Methanedisulfonic acid

Methanedisulfonic acid
Names
Preferred IUPAC name
Methanedisulfonic acid
Other names
methionic acid
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.007.243 Edit this at Wikidata
EC Number
  • 207-966-4
UNII
  • InChI=1S/CH4O6S2/c2-8(3,4)1-9(5,6)7/h1H2,(H,2,3,4)(H,5,6,7)
    Key: OPUAWDUYWRUIIL-UHFFFAOYSA-N
  • C(S(=O)(=O)O)S(=O)(=O)O
Properties
CH4O6S2
Molar mass 176.16 g·mol−1
Appearance colourless solid
Melting point 138–140 °C (280–284 °F; 411–413 K)[1]
Boiling point 209–210 °C (408–410 °F; 482–483 K)(decomposes)[2]
miscible
Acidity (pKa) -0.71 (predicted)
Hazards
GHS labelling:
GHS05: Corrosive
Danger
H314, H413
P261, P264, P271, P280, P302+P352, P304+P340, P305+P351+P338, P312, P321, P332+P313, P337+P313, P362, P403+P233, P405, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Methanedisulfonic acid is the organosulfur compound with the formula CH2(SO3H)2. It is the disulfonic acid of methane. It is prepared by treatment of methanesulfonic acid with oleum. Its acid strength (pKa) is comparable to that of sulfuric acid.[3]

History and synthesis

The acid was first unknowingly prepared in 1833 by Gustav Magnus as a decomposition product of ethanedisulfonic acid during early attempts[4] to synthesize diethyl ether from ethanol and anhydrous sulfuric acid by Magnus.[5] Early investigations focused on ether production from alcohols and strong anhydrous acids. Liebig provided a detailed overview of the various sulfonic acids obtained from these reactions, and introduced the name "ethionic acid" for the sulfooxyethanesulfonic acid previously termed "Weinschwefelsäure".[6] Josef Redtenbacher subsequently analyzed the barium salt of MDA and coined the name (still occasionally used) methionic acid, following Liebig's convention.[7][5]

In 1856, Adolph Strecker analyzed various methionate salts and improved the synthesis from ether and anhydrous sulfuric acid by trapping evolving gases within the reaction vessel to maximize conversion.[8][9] The same year, Buckton and Hofmann discovered a synthesis reaction from acetonitrile or acetamide with fuming sulfuric acid but didn't identify their product, designating it methylotetrasulphuric acid.[10][9]

Georg Schroeter [de] developed another method in 1897, treating acetylene with fuming sulfuric acid to obtain acetaldehyde disulfonic acids, which he then decomposed to methionic acid upon boiling in alkaline solution.[11][5]

C2H2 + H2SO4 → CH3CH(SO3H)2

However, all these early synthetic routes suffered from numerous byproducts. A higher-yielding synthesis was introduced by Hilmar Johannes Backer [nl] in 1929, treating dichloromethane (CH2Cl2) with potassium sulfite under hydrothermal conditions to get a methionate salt.[12]

CH2Cl2 + 2 K2SO3 → CH2(SO3K)2 + 2 KCl

See also

References

  1. ^ Goldwhite, H.; Gibson, M.S.; Harris, C. (January 1965). "Free radical addition reactions—IV". Tetrahedron. 21 (10): 2743–2747. doi:10.1016/S0040-4020(01)98360-7.
  2. ^ Swan, G. A.; Satchell, D. P. N.; Sykes, K. W.; Michelson, A. M.; Boyd, A. N.; Southern, P. F.; Waters, William A.; Cummings, W. A. W.; Harvey, W. E.; Moore, C. G.; Porter, M.; Menzies, I. A.; Owen, L. W.; Mulley, B. A.; de Ruyter van Steveninck, A. W.; Taylor, E. P. (1958). "Notes". Journal of the Chemical Society (Resumed): 2051–2068. doi:10.1039/JR9580002051. See note at pages 2058-2060; Cummings, W. A. W. "Some New Sulphur-containing Diacids".
  3. ^ Kosswig, Kurt (2000). "Sulfonic Acids, Aliphatic". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a25_503. ISBN 3527306730.
  4. ^ G. Magnus (1833). "Ueber die Weinschwefelsäure, ihren Einfluss auf die Aetherbildung, und über zwei neue Säuren ähnlicher Zusammensetzung". Annalen der Physik (in German). 103 (2): 367–388. doi:10.1002/ANDP.18331030213. ISSN 0003-3804. Wikidata Q56287185.
  5. ^ a b c Mertens, Alisha (2024). Studies on Halogenated Methane Sulphonates and Polysulphonated Methane Derivatives (text.thesis.doctoral thesis) (in German). Universität zu Köln. p. 14.
  6. ^ Liebig, J. (1835). "Thatsachen zur Geschichte des Aethers". Annalen der Pharmacie (in German). 13 (1): 27–39. doi:10.1002/jlac.18350130105. ISSN 0365-5490.
  7. ^ Redtenbacher, Jos. (1840). "Analyse des methionsauren Baryts". Annalen der Chemie und Pharmacie (in German). 33 (3): 356–358. doi:10.1002/jlac.18400330311. ISSN 0075-4617.
  8. ^ Strecker, Adolph (1856). "Ueber die Methionsäure". Justus Liebigs Annalen der Chemie. 100 (2): 199–206. doi:10.1002/jlac.18561000206. ISSN 0075-4617.
  9. ^ a b The Chemical Gazette, Or, Journal of Practical Chemistry, in All Its Applications to Pharmacy, Arts, and Manufactures. R. and J.E. Taylor. 1857.
  10. ^ "Researches on the action of sulphuric acid upon the amides and nitriles, together with remarks upon the conjugate sulpho-acids". Philosophical Transactions of the Royal Society of London. 146: 453–479. 1856. doi:10.1098/rstl.1856.0021. ISSN 0261-0523.
  11. ^ Schroeter, G. (1898). "Ueber die Einwirkung von Acetylen auf rauchende Schwefelsäure". Berichte der deutschen chemischen Gesellschaft. 31 (2): 2189–2190. doi:10.1002/cber.189803102171. ISSN 0365-9496.
  12. ^ Backer, H. J. (1929). "Préparation Simple de L'acide Methionique". Recueil des Travaux Chimiques des Pays-Bas. 48 (9): 949–952. doi:10.1002/recl.19290480920. ISSN 0165-0513.