucleophilic substitution via the enone tautomer.

Nitration with concentrated nitric acid in the presence of cold concentrated sulfuric acid yields trinitro-resorcin (styphnic acid), an explosive.

Occurrence[edit]

Resorcinol per se does not appear to occur naturally in the free state. It is found in argan oil.[12]

Parts of a molecule of catechin, another natural compound that is present in tea, has the resorcinol skeleton structure in it.

Alkylresorcinols are a marker of whole grain diet.

Applications[edit]

Resorcinol is mainly used in the production of resins. As a mixture with phenol, it condenses with formaldehyde to afford adhesives.[5]

Medical[edit]

It is present in over-the-counter topical acne treatments at 2% or less concentration, and in prescription treatments at higher concentrations.[13] Monoacetylresorcinol, C6H4(OH)(O-COCH3), is used under the name of euresol.[14] Resorcinol is one of the active ingredients in products such as Resinol, Vagisil, and Clearasil.

4-Hexylresorcinol is an anesthetic found in throat lozenges.

Chemical[edit]

Resorcinol is also used as a chemical intermediate for the synthesis of pharmaceuticals and other organic compounds. It is used in the production of diazo dyes and plasticizers and as a UV absorber in resins.

Resorcinol is an analytical reagent for the qualitative determination of ketoses (Seliwanoff's test).

Resorcinol is the starting material for resorcinarene molecules and the initiating explosive lead styphnate.[15]

Resorcinol reacts with formaldehyde to form a thermoset resin which can form the basis of an aerogel.

Related compounds[edit]

Resazurin, C12H7NO4, obtained by the action of nitrous acid on resorcinol,[16] forms small dark red crystals possessing a greenish metallic glance. When dissolved in concentrated sulfuric acid and warmed to 210 °C, the solution on pouring into water yields a precipitate of resorufin, C12H7NO3, an oxyphenoxazone, which is insoluble in water, but is readily soluble in hot concentrated hydrochloric acid, and in solutions of caustic alkalis. The alkaline solutions are of a rose-red color and show a cinnabar-red fluorescence. A tetrabromresorufin is used as a dye-stuff under the name of Fluorescent Resorcin Blue.

Thioresorcinol is obtained by the action of zinc and hydrochloric acid on the chloride of benzene meta-disulfonic acid. It melts at 27 °C and boils at 243 °C. Resorcinol disulfonic acid, (HO)2C6H2(HSO3)2, is a deliquescent mass obtained by the action of sulfuric acid on resorcin.[17] It is readily soluble in water and ethanol.

Resorcinol is also a common scaffold that is found in a class of anticancer agents, some of which (luminespib, ganetespib, KW-2478, and onalespib) were in clinical trials as of 2014.[18][19] Part of the resorcinol structure binds to inhibits the N-terminal domain of heat shock protein 90, which is a drug target for anticancer treatments.[18]

History, etymology, and nomenclature[edit]

Austrian chemist Heinrich Hlasiwetz (1825–1875) is remembered for his chemical analysis of resorcinol and for his part in the first preparation of resorcinol, along with Ludwig Barth, which was published in 1864.[20]:10[21]

Benzene-1,3-diol is the name recommended by the International Union of Pure and Applied Chemistry (IUPAC) in its 1993 Recommendations for the Nomenclature of Organic Chemistry.[22]

Resorcinol is so named because of its derivation from ammoniated resin gum, and for its relation to the chemical orcin.[23]

See also[edit]

References[edit]

  1. ^ a b "Front Matter". Nomenclature of Organic Chemistry : IUPAC Recommendations and Preferred Names 2013 (Blue Book). Cambridge: The Royal Society of Chemistry. 2014. p. 691. doi:10.1039/9781849733069-FP001. ISBN 978-0-85404-182-4.
  2. ^ a b c d e f g h NIOSH Pocket Guide to Chemical Hazards. "#0543". National Institute for Occupational Safety and Health (NIOSH).
  3. ^ Gawron, O.; Duggan, M.; Grelechi, C. (1952). "Manometric Determination of Dissociation Constants of Phenols". J. Anal. Chem. 24 (6): 969–970. doi:10.1021/ac60066a013.
  4. ^ Lander, John J.; Svirbely, John J. Lander, W. J. (1945). "The Dipole Moments of Catechol, Resorcinol and Hydroquinone". Journal of the American Chemical Society. 67 (2): 322–324. doi:10.1021/ja01218a051.
  5. ^ a b c K. W. Schmiedel, D. Decker (2012). "Resorcinol". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a23_111.pub2.CS1 maint: uses authors parameter (link)
  6. ^ Meyer, J (1897). "Notiz über die Umwandlung von Aminen in Phenole". Ber. 30 (3): 2568–2569. doi:10.1002/cber.18970300334.
  7. ^ Nencki, M.; Sieber, N. (1881). "Über die Verbindungen der ein- und zweibasischen Fettsäuren mit Phenolen". Journal für Praktische Chemie. 23: 147–156. doi:10.1002/prac.18810230111.
  8. ^ A. Seyewitz, Bull. Soc. Chins., 1890, 3, p. 811
  9. ^ Traub, M. C.; Hock, C. (1884). "Ueber ein Lakmoid" (PDF). Berichte der Chemischen Gesellschaft. 17 (2): 2615–2617. doi:10.1002/cber.188401702192.
  10. ^ J. T. Hewitt and F. G. Pope, Jour. C/tern. Soc., 1897, 75, p. 1084
  11. ^ Michael, Arthur (1888). "Ueber das Verhalten von Natriummalonäther gegen Resorcinol". Journal für Praktische Chemie. 37: 469–471. doi:10.1002/prac.18880370144.
  12. ^ Phenols and Polyphenols from Argania spinosa. Z. Charrouf and D. Guillaume, American Journal of Food Technology, 2007, 2, pages 679-683, doi:10.3923/ajft.2007.679.683
  13. ^ Boer, J; Jemec, GB (2010). "Resorcinol peels as a possible self-treatment of painful nodules in hidradenitis suppurativa". Clin Exp Dermatol. 35 (1): 36–40. doi:10.1111/j.1365-2230.2009.03377.x. PMID 19549239.
  14. ^ Euresol, PubChem
  15. ^ "Military Explosives," Department of the Army Technical Manual, TM-9-1300-214 (Washington, D.C.: Department of the Army, September 1984), p. 7-12.
  16. ^ Weselsky, P (1871). "Neue Derivate des Resorcins" [New derivatives of resorcinol]. Berichte der Deutschen Chemischen Gesellschaft. 4: 32–33. doi:10.1002/cber.18710040114.
  17. ^ Piccard, J.; Humbert, A. (1876). "Ueber eine Resorcindisulfosäure" [On a resorcinol disulfonic acid]. Berichte der Deutschen Chemischen Gesellschaft. 9 (2): 1479–1483. doi:10.1002/cber.187600902133.
  18. ^ a b Sidera, K.; Patsavoudi, E. (Jan 2014). "HSP90 inhibitors: current development and potential in cancer therapy". Recent Pat. Anticancer Drug Discov. 9 (1): 1–20. doi:10.2174/15748928113089990031. PMID 23312026.
  19. ^ Biamonte, M. A.; Van de Water, R.; Arndt, J. W.; Scannevin, R. H.; Perret, D.; Lee, W.-C. (Jan 2010). "Heat shock protein 90: Inhibitors in clinical trials". J. Med. Chem. 53 (1): 3–17. doi:10.1021/jm9004708. PMID 20055425.
  20. ^ Raj B. Durairaj. Resorcinol: Chemistry, Technology and Applications. Springer Science & Business Media, 2005 ISBN 9783540280903
  21. ^ McConnell, Virginia F. (1953). "Hlasiwetz and Barth — Pioneers in the structural aspects of plant products". Journal of Chemical Education. 30 (8): 380. doi:10.1021/ed030p380.
  22. ^ Panico, R.; & Powell, W. H. (Eds.) (1994). A Guide to IUPAC Nomenclature of Organic Compounds 1992. Oxford: Blackwell Science. ISBN 978-0-632-03488-8.CS1 maint: multiple names: authors list (link) CS1 maint: extra text: authors list (link)
  23. ^ H. Hlasiwetz and L. Barth (1864) "Ueber einen neuen, dem Orcin homologen Körper" (On a new substance homologous to orcin), Annalen der Chemie, 130 (3) : 354-359. Resorcinol is named on p. 358: "Wir nennen den neuen Körper, da wir gefunden haben, dass er auch aus dem Ammoniakgummiharz erhalten werden kann, Resorcin, um an seine Entstehung aus Harzen und seine Beziehung zum Orcin zu erinnern." (We name the new substance, since we've found that it can be obtained from ammoniated resin gum, resorcin, in order to recall its creation from resin and its relation to orcin [i.e., orcinol].)

External links[edit]

 This article incorporates text from a publication now in the public domainChisholm, Hugh, ed. (1911). "Resorcin". Encyclopædia Britannica. 23 (11th ed.). Cambridge University Press. pp. 183–184.