Chemistry:1,3-Diphenylisobenzofuran

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1,3-Diphenylisobenzofuran
1,3-Diphenylisobenzofuran Struktur.svg
1,3-Diphenylisobenzofuran sample.jpg
Names
Preferred IUPAC name
1,3-Diphenyl-2-benzofuran
Identifiers
ChemSpider
UNII
Properties
C20H14O
Molar mass 270.33 g·mol−1
Appearance pale yellow[1] to dark yellow crystalline powder[2]
Density 1.0717 g·cm−3 bei 25 °C[3]
Melting point * 125–126 °C[4]
  • 128–130 °C[2]
almost insoluble
Solubility in acetonitrile, benzene, dichloromethane, chloroform, dimethylsulfoxide, tetrahydrofuran or toluene soluble[5]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references
Tracking categories (test):

1,3-Diphenylisobenzofuran is a highly reactive diene that can scavenge unstable and short-lived dienophiles in a Diels-Alder reaction. It is furthermore used as a standard reagent[6] for the determination of singlet oxygen,[7] even in biological systems.[8] Cycloadditions with 1,3-diphenylisobenzofuran and subsequent oxygen cleavage provide access to a variety of polyaromatics.

Preparation

The first synthesis of 1,3-diphenylisobenzofuran was reported in 1905 by A. Guyot and J. Catel.[9][10] Phenylmagnesium bromide was reacted with 3-phenylphthalide (the latter accessible from the methyl ester of 3-hydroxyphthalide with phenylboronic acid in 95% yield[11]) to a lactol, which gives with mineral acids upon elimination of water 1,3-diphenylisobenzofuran with 87% yield.[12]

Synthese von 1,3-Diphenylisobenzofuran aus 3-Phenylphthalid

The patent literature describes the preparation of 1,3-diphenylisobenzofuran by [4+2]cycloaddition of 1,3-butadiene and dibenzoylethylene (1,4-diphenyl-2-butene-1,4-dione, accessible from fumaryl chloride and benzene in the presence of aluminium chloride.[13]).[14] Dibenzoylethylene is predominantly present in the trans configuration[15] but it can be converted into the needed cis configuration by simple heating.[16]

Synthese von 1,3-Diphenylisobenzofuran aus Butadien und Dibenzoylethylen

The 4,5-dibenzoylcyclohexene formed previously is cyclized with acetic anhydride to the dihydroisobenzofuran. By bromine addition and hydrogen bromide elimination, 1,2-dibenzoylbenzene is formed and recyclized with zinc acetic acid to the final product 1,3-diphenylisobenzofuran.[17] A publication from 1940 describes high yields for the individual stages of the extensive reaction sequence.[4]

The (much cheaper) phthaloyl chloride gives also access to 1,2-dibenzoylbenzene via Friedel-Crafts acylation with benzene,[18] which is reduced to 1,3-diphenylisobenzofuran in 78% yield using potassium borohydride.[19]

Synthese von 1,3-Diphenylisobenzofuran aus 1,2-Dibenzoylbenzol

The synthesis of 1,3-diarylisobenzofurans from 2-acylbenzaldehydes and boronic acids is less cumbersome and gives better yields,[20]

Synthese von 1,3-Diphenylisobenzofuran aus 2-Formylbenzophenon

just like the synthesis from salicylaldehydes via phenacylhydrazones, which undergo oxidation with lead(IV) acetate to give ortho-diketones,[21] followed by the reaction with an aryl Grignard reagent.[22]

Synthese von 1,3-Diphenylisobenzofuran aus Salicylaldehyd

Properties

1,3-Diphenylisobenzofuran is a yellow, light- and air-sensitive, crystalline solid that is soluble in many organic solvents with a maximum absorption around 420 nm (in solution), which generates intense fluorescence.[23] Fluorescence measurements can be performed in DMF and DMSO because of the stability of 1,3-DPBF in those solvents. In chloroform and carbon tetrachloride the dissolved 1,3-diphenylisobenzofuran is rapidly photolyzed by attack of CHCl2 and CCl3 radicals, even in the absence of oxygen.[24] [24 ]

With ethanol, 1,3-diphenylisobenzofuran forms an orange-yellow, fluorescent solution. On irradiation, it forms a colorless photodimer (upon with exclusion of oxygen), upon discolouration of the solution.[25]

Photodimerisierung von 1,3-Diphenylisobenzofuran

The compound's refractive index is 1,6700 at 25 °C and 589 nm.[3]

Use

Reagent for determination of singlet oxygen

1,3-Diphenylisobenzofuran Reaktion mit Singulett-Sauerstoff
Graph showing change in absorbance of DPBF vs. irradiation time in the presence of photosensitizer (porphyrin)[26]
Electron absorption spectrum showing photodegradation of DPBF in the presence of a porphyrin photosensitzier, during intermittent periods of irradiation with ~630 nm light

In the presence of methylene blue irradiated with red laser light, 1,3-diphenylisobenzofuran reacts with intermediate singlet oxygen 1O2, forming an unstable peroxide that decomposes into (colorless) 1,2-dibenzoylbenzene.[27] The detection of singlet oxygen by 1,3-diphenylisobenzofuran is based on this reaction, even in biological systems. For biological systems, water-soluble derivatives of 1,3-diphenylisobenzofuran were developed.[28] The singlet oxygen generation of photosensitizers were monitored by photolysis of 1,3-diphenylisobenzofuran (DPBF). 1,2-Dibenzoylbenzene absorbs at <300 nm, therefore making DPBF an optimal chemical trap for detecting singlet oxygen, as most photosensitizers absorb <400-600 nm. This allows for an accurate determination of the photodegradation of the molecule.

Dienophile in Diels-Alder reactions

Isobenzofurans like 1,3-diphenylisobenzofuran are among the most reactive Diels-Alder dienes known to date,[29] and are useful for scavenging short-lived and unstable olefins and alkynes. The group led by Georg Wittig made important contributions to this topic.

With the unstable cyclohexyne, 1,3-diphenylisobenzofuran reacts to a tricyclic compound that gives a 9,10-diphenylcyclohexenonaphthalene after hydrogenation and hydrogen abstraction.[30]

Reaktion von 1,3-Diphenylisobenzofuran mit Cyclohexin

1,3-Diphenylisobenzofuran gives similarly with benzyne (dehydrobenzene) an oxygen-bridged anthracene (in 85% yield), which can be reduced with zinc to 9,10-diphenylanthracene (88% yield).[31]

Reaktion von 1,3-Diphenylisobenzofuran mit Dehydrobenzol

Cyclopropenone (which is unstable above its melting point of -29 °C) reacts quantitatively at room temperature with 1,3-diphenylisobenzofuran to form a Diels-Alder adduct,[32] which is exclusively an exo isomer.[33]

Reaktion von 1,3-Diphenylisobenzofuran mit Cyclopropenon

Dimethyl acetylenedicarboxylate reacts with 1,3-diphenylisobenzofuran as dienophile in 84% yield to yield the corresponding adduct.[34]

Reaktion von 1,3-Diphenylisobenzofuran mit Acetylendicarbonsäureester

1,3-Diphenylisobenzofuran reacts also with heterocyclic dienophiles such as 3-sulfolene to the corresponding Diels-Alder adduct.[35]

Molecular building block for polyaromatics

Polyaromatic hydrocarbons (PAHs) are of interest as precursors to graphite but also raise concern as ingredients of pollution. They have persistence and carcinogenicity. 1,3-diphenylisobenzofuran reacts quantitatively with acenaphthylene when heated to 160 °C to give 7,12-diphenylbenzo[k]fluoranthene.[36]

Reaktion von 1,3-Diphenylisobenzofuran mit Acenaphthylen

The twice occurring Diels-Alder reaction of 1,3-diphenylisobenzofuran with p-benzoquinone yields almost quantitatively a product that can be reacted further with p-toluenesulfonic acid to give a pentacene derivative in 49% yield.[37]

Reaktion von 1,3-Diphenylisobenzofuran zum Pentacen

Literature

References

  1. ↑ "1,3-Diphenylisobenzofuran 5471-63-6 | TCI Deutschland GmbH" (in de). http://www.tcichemicals.com/eshop/de/de/commodity/D1520. 
  2. ↑ 2.0 2.1 Sigma-Aldrich Co., product no. 105481.
  3. ↑ 3.0 3.1 Carl L. Yaws (2015), Thermophysical Properties of Chemicals and Hydrocarbons, 2nd Edition, Oxford, UK: Elsevier Inc., p. 604, ISBN 978-0-323-28659-6 
  4. ↑ 4.0 4.1 R. Adams; M.H. Gold (1940), "The Synthesis of 1,3-Diphenyldihydroisobenzofurans, 1,3-Diphenylisobenzofurans and o-Dibenzoylbenzenes from the Diene Addition Products to Dibenzoylethylene", Journal of the American Chemical Society 62 (1): 56–61, doi:10.1021/ja01858a012 
  5. ↑ P.C. Kierkus (2001), "1,3-Diphenylisobenzofuran", E-EROS Encyclopedia of Reagents for Organic Synthesis, doi:10.1002/047084289X.rd420, ISBN 0471936235 
  6. ↑ R.H. Young; K. Wehrly; R.L. Martin (1971), "Solvent effects in dye-sensitized photooxidation reactions", Journal of the American Chemical Society 93 (22): 5774–5779, doi:10.1021/ja00751a031 
  7. ↑ J.A. Howard; G.D. Mendenhall (1975), "Autoxidation and photooxidation of 1,3-diphenylisobenzofuran: A kinetic and product study", Canadian Journal of Chemistry 53 (14): 2199–2201, doi:10.1139/v75-307 
  8. ↑ P. Carloni (1993), "On the use of 1,3-diphenylisobenzofuran (DPBF). Reactions with carbon and oxygen centered radicals in model and natural systems", Res. Chem. Intermed. 19 (5): 395–405, doi:10.1163/156856793X00181 
  9. ↑ A. Guyot, J. Catel, Bull. Soc. Chim. France, [3] (35), 1124 (1906)
  10. ↑ A. Guyot, J. Catel, Compt. Rend. Hebd. Acad. Sci., Ser. C140, 1348 (1905)
  11. ↑ M. Kuriyama; N. Ishiyama; R. Shimazawa; R. Shirai; O. Onomura (2009), "Efficient synthesis of 3-arylphthalides using palladium-catalyzed arylation of aldehydes with organoboronic acids", Journal of Organic Chemistry 74 (23): 9210–9213, doi:10.1021/jo901964k, PMID 19873994 
  12. ↑ M. S. Newman (1961), "Evidence favoring a two-step mechanism for the Diels-Alder reaction", Journal of Organic Chemistry 26 (8): 2630–2633, doi:10.1021/jo01066a004 
  13. ↑ "trans-Dibenzoylethylene". Organic Syntheses. doi:10.15227/orgsyn.020.0029. 
  14. ↑ "Dehydroisobenzofurans and process for preparing them" US patent 2325727, published 1943-08-03
  15. ↑ "1,2-Dibenzoylethylene, predominantly trans, 96%". https://www.thermofisher.com/order/catalog/product/L12643.03?SID=srch-srp-L12643.06. 
  16. ↑ D.V. Klemm; A. Tuncay (1989), "Photochemical and thermal isomerization of trans- and cis-1,2-dibenzoylethylene: A microscale approach", J. Chem. Educ. 66 (6): 519, doi:10.1021/ed066p519, Bibcode: 1989JChEd..66..519K 
  17. ↑ "1,3-Diphenylisobenzofurans and process for preparing the same" US patent 2356907, published 1944-08-29
  18. ↑ Houben-Weyl Methods of Organic Chemistry (1973), Organometallic Compounds of Group II of the Periodic Table, 4th Edition, XIII/2a, Stuttgart: Thieme, p. 419, ISBN 978-3-13-213204-7 
  19. ↑ M. Cava; M.J. Mitchell; A.A. Deana (1960), "Condensed cyclobutane aromatic compounds. XIII. An attempted synthesis of 1,2-diphenylbenzocyclobutene", Journal of Organic Chemistry 25 (9): 1481–1484, doi:10.1021/jo01079a005 
  20. ↑ J. Jacq; B. Bessières; C. Einhorn; J. Einhorn (2010), "Regiospecific synthesis of functionalised 1,3-diarylisobenzofurans via palladium- and rhodium-catalysed reaction of boronic acids with o-acylbenzaldehydes under thermal or microwave activation", Org. Biomol. Chem. 8 (21): 4927–4933, doi:10.1039/c0ob00110d, PMID 20740250 
  21. ↑ A. Kotali; P.G. Tsoungas (1987), "Oxidation of N-aroylhydrazones of o-hydroxyaryl ketones with lead(IV)acetate: A facile route to aromatic o-diketones", Tetrahedron Lett. 28 (37): 4321–4322, doi:10.1016/S0040-4039(00)96497-9 
  22. ↑ J. Jacq; C. Einhorn; J. Einhorn (2008), "A versatile and regiospecific synthesis of functionalised 1,3-diarylisobenzofurans", Org. Lett. 10 (17): 3757–3760, doi:10.1021/ol801550a, PMID 18666776 
  23. ↑ M. Wozniak; F. Tanfani; E. Bertoli; G. Zolese; J. Antonsiewicz (1991), "A new fluorescence method to detect singlet oxygen inside phospholipid model membranes", Biochim. Biophys. Acta 1082 (1): 94–100, doi:10.1016/0005-2760(91)90304-Z, PMID 1849016 
  24. ↑ X.-F. Zhang; X. Liu (2011), "The photostability and fluorescence properties of diphenylisobenzofuran", Journal of Luminiscence 131 (11): 2263–2266, doi:10.1016/j.jlumin.2011.05.048, Bibcode: 2011JLum..131.2263Z 
  25. ↑ A. Schönberg; A. Mustafa; G. Aziz (September 1, 1954), "Diels-Alder Reaction. II. Experiments with 2-Styrylchromones. On the Nature of the Dimer of 1,3-Diphenylisobenzofuran", Journal of the American Chemical Society 76 (18): 4576–4577, doi:10.1021/ja01647a020 
  26. ↑ Soman, Rahul; Raghav, Darpan; Sujatha, Subramaniam; Rathinasamy, Krishnan; Arunkumar, Chellaiah (30 Jun 2015). "Axial ligand modified high valent tin(iv) porphyrins: synthesis, structure, photophysical studies and photodynamic antimicrobial activities on Candida albicans". RSC Adv. 5 (75): 61103. doi:10.1039/C5RA09343K. Bibcode: 2015RSCAd...561103S. https://pubs.rsc.org/en/content/articlelanding/2015/ra/c5ra09343k. 
  27. ↑ "Grundpraktikum Physikalische Chemie, V28, Photooxidation von Diphenylisobenzofuran, Untersuchung der Reaktionskinetik durch Photometrie" (in German). Universität Ulm. 2010-12-06. https://www.uni-ulm.de/physchem-praktikum/media/ap/v_28.pdf. 
  28. ↑ C. Schmitz; J.M. Aubry; J. Rigaudy (1982), "A new access to the anthracene core: Synthesis of two water soluble singlet oxygen traps derived from 1,3-diphenylisobenzofuran and 9,10-diphenylanthracene", Tetrahedron 38 (10): 1425–1430, doi:10.1016/0040-4020(82)80224-X 
  29. ↑ D. Tobia; B. Rickborn (1987), "Substituent effects on rates of inter- and intramolecular cycloaddition reactions of isobenzofurans", Journal of Organic Chemisty 52 (12): 2611–2615, doi:10.1021/jo00388a055 
  30. ↑ G. Wittig (1963), "Über kleine Ringe mit Kohlenstoffdreifachbindung – noch eine Chemie des "Als ob"" (in German), Pure Appl. Chem. 7 (2–3): 173–192, doi:10.1351/pac196307020173 
  31. ↑ G. Wittig; E. Knauss; K. Niethamer (1960), "Über 9,10-Dihydroanthracen-Derivate mit Heterobrückenatomen" (in German), Justus Liebigs Ann. Chem. 630 (1): 10–18, doi:10.1002/jlac.19606300103 
  32. ↑ R. Breslow; M. Oda (1972), "Isolation and characterization of pure cyclopropenone", Journal of the American Chemical Society 94 (13): 4787–4788, doi:10.1021/ja00768a089 
  33. ↑ "Exo selectivity of the Diels-Alder addition of cyclopropenone and 1-3-diphenylisobenzofuran". http://www.ch.ic.ac.uk/motm/porphyrins/P2.html. 
  34. ↑ J.A. Berson (1953), "Reactions of 1,3-diphenylisobenzofuran with acetylenic dienophiles", Journal of the American Chemical Society 75 (5): 1240–1241, doi:10.1021/ja01101a503 
  35. ↑ M.P. Cava; J.P. VanMeter (1969), "Condensed cyclobutane aromatic compounds. XXX. Synthesis of some unusual 2,3-naphthoquinonoid heterocycles. A synthetic route to derivatives of naphtho[2,3-b]biphenylene and anthra[b]cyclobutene", Journal of Organic Chemistry. Org. Chem. 34 (3): 538–545, doi:10.1021/jo01255a012 
  36. ↑ Houben-Weyl Science of Synthesis (2009), Compounds with All-Carbon Functions, 45b, Stuttgart: Thieme, p. 1038, ISBN 978-3-13-146551-1 
  37. ↑ G.P. Miller; J. Briggs (2002), "Progress towards the synthesis of tris- and tetrakis[60]fullerene adducts", Electrochem. Soc. Proc. 2002-12: 279–284, ISBN 1-56677-333-4 



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