| Revision as of 18:57, 17 May 2011 editNono64 (talk | contribs)Autopatrolled, Pending changes reviewers, Rollbackers96,246 editsm Dimer (chemistry)← Previous edit |
Latest revision as of 20:50, 16 January 2025 edit undoLyndis Parlour (talk | contribs)157 editsm →Reactivity: add a link |
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{{Chembox |
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| verifiedrevid = 429603289 |
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| ImageFile1 = Thiobenzophenone-2D-skeletal.png |
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| ImageFile1 = Thiobenzophenone-2D-skeletal.png |
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| ImageSize1 = 200px |
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| ImageSize1 = |
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| ImageFile2 = Thiobenzophenone-from-xtal-3D-balls.png |
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| ImageFile2 = Ph2CS.JPG |
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| ImageSize2 = 200px |
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| ImageFile3 = Thiobenzophenone-from-xtal-3D-balls.png |
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| IUPACName = Diphenylmethanethione |
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| PIN = Diphenylmethanethione |
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| OtherNames = |
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| Section1 = {{Chembox Identifiers |
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|Section1={{Chembox Identifiers |
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| CASNo_Ref = {{cascite|correct|??}} |
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| CASNo = 1450-31-3 |
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| PubChem = |
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| CASNo = 1450-31-3 |
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| UNII_Ref = {{fdacite|correct|FDA}} |
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| SMILES = S=C(C1=CC=CC=C1)C2=CC=CC=C2}} |
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| UNII = JYQ6P4G3UJ |
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| Section2 = {{Chembox Properties |
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| PubChem = 578536 |
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| C=13|H=10|S=1 |
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| ChemSpiderID_Ref = {{chemspidercite|changed|chemspider}} |
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| Appearance = Deep blue solid |
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| ChemSpiderID = 502886 |
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| SMILES = S=C(C1=CC=CC=C1)C2=CC=CC=C2 |
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| MeltingPt = 53-54 °C |
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| InChI = 1/C13H10S/c14-13(11-7-3-1-4-8-11)12-9-5-2-6-10-12/h1-10H |
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| BoilingPt = 174 °C |
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| InChIKey = XDDVRYDDMGRFAZ-UHFFFAOYAD |
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| StdInChI = 1S/C13H10S/c14-13(11-7-3-1-4-8-11)12-9-5-2-6-10-12/h1-10H |
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| StdInChIKey_Ref = {{stdinchicite|changed|chemspider}} |
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| FlashPt = no |
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| StdInChIKey = XDDVRYDDMGRFAZ-UHFFFAOYSA-N}} |
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|Section2={{Chembox Properties |
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| C=13 | H=10 | S=1 |
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| Appearance = Deep blue solid |
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| MeltingPtC = 53 to 54 |
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| BoilingPtC = 174 |
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'''Thiobenzophenone''' is an ] with the formula (C<sub>6</sub>H<sub>5</sub>)<sub>2</sub>CS. It is the prototypical ]. Unlike other thioketones that tend to ]ize to form rings and polymers, thiobenzophenone is quite stable, although it photoxidizes in air to form benzophenone and sulfur.<ref name="Organosulfur" >Organosulfur Chemistry I: Topics in Current Chemistry, 1999, Volume 204/1999, 127-181, DOI: 10.1007/3-540-48956-8_2</ref> Thiobenzophenone is deep blue and dissolves readily in many organic solvents. |
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'''Thiobenzophenone''' is an ] with the formula (C<sub>6</sub>H<sub>5</sub>)<sub>2</sub>CS. It is the prototypical ]. Unlike other thioketones that tend to ]ize to form rings and polymers, thiobenzophenone is quite stable, although it photoxidizes in air back to ] and sulfur.<ref name="Organosulfur" >{{cite book | doi = 10.1007/3-540-48956-8_2| chapter = Thiocarbonyl Compounds as Specific Tools for Organic Synthesis| title = Organosulfur Chemistry I| volume = 204| pages = 127–181| series = Topics in Current Chemistry| year = 1999| last1 = Metzner| first1 = Patrick| isbn = 978-3-540-65787-3}}</ref> Thiobenzophenone is deep blue and dissolves readily in many organic solvents. |
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==Structure== |
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==Structure== |
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According to the double bond rule, the C=S double bond of most thioketones is unstable with respect to dimerization making the stability of thiobenzophenone valuable for studying C=S chemistry.<ref name="Organosulfur" /> The energy difference between the p orbitals of sulfur and carbon is greater than that between oxygen and carbon in ketones.<ref name="Fisera" >Fisera, L.; Huisgen, R.; Kalwinsch, I.; Langhals,E.; Li, X.; Mloston, G.; Polborn, K.; Rapp, J.; Sicking, W.; Sustmann, R. “New Thione Chemistry”. Pure & Appl. Chem., 1996, 68, 789-798. {{DOI|10.1351/pac199668040789}}</ref> The relative difference in energy and diffusity of the atomic orbitals of sulfur compared to carbon results in poor overlap of the orbitals and the energy gap between the HOMO and LUMO is thus reduced for C=S relative to C=O.<ref name="Sustmann" >Sustmann, R.; Sicking, W.; Huisgen, R. “A Computational Study of the Cycloaddition of Thiobenzophenone S-Methylide to Thiobenzophenone”. J. Am. Chem. Soc. 2003, 125, 14425-14434. DOI: 10.1021/ja0377551</ref> The striking blue appearance of thiobenzophenone is due to π→ π* transitions upon the absorption of light with a wavelength of 314.5 nm.<ref name="Fisera" /> The C=S bond length of thiobenzophenone is 1.63 Å, which is comparable to 1.64 Å, the C=S bond length of thioformaldehyde, measured in the gas phase. Due to steric interactions, the phenyl groups are not coplanar and the dihydral angle SC-CC is 36°.<ref name="Sustmann" /> A variety of thiones with structures and stability related to thiobenzophenone have also been prepared.<ref name="Organosulfur" /> |
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The C=S bond length of thiobenzophenone is 1.63 Å, which is comparable to 1.64 Å, the C=S bond length of thioformaldehyde, measured in the gas phase. Due to steric interactions, the phenyl groups are not coplanar and the dihedral angle SC-CC is 36°.<ref name="Sustmann" >Sustmann, R.; Sicking, W.; Huisgen, R. "A Computational Study of the Cycloaddition of Thiobenzophenone S-Methylide to Thiobenzophenone". J. Am. Chem. Soc. 2003, 125, 14425-14434. {{doi|10.1021/ja0377551}}</ref> A variety of thiones with structures and stability related to thiobenzophenone have also been prepared.<ref name="Organosulfur" /> |
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==Synthesis== |
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==Synthesis== |
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One of the first reported syntheses of thiobenzophenone involves the reaction of ] and benzophenone dichloride:<ref>Organic Syntheses, Coll. Vol. 4, p.927 (1963); Vol. 35, p.97 (1955).</ref> |
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One of the first reported syntheses of thiobenzophenone involves the reaction of ] and ]:<ref>], H. Freudenberger "Thiobenzophenone" Organic Syntheses, 1931, Vol. 11, p.94. {{doi|10.15227/orgsyn.011.0094}}</ref> |
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:Ph<sub>2</sub>CCl<sub>2</sub> + 2 NaSH → Ph<sub>2</sub>C=S + 2 NaCl + H<sub>2</sub>S |
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:Ph<sub>2</sub>CCl<sub>2</sub> + 2 NaSH → Ph<sub>2</sub>C=S + 2 NaCl + H<sub>2</sub>S |
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An updated method involves sulfiding of benzophenone:<ref>B. F. Gofton and E. A. Braude "Thiobenzophenone" Org. Synth. 1955, vol. 35, 97. {{doi|10.15227/orgsyn.035.0097}}</ref> |
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A method adapted from the sequence above that has been found to be more convenient and gives more reproducible results involves the use of benzophenone as the starting material:<ref>Org. Syntheses Coll. Vol. 2, 573 (1943).</ref> |
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:Ph<sub>2</sub>C=O + H<sub>2</sub>S → Ph<sub>2</sub>C=S + H<sub>2</sub>O |
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:Ph<sub>2</sub>C=O + H<sub>2</sub>S → Ph<sub>2</sub>C=S + H<sub>2</sub>O |
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In the above reaction scheme, a mixture of gaseous hydrogen chloride and ] are passed into a cooled solution of benzophenone in ethanol. Thiobenzophenone can also be produced by a ] of thiobenzoyl chloride and benzene.<ref>Horst Viola, Steffen Scheithauer and Roland Mayer "Organische Schwefelverbindungen,97. Friedel-Crafts-Reaktionen mit Thiosäurechloriden" Chem. Ber. 1968, volume 101, pages 3517–3529. {{DOI|10.1002/cber.19681011024}}</ref> |
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In the above reaction scheme, a mixture of gaseous hydrogen chloride and ] are passed into a cooled solution of benzophenone in ethanol. Thiobenzophenone can also be produced by a ] of thiobenzoyl chloride and benzene.<ref>Horst Viola, Steffen Scheithauer and Roland Mayer "Organische Schwefelverbindungen,97. Friedel-Crafts-Reaktionen mit Thiosäurechloriden" Chem. Ber. 1968, volume 101, pages 3517–3529. {{doi|10.1002/cber.19681011024}}</ref> |
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==Reactivity== |
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==Reactivity== |
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Due to the weakness of the C=S bond, thiobenzophenone is more reactive than its C=O benzophenone counterpart. Thiobenzophenone as well as other thioketones are considered to be superdipolarophiles and ]s that rapidly combine with 1,3-dienes in Diels-Alder cycloadditions.<ref name="Fisera" /> The rate of thioketones in cycloadditions is related but not limited to the size of the small HOMO/LUMO energy gap of the π-MOs of the C=S double bond.<ref name="Sustmann" /> Reactions between thiobenzophenone and most dienes yield Diels-Alder adducts whereas reactions with monoolefins yield bicyclic compounds.<ref>Okuma, K.; Yamamoto, T.; Shirokawa, T.; Kitamura, T.; Fujiwara, Y. “The First Isolation of Benzyne-Thiobenzophenone Adducts”. Tetrahedron Letters, 1996, 49, 8883-8886. {{DOI|10.1016/S0040-4039(96)02074-6}}</ref> |
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Due to the relative weakness of the C=S bond, thiobenzophenone is more reactive than benzophenone. Thiobenzophenone (as well as other thioketones) is a dipolarophiles and ]s. For example, it combines with 1,3-dienes in ].<ref name="Fisera" >{{cite journal|doi=10.1351/pac199668040789 |title=New Thione Chemistry |year=1996 |last1=Fisera |first1=Lubor |last2=Huisgen |first2=R. |last3=Kalwinsch |first3=Ivars |last4=Langhals |first4=Elke |last5=Li |first5=X. |last6=Mloston |first6=G. |last7=Polborn |first7=K. |last8=Rapp |first8=J. |last9=Sicking |first9=W. |last10=Sustmann |first10=R. |journal=Pure and Applied Chemistry |volume=68 |issue=4 |pages=789–798 |s2cid=97484311 |doi-access=free }}</ref> The rate of thioketones in cycloadditions is related but not limited to the size of the small HOMO/LUMO energy gap of the π-MOs of the C=S double bond.<ref name="Sustmann" /> Reactions between thiobenzophenone and most dienes yield Diels-Alder adducts whereas reactions with monoolefins yield bicyclic compounds.<ref>{{cite journal|doi=10.1016/S0040-4039(96)02074-6 |title=The First Isolation of Benzyne-Thiobenzophenone Adducts |year=1996 |last1=Okuma |first1=Kentaro |last2=Yamamoto |first2=Toshiro |last3=Shirokawa |first3=Takafumi |last4=Kitamura |first4=Tsugio |last5=Fujiwara |first5=Yuzo |journal=Tetrahedron Letters |volume=37 |issue=49 |pages=8883–8886 }}</ref> |
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== References == |
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== References == |
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