1,4-Benzoquinone

Chemical compound September 2022 changed changed 477205894 P-Benzochinon.svg skin-invert-image 60px Skeletal formula 1,4-benzoquinone-3D-vdW.png Space-filling model Para-Benzoquinone needles.jpg Cyclohexa-2,5-diene-1,4-dione Nomenclature of Organic Chemistry : IUPAC Recommendations and Preferred Names 2013 (Blue Book) The Royal Society of Chemistry 2014 Cambridge 723–724 10.1039/9781849733069-FP001 978-0-85404-182-4 1,4-BenzoquinoneBenzoquinonep-Benzoquinonep-Quinone 6307 correct chemspider correct EBI 16509 4489 correct FDA 3T006GV98U correct kegg C00472 B01254 203-405-2 2587 2741 773967 1/C6H4O2/c7-5-1-2-6(8)4-3-5/h1-4H AZQWKYJCGOJGHM-UHFFFAOYAR C1=CC(=O)C=CC1=O correct EBI 8320 correct chemspider 1S/C6H4O2/c7-5-1-2-6(8)4-3-5/h1-4H correct chemspider AZQWKYJCGOJGHM-UHFFFAOYSA-N correct CAS 106-51-4 4650 O=C\1\C=C/C(=O)/C=C/1 DK2625000 6 4 2 Yellow solid Acrid, chlorine-like 1.318 g/cm3 at 20 °C 115 Sublimes 11 g/L (18 °C) Slightly soluble in petroleum ether; soluble in acetone; 10% in ethanol, benzene, diethyl ether 0.1 mmHg (25 °C) −38.4·10−6 cm3/mol Toxic 100 to 200 06 07 09 Danger 301 315 319 331 335 400 261 264 270 271 273 280 301+310 302+352 304+340 305+351+338 311 312 321 330 332+313 337+313 362 391 403+233 405 501 TWA 0.4 mg/m3 (0.1 ppm)0542 100 mg/m3 TWA 0.4 mg/m3 (0.1 ppm) 296 mg/kg (mammal, subcutaneous)93.8 mg/kg (mouse, subcutaneous)8.5 mg/kg (mouse, IP)5.6 mg/kg (rat)130 mg/kg (rat, oral)25 mg/kg (rat, IV)106514 Quinone Ketone 1,2-Benzoquinone 1,4-Benzoquinone, commonly known as para-quinone, is a chemical compound with the formula C6H4O2. In a pure state, it forms bright-yellow crystals with a characteristic irritating odor, resembling that of chlorine, bleach, and hot plastic or formaldehyde. This six-membered ring compound is the oxidized derivative of 1,4-hydroquinone. Underwood, H. W. Jr. Walsh, W. L. Quinone 1936 16 73 2 553 10.15227/orgsyn.002.0085 The molecule is multifunctional: it exhibits properties of a ketone, being able to form oximes; an oxidant, forming the dihydroxy derivative; and an alkene, undergoing addition reactions, especially those typical for α,β-unsaturated ketones. 1,4-Benzoquinone is sensitive toward both strong mineral acids and alkali, which cause condensation and decomposition of the compound.10.1002/9780470772119 The Quinonoid Compounds: Vol. 1 (1988) 1988 978-0-470-77211-9 Patai Saul Rappoport Zvi10.1002/9780470772126 The Quinonoid Compounds: Vol. 2 (1988) 1988 978-0-470-77212-6 Patai Saul Rappoport Zvi Preparation 1,4-Benzoquinone is prepared industrially by oxidation of hydroquinone, which can be obtained by several routes. One route involves oxidation of diisopropylbenzene and the Hock rearrangement. The net reaction can be represented as follows: C6H4(CHMe2)2 + 3 O2 -> C6H4O2 + 2 OCMe2 + H2O The reaction proceeds via the bis(hydroperoxide) and the hydroquinone. Acetone is a coproduct.Gerhard Franz, Roger A. Sheldon "Oxidation" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2000 10.1002/14356007.a18_261 Another major process involves the direct hydroxylation of phenol by acidic hydrogen peroxide: C6H5OH + H2O2 -> C6H4(OH)2 + H2O Both hydroquinone and catechol are produced. Subsequent oxidation of the hydroquinone gives the quinone.Phillip M. Hudnall "Hydroquinone" in Ullmann's Encyclopedia of Industrial Chemistry, 2002, Wiley-VCH, Weinheim. 2005 Wiley-VCH, Weinheim. 10.1002/14356007.a13_499. 1,4-Benzoquinone was originally prepared industrially by oxidation of aniline, for example by manganese dioxide. http://monographs.iarc.fr/ENG/Monographs/vol71/mono71-63.pdf 1,4-Benzoquinone (para-Quinone) Re-evaluation of Some Organic Chemicals, Hydrazine and Hydrogen Peroxide (Part 1, Part 2, Part 3) IARC Monographs This method is mainly practiced in China where environmental regulations are more relaxed. Oxidation of hydroquinone is facile. Vliet, E. B. Quinone 1922 2 85 1 482 10.15227/orgsyn.016.0073 One such method makes use of hydrogen peroxide as the oxidizer and iodine or an iodine salt as a catalyst for the oxidation occurring in a polar solvent such as isopropyl alcohol. US patent 4973720 Process for the preparation of p-benzoquinone When heated to near its melting point, 1,4-benzoquinone sublimes, even at atmospheric pressure, allowing for an effective purification. Impure samples are often dark-colored due to the presence of quinhydrone, a dark green 1:1 charge-transfer complex of quinone with hydroquinone.Sakurai, T. On the refinement of the crystal structures of phenoquinone and monoclinic quinhydrone Acta Crystallographica Section B 1968 24 3 403–412 10.1107/S0567740868002451 1968AcCrB..24..403S Structure and redox class=skin-invert-image|thumb|left|C–C and C–O bond distances in benzoquinone (Q), its 1e reduced derivative (Q−), and hydroquinone (H2Q). Benzoquinone is a planar molecule with localized, alternating C=C, C=O, and C–C bonds. Reduction gives the semiquinone anion C6H4O2−}, which adopts a more delocalized structure. Further reduction coupled to protonation gives the hydroquinone, in which the electrons of the C6 ring are fully delocalized. 10.1021/ja066471o 17177421 Quinones as Electron Acceptors. X-Ray Structures, Spectral (EPR, UV−vis) Characteristics and Electron-Transfer Reactivities of Their Reduced Anion Radicals as Separated vs Contact Ion Pairs Journal of the American Chemical Society 128 51 16708–19 2006 Lü Jian-Ming Rosokha Sergiy V Neretin Ivan S Kochi Jay K Reactions and applications Benzoquinonium is a skeletal muscle relaxant, ganglion blocking agent that is made from benzoquinone.Cavallito Chester J. Soria Albert E. Hoppe James O. Amino- and Ammonium-alkylaminobenzoquinones as Curarimimetic Agents Journal of the American Chemical Society 72 6 1950 2661–2665 0002-7863 10.1021/ja01162a088 Organic synthesis It is used as a hydrogen acceptor and oxidant in organic synthesis.Yang, T.-K. Shen, C.-Y. Encyclopedia of Reagents for Organic Synthesis L. Paquette 2004 J. Wiley & Sons New York 10.1002/047084289X.rb033 1,4-Benzoquinone 978-0-471-93623-7 1,4-Benzoquinone serves as a dehydrogenation reagent. It is also used as a dienophile in Diels-Alder reactions. Oda, M. Kawase, T. Okada, T. Enomoto, T. 2-Cyclohexene-1,4-dione 1996 73 253 9 186 10.15227/orgsyn.073.0253 Benzoquinone reacts with acetic anhydride and sulfuric acid to give the triacetate of hydroxyquinol.Vliet E. B. Hydroquinone Triacetate Organic Syntheses 1941 1 317 10.15227/orgsyn.004.0035 freeKnowles M. B. Process for production of 2,4,5-trihydroxyacetophenone 1952 https://drive.google.com/viewerng/viewer?url=patentimages.storage.googleapis.com/pdfs/US2763691.pdf Google Patents Eastman Kodak Co. 24 December 2014 This reaction is called the Thiele reaction or Thiele–Winter reactionMcOmie J. F. W. Blatchly J. M. Organic Reactions The Thiele-Winter Acetoxylation of Quinones 19 199–277 10.1002/0471264180.or019.03 978-0-471-19619-8 2011 Thiele, J. Ueber die Einwirkung von Essigsäure-anhydrid auf Chinon und auf Dibenzoylstyrol Berichte der Deutschen Chemischen Gesellschaft 1898 31 1 1247–1249 10.1002/cber.189803101226 https://zenodo.org/record/1425900 after Johannes Thiele, who first described it in 1898, and after Ernst Winter, who further described its reaction mechanism in 1900. An application is found in this step of the total synthesis of Metachromin A: Almeida W. P. Correia C. R. D. Stereoselective Total Synthesis and Enantioselective Formal Synthesis of the Antineoplastic Sesquiterpene Quinone Metachromin A Journal of the Brazilian Chemical Society 1999 10 5 401–414 10.1590/S0103-50531999000500011 http://www.scielo.br/pdf/jbchs/v10n5/a11v10n5.pdf free class=skin-invert-image|400px|left|An application of the Thiele reaction, involving a benzoquinone derivative. Benzoquinone is also used to suppress double-bond migration during olefin metathesis reactions. An acidic potassium iodide solution reduces a solution of benzoquinone to hydroquinone, which can be reoxidized back to the quinone with a solution of silver nitrate. Due to its ability to function as an oxidizer, 1,4-benzoquinone can be found in methods using the Wacker-Tsuji oxidation, wherein a palladium salt catalyzes the conversion of an alkene to a ketone. This reaction is typically carried out using pressurized oxygen as the oxidizer, but benzoquinone can sometimes preferred. It is also used as a reagent in some variants on Wacker oxidations. 1,4-Benzoquinone is used in the synthesis of Bromadol and related analogs. thumb|left|Structure of Cp*Rh(para-quinone).η5-Semiquinone Complexes and the Related η4-Benzoquinone of (Pentamethylcyclopentadienyl)rhodium and -iridium: Synthesis, Structures, Hydrogen Bonding, and Electrochemical Behavior Jamal Moussa Carine Guyard-Duhayon Patrick Herson Hani Amouri Marie Noelle Rager Anny Jutand Organometallics 2004 23 26 6231–6238 10.1021/om049292t Related 1,4-benzoquinones Quinone 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) is a stronger oxidant and dehydrogenation agent than 1,4-benzoquinone. Vogel, E. Klug, W. Breuer, A. 1,6-Methano[10]annulene 1974 54 11 6 731 10.15227/orgsyn.054.0011 Chloranil 1,4-C6Cl4O2 is another potent oxidant and dehydrogenation agent. Monochloro-p-benzoquinone is yet another but milder oxidant. Harman, R. E. Chloro-p-benzoquinone 1955 35 22 4 148 10.15227/orgsyn.035.0022 Metabolism 1,4-Benzoquinone is a toxic metabolite found in human blood and can be used to track exposure to benzene or mixtures containing benzene and benzene compounds, such as petrol. Lin Y. S. McKelvey W. Waidyanatha S. Rappaport S. M. Variability of Albumin Adducts of 1,4-Benzoquinone, a Toxic Metabolite of Benzene, in Human Volunteers Biomarkers 2006 11 1 14–27 10.1080/13547500500382975 16484134 13198966 The compound can interfere with cellular respiration, and kidney damage has been found in animals receiving severe exposure. It is excreted in its original form and also as variations of its own metabolite, hydroquinone. Safety thumb|left|The bombardier beetle sprays 1,4-benzoquinone to deter predators 1,4-Benzoquinone is able to stain skin dark brown, cause erythema (redness, rashes on skin) and lead on to localized tissue necrosis. It is particularly irritating to the eyes and respiratory system. Its ability to sublime at commonly encountered temperatures allows for a greater airborne exposure risk than might be expected for a room-temperature solid. IARC has found insufficient evidence to comment on the compound's carcinogenicity, but has noted that it can easily pass into the bloodstream and that it showed activity in depressing bone marrow production in mice and can inhibit protease enzymes involved in cellular apoptosis. See also Tetrahydroxybenzoquinone Benzoquinonetetracarboxylic acid 1,2-Benzoquinone Quinones Duroquinone Ardisiaquinone References Category:Oxidizing agents Category:Enones ja:ベンゾキノン#1,4-ベンゾキノン