P-Toluenesulfonic acid: Difference between revisions
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{{DISPLAYTITLE:''p''-Toluenesulfonic acid}} |
{{DISPLAYTITLE:''p''-Toluenesulfonic acid}} |
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{{ |
{{Chembox |
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| Name = ''p''-Toluenesulfonic acid |
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| Name = ''p''-Toluenesulfonic acid |
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| ImageSize = 200px |
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| ImageFileL1 = Tosic acid.png |
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| ImageFileR1 = Tosic-acid-3D-balls.png |
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| ImageFile2 = P-toluenesulfonic acid.png |
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| ImageSize1 = 200px |
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| ImageCaption2 = Slightly impure sample of the monohydrate |
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| IUPACName = 4-methylbenzenesulfonic acid |
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| PIN = 4-Methylbenzene-1-sulfonic acid |
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| OtherNames = Tosylic acid <br />tosic acid<br />PTSA |
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| OtherNames = 4-Methylbenzenesulfonic acid<br />Tosylic acid <br />Tosic acid<br />''para''-Toluenesulfonic acid<br>PTSA<br>''p''TsOH<br>TsOH |
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|Section1={{Chembox Identifiers |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID = 5876 |
| ChemSpiderID = 5876 |
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| PubChem = 6101 |
| PubChem = 6101 |
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| KEGG_Ref = {{keggcite|correct|kegg}} |
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| KEGG = C06677 |
| KEGG = C06677 |
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| InChI = 1/C7H8O3S/c1-6-2-4-7(5-3-6)11(8,9)10/h2-5H,1H3,(H,8,9,10) |
| InChI = 1/C7H8O3S/c1-6-2-4-7(5-3-6)11(8,9)10/h2-5H,1H3,(H,8,9,10) |
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| InChIKey = JOXIMZWYDAKGHI-UHFFFAOYAG |
| InChIKey = JOXIMZWYDAKGHI-UHFFFAOYAG |
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| ChEMBL_Ref = {{ebicite|correct|EBI}} |
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| ChEMBL = 541253 |
| ChEMBL = 541253 |
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| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey = JOXIMZWYDAKGHI-UHFFFAOYSA-N |
| StdInChIKey = JOXIMZWYDAKGHI-UHFFFAOYSA-N |
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| CASNo_Ref = {{cascite|correct|CAS}} |
| CASNo_Ref = {{cascite|correct|CAS}} |
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| CASNo =104-15-4 |
| CASNo = 104-15-4 |
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| CASNo2_Ref = {{cascite|correct|CAS}} |
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| CASOther = <br />6192-52-5 (monohydrate) |
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| CASNo2 = 6192-52-5 |
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| CASNo2_Comment = (monohydrate) |
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| UNII_Ref = {{fdacite|correct|FDA}} |
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| UNII = QGV5ZG5741 |
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| UNII1_Ref = {{fdacite|correct|FDA}} |
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| UNII1 = 3BTO78GAFF |
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| UNII1_Comment = ((monohydrate) |
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| DrugBank_Ref = {{drugbankcite|correct|drugbank}} |
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| DrugBank = DB03120 |
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| ChEBI_Ref = {{ebicite|correct|EBI}} |
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| ChEBI = 27849 |
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|Section2={{Chembox Properties |
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| Formula = C<sub>7</sub>H<sub>8</sub>O<sub>3</sub>S |
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| MolarMass = 172.20 g/mol (anhydrous)<br />190.22 g/mol (monohydrate) |
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| MeltingPt = {{convert|105|to|107|C|F K}} (monohydrate)<ref name="Armarego_2003" /> <br />{{convert|38|C|F K}} (anhydrous)<ref name="Armarego_2003" /> |
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| MeltingPt = 106-107 °C<br />103-106 °C (monohydrate) |
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| BoilingPtC = 140 |
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| BoilingPt_notes = at 20 mmHg |
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| Appearance = colorless (white) solid |
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| Density = 1.24 g/cm<sup>3</sup> |
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| Solubility = 67g/100 ml |
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| Solubility = 67 g/100 mL |
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| pKa = −2.8 (water) reference for benzenesulfonic acid,<ref>Guthrie, J. P. Hydrolysis of esters of oxy acids: p''K''<sub>a</sub> values for strong acids. ''Can. J. Chem''. '''1978''', ''56'', 2342-2354.</ref><br /> |
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8.5 ([[acetonitrile]])<ref>Eckert, F.; Leito, I.; Kaljurand, I.; Kütt, A.; Klamt, A.; Diedenhofen, M. Prediction of Acidity in Acetonitrile Solution with COSMO-RS. ''J. Comput. Chem''. '''2009''', ''30'', 799-810. {{doi|10.1002/jcc.21103}}</ref> |
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|Section3={{Chembox Structure |
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| MolShape = tetrahedral at S |
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| Dipole = |
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|Section7={{Chembox Hazards |
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| ExternalSDS = [http://hazard.com/msds/mf/baker/baker/files/t4030.htm External MSDS] |
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| MainHazards = skin irritant |
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| GHSPictograms = {{GHS07}} |
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| RPhrases = 36/37/38 |
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| GHSSignalWord = Warning |
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| SPhrases = 26 |
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| HPhrases = {{HPhrases|H315|319|335}} |
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| PPhrases = {{PPhrases|P302+352|305+351+338}} |
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| GHS_ref = <ref>GHS: [https://gestis.dguv.de/data?name=510754 GESTIS 510754]</ref> |
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|Section8={{Chembox Related |
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| OtherAnions = |
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| OtherCations = |
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| OtherFunction_label = sulfonic acids |
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| OtherFunction = [[Benzenesulfonic acid]]<br />[[Sulfanilic acid]] |
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| OtherCompounds = |
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'''''p''-Toluenesulfonic acid''' ('''PTSA''') or '''tosylic acid''' ('''TsOH''') is an [[organic compound]] with the formula [[methyl group|CH<sub>3</sub>]][[benzene|C<sub>6</sub>H<sub>4</sub>]][[Sulfonic acid|SO<sub>3</sub>H]]. It is a white solid that is soluble in water, [[alcohol]]s, and other [[Chemical polarity|polar]] organic solvents. Most often, TsOH refers to the |
'''''p''-Toluenesulfonic acid''' ('''PTSA''', '''pTSA''', or '''''p''TsOH''') or '''tosylic acid''' ('''TsOH''') is an [[organic compound]] with the formula [[methyl group|CH<sub>3</sub>]][[benzene|C<sub>6</sub>H<sub>4</sub>]][[Sulfonic acid|SO<sub>3</sub>H]]. It is a white extremely hygroscopic solid that is soluble in water, [[Alcohol (chemistry)|alcohol]]s, and other [[Chemical polarity|polar]] organic solvents.<ref name="Baghernejad_2011">{{cite journal |last1=Baghernejad |first1=Bita |title=Application of p-toluenesulfonic Acid (PTSA) in Organic Synthesis |journal=Current Organic Chemistry |date=31 August 2011 |volume=15 |issue=17 |pages=3091–3097 |doi=10.2174/138527211798357074}}</ref> The CH<sub>3</sub>C<sub>6</sub>H<sub>4</sub>SO<sub>2</sub> group is known as the '''[[tosyl]]''' group and is often abbreviated as Ts or Tos. Most often, TsOH refers to the [[monohydrate]], TsOH<sup>.</sup>H<sub>2</sub>O.<ref name="Baghernejad_2011" /> |
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TsOH is a strong [[organic acid]] |
As with other aryl [[sulfonic acid]]s, TsOH is a strong [[organic acid]]. It is about one million times stronger than [[benzoic acid]].<ref name="Baghernejad_2011" /> It is one of the few strong acids that is solid and therefore is conveniently weighed and stored. |
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==Preparation and |
==Preparation and uses== |
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TsOH is prepared on an industrial scale by the [[Aromatic sulfonation|sulfonation]] of [[toluene]]. |
TsOH is prepared on an industrial scale by the [[Aromatic sulfonation|sulfonation]] of [[toluene]]. Common impurities include [[benzenesulfonic acid]] and sulfuric acid. TsOH is most often supplied as the monohydrate, and it may be necessary to remove the complexed water before use. Impurities can be removed by recrystallization from its concentrated aqueous solution followed by [[azeotrope|azeotropic]] drying with toluene.<ref name="Armarego_2003">{{cite book |last1=Armarego |first1=W. L. F. |title=Purification of Laboratory Chemicals. |date=2003 |publisher=Elsevier Science |location=Oxford |isbn=978-0-12-805457-4 |page=612 |edition=8th}}</ref> |
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TsOH finds use in [[organic synthesis]] as an "organic-soluble" strong acid. Examples of uses include: |
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*[[Acetal]]ization of an [[aldehyde]].<ref>{{OrgSynth | author = H. Griesser, H. |
*[[Acetal]]ization of an [[aldehyde]].<ref>{{OrgSynth | author = H. Griesser, H. | author2 = Öhrlein, R. | author3 = Schwab, W. | author4 = Ehrler, R. | author5 = Jäger, V. | title = 3-Nitropropanal, 3-Nitropropanol, and 3-Nitropropanal Dimethyl Acetal | year = 2004 | collvol = 10 | collvolpages = 577 | prep = v77p0236}}</ref> |
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*[[ |
*[[Fischer–Speier esterification]]<ref>{{OrgSynth | author = Furuta, K. | author2 = Gao, Q.-z. | author3 = Yamamoto, H. | title = Chiral (Acyloxy)borane Complex-catalyzed Asymmetric Diels-Alder Reaction: (1R)-1,3,4-Trimethyl-3-cyclohexene-1-carboxaldehyde | year = 1998 | collvol = 9 | collvolpages = 722 | prep = cv9p0722}}</ref> |
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*[[Transesterification]] |
*[[Transesterification]] reactions<ref>{{OrgSynth | author = Imwinkelried, R. | author2 = Schiess, M. | author3 = Seebach, D. | title = Diisopropyl (2S,3S)-2,3-O-isopropylidenetartrate | year = 1993 | collvol = 8 | collvolpages = 201 | prep = cv8p0201}}</ref> |
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== |
==Tosylates== |
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Alkyl tosylates are [[alkylating agent]]s because tosylate is [[electron withdrawing group|electron-withdrawing]] as well as a good [[leaving group]]. Tosylate is a [[pseudohalide]]. Toluenesulfonate esters undergo [[nucleophile|nucleophilic attack]] or [[elimination reaction|elimination]]. Reduction of tosylate esters gives the hydrocarbon. Thus, tosylation followed by reduction allows for the deoxygenation of alcohols. |
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[[Image:Tosylate-3D-balls.png|thumb|right|175px|[[Ball-and-stick model]] of the tosylate anion]] |
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A tosylate ester has a limited shelf life in air due to its ready [[hydrolysis]] in the presence of light. The tosyl group is [[electron withdrawing group|electron-withdrawing]] which makes tosylates excellent [[leaving group]]s. The tosyl group is also a [[protecting group]] for [[alcohol]]s and [[amine]]s, prepared by combining the alcohol with 4-toluenesulfonyl chloride, usually in an [[aprotic solvent]], often [[pyridine]], the [[basicity]] of which activates the reaction<ref>[http://www.chem.ucalgary.ca/courses/350/Carey5th/Ch08/ch8-10-1.html Nucleophilic Substitution]</ref>. Toluenesulfonate esters undergo [[nucleophile|nucleophilic attack]] or [[elimination]]. |
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[[File:Non-classical_7-norbornenyl_Structure.png|thumb|left|Structures of the 7-norbornenyl cation with p-orbital stabilization.]] |
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In a famous and illustrative use of tosylate as a leaving group, the [[2-Norbornyl cation|2-norbornyl cation]] was formed by an elimination reaction of 7-norbornenyl tosylate. The elimination occurs 10<sup>11</sup> times faster than the solvolysis of ''anti''-7-norbornyl ''p''-toluenesulfonate.<ref name=":0">{{Cite journal|last1=Winstein|first1=S.|last2=Shatavsky|first2=M.|last3=Norton|first3=C.|last4=Woodward|first4=R. B.|date=1955-08-01|title=7-Norbornenyl and 7-Norbornyl cations|journal=Journal of the American Chemical Society|volume=77|issue=15|pages=4183–4184|doi=10.1021/ja01620a078|issn=0002-7863}}</ref> |
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Tosylates are also [[protecting group]]s for [[Alcohol (chemistry)|alcohol]]s. They are prepared by combining the alcohol with [[4-toluenesulfonyl chloride]] in the presence of a base. These reactions are usually performed in an [[aprotic solvent]], often [[pyridine]], which additionally acts as a base.<ref>{{cite web|url=http://www.chem.ucalgary.ca/courses/350/Carey5th/Ch08/ch8-10-1.html|title=Nucleophilic Substitution}}</ref> |
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* When toluene sulphonic acid (o-, m-, p-,) is boiled with [[HCl]] or treated with super-heated steam, [[toluene]] is formed along with H<sub>2</sub>SO<sub>4</sub> |
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{{clear left}} |
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⚫ | * TsOH may be converted to [[p-toluenesulfonic anhydride|''p''-toluenesulfonic anhydride]] by heating with [[phosphorus pentoxide]].<ref>{{OrgSynth | title = ''p''-Toluenesulfonic Anhydride | collvol = 4 | collvolpages = 940 | year = 1963 | author = L. Field | author2 = J. W. McFarland | name-list-style=amp|prep=cv4p0940}}</ref> |
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* When heated with acid and water, TsOH undergoes [[hydrolysis]] to [[toluene]]: |
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This reaction is general for [[aryl]] [[sulfonic acid]]s.<ref>{{Cite book | author = C. M. Suter | date = 1944 | title = The Organic Chemistry of Sulfur | pages = 387–388 | publisher = John Wiley & Sons | location = New York}}</ref><ref>{{cite journal | author = J. M. Crafts | date = 1901 | title = Catalysis in concentrated solutions | journal = J. Am. Chem. Soc. | volume = 23 | issue = 4 | pages = 236–249| doi = 10.1021/ja02030a007 | url = https://zenodo.org/record/1901301 }}</ref> |
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==See also== |
==See also== |
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*[[Tosyl]] |
*[[Tosyl]] |
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*[[ |
*[[Collidinium p-toluenesulfonate|Collidinium ''p''-toluenesulfonate]] |
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==References== |
==References== |
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{{ |
{{Reflist}} |
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{{DEFAULTSORT:Toluenesulfonic |
{{DEFAULTSORT:Toluenesulfonic Acid, P-}} |
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[[Category:Benzenesulfonic acids]] |
[[Category:Benzenesulfonic acids]] |
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[[Category:Reagents for organic chemistry]] |
[[Category:Reagents for organic chemistry]] |
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[[Category:Acid catalysts]] |
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[[de:P-Toluolsulfonsäure]] |
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[[Category:P-Tosyl compounds]] |
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[[fr:Acide paratoluènesulfonique]] |
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[[id:Asam p-toluenasulfonat]] |
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[[it:Acido p-toluensolfonico]] |
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[[nl:P-tolueensulfonzuur]] |
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[[ja:P-トルエンスルホン酸]] |
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[[pl:Kwas p-toluenosulfonowy]] |
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[[pt:Ácido p-toluenossulfônico]] |
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[[fi:P-Tolueenisulfonihappo]] |
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[[sv:Toluensulfonsyra]] |
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[[zh:对甲苯磺酸]] |