Methanesulfonic acid

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Structural formula
Structural formula of methanesulfonic acid
General
Surname Methanesulfonic acid
other names

Methyl sulfonic acid (MSS)

Molecular formula CH 4 O 3 S
Brief description

colorless and odorless, viscous liquid

External identifiers / databases
CAS number 75-75-2
EC number 200-898-6
ECHA InfoCard 100,000,817
PubChem 6395
Wikidata Q414168
properties
Molar mass 96.11 g mol −1
Physical state

solid or liquid

density

1.48 g cm −3

Melting point

19 ° C

boiling point

167 ° C (13 hPa )

Vapor pressure

100 mPa (23 ° C)

pK s value

−1.9

solubility
safety instructions
GHS hazard labeling from  Regulation (EC) No. 1272/2008 (CLP) , expanded if necessary
05 - Corrosive 07 - Warning

danger

H and P phrases H: 290-302-312-314-335
P: 260-280-303 + 361 + 353-305 + 351 + 338-310-390
Toxicological data

649 mg kg −1 ( LD 50 ,  rat ,  oral )

As far as possible and customary, SI units are used. Unless otherwise noted, the data given apply to standard conditions .

Methanesulfonic acid (MSA, from English m ethane s ulfonic a cid ) is the simplest sulfonic acid . The organic salts and esters of methanesulfonic acid are referred to as methanesulfonates or mesylates or mesilates .

presentation

Methanesulfonic acid can be prepared on a laboratory scale through a number of reactions; so z. B. by oxidation of methanethiol or dimethyl disulfide with chlorine , oxygen or nitric acid . Another variant of the reaction is the reaction of sodium sulfite with dimethyl sulfate in aqueous solution at 100 ° C. and a pH greater than 6, which gives methanesulfonic acid yields of 75-85%.

MSA from sulfite and dimethyl sulfate

The reaction of sulfur trioxide with methane is possible, but gave only low yields for a long time. The latest work describes high pressure reactions in stirred tank reactors or (semi) continuous flow reactors in the presence of free radical initiators such as dialkylsulfonyl peroxides, in particular bis (methanesulfonyl) peroxide CH 3 -SO 2 -OO-SO 2 -CH 3 (DMSP) or monomethylsulfonyl peroxides ,

Direct synthesis of MA from methane and sulfur trioxide

in which yields of methanesulfonic acid of over 90% can be achieved.

Industrially, they are mainly produced by the oxidation of methanethiol or dimethyl disulfide with chlorine. In addition, MA has been obtained on an industrial scale for a number of years via the catalytic oxidation of dimethyl disulfide with atmospheric oxygen and nitric acid.

The conversion of methane with sulfur trioxide was made ready for large-scale production in 2016. A system for this is being planned. The start of production is expected in 2019.

properties

Methanesulfonic acid is a strong acid, its pKa value is given as −0.6 or the more likely −1.9. It can be mixed with water in any ratio and can itself serve as a solvent . The cryoscopic constant is 5.69 K. At normal pressure, MSA, which is very difficult to ignite, decomposes in an air atmosphere from about 220 ° C to carbon monoxide , carbon dioxide , sulfur trioxide and water. The vapor pressure is under standard conditions with 5.4265 × 10 -5 similarly low hPa as that of sulfuric acid . MSA does not have an oxidizing effect even in high concentrations. The high conductivity of aqueous MA solutions correlates with the acid strength, which reaches its maximum at 20–40% by weight with over 500 mS / cm and is comparable to that of inorganic acids. Due to autoprotolysis , pure MSA conducts the electrical current:

The observed proton transfer mechanism between the ions is comparable to that of other sulfonic acids . After a few days in the air, an MSA concentration of around 49% is achieved with 70–100% mixtures. Like sulfuric acid, MSA has a strong dehydrating effect and can therefore carbonize organic substances that contain hydroxyl groups . The slightly yellow-brown color of the MSA, which can occasionally be observed, is based on this property. MSA cannot be hydrolyzed by hot water or hot aqueous alkalis. The electrochemical window of the MSA is quite wide - at an applied voltage of −1.40 V there is a reduction of the acid protons, at +2.35 V there is an oxidative decomposition of the acid. It is only slightly corrosive and, even in high concentrations at temperatures around 100 ° C, cannot dissolve oxide layers of metals such as aluminum , titanium or niobium .

INN nomenclature

In the medical and pharmaceutical sector, the internationally recognized short form for the anion of methanesulphonic acid (methanesulphonate) according to the INN rules is "mesilate". Such short forms are created for molecular components if their systematic designation is too long. The “modified INN” (INNm) is created by combining a short form with the INN of the active component of the drug. One example is the drug doxazosin mesilate, derived from the nitrogenous base doxazosin .

In English there is a variant ( “mesylate” ) that corresponds to the spelling of the INN nomenclature ( “mesilate” ), which corresponds to the spelling of the United States Adopted Name Council .

use

MA serves as a solvent and catalyst for various organic reactions such as B. alkylations , esterifications , polymerizations or heterocycle syntheses . Using thionyl chloride , it can be converted into reactive methanesulfonyl chloride, with which hydroxyl groups can be converted into methanesulfonic acid esters - the methanesulfonate anion represents the significantly better leaving group in the context of nucleophilic substitutions because it is less reactive Compound, despite its strong acidity (stronger than phosphoric acid), is significantly safer than classic cleaning acids such as phosphoric, hydrochloric and sulfuric acid. The resulting alkaline earth, iron and manganese methanesulfonates are very soluble in water. Since the mercury, lead and silver methanesulfonates, in contrast to the corresponding insoluble hydrochloric and sulfuric acid salts, also dissolve very well in water, they can be used as electrolytes in methanesulfonic acid electroplating baths . Some basic drugs are used as methanesulfonic acid salts, e.g. B. rasagiline .

links

In many cases methanesulfonates can be obtained from the acid and the carbonate , hydroxide or oxide of the respective metal cation. Electrolytic production is also possible , in which the metal to be oxidized is anodically connected in an MSA bath. The methanesulfonates of various nitrogenous bases such as. B. ammonia , methylamine or 1-ethyl-3-methylimidazolium (EMIM, see 1-ethyl-3-methylimidazolium chloride , EMIM [Cl]). The reaction with EMIM results in an ionic liquid . The salts of the MA are basically very soluble in water, since the formation of a stable ion lattice is made more difficult by the monovalent nature of the anion and the non-polar methyl radical. The latter enables both the acid and the salts to dissolve to a certain extent in non-polar solvents. Most methanesulfonates are stable up to around 400 ° C, after which thermal decomposition of the organic methyl group occurs. The salts are therefore more temperature-resistant than the acid itself.

The anion has already been investigated in terms of its structural chemistry; it has approximately C 3v symmetry . It is also able to function as a complex ligand . The classification in the spectrochemical series is based on Cl - <F - ~ SO 3 Cl - ~ SO 3 F - <SO 4 2− <CH 3 SO 3 - <H 2 O, in the nephelauxetic series according to Cl - <CH 3 SO 3 - <SO 4 2− <SO 3 Cl - ~ SO 3 F - ~ H 2 O <F - . The catalytic properties of some methanesulfonates - among others as chloride-free Lewis acids - have been investigated intensively for several years; For example, lanthanide methanesulfonates achieve positive effects in some esterification reactions.

Environmental chemistry

MSA is an indicator of the amount of sulfur emissions of oceanic origin that enter the atmosphere. It is therefore also an indicator of the acidity of the atmosphere. There, MSA is created as an intermediate product of the natural sulfur cycle during the photochemical conversion of dimethyl sulfide to sulfate aerosols .

According to OECD guideline 301 A, MSA is easily biodegradable, with carbon dioxide and sulfate being produced as degradation products.

Web links

Commons : Methanesulfonic Acid  - Collection of pictures, videos and audio files
Wiktionary: Methanesulfonic acid  - explanations of meanings, word origins, synonyms, translations

Individual evidence

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See also