chemchemical
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methanesulfonic acid
Ok, I've been interested in obtaining some of this for awhile now but can never find it online and the only synths I found seem pretty complicated.
Can anyone point me in a good direction or can we start discussing the synth of this reagent?
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smuv
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I once saw this sold for electroplating.
It can be made from methanethiol and a suitable oxidizing agent (industrially, nitric acid). It would not be all that hard to make; except for the
stench of thiols.
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Klute
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It can also be made by chlorinating methyl thiosulfate or methylisothiourea, adducts of MeI with resp. sodium thiosulfate or thiourea.
It is a fairly common reagent though, you might better try looking harder as it isn't that expensive.
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chemchemical
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I've looked pretty hard. Googled it and went like 10 pages deep, also tried other names like Methylsulfonic acid and methanesulphonic acid. The places
I found either sold drums of it, were in China, or didnt sell to individuals.
Even our lab doesnt have it.
I wouldnt mind more info on how to make it. I imagine it would be harder to get methanethiol since it is a gas, not to mention it sounds like it
smells horrible.
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Klute
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BTW, sorry, it's the sulfonyl chlorides that can be obtaine dby chlorination of the above adducts... I think HNO3 oxidation gives the sulfonic acid
directly.
I think methyl disulfide is much more practical to handle than methane thiol, but if you can get CH3SH, you can surely get CH3SO3H...
I guess your best route would be from either MeI or dimethylsulfate, forming the Bunte salts and chlorinating in dilute AcOH, further heating will
hydrolyze the sulfonyl chloride tothe acid. Treat Johnson wrote sevral articles on the subject, some of which are availble at the ref forum.
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smuv
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This might not be the answer you want; but for usage as an acid catalyst, often Toluenesulfonic acid is a direct replacement.
Chances are if you can't buy MSA you wont be able to buy any reasonable precursors needed to make it; leaving you with a multistep synthesis to make
what you probably will just use as an acid catalyst.
P.S. Methanethiol should not be hard to make; as it is fromed you could bubble it through wash bottles of an oxidant. Then again this is a
big pain in the ass.
P.P.S. From the merck index
Monograph Number: 0005954
Title: Methanesulfonic Acid
CAS Registry Number: 75-75-2
Additional Names: Methylsulfonic acid
Molecular Formula: CH4O3S
Molecular Weight: 96.11
Percent Composition: C 12.50%, H 4.19%, O 49.94%, S 33.36%
Line Formula: CH3SO2OH
Literature References: Prepd from sulfur trioxide and methane: Snyder, Grosse, US 2493038 (1950 to Houdry Process); by oxidation of
dimethyl disulfide: Johnson, Wolff, US 2697722 (1954 to Standard Oil of Indiana); Proell et al., Ind. Eng. Chem. 40, 1129 (1948). Other prepns and
chemistry: Suter, The Organic Chemistry of Sulfur (Wiley, New York, 1944).
Properties: Solid. d418 1.4812. mp 20°. bp10 167°; bp1 122°. Soly at 26-28° in wt %: hexane, 0; methylcyclopentane, 0; benzene, 1.50;
toluene, 0.38; o-chlorotoluene, 0.23; ethyl disulfide, 0.47. Thermally stable at moderately elevated temps. Not hydrolyzed by boiling water or hot
aq alkali. Corrosive to iron, steel, brass, copper, lead.
Melting point: mp 20°
Boiling point: bp10 167°; bp1 122°
Density: d418 1.4812
Derivative Type: Ethyl ester see Ethyl Methanesulfonate
Derivative Type: Methyl ester see Methyl Methanesulfonate
CAUTION: Strong irritant.
Use: As catalyst in polymerization, alkylation and esterification reactions; as a solvent.
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chemchemical
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I'll look into the literature about toleunesulfonic acid as a replacement. I found a few good leads and other people only sold bulk, like 500kgs
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Klute
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Where do you live? You really are not looking at the right places... If googling directly the chemical name, indeed, you mostly find exportation
offers, chinese or american industrials, etc
Try acros.com; vwr.com; sigmaaldrich.com, etc
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chemchemical
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I'll look at those places, I think I may have found it unless I need to supply company information, which I donot have yet.
I didnt think companies like vwr/sigma sold to individuals? or are those just for the hazardous chems?
edit: I live in the US, I dont think this is a watched chem or anything so I dont see why it is so hard to get.
[Edited on 22-8-2008 by chemchemical]
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Nicodem
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| Quote: | Originally posted by chemchemical
edit: I live in the US, I dont think this is a watched chem or anything so I dont see why it is so hard to get. |
It is only you that claim the methanesulfonic or toluenesulfonic are hard to get, while just about any chemical supplier sells them. It appears to me
you just make these irrational claims without even checking the catalogs first.
…there is a human touch of the cultist “believer” in every theorist that he must struggle against as being
unworthy of the scientist. Some of the greatest men of science have publicly repudiated a theory which earlier they hotly defended. In this lies their
scientific temper, not in the scientific defense of the theory. - Weston La Barre (Ghost Dance, 1972)
Read the The ScienceMadness Guidelines!
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497
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Could it possibly be synthesized from methylsulfonylmethane (MSM)? It is available as a joint supplement and can be had in pure powder form for less
that 10 $/lb. Is there any easy way to rip that little CH3 off and replace it with an OH?
MSM is an interesting high temperature solvent, mp: 109*C, bp: 238*C. I can't think of many other organic solvents that can handle that. Apparently
similar solvent properties to DMSO, but less polar.
[Edited on 26-8-2008 by 497]
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tapira1
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MSM
MSM looks to me as dimethyl sulfone. There is no inexpensive and direct way to get MsOH from it
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chemchemical
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| Quote: | Originally posted by Nicodem
It is only you that claim the methanesulfonic or toluenesulfonic are hard to get, while just about any chemical supplier sells them. It appears to me
you just make these irrational claims without even checking the catalogs first. |
Please read what I wrote in the fourth post down. The statement "I've looked pretty hard" means that I have checked the catalogs. I said companies
sold them, I also said not to individuals in the USA. So my statement that they are hard to get is correct. I would very much like you to prove me
wrong though.
So does anyone know where an individual can purchase methane sulfonic acid? I have only found bulk and the sale to institutions.
Yes, just about every chemical supplier does sell them but not to residential addresses and I do not want to go through my lab for this.
[Edited on 19-11-2008 by chemchemical]
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Ozone
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"it sounds like it smells horrible"
Not really, it is rather heavy and non-volatile; it does not (at lest to me) smell like much of anything. We use it as an H2SO4 substitute (catalyst
and HPLC eluents). The only problem with the material is that eventually, the bakelite cap will be attacked, and your acid will go brown.
Do not esterify the stuff--The methanesulfonates are nasty (the ethyl ester is a standard mutagen, suspected carcinogen).
My "in-depth" search (the catalog on my bookshelf) indicates that, with proper credentials (if you work in a lab you probably have access to an accout
number), methanesulfonic acid (>99.5%) can be had for ~$44 (500mL) to $128 (2L). It is also, apparently,available in a 5L poly drum.
Cheers,
O3
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smuv
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@Ozone, Are you sure the acid degraded the cap? I've worked with some pretty old (years) MSA and it was water clear. I'm wondering if there is
another degradation process to MSA, as the aldrich bottle specifies to store the acid cold, although we never did.
"Titanium tetrachloride…You sly temptress." --Walter Bishop
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Nitro-esteban
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I did some investigation and apparently it can be made by reacting methane with sulfur trioxide or sulphuric acid
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woelen
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I'm 100% sure that the reaction of methane with sulphuric acid will not occur, or maybe at hundreds of degrees centigrade and high pressure, but it
certainly is not an easy reaction. Methane is rather inert at normal temperatures and does not react with H2SO4.
I even doubt that CH4 reacts with SO3 at normal temperatures.
But as you said, you did some investigations. Can you provide a link or a reference to some book or paper, which tells more about the reaction of
methane with H2SO4 or SO3?
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Dr.Bob
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SMUV provided one above on 19-8-2008 at 21:13:
http://www.sciencemadness.org/talk/viewthread.php?tid=11044&...
"Literature References: Prepd from sulfur trioxide and methane: Snyder, Grosse, US 2493038 (1950 to Houdry Process); by oxidation of dimethyl
disulfide: Johnson, Wolff, US 2697722 (1954 to Standard Oil of Indiana); Proell et al., Ind. Eng. Chem. 40, 1129 (1948). Other prepns and chemistry:
Suter, The Organic Chemistry of Sulfur (Wiley, New York, 1944)."
I think the OP likely either found it or gave up by now...
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DraconicAcid
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Quote: Originally posted by Ozone  | "it sounds like it smells horrible"
Not really, it is rather heavy and non-volatile; it does not (at lest to me) smell like much of anything. We use it as an H2SO4 substitute (catalyst
and HPLC eluents). The only problem with the material is that eventually, the bakelite cap will be attacked, and your acid will go brown.
|
I think the comment about it smelling horrible was referring to methanethiol, not the acid.
Please remember: "Filtrate" is not a verb.
Write up your lab reports the way your instructor wants them, not the way your ex-instructor wants them.
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aliced25
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Preparation of Methanesulfonyl Chloride-d3 from Dimethyl Sulfoxide-d6
Kazuhiko Hanai & Takachiyo Okuda
Chem. Pharm. Bull.
Vol.25(4) 1977, pp.815-816.
Abstract
A convenient method for the preparation of methanesulfonyl chloride-d3 is described. The procedure consists of the anhydrous
chlorination of dimethyl sulfoxide-d6 with chlorine and the aqueous chlorination. Methanesulfonyl chloride-d3
was obtained in 52% yield, and a small amount of dimethyl sulfone-d6 was also isolated. Trichloromethyl methyl sulfide
(-d3) was found to be one of the intermediates in this reaction.
Attachment: Habau.Okuda.Preparation.of.Methanesulfonyl.Chloride.fromDimethylsulfoxide.pdf (428kB)
This file has been downloaded 672 times
[Edited on 29-4-2013 by aliced25]
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clearly_not_atara
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https://en.wikipedia.org/wiki/Sulfonate#Sulfonate_salts
I looked this up and I was shocked that such a simple method went completely unnoticed here. It's discussed in these papers, but it's really old so
it's hard to find a direct reference:
https://www.researchgate.net/profile/Freneil_Jariwala/public... (free article)
http://pubs.acs.org/doi/abs/10.1021/cr60226a001
http://pubs.rsc.org/is/content/articlehtml/1971/j2/j29710001...
[Edited on 4-2-2016 by clearly_not_atara]
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sachabinky
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BASF currently produces the acid via a two-step process in which methanol and elemental sulfur react to give dimethyl disulfide, which is then
oxidized to the final product.
http://pubs.acs.org/doi/abs/10.1021/ef9600671?journalCode=en...
Also read the part about the almost exclusive ozonation products of aqueous solutions of dimethyl disulfide..,,- it's some way down the page on the
link below.
http://scholarworks.umt.edu/cgi/viewcontent.cgi?article=2605...
Also,
http://www.google.com.pg/patents/US7282603
[Edited on 10-8-2017 by sachabinky]
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clearly_not_atara
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Yes, but this method is still not even close to being as simple as the Strecker sulfite alkylation.
https://www.researchgate.net/profile/Freneil_Jariwala/public...
"1-Bromopentane (50 mg, 0.331 mmol), 1-bromoheptane (50 mg, 0.279 mmol), benzyl bromide (50 mg, 0.292 mmol), or 2-phenylethyl bromide (50 mg,
0.270 mmol), was refluxed with an aqueous solution of sodium sulfite (1.0 M; 10 ml) at 110 C for 12 h. The reaction mixture was then acidified with
conc. HCl to a pH of 1.0, and the resulting sulfonic acids were purified by flash chromatography (32–63mm of silica gel) using methanol as the
eluting solvent. The sulfonic acids in methanol were dried under a stream N2 and were crystalline in nature."
It's possible that sodium methyl- or ethyl- sulfates could be useful here since they are less volatile than the corresponding halides.
[Edited on 10-8-2017 by clearly_not_atara]
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Melgar
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You could just buy the toluenesulfonyl chloride on Amazon:
https://www.amazon.com/dp/B00DYO7Z8Y
I saw it and almost bought it, but then couldn't find any reactions that used it that didn't also need other stuff that either I don't have, is
prohibitively expensive, or I really don't like using. I figured I may as well just wait until I can come up with a use for it to buy it.
The first step in the process of learning something is admitting that you don't know it already.
I'm givin' the spam shields max power at full warp, but they just dinna have the power! We're gonna have to evacuate to new forum software!
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sachabinky
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,,,-or you could make it
http://www.prepchem.com/synthesis-of-4-toluenesulfonyl-chlor...
Different strokes,,,- Choice of method will rely on the ability of the individual, and the ingredients and facilities at their disposal.
My interest in Methanesulfonic Acid would be for use in electrofinishing plated products, and it was by that research, i was bought to this thread,
and found the answer that finally suited me.
[Edited on 14-8-2017 by sachabinky]
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