p-Toluenesulfonic acid

p-Toluenesulfonic acid^[1]
	; Slightly impure sample of the monohydrate
Names
	Preferred IUPAC name 4-Methylbenzene-1-sulfonic acid
	Other names 4-Methylbenzenesulfonic acid; Tosylic acid ; Tosic acid; para-Toluenesulfonic acid; PTSA; pTsOH; TsOH
Identifiers
CAS Number	104-15-4 ; 6192-52-5 (monohydrate) ;
3D model (JSmol)	Interactive image;
ChEBI	CHEBI:27849 ;
ChEMBL	ChEMBL541253 ;
ChemSpider	5876 ;
DrugBank	DB03120 ;
ECHA InfoCard	100.002.891
KEGG	C06677 ;
PubChem CID	6101;
UNII	QGV5ZG5741 ; 3BTO78GAFF ((monohydrate) ;
CompTox Dashboard (EPA)	DTXSID0026701 ;
	InChI InChI=1S/C7H8O3S/c1-6-2-4-7(5-3-6)11(8,9)10/h2-5H,1H3,(H,8,9,10) Key: JOXIMZWYDAKGHI-UHFFFAOYSA-N ; InChI=1/C7H8O3S/c1-6-2-4-7(5-3-6)11(8,9)10/h2-5H,1H3,(H,8,9,10) Key: JOXIMZWYDAKGHI-UHFFFAOYAG;
	SMILES Cc1ccc(cc1)S(=O)(=O)O;
Properties
Chemical formula	C7H8O3S
Molar mass	172.20 g/mol (anhydrous); 190.22 g/mol (monohydrate)
Appearance	colorless (white) solid
Density	1.24 g/cm3
Melting point	105 to 107 °C (221 to 225 °F; 378 to 380 K) (monohydrate) ; 38 °C (100 °F; 311 K) (anhydrous)
Boiling point	140 °C (284 °F; 413 K) at 20 mmHg
Solubility in water	67 g/100 mL
Acidity (pKa)	−2.8 (water) reference for benzenesulfonic acid,; 8.5 (acetonitrile)
Structure
Molecular shape	tetrahedral at S
Hazards
	Occupational safety and health (OHS/OSH):
Main hazards	skin irritant
	GHS labelling:
Pictograms
Signal word	Warning
Hazard statements	H315, H319, H335
Precautionary statements	P302+P352, P305+P351+P338
Safety data sheet (SDS)	External MSDS
Related compounds
Related sulfonic acids	Benzenesulfonic acid; Sulfanilic acid
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). verify (what is ?) Infobox references

p-Toluenesulfonic acid (PTSA, pTSA, or pTsOH) or tosylic acid (TsOH) is an organic compound with the formula CH₃ C₆H₄ SO₃H. It is a white extremely hygroscopic solid that is soluble in water, alcohols, and other polar organic solvents.^[6] The CH₃C₆H₄SO₂ group is known as the tosyl group and is often abbreviated as Ts or Tos. Most often, TsOH refers to the monohydrate, TsOH^.H₂O.^[6]

As with other aryl sulfonic acids, TsOH is a strong organic acid. It is about one million times stronger than benzoic acid.^[6] It is one of the few strong acids that is solid and therefore is conveniently weighed and stored.

Preparation and uses

TsOH is prepared on an industrial scale by the 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 azeotropic drying with toluene.^[2]

TsOH finds use in organic synthesis as an "organic-soluble" strong acid. Examples of uses include:

Tosylates

Alkyl tosylates are alkylating agents because tosylate is electron-withdrawing as well as a good leaving group. Tosylate is a pseudohalide. Toluenesulfonate esters undergo nucleophilic attack or elimination. Reduction of tosylate esters gives the hydrocarbon. Thus, tosylation followed by reduction allows for the deoxygenation of alcohols.

Structures of the 7-norbornenyl cation with p-orbital stabilization.

In a famous and illustrative use of tosylate as a leaving group, the 2-norbornyl cation was formed by an elimination reaction of 7-norbornenyl tosylate. The elimination occurs 10¹¹ times faster than the solvolysis of anti-7-norbornyl p-toluenesulfonate.^[10]

Tosylates are also protecting groups for alcohols. 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.^[11]

Reactions

TsOH may be converted to p-toluenesulfonic anhydride by heating with phosphorus pentoxide.^[12]
When heated with acid and water, TsOH undergoes hydrolysis to toluene:

CH₃C₆H₄SO₃H + H₂O → C₆H₅CH₃ + H₂SO₄

This reaction is general for aryl sulfonic acids.^[13]^[14]

References

^ Merck Index, 11th Edition, 9459.
^ ^a ^b ^c Armarego, W. L. F. (2003). Purification of Laboratory Chemicals (8th ed.). Oxford: Elsevier Science. p. 612. ISBN 978-0-12-805457-4.
^ Guthrie, J. P. Hydrolysis of esters of oxy acids: pK_a values for strong acids. Can. J. Chem. 1978, 56, 2342-2354. doi:10.1139/v78-385
^ 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
^ GHS: GESTIS 510754
^ ^a ^b ^c Baghernejad, Bita (31 August 2011). "Application of p-toluenesulfonic Acid (PTSA) in Organic Synthesis". Current Organic Chemistry. 15 (17): 3091–3097. doi:10.2174/138527211798357074.
^ H. Griesser, H.; Öhrlein, R.; Schwab, W.; Ehrler, R.; Jäger, V. (2004). "3-Nitropropanal, 3-Nitropropanol, and 3-Nitropropanal Dimethyl Acetal". Organic Syntheses; Collected Volumes, vol. 10, p. 577.
^ Furuta, K.; Gao, Q.-z.; Yamamoto, H. (1998). "Chiral (Acyloxy)borane Complex-catalyzed Asymmetric Diels-Alder Reaction: (1R)-1,3,4-Trimethyl-3-cyclohexene-1-carboxaldehyde". Organic Syntheses; Collected Volumes, vol. 9, p. 722.
^ Imwinkelried, R.; Schiess, M.; Seebach, D. (1993). "Diisopropyl (2S,3S)-2,3-O-isopropylidenetartrate". Organic Syntheses; Collected Volumes, vol. 8, p. 201.
^ Winstein, S.; Shatavsky, M.; Norton, C.; Woodward, R. B. (1955-08-01). "7-Norbornenyl and 7-Norbornyl cations". Journal of the American Chemical Society. 77 (15): 4183–4184. doi:10.1021/ja01620a078. ISSN 0002-7863.
^ "Nucleophilic Substitution".
^ L. Field & J. W. McFarland (1963). "p-Toluenesulfonic Anhydride". Organic Syntheses; Collected Volumes, vol. 4, p. 940.
^ C. M. Suter (1944). The Organic Chemistry of Sulfur. New York: John Wiley & Sons. pp. 387–388.
^ J. M. Crafts (1901). "Catalysis in concentrated solutions". J. Am. Chem. Soc. 23 (4): 236–249. doi:10.1021/ja02030a007.

[1] Merck Index, 11th Edition, 9459.

[Armarego_2003-2] Armarego, W. L. F. (2003). Purification of Laboratory Chemicals (8th ed.). Oxford: Elsevier Science. p. 612. ISBN 978-0-12-805457-4.

[3] Guthrie, J. P. Hydrolysis of esters of oxy acids: pK_a values for strong acids. Can. J. Chem. 1978, 56, 2342-2354. doi:10.1139/v78-385

[4] 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

[5] GHS: GESTIS 510754

[Baghernejad_2011-6] Baghernejad, Bita (31 August 2011). "Application of p-toluenesulfonic Acid (PTSA) in Organic Synthesis". Current Organic Chemistry. 15 (17): 3091–3097. doi:10.2174/138527211798357074.

[7] H. Griesser, H.; Öhrlein, R.; Schwab, W.; Ehrler, R.; Jäger, V. (2004). "3-Nitropropanal, 3-Nitropropanol, and 3-Nitropropanal Dimethyl Acetal". Organic Syntheses; Collected Volumes, vol. 10, p. 577.

[8] Furuta, K.; Gao, Q.-z.; Yamamoto, H. (1998). "Chiral (Acyloxy)borane Complex-catalyzed Asymmetric Diels-Alder Reaction: (1R)-1,3,4-Trimethyl-3-cyclohexene-1-carboxaldehyde". Organic Syntheses; Collected Volumes, vol. 9, p. 722.

[9] Imwinkelried, R.; Schiess, M.; Seebach, D. (1993). "Diisopropyl (2S,3S)-2,3-O-isopropylidenetartrate". Organic Syntheses; Collected Volumes, vol. 8, p. 201.

[:0-10] Winstein, S.; Shatavsky, M.; Norton, C.; Woodward, R. B. (1955-08-01). "7-Norbornenyl and 7-Norbornyl cations". Journal of the American Chemical Society. 77 (15): 4183–4184. doi:10.1021/ja01620a078. ISSN 0002-7863.

[11] "Nucleophilic Substitution".

[12] L. Field & J. W. McFarland (1963). "p-Toluenesulfonic Anhydride". Organic Syntheses; Collected Volumes, vol. 4, p. 940.

[13] C. M. Suter (1944). The Organic Chemistry of Sulfur. New York: John Wiley & Sons. pp. 387–388.

[14] J. M. Crafts (1901). "Catalysis in concentrated solutions". J. Am. Chem. Soc. 23 (4): 236–249. doi:10.1021/ja02030a007.

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p-Toluenesulfonic acid

Contents

Preparation and uses

Tosylates

Reactions

See also

References