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Author: Subject: DMSO: Some Uses
BromicAcid
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[*] posted on 16-4-2005 at 18:51
DMSO: Some Uses


Dimethyl Sulfoxide (DMSO)
Bp 189 C (No strong azeotrope with water)
Mp 19C
Leaves a nasty metallic garlic taste in mouth if it gets on skin (Impure only?)
Stable toward acids and bases below 100C



I've been tinkering with DMSO for some time now and I must say it is quite the interesting solvent. And with the help of bulletin 105 available on the site below I have been trying to explore some of these properties.

Today I reacted a few milliliters with a large excess of NaOCl, according to the bulletin Cl<sub>3</sub>CSOCCl<sub>3</sub> should have been the major product, the reaction instantly heated almost too hot to hold and within a few hours there was a precipitate (as expected). I filtered and the resulting solid smelled a lot like hexachloroethane. Not much but then again I didn't use much DMSO.

DMSO can create cyclic ethers from diols. If we had access to 1,4-butanediol then it would simply be a matter of heating it with DMSO and distilling the THF straight from it. Yields go down with longer chains but it might be worth it to try reacting diethylene glycol under these conditions to see if one could distill dioxane.

DMSO decarboxylates aromatics somewhat readily. Possibly it would be within reason to mix together benzoic acid and DSMO and distill off the benzene straight from it. The yields for some such reactions are high and technically your DMSO shouldn't be consumed, maybe a continuous process?

The Dimsyl anion is of course a strong reducing agent produced from sodium hydride reacting with DMSO. And it is quite useful. During my attempts at lithium electrolysis from DMSO I believe this may have been one of my main products, methyl lithium was also possibly produced. Basicity as a whole appears to be increased in DMSO.

Speaking of a solvent for electrolysis, although the alkali metals seem difficult (according to the PDF's impossible) to win from the solvent, it is still good for electrolysis, one of the best non-aqueous I've used, definitely something fun to tinker around with for non-aqueous work.

There are many other uses for this wonder solvent too, including the obvious 'Make things go straight through the skin into the blood' feet DMSO is famous for. There are many organic reactions that are aided or made possible by running in DMSO as well.

Still available over the counter for now in America I encourage everyone to be sure to have some in stock in case it does in fact get removed from the common market place in upcoming years.

I will add to this thread as my experiments progress, other then that what else has everyone done with this reagent?

There is much information on DMSO available from: http://www.gaylordchemical.com/bulletins/ especially check out bulletin 105, good stuff.




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chloric1
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[*] posted on 16-4-2005 at 19:46


I have the same report on file. Great toilet literature for sure:P. Anywho that chlorinated specie you isolated, does it have oxidizing properties? Will it chlorinate? I am in a financial crisis for the next month or two but this is one chem high on my priority list. I can get a gallon for $38 which far less than what I paid for equal quanties of some of my other solvents and acids.

There is one problem, Indiana has cold, although warmer than Michigan, winters. I prefer not to have chems in my living quarters but this might have to be stored indoors when the weather turns cold. With kids around this wil have to be locked up for sure probably near the water heater :)




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[*] posted on 17-4-2005 at 04:24


Dioxane is easier procduced from ethylene glycol and sulfuric acid: http://www.frogfot.com/synthesis/dioxane.html

The required amount of H2SO4 is remarkably small, and the yield is acceptable, especially since ethanediol is so cheap and easy to get.

If benzoic acid could be decarboxylated efficiently with DMSO, it would be great. Sodium benzoate + calcium hydroxide gives rather low yields, and with the higher- yielding NaOH you have to use metal reaction vessels.

Someone once tried a reaction with sodium borohydride in DMSO, and extremely stinky "sewer gas" was produced. The whole fume hood had to be cleaned with permanganate to make the stench bearable. I have no doubt that this was dimethyl sulfide from the reduction of DMSO.

In industry, DMSO is produced by oxidation of dimethyl sulfide with N2O4/oxygen mixture.

In laboratory, DMSO can be prepared by oxidation of dimethyl sulfide with a stochiometric amount of hydrogen peroxide or dilute nitric acid (according to omikron chemical lexicon).
The dimethyl sulfide would have to be used as an ethereal solution, since it is a gas (IIRC).
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[*] posted on 4-10-2015 at 10:44


I've recently found that DMSO is sold in drugstores in my country, and this piqued my interest in this solvent. I've heard that it is good at dissolving inorganic salts. So I became interested: are there any interesting double displacement reactions that are impossible in water, but work in DMSO?



Smells like ammonia....
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[*] posted on 4-10-2015 at 11:09


Holy thread necro, batman. Over 10 years!

I don't know about inorganic salts, but it does have some nice organic chemistry possibilities. The Swern and Kornblum oxidations come to mind. It can be reacted with MeI to make trimethylsulfoxonium iodide, and deprotonated to a sulfur ylide that converts ketones to epoxides, imines to aziridines, and enones into acylcyclopropanes (Corey-Chaykovsky Reaction). Treatment with bromine produces trimethylsulfonium bromide which can be used to methylate phenols and similar targets (http://www.sciencemadness.org/talk/viewthread.php?tid=15704). It forms a stable superbase (dimsyl sodium) when treated with sodium amide or sodium hydride and is an excellent solvent to perform unstabilized wittig reactions in (pioneered by Corey).
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[*] posted on 29-10-2015 at 00:17


I have over a gallon of this stuff from fisher scientific (purchased on ebay.)
I haven't used it yet, but I plan on experimenting with it with either lidocaine or benzocaine as a topical solution.
Definitely going to consider more uses in the future when it seems reasonable.

I understand chloric1 posted in 2005, and it's now almost 2016, but wow... $28/gallon?
I paid $150 for my gallon, and fisher scientific retails a gallon for $358.20
(https://www.fishersci.com/shop/products/dimethyl-sulfoxide-f...)

There's pet pharmacy's and other retailers selling much cheaper, but they are all in plastic containers.
DMSO should never be in contact with plastic containers if it's going to be used for topical solutions (from what I've read.) This is the reason why I spent the extra money for the 1.1gal dark glass jug from fisher.
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[*] posted on 30-10-2015 at 18:28


In the interest of restoring a dead link so as to make the thread more useful and informative I retrieved the link garage chemist provided to Frogfot's page ten years ago and pasted it below.

In general:

https://web.archive.org/web/20080516205707/http://www.frogfo...

https://web.archive.org/web/20080410193737/http://www.frogfo...

1,4-dioxane (C4H8O2)

Dioxane is easily prepared from ethylene glycol using sulfuric acid as a catalyst. The reaction path/mechanism is quite similar to that of diethyl ether formation beginning with sulphonation of the alcohol groups:

HO-CH2-CH2-OH =H2SO4=> HO-CH2-CH2-OSO3H =H2SO4=> HO3SO-CH2-CH2-OSO3H

The mono- and disulphonated dioxanes thereby obtained react with excess of free dioxane to form an ether, for example:

HO-CH2-CH2-OSO3H + HO-CH2-CH2-OH ==> HO-CH2-CH2-O-CH2-CH2-OH

Formed di- ethylene glycol ether can be sulphonated further. When one of the ends gets sulphonated, the other end (free alcohol) substitutes the sulphone group to give a cyclic ether - dioxane. This last step (cyclisation) is fast since it's intramolecular.

Although dioxane is the favored product, note that there's a possibility that reaction also forms larger cyclic and linear poly-ethers. The former type of compounds are known as crown ethers, which are not healthy to have around...

Materials to prepare dioxane are easy to get. As ethylene glycol I've used a brand of antifreeze that told to be an aqueous solution of ethylene glycol (also had some blue dye), glycol was dried prior to use, by heating slowly to 198oC.


Procedure

Materials:
Ethylene glycol ((CH2OH)2) (dry)
Sulfuric acid (H2SO4) 96%
Potassium carbonate (K2CO3)
Potassium hydroxide (KOH) (can be substituted by NaOH)
Sodium (Na) (optional, to give more compleate drying)

Whole procedure is done outside!
Place 30 ml dry ethylene glycol and 2,9 ml 96% H2SO4 into 100 ml roundbottomed flask equipped with a Vigreux column with a thermometer and a downward distiller. Reaction flask is placed on a gauze and carefully heated with a gas burner to a boil (I heated it on a hotplate with no problems). Product starts to distil after a while (if not, both Vigroux column and reaction flask are isolated by glasswool). Temperature will remain at 84-90*C in the beginning, and raise to 102*C in the end.

Distilation is ceased when reaction mixture becomes black, starts to foam alot and evolve SO2.

With increased temperature and concentration of H2SO4, rates of some byreactions will increase: first, dehydration of ethylene glycole to form acetaldehyde and second, oxidation-reduction reactions which leads to charring of reaction mixture and evolution of SO2.

Next, product is salted out: powdered potassium carbonate is added to the colorless distillate until solution separates in two layers. Upper dioxane layer is separated and dried first by dry potassium carbonate and then by potassium hydroxide. On addition of potassium hydroxide, solution becomes orange-brown because acetaldehyde (a byproduct) polymerises in basic conditions. First pieces of KOH dissolves on stirring (an additional layer separates), while following pieces remains unchanged.

Dried product is transfered to another flask, a peasize piace of metallic sodium is added and dioxane is destilled collecting a fraction of 100-103oC. Yield is 12 g (51% from theoretical).
Adding sodium is optional, this is basically an additional drying step. Instead of sodium one can add couple of KOH pieces simply to be sure that no peroxide accumulates during the distilation (well, just to be on the safer side).

Dioxane is a colorless liquid, mixes with water, ethanole and diethyl ether. mp = 11,7oC; bp = 101,3oC; dencity at 20oC = 1,03375.
On storage dioxane forms explosive peroxides (as many other ethers).


References

1. Pricina O. A., Kupletskaya N. V. (and so on..); Laboratory works in Organic synthesis; 1979




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[*] posted on 28-2-2016 at 19:32
Excellent reference on DMSO as a solvent.


Just about everything dissolves in DMSO, from ibuprofen to TNT. I was working on the Urea wiki page when I googled this most excellent PDF from some gaylords in bogalusa...

http://www.gaylordchemical.com/uploads/images/pdfs/literatur...




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[*] posted on 29-2-2016 at 22:07


I always wondered it it was possible to dissolve Scopolamine in DMSO.
I had the idea from a role playing game though I think some of Tom Clancy's "Op Center" mentioned it too.

I'm really not into *that* kind of drug but I Wonder what effect if would have on people if Scopolamine were soluble in DMSO.
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