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P-Toluenesulfonic acid: Difference between revisions

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Revision as of 14:18, 19 January 2011 editBeetstra (talk | contribs)Edit filter managers, Administrators172,084 edits Script assisted update of identifiers from ChemSpider, CommonChemistry and FDA for the Chem/Drugbox validation project - Updated: ChEMBL KEGG.← Previous edit Latest revision as of 16:59, 22 October 2024 edit undo173.251.116.66 (talk) added doi for pka value 
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{{DISPLAYTITLE:''p''-Toluenesulfonic acid}} {{DISPLAYTITLE:''p''-Toluenesulfonic acid}}
{{chembox {{Chembox
| Verifiedfields = changed
| verifiedrevid = 401610062
| Watchedfields = changed
| Name = ''p''-Toluenesulfonic acid
| verifiedrevid = 408786402
| Reference =<ref>''Merck Index'', 11th Edition, '''9459'''.</ref>
| ImageFile = Tosic acid.png | Name = ''p''-Toluenesulfonic acid
| Reference =<ref>''Merck Index'', 11th Edition, '''9459'''.</ref>
| ImageSize = 200px
| ImageName = P-Toluenesulfonic acid | ImageFileL1 = Tosic acid.png
| ImageFile1 = Tosic-acid-3D-balls.png | ImageFileR1 = Tosic-acid-3D-balls.png
| ImageFile2 = P-toluenesulfonic acid.png
| ImageSize1 = 200px
| ImageCaption2 = Slightly impure sample of the monohydrate
| IUPACName = 4-methylbenzenesulfonic acid
| PIN = 4-Methylbenzene-1-sulfonic acid
| OtherNames = Tosylic acid <br />tosic acid<br />PTSA
| OtherNames = 4-Methylbenzenesulfonic acid<br />Tosylic acid <br />Tosic acid<br />''para''-Toluenesulfonic acid<br>PTSA<br>''p''TsOH<br>TsOH
| Section1 = {{Chembox Identifiers |Section1={{Chembox Identifiers
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} | ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
| ChemSpiderID = 5876 | ChemSpiderID = 5876
| PubChem = 6101 | PubChem = 6101
| KEGG_Ref = {{keggcite|correct|kegg}}
| KEGG = C06677 | KEGG = C06677
| 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)
| InChIKey = JOXIMZWYDAKGHI-UHFFFAOYAG | InChIKey = JOXIMZWYDAKGHI-UHFFFAOYAG
| ChEMBL_Ref = {{ebicite|correct|EBI}}
| ChEMBL = 541253 | ChEMBL = 541253
| StdInChI_Ref = {{stdinchicite|correct|chemspider}} | StdInChI_Ref = {{stdinchicite|correct|chemspider}}
Line 24: Line 27:
| StdInChIKey = JOXIMZWYDAKGHI-UHFFFAOYSA-N | StdInChIKey = JOXIMZWYDAKGHI-UHFFFAOYSA-N
| CASNo_Ref = {{cascite|correct|CAS}} | CASNo_Ref = {{cascite|correct|CAS}}
| CASNo =104-15-4 | CASNo = 104-15-4
| CASNo2_Ref = {{cascite|correct|CAS}}
| CASOther = <br />6192-52-5 (monohydrate)
| CASNo2 = 6192-52-5
| SMILES = Cc1ccc(cc1)S(=O)(=O)O
| CASNo2_Comment = (monohydrate)
| RTECS =

| UNII_Ref = {{fdacite|correct|FDA}}
| UNII = QGV5ZG5741
| UNII1_Ref = {{fdacite|correct|FDA}}
| UNII1 = 3BTO78GAFF
| UNII1_Comment = ((monohydrate)

| DrugBank_Ref = {{drugbankcite|correct|drugbank}}
| DrugBank = DB03120
| ChEBI_Ref = {{ebicite|correct|EBI}}
| ChEBI = 27849
| SMILES = Cc1ccc(cc1)S(=O)(=O)O
| RTECS =
}} }}
| Section2 = {{Chembox Properties |Section2={{Chembox Properties
| Formula = C<sub>7</sub>H<sub>8</sub>O<sub>3</sub>S | Formula = C<sub>7</sub>H<sub>8</sub>O<sub>3</sub>S
| MolarMass = 172.20 g/mol<br />190.22 g/mol (monohydrate) | MolarMass = 172.20 g/mol (anhydrous)<br />190.22 g/mol (monohydrate)
| MeltingPt = {{convert|105|to|107|C|F K}} (monohydrate)<ref name="Armarego_2003" /> <br />{{convert|38|C|F K}} (anhydrous)<ref name="Armarego_2003" />
| MeltingPt = 106-107 °C<br />103-106 °C (monohydrate)
| BoilingPt = 140 °C at 20 mmHg | BoilingPtC = 140
| BoilingPt_notes = at 20 mmHg
| Appearance = colorless (white) solid | Appearance = colorless (white) solid
| Density = 1.24 g/mL | Density = 1.24 g/cm<sup>3</sup>
| Solubility = 67g/100 ml
| pKa = -2.8 | Solubility = 67 g/100 mL
| 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. {{doi|10.1139/v78-385}}</ref><br />
8.5 (])<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>
}} }}
| Section3 = {{Chembox Structure |Section3={{Chembox Structure
| MolShape = tetrahedral at S | MolShape = tetrahedral at S
| Dipole = | Dipole =
}} }}
| Section7 = {{Chembox Hazards |Section7={{Chembox Hazards
| ExternalMSDS = | ExternalSDS =
| MainHazards = skin irritant | MainHazards = skin irritant
| GHSPictograms = {{GHS07}}
| RPhrases = 36/37/38
| GHSSignalWord = Warning
| SPhrases = 26
| HPhrases = {{HPhrases|H315|319|335}}
| PPhrases = {{PPhrases|P302+352|305+351+338}}
| GHS_ref = <ref>GHS: </ref>
}} }}
| Section8 = {{Chembox Related |Section8={{Chembox Related
| OtherAnions = | OtherAnions =
| OtherCations = | OtherCations =
| Function = sulfonic acids | OtherFunction_label = sulfonic acids
| OtherFunctn = ]<br>] | OtherFunction = ]<br />]
| OtherCpds = | OtherCompounds =
}} }}
}} }}


'''''p''-Toluenesulfonic acid''' ('''PTSA''') or '''tosylic acid''' ('''TsOH''') is an ] with the formula ]]]. It is a white solid that is soluble in water, ]s, and other ] organic solvents. Most often, TsOH refers to the mono], TsOH<sup>.</sup>H<sub>2</sub>O. '''''p''-Toluenesulfonic acid''' ('''PTSA''', '''pTSA''', or '''''p''TsOH''') or '''tosylic acid''' ('''TsOH''') is an ] with the formula ]]]. It is a white extremely hygroscopic solid that is soluble in water, ]s, and other ] 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 ''']''' group and is often abbreviated as Ts or Tos. Most often, TsOH refers to the ], TsOH<sup>.</sup>H<sub>2</sub>O.<ref name="Baghernejad_2011" />


TsOH is a strong ], about a million times stronger than ]. It is one of the few strong acids that are<!--or "It is a strong acid that IS"--> solid and, hence, conveniently weighed. Also, unlike some of the strong mineral acids (especially ], ], and ]), TsOH is non-oxidizing. As with other aryl ]s, TsOH is a strong ]. It is about one million times stronger than ].<ref name="Baghernejad_2011" /> It is one of the few strong acids that is solid and therefore is conveniently weighed and stored.


==Preparation and handling== ==Preparation and uses==
TsOH is prepared on an industrial scale by the ] of ]. It hydrates readily. Common impurities include ] and sulfuric acid. Impurities can be removed by recrystallization from concentrated ] followed by ] drying.<ref>Perrin, D. D. and Armarego, W. L. F., Purification of Laboratory Chemicals, Pergamon Press: Oxford, 1988.</ref> TsOH is prepared on an industrial scale by the ] of ]. Common impurities include ] 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 ] 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>


Toluenesulfonic acid finds use in ] as an "organic-soluble" acid catalyst. Examples of uses: TsOH finds use in ] as an "organic-soluble" strong acid. Examples of uses include:
*]ization of an ].<ref>{{OrgSynth | author = H. Griesser, H.; Öhrlein, R.; Schwab, W.; Ehrler, R.; Jäger, V. | title = 3-Nitropropanal, 3-Nitropropanol, and 3-Nitropropanal Dimethyl Acetal | year = 2004 | collvol = 10 | collvolpages = 577 | prep = v77p0236}}</ref> *]ization of an ].<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>
*] of ]s.<ref>{{OrgSynth | author = Furuta, K. Gao, Q.-z.; 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> *]<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>
*] of an ].<ref>{{OrgSynth | author = Imwinkelried, R.; Schiess, M.; Seebach, D. | title = Diisopropyl (2S,3S)-2,3-O-isopropylidenetartrate | year = 1993 | collvol = 8 | collvolpages = 201 | prep = cv8p0201}}</ref> *] 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>


==Tosylate esters== ==Tosylates==
Alkyl tosylates are ]s because tosylate is ] as well as a good ]. Tosylate is a ]. Toluenesulfonate esters undergo ] or ]. Reduction of tosylate esters gives the hydrocarbon. Thus, tosylation followed by reduction allows for the deoxygenation of alcohols.
] of the tosylate anion]]
A tosylate ester has a limited shelf life in air due to its ready ] in the presence of light. The tosyl group is ] which makes tosylates excellent ]s. The tosyl group is also a ] for ]s and ]s, prepared by combining the alcohol with 4-toluenesulfonyl chloride, usually in an ], often ], the ] of which activates the reaction<ref></ref>. Toluenesulfonate esters undergo ] or ].


]
==Reactions==
In a famous and illustrative use of tosylate as a leaving group, the ] 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>
* ''p''-Toluenesulfonic acid may be converted to ] by heating with ].<ref>{{OrgSynth | title = ''p''-Toluenesulfonic Anhydride | collvol = 4 | collvolpages = 940 | year = 1963 | author = L. Field and J. W. McFarland}}</ref>


Tosylates are also ]s for ]s. They are prepared by combining the alcohol with ] in the presence of a base. These reactions are usually performed in an ], often ], 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>
* When toluene sulphonic acid (o-, m-, p-,) is boiled with ] or treated with super-heated steam, ] is formed along with H<sub>2</sub>SO<sub>4</sub>
{{clear left}}


==Reactions==
CH<sub>3</sub>C<sub>6</sub>H<sub>4</sub>SO<sub>3</sub>H (Toluene Sulphonic acid) + HOH (steam) → C<sub>6</sub>H<sub>5</sub>CH<sub>3</sub> (]) + H<sub>2</sub>SO<sub>4</sub> (])
* TsOH may be converted to ] by heating with ].<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>
* When heated with acid and water, TsOH undergoes ] to ]:
:CH<sub>3</sub>C<sub>6</sub>H<sub>4</sub>SO<sub>3</sub>H + H<sub>2</sub>O → C<sub>6</sub>H<sub>5</sub>CH<sub>3</sub> + H<sub>2</sub>SO<sub>4</sub>

This reaction is general for ] ]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>


==See also== ==See also==
*] *]
*] *]


==References== ==References==
{{reflist}} {{Reflist}}


{{DEFAULTSORT:Toluenesulfonic acid, p-}} {{DEFAULTSORT:Toluenesulfonic Acid, P-}}
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