(E)-Stilbene

the class of antioxidant compounds that share the same chemical skeleton stilbenoid changed changed 477200997 (E)-Stilbene Stilbene_trans_structure.svg 150px trans-stilbene - skeletal formula Trans-stilbene-from-xtal-3D-balls.png trans-stilbene - ball-and-stick model (E)-StilbeneInternational Union of Pure and Applied Chemistry 2014 Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013 The Royal Society of Chemistry 379 10.1039/9781849733069 978-0-85404-182-4 1,1-[(E)-Ethene-1,2-diyl]dibenzene Bibenzylidenetrans-α,β-Diphenylethylene(E)-1,2-Diphenylethylene((1E)-2-Phenylvinyl)benzenetrans-Stilbene[(E)-2-Phenylethenyl]benzene correct CAS 103-30-0 1616740 correct EBI 113028 203-098-5 4381 638088 changed FDA 3FA7NW80A0 3077 PJANXHGTPQOBST-VAWYXSNFBV 1/C14H12/c1-3-7-13(8-4-1)11-12-14-9-5-2-6-10-14/h1-12H/b12-11+ correct chemspider 1S/C14H12/c1-3-7-13(8-4-1)11-12-14-9-5-2-6-10-14/h1-12H/b12-11+ correct chemspider PJANXHGTPQOBST-VAWYXSNFSA-N c2(\C=C\c1ccccc1)ccccc2 c1ccc(cc1)/C=C/c2ccccc2 correct chemspider correct EBI 36007 553649 14 12 Solid 0.9707 g/cm3 Practically insoluble 122 to 125 305 to 307 > 112 External MSDS 1 1 0 (E)-Stilbene, commonly known as trans-stilbene, is an organic compound represented by the condensed structural formula C6H5CH=CHC6H5. Classified as a diarylethene, it features a central ethylene moiety with one phenyl group substituent on each end of the carbon–carbon double bond. It has an (E) stereochemistry, meaning that the phenyl groups are located on opposite sides of the double bond, the opposite of its geometric isomer, cis-stilbene. Trans-stilbene occurs as a white crystalline solid at room temperature and is highly soluble in organic solvents. It can be converted to cis-stilbene photochemically, and further reacted to produce phenanthrene. Stilbene was discovered in 1843 by the French chemist Auguste Laurent.Laurent Auguste Mémoire sur la série stilbique Comptes rendus 1843 16 856–860 https://books.google.com/books?id=hzEt49manA8C&pg=PA167 Memoir on the stilbene series French From p. 857: "En soumettant ce sulfure à la distillation, il donne plusieurs produits, et entre autres, un composé fort remarquable que je nomme stilbène." (On submitting this sulfide [i.e., phenyl thioaldehyde, C6H5(CS)H] to [dry] distillation, it gives several products, and among others, a very remarkable compound which I name "stilbene".) The name "stilbene" is derived from the Greek word στίλβω (stilbo), which means "I shine", on account of the lustrous appearance of the compound.Miller William Allen Elements of Chemistry: Theoretical and Practical 1880 Longmans, Green and Co. London, England 366 3 5th https://books.google.com/books?id=H4kMAQAAIAAJ&pg=PA366 Isomers center|400px|thumb|The isomerization of stilbene under the influence of radiation. Stilbene exists as two possible stereoisomers. One is trans-1,2-diphenylethylene, called (E)-stilbene or trans-stilbene. The second is cis-1,2-diphenylethylene, called (Z)-stilbene or cis-stilbene, and is sterically hindered and less stable because the steric interactions force the aromatic rings out-of-plane and prevent conjugation.Eliel Ernest L. Wilen Samuel H. Stereochemistry of Organic Compounds https://archive.org/details/stereochemistryo0000elie_a9t3 registration 1994 John Wiley and Sons 0-471-01670-5 566-567 Cis-stilbene is a liquid at room temperature (melting point: 5 – 6 C), while trans-stilbene is a crystalline solid which does not melt until around 125 C, illustrating the two isomers have significantly different physical properties. Robert E. Buckles Norris G. Wheeler cis-Stilbene 1953 33 88 10.15227/orgsyn.033.0088 CV4P0857 4 857 Preparation and reactions Many syntheses have been developed. One popular route entails reduction of benzoin using zinc amalgam. R. L. Shriner Alfred Berger trans-Stilbene 1943 23 86 10.15227/orgsyn.023.0086 CV3P0786 3 786 C6H5–CH(OH)–C(=O)–C6H5 ->[\ce{Zn(Hg)}][\ce{HCl} \text{, } \ce{CH3CH2OH}] trans-C6H5–CH=CH–C6H5 Both isomers of stilbene can be produced by decarboxylation of α-phenylcinnamic acid, trans-stilbene being produced from the (Z)-isomer of the acid. Richard F. Heck Palladium-catalyzed vinylic hydrogen substitution reactions with aryl, benzyl, and styryl halides Richard F. Heck Heck R. F. Nolley J. P. J. Org. Chem. 1972 37 14 2320–2322 10.1021/jo00979a024 and Tsutomu Mizoroki Mizoroki Tsutomu Mori Kunio Ozaki Atsumu Bull. Chem. Soc. Jpn. 1971 Arylation of Olefin with Aryl Iodide Catalyzed by Palladium 44 2 581 10.1246/bcsj.44.581 independently reported the synthesis of trans-stilbene by coupling of iodobenzene and styrene using a palladium(II) catalyst, in what is now known as the Mizoroki-Heck reaction. Heck Richard F. Organic Reactions Palladium-Catalyzed Vinylation of Organic Halides Richard F. Heck 1982 27 345–390 10.1002/0471264180.or027.02 0471264180 The Heck Reaction as a Sharpening Stone of Palladium Catalysis Irina Beletskaya Beletskaya Irina P. Cheprakov Andrei V. Chem. Rev. 2000 100 8 3009–3066 10.1021/cr9903048 11749313 The Mizoroki approach produced the higher yield. 500px Stilbene undergoes reactions typical of alkenes. Trans-stilbene undergoes epoxidation with peroxymonophosphoric acid, H3PO5, producing a 74% yield of trans-stilbene oxide in dioxane. Oxidation of trans-stilbene with peroxymonophosphoric acid Yoshiro Ogata Kohtaro Tomizawa Toshiyuki Ikeda J. Org. Chem. 1979 44 14 2362–2364 10.1021/jo01328a006 The epoxide product formed is a racemic mixture of the two enantiomers of 1,2-diphenyloxirane. The achiral meso compound (1R,2S)-1,2-diphenyloxirane arises from cis-stilbene, though peroxide epoxidations of the cis-isomer produce both cis- and trans-epoxide products. For example, using tert-butyl hydroperoxide, oxidation of cis-stilbene produces 0.8% cis-stilbene oxide, 13.5% trans-stilbene oxide, and 6.1% benzaldehyde. Olefin Epoxidation by Alkyl Hydroperoxide with a Novel Cross-Bridged Cyclam Manganese Complex: Demonstration of Oxygenation by Two Distinct Reactive Intermediates Guochuan Yin Andrew M. Danby David Kitko John D. Carter William M. Scheper Daryle H. Busch Daryle H. Busch Inorg. Chem. 2007 46 6 2173–2180 10.1021/ic061957r 17295471 Lewis Acid Catalyzed Epoxidation of Olefins Using Hydrogen Peroxide: Growing Prominence and Expanding Range 119–153 https://books.google.com/books?id=xJpkegngTqAC&pg=PA143 Mechanisms in Homogeneous and Heterogeneous Epoxidation Catalysis S. Ted Oyama Daryle H. Busch Guochuan Yin Hyun-Jin Less Daryle H. Busch Elsevier 2011 9780080558011 Enantiopure stilbene oxide has been prepared by Nobel laureate Karl Barry Sharpless. Molar Scale Synthesis of Enantiopure Stilbene Oxide Han-Ting Chang K. Barry Sharpless Karl Barry Sharpless J. Org. Chem. 1996 61 18 6456–6457 10.1021/jo960718q 11667495 500px Stilbene can be cleanly oxidised to benzaldehyde by ozonolysis Mechanisms of ozonolysis. The cis, trans-stilbene system Clyde E. Bishop Donald D. Denson Paul R. Story Tetrahedron Lett. 9 55 1968 5739–5742 10.1016/S0040-4039(00)76338-6 or Lemieux–Johnson oxidation, and stronger oxidants such as acidified potassium permanganate will produce benzoic acid. Vicinal diols can be produced via the Upjohn dihydroxylation or enantioselectively using Sharpless asymmetric dihydroxylation Asymmetric dihydroxylation via ligand-accelerated catalysis Eric N. Jacobsen Istvan Marko William S. Mungall Georg Schroeder K. Barry Sharpless Karl Barry Sharpless J. Am. Chem. Soc. 1988 110 6 1968–1970 10.1021/ja00214a053 1988JAChS.110.1968J Catalytic Asymmetric Dihydroxylation Hartmuth C. Kolb Michael S. VanNieuwenhze K. Barry Sharpless Karl Barry Sharpless Chem. Rev. 1994 94 8 2483–2547 10.1021/cr00032a009 with enantiomeric excesses as high as 100%. A Solid-to-Solid Asymmetric Dihydroxylation Procedure for Kilogram-Scale Preparation of Enantiopure Hydrobenzoin Zhi-Min Wang K. Barry Sharpless Karl Barry Sharpless J. Org. Chem. 1994 59 26 8302–8303 10.1021/jo00105a065 (R,R)-1,2-Diphenyl-1,2-ethanediol (Stilbene Diol) 1992 70 47 10.15227/orgsyn.070.0047 CV9P0383 9 383 Blaine H. McKee Declan G. Gilheany K. Barry Sharpless Karl Barry Sharpless Asymmetric Hydroxylations 406–410 https://books.google.com/books?id=BJfbBwAAQBAJ&pg=PA408 Stereoselectove Synthesis in Organic Chemistry Atta-ur-Rahman Zahir Shah Springer-Verlag 1993 9781461383277 Bromination of trans-stilbene produces predominantly meso-1,2-dibromo-1,2-diphenylethane (sometimes called meso-stilbene dibromide), in line with a mechanism involving a cyclic bromonium ion intermediate of a typical electrophilic bromine addition reaction; 10.6 – Bromination of Alkenes 376–383 https://books.google.com/books?id=8wIQwCmWz9EC&pg=PA376 Experimental Organic Chemistry: A Miniscale and Microscale Approach John C. Gilbert Stephen F. Martin Stephen F. Martin Cengage Learning 2010 5th 9781439049143 cis-stilbene yields a racemic mixture of the two enantiomers of 1,2-dibromo-1,2-diphenylethane in a non-polar solvent such as carbon tetrachloride, but the extent of production of the meso compound increases with solvent polarity, with a yield of 90% in nitromethane. Stereospecificity of the Addition of Bromine to cis- and trans-Stilbene Robert E. Buckles Jane M. Bader Roland J. Thurmaier J. Org. Chem. 1962 27 12 4523–4527 10.1021/jo01059a097 The formation of small quantities of the two enantiomers of stilbene dibromide from the trans-isomer suggests that the bromonium ion intermediate exists in chemical equilibrium with a carbocation intermediate PhCHBr–C+(H)Ph with a vacant p orbital vulnerable to nucleophilic attack from either face. The addition of bromide or tribromide salts restores much of the stereospecificity even in solvents with a dielectric constant above 35. Stereoselectivity and reversibility of electrophilic bromine addition to stilbenes in chloroform: influence of the bromide-tribromide-pentabromide equilibrium in the counteranion of the ionic intermediates Roberto Bianchini Cinzia Chiappe J. Org. Chem. 1992 57 24 6474–6478 10.1021/jo00050a021 Upon UV irradiation it converts to cis-stilbene, a classic example of a photochemical reaction involving trans-cis isomerization, and can undergo further reaction to form phenanthrene. High level theoretical study of the structure and rotational barriers of trans-stilbene S. P. Kwasniewski L. Claes J.-P. François M. S. Deleuze J. Chem. Phys. 2003 118 17 7823–7836 10.1063/1.1563617 2003JChPh.118.7823K 800px Derivatives and uses Synthetic (E)-Stilbene itself is of little value, but it is a precursor to other derivatives used as dyes, optical brighteners, phosphors, and scintillators. Peter F. Vogt John J. Gerulis Amines, Aromatic Ullmann's Encyclopedia of Industrial Chemistry 2000 Wiley-VCH Weinheim 10.1002/14356007.a02_037 3527306730 Stilbene is one of the gain mediums used in dye lasers. thumb|left|4,4-diamino-2,2-stilbenedisulfonic acid is a popular optical brightener used in some laundry detergents. thumb|left|Diethylstilbestrol exhibits estrogenic properties, even though it is not a steroid. Disodium 4,4'-dinitrostilbene-2,2'-disulfonate is prepared by the sulfonation of 4-nitrotoluene to form 4-nitrotoluene-2-sulfonic acid, which can then be oxidatively coupled using sodium hypochlorite to form the (E)-stilbene derivative Systematic Organic Chemistry: Modern Methods of Preparation and Estimation 1926 William M. Cumming I. Vance Hopper T. Sherlock Wheeler 314 D. Van Nostrand Company New York Preparation 294.—Dinitro-Stilbene-Disulphonic Acid (Na salt) https://archive.org/details/systematicorgani00cumm_0 in a process originally developed by Arthur George Green and André Wahl in the late nineteenth century. Ueber die Oxydation von Paranitrotoluolsulfosäure German On the oxidation of para-nitrotoluenesulfonic acid Arthur G. Green Arthur George Green André R. Wahl Ber. Dtsch. Chem. Ges. 1897 30 3 3097–3101 10.1002/cber.189703003128 https://zenodo.org/record/1425882 Ueber die Oxydation der Paranitrotoluolsulfosäure German On the oxidation of para-nitrotoluenesulfonic acid Arthur G. Green Arthur George Green André R. Wahl Ber. Dtsch. Chem. Ges. 1898 31 1 1078–1080 10.1002/cber.189803101195 https://zenodo.org/record/1425898 Improvements to the process with higher yields have been developed, using air oxidation in liquid ammonia. US 5041632 patent Process for the preparation of 4,4'-dinitrostilbene-2,2-disulfonic acid 1991-08-20 1991-08-20 1988-06-07 1987-08-12 Guglielmetti Leonardo Ciba-Geigy Corporation http://www.google.com/patents/US5041632 The product is useful as its reaction with aniline derivatives results in the formation of azo dyes. Commercially important dyes derived from this compound include Direct Red 76, Direct Brown 78, and Direct Orange 40. Klaus Hunger Peter Mischke Wolfgang Rieper Roderich Raue Klaus Kunde Aloys Engel Azo Dyes Ullmann's Encyclopedia of Industrial Chemistry 2000 Wiley-VCH Weinheim 10.1002/14356007.a03_245 3527306730 Natural stilbenes The stilbenoids are naturally occurring stilbene derivatives. Examples include resveratrol and its cousin, pterostilbene. The stilbestrols, which are structurally but not synthetically related to (E)-stilbene, exhibit estrogenic activity. Members of this group include diethylstilbestrol, fosfestrol, and dienestrol. Some such derivative are produced by condensation of coenzyme A derivatives of cinnamic acid or 4-hydroxycinnamic acid and the malonic acid. Appendix Table 1. Vapor pressuresLide David CRC Handbook of Chemistry and Physics 76th 1995 CRC Press, Inc. USA 0-8493-0476-8 6–107 Isomer Temperature, °C Vapor pressure, kPa cis-stilbene 100 0.199 cis-stilbene 125 0.765 cis-stilbene 150 2.51 trans-stilbene 150 0.784 References External links (E)-Stilbene on ChemExper Category:Luminescence Category:Fluorescent dyes Category:Phosphors and scintillators Category:Laser gain media Category:Stilbenoids Category:Phenyl compounds