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Benzophenone: Difference between revisions - Wikipedia

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Benzophenone: Difference between revisions

Jump to navigation Jump to search Browse history interactively Revision as of 22:32, 6 August 2011 (edit) Beetstra (talk | contribs) (Script assisted update of identifiers for the Chem/Drugbox validation project (updated: 'DrugBank', 'ChEBI').) ← Previous edit Latest revision as of 02:27, 14 September 2019 (edit) (undo) Monkbot (talk | contribs) m (→‎Uses: Task 16: replaced (1×) / removed (0×) deprecated |dead-url= and |deadurl= with |url-status=;) Tags: AWB PHP7 (141 intermediate revisions by 80 users not shown) Line 1: Line 1: {{about|the basic chemical|benzophenone-1 – benzophenone-12|benzophenone-n}} {{about|the basic chemical|benzophenone-1 – benzophenone-12|benzophenone-n}} − {{chembox {{chembox + | Watchedfields = changed − | verifiedrevid = 413888278 + | verifiedrevid = 443416927 | ImageFile = Benzophenon.svg | ImageFile = Benzophenon.svg | ImageFile1 = Benzophenone-3D-vdW.png | ImageFile1 = Benzophenone-3D-vdW.png − | ImageFileL1 = Benzophenone-from-xtal-metastable-phase-2000-3D-vdW.png − | ImageFileR1 = Benzophenone-from-xtal-stable-phase-1968-3D-vdW.png | ImageFile2 = Benzophenone-3D-balls.png | ImageFile2 = Benzophenone-3D-balls.png + | PIN = Diphenylmethanone<ref name=iupac2013>{{cite book | title = Nomenclature of Organic Chemistry : IUPAC Recommendations and Preferred Names 2013 (Blue Book) | publisher = [[Royal Society of Chemistry|The Royal Society of Chemistry]] | date = 2014 | location = Cambridge | pages = 723–724, 726 | doi = 10.1039/9781849733069-FP001 | isbn = 978-0-85404-182-4| chapter = Front Matter }}</ref> − | ImageFileL2 = Benzophenone-from-xtal-metastable-phase-2000-3D-balls.png + | OtherNames = Benzophenone<ref name=iupac2013 /><br />Phenyl ketone<br />Diphenyl ketone<br />Benzoylbenzene<br />Benzoylphenyl − | ImageFileR2 = Benzophenone-from-xtal-stable-phase-1968-3D-balls.png + |Section1={{Chembox Identifiers − | ImageSizeL1 = 140 + | UNII_Ref = {{fdacite|correct|FDA}} − | ImageSizeR1 = 140 − | ImageSizeL2 = 140 − | ImageSizeR2 = 140 − | IUPACName = diphenylmethanone − | OtherNames = phenyl ketone; diphenyl ketone; benzoylbenzene − | Section1 = {{Chembox Identifiers − | UNII_Ref = {{fdacite|correct|FDA}} | UNII = 701M4TTV9O | UNII = 701M4TTV9O | KEGG_Ref = {{keggcite|correct|kegg}} | KEGG_Ref = {{keggcite|correct|kegg}} Line 32: Line 24: | ChemSpiderID=2991 | ChemSpiderID=2991 | CASNo = 119-61-9 | CASNo = 119-61-9 − | PubChem = 3102 + | PubChem = 3102 + | DrugBank_Ref = {{drugbankcite|correct|drugbank}} − | DrugBank = DB01878 + | DrugBank = DB01878 + | ChEBI_Ref = {{ebicite|correct|EBI}} | ChEBI = 41308 | ChEBI = 41308 | SMILES = O=C(c1ccccc1)c2ccccc2 | SMILES = O=C(c1ccccc1)c2ccccc2 − | InChI = 1/C13H10O/c14-13(11-7-3-1-4-8-11)12-9-5-2-6-10-12/h1-10H + | InChI = 1/C13H10O/c14-13(11-7-3-1-4-8-11)12-9-5-2-6-10-12/h1-10H }} }} − | Section2 = {{Chembox Properties + |Section2={{Chembox Properties + | C=13 | H=10 | O=1 − | Formula = C<sub>13</sub>H<sub>10</sub>O − | MolarMass = 182.217 g/mol + | Appearance = White solid + | Odor = [[Geranium]]-like<ref name=Merck>{{cite book|title=Merck Index|edition=11th|page=1108|title-link=Merck Index}}</ref> − | Appearance = White solid − | Density = 1.11 g/cm<sup>3</sup>, solid + | Density = 1.11 g/cm<sup>3</sup><ref name=Merck/> − | MeltingPt = 47.9 °C + | MeltingPtC = 48.5 + | MeltingPt_ref = <ref name=Merck/> − | BoilingPt = 305.4 °C + | MagSus = -109.6·10<sup>−6</sup> cm<sup>3</sup>/mol − | Solubility = Insoluble + | BoilingPtC = 305.4 − | SolubleOther = [[Benzene]], [[THF]], [[ethanol]], [[propylene glycol]] + | BoilingPt_ref = <ref name=Merck/> − | Solvent = + | Solubility = Insoluble<ref name=Merck/> − }} + | Solubility1 = 1 g/7.5 mL in [[ethanol]]<ref name=Merck/><br>1 g/6 mL in [[diethyl ether]].<ref name=Merck/> Alkanes + [[tetrachloromethane]]: better with increasing tetrachloromethane content<ref>{{cite journal|last1=Azizian|first1=Saeid|last2=Haydarpour|first2=Afshin|title=Solubility of Benzophenone in Binary Alkane + Carbon Tetrachloride Solvent Mixtures|journal=Journal of Chemical & Engineering Data|date=November 2003|volume=48|issue=6|pages=1476–1478|doi=10.1021/je0340497}}</ref> − | Section3 = {{Chembox Hazards + | Solvent1 = organic solvents − | MainHazards = Harmful (XN) + }} − | FlashPt = + |Section3={{Chembox Hazards − | Autoignition = + | MainHazards = Harmful (XN) − | NFPA-H = 3 − | NFPA-F = 1 + | FlashPtC = 110 + | AutoignitionPtC = − | NFPA-R = 0 − | NFPA-O = + | NFPA-H = 1 + | NFPA-F = 1 − | ExternalMSDS = [http://hazard.com/msds/mf/baker/baker/files/b1488.htm External MSDS by JT Baker] + | NFPA-R = 0 + | NFPA-S = + | ExternalSDS = [http://hazard.com/msds/mf/baker/baker/files/b1488.htm External MSDS by JT Baker] }} }} }} }} + − '''Benzophenone''' is the [[organic compound]] with the formula ([[carbon|C]]<sub>6</sub>[[hydrogen|H]]<sub>5</sub>)<sub>2</sub>C[[oxygen|O]], generally abbreviated [[phenyl|Ph]]<sub>2</sub>CO. Benzophenone is a widely used building block in organic chemistry, being the parent diarylketone. + '''Benzophenone''' is the [[organic compound]] with the formula (C<sub>6</sub>H<sub>5</sub>)<sub>2</sub>CO, generally abbreviated [[phenyl|Ph]]<sub>2</sub>CO. It is a white solid that is soluble in organic solvents. Benzophenone is a widely used [[Building block (chemistry)|building block]] in organic chemistry, being the parent diarylketone. ==Uses== ==Uses== − Benzophenone can be used as a [[Photoinitiator|photo initiator]] in UV-curing applications such as inks, imaging, and clear coatings in the [[printing]] industry. Benzophenone prevents ultraviolet ([[UV]]) light from damaging scents and colors in products such as perfumes and soaps. It can also be added to the plastic packaging as a UV blocker. Its use allows manufacturers to package the product in clear glass or plastic. Without it, opaque or dark packaging would be required. + Benzophenone can be used as a [[Photoinitiator|photo initiator]] in UV-curing applications<ref>{{cite journal|title=Patterning dewetting in thin polymer films by spatially directed photocrosslinking|author1=Carroll, G.T. |author2=Turro, N.J. |author3=Koberstein, J.T. |journal=Journal of Colloid and Interface Science|year=2010|volume=351|issue=2|pages=556–560|doi=10.1016/j.jcis.2010.07.070|pmid=20728089 |bibcode=2010JCIS..351..556C }}</ref> such as inks, imaging, and clear coatings in the [[printing]] industry. Benzophenone prevents ultraviolet ([[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).<ref>{{cite web|last1=Dornath |first1=Paul John |title=Analysis of Chemical Leaching from Common Consumer Plastic Bottles Under High Stress Conditions |url=https://ir.library.oregonstate.edu/xmlui/bitstream/handle/1957/17627/Dornath%20thesis.pdf?sequence=1 |accessdate=26 February 2015 |page=32 |date=2010 |url-status=dead |archiveurl=https://web.archive.org/web/20150226053029/https://ir.library.oregonstate.edu/xmlui/bitstream/handle/1957/17627/Dornath%20thesis.pdf?sequence=1 |archivedate=26 February 2015 }}</ref> 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.<ref>{{cite journal|last=Dorman|first=Gyorgy|author2=Prestwich, Glenn D.|title=Benzophenone Photophores in Biochemistry|journal=Biochemistry|date=1 May 1994|volume=33|issue=19|pages=5661–5673|doi=10.1021/bi00185a001}}</ref> + + Benzophenone is used as an additive in flavorings or perfumes for "sweet-woody-geranium-like notes."<ref>{{Cite book|title=Perfume And Flavor Chemicals: (Aroma Chemicals)|last=Arctander|first=Steffen|publisher=|year=|isbn=|location=|pages=}}</ref> ==Synthesis== ==Synthesis== + Benzophenone is produced by the copper-catalyzed oxidation of [[diphenylmethane]] with air.<ref name=Ull>{{Ullmann|first1=Hardo |last1=Siegel |first2=Manfred |last2=Eggersdorfer |title=Ketones |doi=10.1002/14356007.a15_077}}</ref> − Benzophenone can be prepared by the reaction of benzene with [[carbon tetrachloride]] followed by hydrolysis of the resulting [[diphenyldichloromethane]],<ref>{{OrgSynth | author = Marvel, C. S.; Sperry, W. M. | title = Benzophenone | prep = cv1p0095 | collvol = 1 | collvolpages = 95 | year = 1941}}</ref> or by [[Friedel-Crafts acylation]] of [[benzene]] with [[benzoyl chloride]] in the presence of a [[Lewis acid]] (e.g. [[aluminium chloride]]) catalyst. The industrial synthesis relies on the copper-catalyzed oxidation of [[diphenylmethane]] with air.<ref>Hardo Siegel, Manfred Eggersdorfer "Ketones" in Ullmann's Encyclopedia of Industrial Chemistry Wiley-VCH, 2002 by Wiley-VCH, Wienheim. DOI: 10.1002/14356007.a15_077</ref> + + A laboratory route involves the reaction of benzene with [[carbon tetrachloride]] followed by hydrolysis of the resulting [[diphenyldichloromethane]].<ref>{{OrgSynth | author = Marvel, C. S. |author2=Sperry, W. M. | title = Benzophenone | prep = cv1p0095 | collvol = 1 | collvolpages = 95 | year = 1941}}</ref> 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. + + Another route of synthesis is through a palladium(II)/oxometalate catalyst. This converts an alcohol to a ketone with two groups on each side.<ref>{{cite journal|last1=Dornan |first1=L. |last2=Muldoon |first2=M. |title=A highly efficient palladium(II)/polyoxometalate catalyst system for aerobic oxidation of alcohols |journal=Catalysis Science & Technology |date=2015 |volume=5 |issue=3 |pages=1428–1432 |doi=10.1039/c4cy01632g}}</ref> + + Another, less well-known reaction to produce benzophenone is the pyrolysis of anhydrous calcium benzoate.<ref>{{cite journal|doi=10.1021/jo50015a003 | volume=18 | issue=9 | title=The Mechanism of the Ketonic Pyrolysis of Calcium Carboxylates | journal=The Journal of Organic Chemistry | pages=1079–1086 | last1 = Lee | first1 = C. C.| year=1953 }}</ref> ==Organic chemistry== ==Organic chemistry== Line 73: Line 83: ===Benzophenone radical anion=== ===Benzophenone radical anion=== {{main|Air-free technique}} {{main|Air-free technique}} + [[File:Making benzophenone radical anion.webm|left|thumb|Addition of a solution of benzophenone in [[Tetrahydrofuran|THF]] to a vial containing THF, sodium metal, and a stir bar, yielding the deep blue benzophenone anion radical. Playback speed 4x original recording.]] − Sodium reduces benzophenone to the deeply colored radical anion, diphenylketyl: + Alkali metals reduce benzophenone to the deeply blue colored [[Radical ion|radical anion]], diphenylketyl:<ref name=":0">{{Cite journal|title = Chemical Redox Agents for Organometallic Chemistry|last = Connelly|first = Neil|date = March 28, 1996|journal = Chemical Reviews|doi = 10.1021/cr940053x|last2 = Geiger|first2 = William|pmid=11848774|volume=96|issue=2|pages=877–910}}</ref> + :M + Ph<sub>2</sub>CO → M<sup>+</sup>Ph<sub>2</sub>CO<sup>•−</sup> + Generally sodium is used as the alkali metal. Although inferior in terms of safety and effectiveness relative to [[molecular sieves]],<ref>{{cite journal|last=Williams |first=D. B. G. |last2=Lawton |first2=M. |title=Drying of Organic Solvents: Quantitative Evaluation of the Efficiency of Several Desiccants |journal=The Journal of Organic Chemistry |date=2010 |volume=75 |issue=24 |pages=8351–4 |doi= 10.1021/jo101589h |pmid=20945830}}</ref> this ketyl is used in the purification of organic solvents, particularly ethers, because it reacts with water and oxygen to give non-volatile products.<ref>{{cite book |first1=W. L. F. |last1=Armarego |first2=C. |last2=Chai | title = Purification of laboratory chemicals | year = 2003 | publisher = Butterworth-Heinemann | location = Oxford | isbn = 978-0-7506-7571-0}}</ref><ref>{{cite book | first1= L. M. |last1=Harwood |first2=C. J.|last2= Moody |first3= J. M. |last3=Percy | title = Experimental Organic Chemistry: Standard and Microscale | year =1999 | publisher = Blackwell Science | location = Oxford | isbn = 978-0-632-04819-9}}</ref> The ketyl is soluble in the organic solvent being dried, so it accelerates the reaction of the sodium with water and oxygen. 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:<ref name=":0" /> − :Na + Ph<sub>2</sub>CO → Na<sup>+</sup>Ph<sub>2</sub>CO<sup>&middot;−</sup> + :M + M<sup>+</sup>Ph<sub>2</sub>CO<sup>•−</sup> → (M<sup>+</sup>)<sub>2</sub>(Ph<sub>2</sub>CO)<sup>2−</sup> + [[File:Solvent pot.JPG|thumb|left|220 px|A solvent pot containing [[dibutyl ether]] solution of sodium benzophenone ketyl, which gives it its purple color.]] + ==Commercially significant derivatives and analogues== − This ketyl is used in the purification of hydrocarbon solvents, because it reacts with water and oxygen to give non-volatile products.<ref>{{cite book | author = W. L. F. Armarego and C. Chai | title = Purification of laboratory chemicals | year = 2003 | publisher = Butterworth-Heinemann | location = Oxford | isbn = 0750675713}}</ref> The ketyl is soluble in the organic solvent being dried, so it reacts quickly with residual water and oxygen. In comparison, sodium is insoluble, and its heterogeneous reaction is much slower. The ketyl radical generally appears blue or purple, depending on the solvent. + There are over 300 natural benzophenones, with great structural diversity and biological activities. They are being investigated as potential sources of new drugs. <ref>{{Cite journal|last=Wu|first=Shi-Biao|last2=Long|first2=Chunlin|last3=Kennelly|first3=Edward J.|date=2014|title=Structural diversity and bioactivities of natural benzophenones|url=http://xlink.rsc.org/?DOI=C4NP00027G|journal=Nat. Prod. Rep.|language=en|volume=31|issue=9|pages=1158–1174|doi=10.1039/C4NP00027G|issn=0265-0568}}</ref> [[Substitution (chemistry)|Substituted]] benzophenones such as [[oxybenzone]] and [[dioxybenzone]] are used in many [[sunscreen]]s. The use of benzophenone-derivatives which structurally resemble a strong [[photosensitizer]] has been criticized (see [[sunscreen controversy]]). + [[Michler's ketone]] has [[aniline|dimethylamino]] [[substituent]]s at each [[aromatic para position|''para'' position]]. The high-strength polymer [[PEEK]] is prepared from derivatives of benzophenone. − ===Commercially significant derivatives=== − [[Substitution (chemistry)|Substituted]] benzophenones such as [[oxybenzone]] and [[dioxybenzone]] are used in some [[sunscreen]]s. The use of benzophenone-derivatives which structurally resemble a strong [[photosensitizer]] has been strongly criticized (see [[sunscreen controversy]]).<ref name=Knowland1993>{{cite journal |author=Knowland, John; McKenzie, Edward A.; McHugh, Peter J.; Cridland, Nigel A. |title= Sunlight-induced mutagenicity of a common sunscreen ingredient | journal= FEBS Letters |volume= 324 | issue = 3 |pages=309–313 |year=1993 |pmid=8405372 |doi= 10.1016/0014-5793(93)80141-G }}</ref> + ==Safety== − ''p'',''p'''-bis(''N'',''N''-dimethylamino)benzophenone or [[Michler's ketone]] has [[aniline|dimethylamino]] [[substituent]]s at each [[aromatic para position|para position]]. + It is considered as "essentially nontoxic."<ref name=Ull/> 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.<ref>{{Cite news|url=https://www.npr.org/sections/thesalt/2018/10/06/655135633/fda-bans-use-of-7-synthetic-food-additives-after-environmental-groups-sue|title=FDA Bans Use of 7 Synthetic Food Additives After Environmental Groups Sue|work=NPR.org|access-date=2018-10-09|language=en}}</ref><ref>{{Federal Register|83|50490}}</ref> 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.<ref>{{cite journal |author1=Consuelo Cuquerella, M. |author2=Lhiaubet-Vallet, V. |author3=Cadet, J. |author4=Miranda, M. A. | journal = Acc. Chem. Res. | volume = 45 |issue=9 | pages = 1558–1570 | year = 2012 | doi=10.1021/ar300054e |pmid=22698517 | title = Benzophenone Photosensitized DNA Damage}}</ref> The interaction with DNA and the successive photo-induced energy transfer is at the base of the benzophenone activity as a DNA photosensitizers and may explain part of its therapeutic potentialities. + In 2014, benzophenones were named Contact [[Allergen of the Year]] by the American Contact Dermatitis Society.<ref>{{cite web |author=Doug Brunk |url=http://www.skinandallergynews.com/single-view/benzophenones-named-2014-contact-allergen-of-the-year/cb086f7e351cccbcfd9dbf5fa806762b.html |title=Benzophenones named 2014 Contact Allergen of the Year : Dermatology News |website=Skinandallergynews.com |date=2014-03-14 |accessdate=2016-06-16 }}{{Dead link|date=November 2018 |bot=InternetArchiveBot |fix-attempted=yes }}</ref> − The high-strength polymers [[PEEK]], polyetherether ketones, are prepared from derivatives of benzophenone. + Benzophenone is an [[endocrine disruptor]] capable of binding to the [[pregnane X receptor]].<ref>{{cite journal | doi = 10.1016/j.taap.2003.08.001| pmid = 14613717| title = Endocrine disruptors induce cytochrome P450 by affecting transcriptional regulation via pregnane X receptor| journal = Toxicology and Applied Pharmacology| volume = 193| issue = 1| pages = 66–72| year = 2003| last1 = Mikamo| first1 = Eriko| last2 = Harada| first2 = Shingo| last3 = Nishikawa| first3 = Jun-Ichi| last4 = Nishihara| first4 = Tsutomu}}</ref> − == See also == − * [[Sunscreen]] ==References== ==References== + {{Reflist}} − <references/> − ==Notes== − * ''Merck Index'', 11th edition, 1108. − − ==Gallery== − <gallery><gallery> − Image:Benzophenone bottle.jpg|A bottle of '''benzophenone''' by Lancaster. − Image:Toluene with sodium-benzophenone.jpg|Toluene is refluxed with [[sodium]] and benzophenone to produce dry, oxygen-free toluene. − Image:Toluene with sodium-benzophenone - brown.jpg|The mixture is still not blue yet indicating that the reaction is not complete. − Image:Toluene with sodium-benzophenone - intense blue.jpg|The intense blue coloration due to the benzophenone ketyl radical shows that the toluene is considered free of air and moisture. − Image:Distillation of dry and oxygen-free toluene.jpg|After the toluene has been thoroughly dried by the sodium and benzophenone, it is distilled at atmospheric pressure under a slight positive pressure of nitrogen to prevent contamination by air into the receiving Schlenk flask. − Image:Solvent_pot.JPG|A solvent pot contains [[dibutyl ether]] dried over [[sodium]] and [[benzophenone]], which gives it its purple color. − </gallery> − − [[Category:Desiccants]] [[Category:Printing materials]] [[Category:Printing materials]] [[Category:Endocrine disruptors]] [[Category:Endocrine disruptors]] − [[Category:Aromatic ketones]] + [[Category:IARC Group 2B carcinogens]] + [[Category:Benzophenones]] − + [[Category:Articles containing video clips]] − [[cs:Benzofenon]] − [[de:Benzophenon]] − [[es:Benzofenona]] − [[fr:Benzophénone]] − [[hr:Benzofenon]] − [[lv:Benzofenons]] − [[nl:Benzofenon]] − [[ja:ベンゾフェノン]] − [[pl:Benzofenon]] − [[pt:Benzofenona]] − [[fi:Bentsofenoni]] − [[tr:Benzofenon]] − [[zh:二苯基甲酮]] Retrieved from "[en.wikipedia.org]"

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