p-Toluenesulfonic acid

p-Toluenesulfonic acid (PTSA or pTsOH) or tosylic acid (TsOH) is an organic compound with the formula CH3C6H4SO3H. It is a white solid that is soluble in water, alcohols, and other polar organic solvents.[5] 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.[5]

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
PTSA
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
DrugBank
ECHA InfoCard 100.002.891
KEGG
UNII
Properties
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)[2]
38 °C (100 °F; 311 K) (anhydrous)[2]
Boiling point 140 °C (284 °F; 413 K) at 20 mmHg
67 g/100 mL
Acidity (pKa) −2.8 (water) reference for benzenesulfonic acid,[3]

8.5 (acetonitrile)[4]

Structure
tetrahedral at S
Hazards
Main hazards skin irritant
Safety data sheet External MSDS
R-phrases (outdated) R36/37/38
S-phrases (outdated) S26
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).
N verify (what is YN ?)
Infobox references

As with other sulfonic acids, TsOH is a strong organic acid. It is about one million times stronger than benzoic acid.[5] It is one of the few strong acids that is solid and, hence, conveniently weighed.

Preparation and handling

TsOH is prepared on an industrial scale by the sulfonation of toluene. It is hygroscopic and hydrates readily. Common impurities include benzenesulfonic acid and sulfuric acid. TsOH monohydrate contains crystalline water as well as water as an impurity. To estimate the total moisture present as impurity, the Karl Fischer method is used. 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" acid catalyst. Examples of uses include:

Tosylates

Alkyl tosylates are alkylating agents because tosylate is electron-withdrawing, which makes the tosylate anion 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.

In a famous and illustrative use of tosylate, 2-norbornyl cation was displaced from the 7-norbornenyl tosylate. The elimination occurs 1011 faster than the solvolysis of anti-7-norbornyl p-toluenesulfonate.[9]

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

Tosylates are also protecting group for alcohols. They are prepared by combining the alcohol with 4-toluenesulfonyl chloride, usually in an aprotic solvent, often pyridine.[10]

Reactions
CH3C6H4SO3H + H2O → C6H5CH3 + H2SO4

This reaction is general for aryl sulfonic acids.[12][13]

See also

References
  1. Merck Index, 11th Edition, 9459.
  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: pKa values for strong acids. Can. J. Chem. 1978, 56, 2342-2354.
  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. Baghernejad, Bita (31 August 2011). "Application of p-toluenesulfonic Acid (PTSA) in Organic Synthesis". Current Organic Chemistry. 15 (17). doi:10.2174/138527211798357074.
  6. H. Griesser, H.; Öhrlein, R.; Schwab, W.; Ehrler, R.; Jäger, V. (2004). "3-Nitropropanal, 3-Nitropropanol, and 3-Nitropropanal Dimethyl Acetal". Organic Syntheses.; Collective Volume, 10, p. 577
  7. 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.; Collective Volume, 9, p. 722
  8. Imwinkelried, R.; Schiess, M.; Seebach, D. (1993). "Diisopropyl (2S,3S)-2,3-O-isopropylidenetartrate". Organic Syntheses.; Collective Volume, 8, p. 201
  9. 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.
  10. "Nucleophilic Substitution".
  11. L. Field & J. W. McFarland (1963). "p-Toluenesulfonic Anhydride". Organic Syntheses.; Collective Volume, 4, p. 940
  12. C. M. Suter (1944). The Organic Chemistry of Sulfur. New York: John Wiley & Sons. pp. 387–388.
  13. J. M. Crafts (1901). "Catalysis in concentrated solutions". J. Am. Chem. Soc. 23 (4): 236–249. doi:10.1021/ja02030a007.
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