| Revision as of 13:06, 10 January 2012 editBeetstra (talk | contribs)Edit filter managers, Administrators172,031 edits Saving copy of the {{chembox}} taken from revid 455892128 of page Thiophenol for the Chem/Drugbox validation project (updated: ''). |
Latest revision as of 08:48, 23 October 2024 edit Citation bot (talk | contribs)Bots5,422,465 edits Removed parameters. | Use this bot. Report bugs. | Suggested by Dominic3203 | Category:Foul-smelling chemicals | #UCB_Category 3/128 |
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{{Distinguish|benzyl mercaptan}} |
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{{ambox | text = This page contains a copy of the infobox ({{tl|chembox}}) taken from revid of page ] with values updated to verified values.}} |
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{{chembox |
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{{chembox |
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| Watchedfields = changed |
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| verifiedrevid = 403355276 |
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| verifiedrevid = 470607455 |
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| ImageFileL1_Ref = {{chemboximage|correct|??}} |
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| ImageFileL1_Ref = {{chemboximage|correct|??}} |
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| ImageFileL1 = Thiophenol-2D.png |
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| ImageFileL1 = Thiophenol-2D.svg |
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| ImageSizeL1 = 100px |
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| ImageSizeL1 = 100px |
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| ImageNameL1 = Skeletal formula |
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| ImageNameL1 = Skeletal formula |
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| ImageSizeR1 = 135px |
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| ImageSizeR1 = 135px |
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| ImageNameR1 = Ball-and-stick model |
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| ImageNameR1 = Ball-and-stick model |
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| PIN = Benzenethiol<ref name="IUPAC2013">{{cite book | title = Nomenclature of Organic Chemistry : IUPAC Recommendations and Preferred Names 2013 (Blue Book) | publisher = ] | year = 2014 | location = Cambridge | pages = P001–P004 | doi = 10.1039/9781849733069-FP001 | isbn = 978-0-85404-182-4| chapter = Front Matter }}</ref> |
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| IUPACName = Thiophenol |
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| OtherNames = Benzenethiol |
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| OtherNames = {{ubl |
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| Thiophenol (or phenylthiol) |
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| Section1 = {{Chembox Identifiers |
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| Phenyl mercaptan |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| Mercaptobenzene |
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}} |
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|Section1={{Chembox Identifiers |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| CASNo = 108-98-5 |
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| Beilstein = 506523 |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID = 7681 |
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| ChemSpiderID = 7681 |
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| ChEMBL_Ref = {{ebicite|correct|EBI}} |
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| ChEMBL_Ref = {{ebicite|correct|EBI}} |
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| ChEMBL = 119405 |
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| ChEMBL = 119405 |
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| EC_number = 203-635-3 |
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| PubChem = 7969 |
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| UNII_Ref = {{fdacite|correct|FDA}} |
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| UNII = 7K011JR4T0 |
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| ChEBI_Ref = {{ebicite|correct|EBI}} |
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| ChEBI = 48498 |
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| SMILES = Sc1ccccc1 |
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| RTECS = DC0525000 |
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| InChI = 1/C6H6S/c7-6-4-2-1-3-5-6/h1-5,7H |
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| InChI = 1/C6H6S/c7-6-4-2-1-3-5-6/h1-5,7H |
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| InChIKey = RMVRSNDYEFQCLF-UHFFFAOYAL |
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| InChIKey = RMVRSNDYEFQCLF-UHFFFAOYAL |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey = RMVRSNDYEFQCLF-UHFFFAOYSA-N |
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| StdInChIKey = RMVRSNDYEFQCLF-UHFFFAOYSA-N |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| CASNo = 108-98-5 |
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| PubChem = 7969 |
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| UNII_Ref = {{fdacite|changed|FDA}} |
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| UNII = 7K011JR4T0 |
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| ChEBI_Ref = {{ebicite|changed|EBI}} |
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| ChEBI = 48498 |
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| SMILES = c1ccc(cc1)S |
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| RTECS = DC0525000 |
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}} |
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}} |
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| Section2 = {{Chembox Properties |
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|Section2={{Chembox Properties |
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| C=6 |
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| Formula = C<sub>6</sub>H<sub>6</sub>S |
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| H=6 |
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| MolarMass = 110.19 g/mol |
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| S=1 |
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| Appearance = colorless liquid, with unpleasant odour. |
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| Appearance = Colorless liquid |
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| Density = 1.0766 g/mL |
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| Odor = Unpleasant, pungent |
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| MeltingPt = -15 °C |
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| BoilingPt = 169 °C |
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| Density = 1.0766 g/mL |
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| Solubility = |
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| MeltingPtC = -15 |
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| BoilingPtC = 169 |
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| SolubileOther = Most organic solvents; aqueous base |
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| Solubility = 0.08%<ref name=PGCH/> |
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| pKa = 8 (H<sub>2</sub>O)<ref>Arnett, E.M., Wu, C.Y., ''J. Am. Chem. Soc.'','''1960''', ''82'', 5660.</ref>, 10 (DMSO)<ref>Arnett, E.M., Venkatasubremanian, K.G., ''J. Org. Chem.'', '''1983''', ''48'', 1569.</ref> |
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| SolubleOther = Most organic solvents; aqueous base |
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| pKa = {{ubl |
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| 6.62 (H<sub>2</sub>O)<ref>Cox, Brian G. Acids and Bases: Solvent Effects on Acid-base Strength. 1st ed. Oxford, UK: Oxford UP, 2013.</ref> |
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| 10.28 (DMSO)<ref>{{cite journal |last1=Bordwell |first1=Frederick G. |last2=Hughes |first2=David L. |title=Thiol acidities and thiolate ion reactivities toward butyl chloride in dimethyl sulfoxide solution. The question of curvature in Broensted plots |journal=The Journal of Organic Chemistry |date=1982 |volume=47 |issue=17 |pages=3224–3232 |doi=10.1021/jo00138a005}}</ref> |
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}} |
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| VaporPressure = 1 mmHg (18°C)<ref name=PGCH/> |
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| MagSus = -70.8·10<sup>−6</sup> cm<sup>3</sup>/mol |
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| Section3 = {{Chembox Hazards |
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|Section3={{Chembox Hazards |
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| MainHazards = Toxic |
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| MainHazards = Toxic |
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| FlashPt = |
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| NFPA-H = 4 |
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| Autoignition = |
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| NFPA-F = 2 |
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| NFPA-R = 1 |
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| RPhrases = {{R10}} {{R24/25}} {{R26}} {{R41}} |
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| NFPA-S = OX |
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| SPhrases = {{S23}} {{S26}} {{S28}} {{S36/37/39}} {{S45}} |
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| FlashPtF = 132 |
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| FlashPt_ref = <ref name = PGCH>{{PGCH|0050}}</ref> |
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| AutoignitionPt = |
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| GHSPictograms = {{GHS02}}{{GHS05}}{{GHS06}}{{GHS07}}{{GHS09}} |
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| GHSSignalWord = Danger |
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| HPhrases = {{H-phrases|226|300|310|314|315|330|410}} |
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| PPhrases = {{P-phrases|210|233|240|241|242|243|260|262|264|270|271|273|280|284|301+310|301+330+331|302+350|302+352|303+361+353|304+340|305+351+338|310|312|320|321|322|330|332+313|361|362|363|370+378|391|403+233|403+235|405|501}} |
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| PEL = none<ref name=PGCH/> |
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| REL = C 0.1 ppm (0.5 mg/m<sup>3</sup>) <ref name=PGCH/> |
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| IDLH = N.D.<ref name=PGCH/> |
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}} |
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| Section8 = {{Chembox Related |
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|Section8={{Chembox Related |
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| OtherFunctn = ]<br>] |
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| OtherFunction = ]<br>] |
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| Function = ]s |
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| OtherFunction_label = ]s |
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| OtherCpds = ]<br>]<br>] |
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| OtherCompounds = ]<br>]<br>] |
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'''Thiophenol''' is an ] with the formula C<sub>6</sub>H<sub>5</sub>SH, sometimes abbreviated as PhSH. This foul-smelling colorless liquid is the simplest ] ]. The ]s of thiophenol and its ] are analogous to ], where the ] ] in the ] (-OH) bonded to the aromatic ring in phenol is replaced by a ] atom. The prefix '''thio-''' implies a sulfur-containing compound and when used before a root word name for a compound which would normally contain an oxygen atom, in the case of 'thiol' that the alcohol oxygen atom is replaced by a sulfur atom. |
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Thiophenols also describes a class of compounds formally derived from thiophenol itself. All have a ] (-SH) ] to an aromatic ring. The organosulfur ligand in the medicine ] is a thiophenol. |
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==Synthesis== |
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There are several methods of synthesis for thiophenol and related compounds, although thiophenol itself is usually purchased for laboratory operations. 2 methods are the reduction of ] with ]<ref>{{OrgSynth | author = Adams, R.; C. S. Marvel, C. S. | title = Thiophenol | collvol = 1 | collvolpages = 504 | prep = cv1p0504}}.</ref> and the action of elemental sulfur on ] or ] followed by acidification. |
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Via the ], phenols ('''1''') can be converted to the thiophenols ('''5''') by conversion to the O-aryl dialkylthiocarbamates ('''3'''), followed by heating to give the isomeric ''S''-aryl derivative ('''4''').<ref>{{OrgSynth | author = Melvin S. Newman and Frederick W. Hetzel | title = Thiophenols from Phenols: 2-Naphthalenethiol |volume = 51 | pages = 139 | year = 1971 | doi = 10.15227/orgsyn.051.0139}}</ref> |
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:]{{clear-left}} |
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In the ], the starting material is an ] through the ] (ArN<sub>2</sub>X) and the ] (ArS(C=S)OR).<ref>], '']'', 41, 189 ('''1890''').</ref><ref>{{OrgSynth|first1 = D. S.|last1 = Tarbell|first2 = D. K.|last2 = Fukushima|title = ''m''-Thiocresol|year = 1947|volume = 27|page = 81|doi = 10.15227/orgsyn.027.0081|collvol = 3|collvolpages = 809|prep = CV3P0809}}</ref> Alternatively, ] and ]s can react in organic solutions and yield thiophenols.<ref name=":0">{{Cite journal|date=2012|title=One-pot synthesis of thiophenols|journal=Synlett|volume=23 |issue=13 |pages=1893–1896|doi=10.1055/s-0032-1316557|last1=Kazem-Rostami|first1=Masoud|last2=Khazaei|first2=Ardeshir|last3=Moosavi-Zare|first3=Ahmad|last4=Bayat|first4=Mohammad|last5=Saednia|first5=Shahnaz|s2cid=196805424 }}</ref> |
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Thiophenol can be manufactured from ] and ] over alumina at {{convert|700|to|1300|F|C}}. The ] is the primary byproduct.<ref>{{ cite patent |
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| country = US |
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| number = 2,490,257 |
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| status = Patent |
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| title = Mono- and Polyalkyl Mono- and Polynuclear Mercaptans |
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| gdate = 1949-12-06 |
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| invent1 = Duncan J. Crowley |
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| invent2 = Alvin L Kosak |
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| assign1 = Socony-Vacuum Oil Co. |
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}} |
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</ref> The reaction medium is corrosive and requires ceramic or similar reactor lining. Aryl iodides and ] in certain conditions may also produce thiophenols.<ref>{{Cite journal|last=Jiang, Y.; Qin, Y.; Xie, S.; Zhang, X.; Dong, J.; Ma, D., A|date=2009|title=General and Efficient Approach to Aryl Thiols: CuI-Catalyzed Coupling of Aryl Iodides with Sulfur and Subsequent Reduction|journal=Organic Letters|volume=22|issue=1|pages=52–56|doi=10.1021/acs.orglett.9b03866|pmid=31833778|s2cid=209341111}}</ref> |
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==Applications== |
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Thiophenols are used in the production of ] including of ]. The antifungal agents ] and ] are derivatives of thiophenols.<ref name=":0" /> |
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==Properties and reactions== |
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===Acidity=== |
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Thiophenol has appreciably greater ]ity than does phenol, as is shown by their ] values (6.62 for thiophenol and 9.95 for phenol). A similar pattern is seen for ] versus H<sub>2</sub>O, and all ]s versus the corresponding ]s. Treatment of PhSH with strong base such as ] (NaOH) or ] metal affords the salt sodium thiophenolate (PhSNa). |
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===Alkylation=== |
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The thiophenolate is highly nucleophilic, which translates to a high rate of alkylation.<ref>{{cite encyclopedia|last = Campopiano|first = O.|title = Thiophenol|encyclopedia = ]|year = 2004|publisher = ]|location = New York|doi = 10.1002/047084289X|isbn = 9780471936237|hdl = 10261/236866|hdl-access = free}}.</ref> Thus, treatment of C<sub>6</sub>H<sub>5</sub>SH with ] in the presence of a base gives methyl phenyl sulfide, C<sub>6</sub>H<sub>5</sub>SCH<sub>3</sub>, a ] often referred to as ]. Such reactions are fairly irreversible. C<sub>6</sub>H<sub>5</sub>SH also adds to α,β-unsaturated carbonyls via ]. |
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===Oxidation=== |
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Thiophenols, especially in the presence of base are easily oxidized to ]: |
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: 4 C<sub>6</sub>H<sub>5</sub>SH + O<sub>2</sub> → 2 C<sub>6</sub>H<sub>5</sub>S-SC<sub>6</sub>H<sub>5</sub> + 2 H<sub>2</sub>O |
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The disulfide can be reduced back the thiol using ] followed by acidification. This redox reaction is also exploited in the use of C<sub>6</sub>H<sub>5</sub>SH as a source of H atoms. |
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===Chlorination=== |
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Phenylsulfenyl chloride, a blood-red liquid (b.p. 41–42 °C, 1.5 mm Hg), can be prepared by the reaction of thiophenol with ] (Cl<sub>2</sub>).<ref>{{OrgSynth | author = Barrett, A. G. M.; Dhanak, D.; Graboski, G. G.; Taylor, S. J. | title = (Phenylthio)nitromethane | collvol = 8 | collvolpages = 550 | year = 1993 | prep = cv8p0550}}</ref> |
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===Coordination to metals=== |
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Metal cations form thiophenolates, some of which are polymeric. One example is "C<sub>6</sub>H<sub>5</sub>SCu," obtained by treating ] with thiophenol.<ref>{{OrgSynth | author = Posner, G. H.; Whitten, C. E. | title = Secondary and Tertiary Alkyl Ketones from Carboxylic Acid Chlorides and Lithium Phenylthio(alkyl)cuprate Reagents: ''tert''-Butyl Phenyl Ketone | collvol = 6 | collvolpages = 248 | prep = cv6p0248}}</ref> |
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==Safety== |
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The US ] has established a ] at a ceiling of 0.1 ppm (0.5 mg m<sup>−3</sup>), and exposures not greater than 15 minutes.<ref></ref> |
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==References== |
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<references/> |
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==External links== |
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* , Toxicology Data Network |
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{{Authority control}} |
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] |
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] |
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] |