Benzophenone

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Benzophenone
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Names
Preferred IUPAC name
Diphenylmethanone[1]
Other names
Benzophenone[1]
Diphenyl ketone
Benzoylbenzene
Benzoylphenyl
Identifiers
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3D model (JSmol)
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1238185
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4256
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UN number 1224
  • InChI=1S/C13H10O/c14-13(11-7-3-1-4-8-11)12-9-5-2-6-10-12/h1-10H checkY
    Key: RWCCWEUUXYIKHB-UHFFFAOYSA-N checkY
  • InChI=1/C13H10O/c14-13(11-7-3-1-4-8-11)12-9-5-2-6-10-12/h1-10H
    Key: RWCCWEUUXYIKHB-UHFFFAOYAX
  • O=C(c1ccccc1)c2ccccc2
Properties
C13H10O
Molar mass 182.222 g·mol−1
Appearance White solid
Odor Geranium-like[2]
Density 1.11 g/cm3[2]
Melting point 48.5 °C (119.3 °F; 321.6 K)[2]
Boiling point 305.4 °C (581.7 °F; 578.5 K)[2]
Insoluble[2]
Solubility in organic solvents 1 g/7.5 mL in ethanol[2]
1 g/6 mL in diethyl ether.[2] Alkanes + tetrachloromethane: better with increasing tetrachloromethane content[3]
−109.6·10−6 cm3/mol
Hazards
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NFPA 704 four-colored diamondHealth 1: Exposure would cause irritation but only minor residual injury. E.g. turpentineFlammability 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g. canola oilInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
1
1
0
Flash point 110 °C (230 °F; 383 K)
Safety data sheet (SDS) External MSDS by Sigma-Aldritch
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Template:Chembox Footer/trackingTemplate:Short description

Benzophenone is a naturally occurring organic compound with the formula (C6H5)2CO, generally abbreviated Ph2CO. Benzophenone has been found in some fungi, fruits and plants, including grapes.[4] It is a white solid with a low melting point and rose-like odor[5] that is soluble in organic solvents. Benzophenone is the simplest diaromatic ketone. It is a widely used building block in organic chemistry, being the parent diarylketone.

History

Carl Graebe of the University of Königsberg, in an early literature report from 1874, described working with benzophenone.[5]

Uses

Benzophenone can be used as a photo initiator in ultraviolet (UV)-curing applications[6] such as inks, imaging, and clear coatings in the printing industry. Benzophenone prevents UV light from damaging scents and colors in products such as perfumes and soaps.

Benzophenone can also be added to plastic packaging as a UV blocker to prevent photo-degradation of the packaging polymers or its contents. Its use allows manufacturers to package the product in clear glass or plastic (such as a PETE water bottle).[7] Without it, opaque or dark packaging would be required.

In biological applications, benzophenones have been used extensively as photophysical probes to identify and map peptide–protein interactions.[8]

Benzophenone is used as an additive in flavorings or perfumes for "sweet-woody-geranium-like notes".[9]

Synthesis

Benzophenone is produced by the copper-catalyzed oxidation of diphenylmethane with air.[10]

A laboratory route involves the reaction of benzene with carbon tetrachloride followed by hydrolysis of the resulting diphenyldichloromethane.[11] It can also be prepared by Friedel–Crafts acylation of benzene with benzoyl chloride in the presence of a Lewis acid (e.g. aluminium chloride) catalyst: since benzoyl chloride can itself be produced by the reaction of benzene with phosgene the first synthesis proceeded directly from those materials.[12]

Another route of synthesis is through a palladium(II)/oxometalate catalyst. This converts an alcohol to a ketone with two groups on each side.[13]

Another, less well-known reaction to produce benzophenone is the pyrolysis of anhydrous calcium benzoate.[14]

Organic chemistry

The Haller–Bauer reaction occurs between a non-enolizable ketone and a strong amide base. In this prototypical example involving benzophenone, the tetrahedral intermediate expels phenyl anion to give benzamide and benzene as the organic products.

Benzophenone is a common photosensitizer in photochemistry. It crosses from the S1 state into the triplet state with nearly 100% yield. The resulting diradical will abstract a hydrogen atom from a suitable hydrogen donor to form a ketyl radical.

Radical anion

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A solvent pot containing dibutyl ether solution of sodium benzophenone ketyl, which gives it its purple color.

Alkali metals reduce benzophenone to the deeply blue colored radical anion, diphenylketyl:[15]

M + Ph2CO → M+Ph2CO•−

Generally sodium is used as the alkali metal. Sodium-benzophenone ketyl is used in the purification of organic solvents, particularly ethers, because it reacts with water and oxygen to give non-volatile products.[16][17] Adsorbents such as alumina, silica gel, and especially molecular sieves are superior and far safer.[18] The sodium-benzophenone method is common since it gives a visual indication that water, oxygen, and peroxides are absent from the solvent. Large scale purification may be more economical using devices which utilize adsorbents such as the aforementioned alumina or molecular sieves.[19] The ketyl is soluble in the organic solvent being dried, which leads to faster purification. In comparison, sodium is insoluble, and its heterogeneous reaction is much slower. When excess alkali metal is present a second reduction may occur, resulting in a color transformation from deep blue to purple:[15]

M + M+Ph2CO•− → (M+)2(Ph2CO)2−

Commercially significant benzophenones

The >300 natural benzophenones exhibit great structural diversity and biological activities.[20] 2-Amino-5-chlorobenzophenone is used in the synthesis of benzodiazepines.[21]

Substituted benzophenones such as oxybenzone and dioxybenzone are used in sunscreens. Their use has been criticized (see sunscreen controversy).

Michler's ketone has dimethylamino substituents at each para position.

The high-strength polymer PEEK is generated from 4,4'-difluorobenzophenone. 4,4′-Dihydroxybenzophenone is also of interest in this context.[22] 4-Chloro-4'-hydroxybenzophenone is used to make related polymers.[23]

Safety

It is considered "essentially nontoxic".[10] Benzophenone is however banned as a food additive by the US Food and Drug Administration, despite the FDA's continuing stance that this chemical does not pose a risk to public health under the conditions of its intended use.[24][25]

The European Union permits it as a flavouring substance,[26] having established a Total Dietary Intake of 0.3mg/kg of body weight per day.[27]

Benzophenone derivatives are known to be pharmacologically active. From a molecular chemistry point of view interaction of benzophenone with B-DNA has been demonstrated experimentally.[28] The interaction with DNA and the successive photo-induced energy transfer is at the base of the benzophenone activity as a DNA photosensitizer and may explain part of its therapeutic potentialities.

In 2014, benzophenones were named Contact Allergen of the Year by the American Contact Dermatitis Society.[29]

Benzophenone is an endocrine disruptor capable of binding to the pregnane X receptor.[30]

References

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  1. ^ a b Page Module:Citation/CS1/styles.css has no content."Front Matter". Nomenclature of Organic Chemistry : IUPAC Recommendations and Preferred Names 2013 (Blue Book). Cambridge: The Royal Society of Chemistry. 2014. pp. 723–724, 726. doi:10.1039/9781849733069-FP001. ISBN 978-0-85404-182-4.
  2. ^ a b c d e f g Page Module:Citation/CS1/styles.css has no content.Merck Index (11th ed.). p. 1108.
  3. ^ Page Module:Citation/CS1/styles.css has no content.Azizian, Saeid; Haydarpour, Afshin (November 2003). "Solubility of Benzophenone in Binary Alkane + Carbon Tetrachloride Solvent Mixtures". Journal of Chemical & Engineering Data. 48 (6): 1476–1478. doi:10.1021/je0340497.
  4. ^ Page Module:Citation/CS1/styles.css has no content.Surana, Khemchand; Chaudhary, Bharatkumar; Diwaker, Monika; Sharma, Satyasheel (2018). "Benzophenone: a ubiquitous scaffold in medicinal chemistry". MedChemComm. 9 (11): 1803–1817. doi:10.1039/C8MD00300A. ISSN 2040-2503. PMC 6238883. PMID 30542530.
  5. ^ a b Page Module:Citation/CS1/styles.css has no content."Molecule of the Week Archive: Benzophenone". American Chemical Society. 11 March 2024. Retrieved 20 May 2024.
  6. ^ Page Module:Citation/CS1/styles.css has no content.Carroll, G.T.; Turro, N.J.; Koberstein, J.T. (2010). "Patterning dewetting in thin polymer films by spatially directed photocrosslinking". Journal of Colloid and Interface Science. 351 (2): 556–560. Bibcode:2010JCIS..351..556C. doi:10.1016/j.jcis.2010.07.070. PMID 20728089.
  7. ^ Page Module:Citation/CS1/styles.css has no content.Dornath, Paul John (2010). "Analysis of Chemical Leaching from Common Consumer Plastic Bottles Under High Stress Conditions" (PDF). p. 32. Archived from the original (PDF) on 26 February 2015. Retrieved 26 February 2015.
  8. ^ Page Module:Citation/CS1/styles.css has no content.Dorman, Gyorgy; Prestwich, Glenn D. (1 May 1994). "Benzophenone Photophores in Biochemistry". Biochemistry. 33 (19): 5661–5673. doi:10.1021/bi00185a001. PMID 8180191.
  9. ^ Page Module:Citation/CS1/styles.css has no content.Arctander, Steffen. Perfume And Flavor Chemicals: (Aroma Chemicals).
  10. ^ a b Script error: No such module "Template wrapper".
  11. ^ Page Module:Citation/CS1/styles.css has no content.Marvel, C. S.; Sperry, W. M. (1941). "Benzophenone". Organic Syntheses; Page Module:Citation/CS1/styles.css has no content.Collected Volumes, vol. 1, p. 95.
  12. ^ Page Module:Citation/CS1/styles.css has no content."Synthesis of benzoic acid and benzophenone". Journal of the Chemical Society, Abstracts. 34: 69–70. 1878. doi:10.1039/CA8783400019.
  13. ^ Page Module:Citation/CS1/styles.css has no content.Dornan, L.; Muldoon, M. (2015). "A highly efficient palladium(II)/polyoxometalate catalyst system for aerobic oxidation of alcohols". Catalysis Science & Technology. 5 (3): 1428–1432. doi:10.1039/c4cy01632g.
  14. ^ Page Module:Citation/CS1/styles.css has no content.Lee, C. C. (1953). "The Mechanism of the Ketonic Pyrolysis of Calcium Carboxylates". The Journal of Organic Chemistry. 18 (9): 1079–1086. doi:10.1021/jo50015a003.
  15. ^ a b Page Module:Citation/CS1/styles.css has no content.Connelly, Neil; Geiger, William (28 March 1996). "Chemical Redox Agents for Organometallic Chemistry". Chemical Reviews. 96 (2): 877–910. doi:10.1021/cr940053x. PMID 11848774.
  16. ^ Page Module:Citation/CS1/styles.css has no content.Armarego, W. L. F.; Chai, C. (2003). Purification of laboratory chemicals. Oxford: Butterworth-Heinemann. ISBN 978-0-7506-7571-0.
  17. ^ Page Module:Citation/CS1/styles.css has no content.Harwood, L. M.; Moody, C. J.; Percy, J. M. (1999). Experimental Organic Chemistry: Standard and Microscale. Oxford: Blackwell Science. ISBN 978-0-632-04819-9.
  18. ^ Page Module:Citation/CS1/styles.css has no content.Williams, D. B. G.; Lawton, M. (2010). "Drying of Organic Solvents: Quantitative Evaluation of the Efficiency of Several Desiccants". The Journal of Organic Chemistry. 75 (24): 8351–4. doi:10.1021/jo101589h. PMID 20945830. S2CID 17801540.
  19. ^ Page Module:Citation/CS1/styles.css has no content.Simas, Alessandro B. C.; Pereira, Vera L. P.; Barreto Jr., Cleber B.; Sales, Daniel L. de; Carvalho, Leandro L. de (2009). "An expeditious and consistent procedure for tetrahydrofuran (THF) drying and deoxygenation by the still apparatus". Química Nova. 32 (9): 2473–2475. doi:10.1590/S0100-40422009000900042. ISSN 0100-4042.
  20. ^ Page Module:Citation/CS1/styles.css has no content.Wu, Shi-Biao; Long, Chunlin; Kennelly, Edward J. (2014). "Structural diversity and bioactivities of natural benzophenones". Nat. Prod. Rep. 31 (9): 1158–1174. doi:10.1039/C4NP00027G. ISSN 0265-0568. PMID 24972079.
  21. ^ Page Module:Citation/CS1/styles.css has no content.Massah, Ahmad R.; Gharaghani, Sajjad; Lordejani, Hamid Ardeshiri; Asakere, Nahad (1 August 2016). "New and mild method for the synthesis of alprazolam and diazepam and computational study of their binding mode to GABAA receptor". Medicinal Chemistry Research. 25 (8): 1538–1550. doi:10.1007/s00044-016-1585-z. ISSN 1554-8120.
  22. ^ David Parker, Jan Bussink, Hendrik T. van de Grampe, Gary W. Wheatley, Ernst-Ulrich Dorf, Edgar Ostlinning, Klaus Reinking "Polymers, High-Temperature" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2002.
  23. ^ Page Module:Citation/CS1/styles.css has no content.Parker, David; Bussink, Jan; Van De Grampel, Hendrik T.; Wheatley, Gary W.; Dorf, Ernst-Ulrich; Ostlinning, Edgar; Reinking, Klaus; Schubert, Frank; Jünger, Oliver; Wagener, Reinhard (2012). "Polymers, High-Temperature". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a21_449.pub4. ISBN 978-3-527-30673-2.
  24. ^ Page Module:Citation/CS1/styles.css has no content."FDA Bans Use of 7 Synthetic Food Additives After Environmental Groups Sue". NPR.org. Retrieved 9 October 2018.
  25. ^ 83 FR 50490
  26. ^ Page Module:Citation/CS1/styles.css has no content.Risk management approach for benzophenone (Report). Health Canada. January 2001.
  27. ^ Page Module:Citation/CS1/styles.css has no content.Silano, Vittorio; et al. (14 November 2017). "Safety of benzophenone to be used as flavouring". EFSA Journal. 15 (11): e05013. doi:10.2903/j.efsa.2017.5013. hdl:2164/9927. PMC 7010149. PMID 32625332.
  28. ^ Page Module:Citation/CS1/styles.css has no content.Consuelo Cuquerella, M.; Lhiaubet-Vallet, V.; Cadet, J.; Miranda, M. A. (2012). "Benzophenone Photosensitized DNA Damage". Acc. Chem. Res. 45 (9): 1558–1570. doi:10.1021/ar300054e. hdl:10251/29549. PMID 22698517.
  29. ^ Page Module:Citation/CS1/styles.css has no content.Doug Brunk (14 March 2014). "Benzophenones named 2014 Contact Allergen of the Year : Dermatology News". Skinandallergynews.com. Archived from the original on 22 March 2016. Retrieved 16 June 2016.
  30. ^ Page Module:Citation/CS1/styles.css has no content.Mikamo, Eriko; Harada, Shingo; Nishikawa, Jun-Ichi; Nishihara, Tsutomu (2003). "Endocrine disruptors induce cytochrome P450 by affecting transcriptional regulation via pregnane X receptor". Toxicology and Applied Pharmacology. 193 (1): 66–72. Bibcode:2003ToxAP.193...66M. doi:10.1016/j.taap.2003.08.001. PMID 14613717.
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