Pages: 1

Author Topic: Ammonium Methyl Sulfate ---> Methyl Hydrogen Sulfate ---> Dimethyl Suflate?  (Read 90 times)

no1uno

  • Global Moderator
  • Foundress Queen
  • *****
  • Posts: 681
Ammonium Methyl Sulfate ---> Methyl Hydrogen Sulfate ---> Dimethyl Suflate?
« on: June 02, 2013, 01:21:38 AM »
Ok, ammonium methyl sulfate is piss easy to make (http://mmm.chemithon.com/Resources/pdfs/Technical_papers/Sulfo%20and%20Sulfa%201.pdf) from unwatched chemicals (albeit methanol is still slightly problematic - can any ozzie bees drop me a line if they have suggestions on small amounts of methanol - ie. not 20L drums). Sulfamic acid (is way cheaper than sodium bisulfite) and methanol are refluxed together, yada yada yada, to product ammonium methyl sulfate. Now, is there a simple route from there to dimethyl sulfate? According to Wikipedia adding H2SO4 in methanol presumably gives the di-alkali sulfate and the dimethyl sulfate, anyone got any ideas?

I need a simple, easily accessible methylating agent. I'll wear a mask, use a hood and wear gloves, but thanks to tweakers iodine is just too hot (and iodomethane isn't that good for you anyway). Any ideas at all?
« Last Edit: June 02, 2013, 02:25:59 AM by no1uno »
"...     "A little learning is a dang'rous thing;
    Drink deep, or taste not the Pierian spring:
    There shallow draughts intoxicate the brain,
    And drinking largely sobers us again.
..."

lugh

  • Global Moderator
  • Foundress Queen
  • *****
  • Posts: 876
Re: Ammonium Methyl Sulfate ---> Methyl Hydrogen Sulfate ---> Dimethyl Suflate?
« Reply #1 on: June 02, 2013, 02:29:43 AM »
The attached patent; US1506228 claims that dialkyl sulfates can be made from the alcohol and sodium pyrosulfate starting from sodium bisulfate  8)
Chemistry is our Covalent Bond

Vesp

  • Administrator
  • Foundress Queen
  • *****
  • Posts: 3,130
Re: Ammonium Methyl Sulfate ---> Methyl Hydrogen Sulfate ---> Dimethyl Suflate?
« Reply #2 on: June 02, 2013, 08:00:58 AM »
I suspect this will be very tricky. Ammonium methyl sulfate rearranges at high temperature to methylamine sulfate I believe.
Bitcoin address: 1FVrHdXJBr6Z9uhtiQKy4g7c7yHtGKjyLy

no1uno

  • Global Moderator
  • Foundress Queen
  • *****
  • Posts: 681
Re: Ammonium Methyl Sulfate ---> Methyl Hydrogen Sulfate ---> Dimethyl Suflate?
« Reply #3 on: June 03, 2013, 12:04:10 AM »
Not looking at rearranging it, just generating it - the purpose being to get methyl hydrogen sulfate by acidification of the formed ammonium salt to free the same. Then Antochno's steps for purifying the same, lime then sodium carbonate, in order to have the purest possible salt. Then acidify that with almost the theoretical amount of H2SO4 to get Na2SO4 and Methyl Hydrogen Sulfate with a little H2SO4 in the pot, without water and without additional methanol. I'm discussing it at SM at present, I'll keep the thread updated.
"...     "A little learning is a dang'rous thing;
    Drink deep, or taste not the Pierian spring:
    There shallow draughts intoxicate the brain,
    And drinking largely sobers us again.
..."

atara

  • Dominant Queen
  • ****
  • Posts: 256
Re: Ammonium Methyl Sulfate ---> Methyl Hydrogen Sulfate ---> Dimethyl Suflate?
« Reply #4 on: June 06, 2013, 04:22:18 AM »
What are you methylating? I imagine monomethylsulfate salts will alkylate other amines as well, if they'll alkylate ammonia. It might be unnecessary to go any further.

no1uno

  • Global Moderator
  • Foundress Queen
  • *****
  • Posts: 681
Re: Ammonium Methyl Sulfate ---> Methyl Hydrogen Sulfate ---> Dimethyl Suflate?
« Reply #5 on: June 06, 2013, 12:08:06 PM »
Phenols, raspberry ketone to be exact, also at least one amine. I suspect strongly that methyl sulfate will methylate either mesyl or tosyl groups, which would be one hell of a bonus for some home chemists.

But a decent route to DMS would be useful, sulfamic acid is essentially a source of strong H2SO4, the ammonia could be displaced with Ca(OH)2 to give the Calcium Methyl Sulfate (I think - I ain't tried it, but it should), allowing for purification via the Sodium Carbonate, then pure Sodium Methyl Sulfate could be treated with conc. H2SO4, with no extra water, no extra methanol and released to give Methyl Sulfate and Sodium Sulfate, ready to be distilled. It should solve pretty much all the problems people have had in the past, which have been caused, essentially, by having extraneous crap in the pot - crap in = crap out.
« Last Edit: June 06, 2013, 12:16:46 PM by no1uno »
"...     "A little learning is a dang'rous thing;
    Drink deep, or taste not the Pierian spring:
    There shallow draughts intoxicate the brain,
    And drinking largely sobers us again.
..."

atara

  • Dominant Queen
  • ****
  • Posts: 256
Re: Ammonium Methyl Sulfate ---> Methyl Hydrogen Sulfate ---> Dimethyl Suflate?
« Reply #6 on: June 06, 2013, 01:36:07 PM »
SM had a thread claiming mesylate is as easy as methyl sulfate and sulfite. That would be quite impressive if true, but the links are in German (!); a further claim is that mesylate itself is an effective methylating agent for phenols.

http://anonym.to/https://www.sciencemadness.org/whisper/viewthread.php?tid=12663

However this claim is not far off from the typical Strecker preparation of sulfonates. As to whether methyl mesylate is therefrom available, well, I'd want to see a reference: MeSO3H has a pKa of -1.3, while H2SO4 is -3 and +1.99. There's no obvious winner here.

no1uno

  • Global Moderator
  • Foundress Queen
  • *****
  • Posts: 681
Re: Ammonium Methyl Sulfate ---> Methyl Hydrogen Sulfate ---> Dimethyl Suflate?
« Reply #7 on: June 06, 2013, 09:39:03 PM »
The mesylate and tosylate are both apparently quite useful for phenols (and everything else, including DNA), but less dangerous. If methyl orthoformate can be used to alkylate either/both, then I strongly suspect a calcium tosylate or calcium mesylate would be alkylated with the precipitation of the calcium sulfate.
"...     "A little learning is a dang'rous thing;
    Drink deep, or taste not the Pierian spring:
    There shallow draughts intoxicate the brain,
    And drinking largely sobers us again.
..."
Pages: 1