waluigi
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Ethane Sulfonyl Chloride Synthesis
I am interested if anyone other than Ullmann have attempted the synthesis ethane sulfonyl chloride?
I would like to synthesize it and I would like some feedback on some questions I have.
First off, here is the relevant thread where Ullmann describes the synthesis: https://www.sciencemadness.org/talk/viewthread.php?tid=9921&...
My question about the synthesis is why is it necessary to remove the acetone and then add glacial acetic acid as the water miscible solvent? According
to the referenced patent US2293971, a solution of acetone in water is suitable. Wouldn't it be easier to just chlorinate the Bunte salt solution in
acetone and water directly?
Here is the relevant part of the patent which can be found here: https://www.google.com/patents/US2293971
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Any water miscible, non-reactive oxygen containing substance such as acetic acid, propionic acid, methanol, dioxane, ethyl alcohol, ethylene glycol,
diethylene glycol, ethylene chlorohydrin, glycerine, glycerine chlorohydrins, B-methoxy ethyl alcohol, acetone, methyl cyanide,
B-ethoxy ethyl alcohol, B-butoxy ethyl alcohol, n-butyric acid, etc., is of use in this improvement. By non-reactive, we mean one that does not react
appreciably with the reactants or the products under the conditions outlined in the examples and specified in the body or the claims. We prefer to
chlorinate a solution which is 50% or higher with respect to the water miscible substance.
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If anyone has tried this please let me know. Otherwise, if I have missed something and misunderstood the patent please explain why this would not
work.
If no one has any objections to this idea, I will try it and post the results.
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Dr.Bob
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I would guess that exposing acetone to chlorine generates enough chloroacetone to burn your eyes out, since it is a potent tear gas, so the switch in
solvents is to prevent that problem. But I am only venturing a guess. I am quite impressed with Ullman's prep, it seems quite detailed and is very
handy as I might need to make some alkyl sulfonyl chlorides sometime soon, and that is a nice writeup.
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waluigi
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That's true, the formation of chloroacetone would be terrible to deal with. Looking at this thread about chloroacetone https://www.sciencemadness.org/talk/viewthread.php?tid=11282... it seems that the formation of chloroacetone by bubbling chlorine gas can be sped
up by heating and H+. Since the acetone would be in an ice bath this might prevent too much chloroacetone from being produced. It might be worth a
try.
The reason I wanted to replace the acetic acid is because I'm not sure how I would work up the finished reaction to get the glacial acetic acid back.
I think a liquid-liquid extraction would be difficult. Maybe react the dilute acid with NaOH to get sodium acetate then use a procedure to get glacial
acetic acid from it such as combining with H2SO4 then distilling?
I guess overall my problem is with the work up of the reaction. Does anyone have any ideas?
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DJF90
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If you have access to dimethyl sulfoxide then chlorination affords methanesulfonyl chloride (aka mesyl chloride, MsCl). Please find attached
a paper describing the preparation.
Attachment: Preparation of methanesulfonyl chloride-d3 from dimethyl sulfoxide-d6.pdf (237kB)
This file has been downloaded 404 times
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Dr.Bob
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Trying to recover the GAA is not very practical, once it is mixed with water. You will have to wash the reaction mixture with aq base to remove the
acetic acid from the product, and you will generate dilute sodium acetate, which is hard to make back into GAA. You might be able to find another
solvent, but not an easy task to recover any water miscible solvent, generally.
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byko3y
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Acetic acid can be recovered with ethyl acetate, methyl t-butyl ether, or another extraction agent (ester or ether). High concetration acetic acid
soluion (20-30%) can be recovered using azeotropic distillation.
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Nicodem
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The quotation from the patent application appears to me as taken from the Description part, which means that those solvents were never tried, but are
listed in order to create a prior art precedence. It is irrelevant if they work, work inefficiently, give only traces of the product, or not work at
all. The point is that by listing a number of solvents they prevent competitors to obviate the patent claims by doing obvious changes to the
conditions claimed.
If you don't want to use acetic acid, use acetonitrile, like in SyntheticPage 597 (DOI: 10.1039/SP597). Besides carboxylic acids, acetonitrile, t-butanol, and possibly dioxane, practically all other
listed solvents are reactive toward chlorine to some degree. t-Butanol is not suitable as it is unstable to the formed highly acidic media.
…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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waluigi
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The DMSO to MsCl seems interesting but unfortunately I don't have any.
I suppose acetone as an alternative solvent is probably not even worth the trouble to try since there is a risk of chloroacetone formation and the
patent doesn't mention any yields using it.
I think what I will try do is recover the acetic acid by creating a dilute sodium salt then converting it back to glacial acetic acid.
I will post my results after I try it.
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clearly_not_atara
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After doing some reading I realized that the pKa of EtsOH is actually quite high, pKa ≈ 1.68. This means that, for example EtsOH will not protonate
NaCl.
And that means that it is possible to dissolve large amounts of HCl in EtsOH containing Na2S2O7. The reaction:
Na2S2O7 + HCl >> NaS2O7H + NaCl
should lean pretty far to the right, although I cannot find the Hammett function of [S2O7H- >> S2O7(2-)]. NaS2O7H is a masked SO3 which can then
dehydrate EtsOH to Ets2O:
EtsO- + S2O7H- >> HSO4- + EtsOSO3-
EtsOSO3- + HCl >> EtsOSO3H + Cl- (not sure which way this leans but shouldn't lean too far either way)
EtsOSO3H + EtsO- >> HSO4- + Ets2O
Ets2O + HCl >> EtsCl + EtsOH (stronger acid >> weaker acid)
EtsCl is reactive but I don't think it's reactive enough to condense with bisulfate and cause problems that way. Bp is reported as 177 C.
So it may be possible to produce Ets2O or EtsCl by passing HCl gas into ethanesulfonic acid containing sodium pyrosulfate. Notably this allows you to
recycle the ethanesulfonate byproduct of using EtsCl as a dehydrating agent to produce more EtsCl. The success of the reaction may depend on the
solubility of HCl in EtsOH.
[Edited on 18-4-2017 by clearly_not_atara]
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