Methyl bisulfate: Difference between revisions

| verifiedrevid = 402026561

| IUPACName =

| OtherNames = Methyl sulfate; Methylsulfuric acid; Methyl hydrogen sulfate; Monomethyl sulfate

| PubChem =

| C=1 | H=4 | O=4 | S=1

| Section3 = {{Chembox Hazards

| Autoignition = }}

'''Methyl bisulfate''' is a chemical compound with the molecular formula CH₃OSO₃H. This compound is the mono-[[methyl]] [[ester]] of [[sulfuric acid]]. The significance of methyl bisulfate is that it is an intermediate in the hydrolysis of the important reagent [[dimethyl sulfate]], (CH₃)₂SO₄:<ref>{{cite journal | year=1966 | title=The Hydrolysis of Dimethyl Sulfate and Diethyl Sulfate in Water | journal=Canadian Journal of Chemistry | volume=44 | pages=1728–1730 | last1=Robertson | first1=R. E. | last2=Sugamon | first2=S.E. | doi=10.1139/v66-260 | issue=14}}</ref>

:(CH₃)₂SO₄ + H₂O → (CH₃)HSO₄ + CH₃OH

Methyl bisulfate is an acid:

:(CH₃)HSO₄ → (CH₃)SO₄^- + H⁺

Methyl bisulfate came into the public view in 1993 with the discovery that certain mercury compounds catalyze the conversion of methane to methylbisulfate in good yields with excellent selectivity in concentrated sulfuric acid.<ref>{{cite journal | title = A Mercury-Catalyzed, High-Yield System for the Oxidation of Methane to Methanol | journal = Science| year = 1993| volume =259 | issue = 5093| pages= 340–343 | last1 = Periana| first1 = R.A. | last2 = Taube | first2 = D.J. | last3 = Evitt | first3 = E.R. | pmid = 17832346 | last4 = Loffler| first4 = D.G. | last5 = Wentrcek | first5 = P.R. | last6 = Voss | first6 =G. | last7 =Masuda | first7 = T. | doi = 10.1126/science.280.5363.493f}}</ref> However, because of the toxicity and concerns with the use of mercury it wasn't until 1998 when platinum complexes were found that catalyze the reaction of [[Methane|CH₄]] by SO₃ and O₂ that it came into the limelight:<ref>{{cite journal | title = The Possible Role of SO₃ as an Oxidizing Agent in Methane Functionalization by the Catalytica Process. A Density Functional Theory Study | journal = Organometallics | year = 2003 | volume =22 | pages= 1668–1674 | last1 = Hristov | first1 = I. H. | last2 = Ziegler | first2 = T. | doi = 10.1021/om020774j | issue = 8}}</ref><ref>{{cite journal | title = High Yield Conversion of Methane to Methyl Bisulfate Catalyzed by Iodine Cations | journal = Chemical Communications | year = 2002 | pages = 2376–2377 | last1 = Periana | first1 = R. A. | last2 = Mirinov | first2 = O. | last3 = Taube | first3 = D. J. | last4 = Gamble | first4 = S | doi = 10.1039/b205366g | issue = 20}}</ref><ref>{{cite journal | author = Wolf, D. | title = High Yields of Methanol from Methane by C-H Bond Activation at Low Temperatures | journal = Angewandte Chemie, International Edition | year = 1999 | volume = 37 | pages = 3351–3353 | doi = 10.1002/(SICI)1521-3773(19981231)37:24<3351::AID-ANIE3351>3.0.CO;2-U | issue = 24}}</ref>

:CH₄ + SO₃ + ¹/₂ O₂ → (CH₃)HSO₄

This discovery pointed to a possible method for upgrading inexpensive and abundantly available methane ([[natural gas]]) into [[methanol]], which is both a more useful chemical and more easily shipped than methane. The process is proposed to proceed via an intermediate containing the Pt-CH₃ group.<ref>{{cite journal | title = Platinum Catalysts for the High-Yield Oxidation of Methane to a Methanol Derivative | journal = Science | year = 1998 | volume = 280 | pages = 560–564 | last1 = Periana | first1 = R. A. | last2 = Taube | first2 = D. J. | last3 = Gamble | first3 = S. | last4 = Taube | first4 = H. | last5 = Satoh | first5 = T. | last6 = Fujii | first6 = H. | doi = 10.1126/science.280.5363.560 | pmid = 9554841 | issue = 5363}}</ref>

Salts of (CH₃)SO₄^- are commercially available, e.g. tris(2-hydroxyethyl)methylammonium methylsulfate (CAS #29463-06-7).

[[Category:Organosulfates]]

[[fr:Acide méthylsulfurique]]