Author Topic: electro MD-P2P with DMSO vs DMF??  (Read 1736 times)

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improv_chem

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electro MD-P2P with DMSO vs DMF??
« on: March 25, 2001, 03:22:00 PM »
SWIM is wondering if festers recipe for Ketones using the graphite, stainless steel cell with NaBr, h2o, DMF, and isosafrole could be used with DMSO instead of the DMF.   SWIM has lots of DMSO around but doesn't have any DMF or acetonitrile.  The LiI and the ethyl acetate used to form the ketone form the epoxide could be made form Lithium batteries and Iodine, etOH and GAA. 
If DMSO could be used this would be a very OTC way to make Ketones.
Anyone have any ideas about the slovents for this rxn??
Any help is greatly appriciated :)


--Preventing odors from escaping to nearby noses is essential.....

Osmium

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Re: electro MD-P2P with DMSO vs DMF??
« Reply #1 on: March 28, 2001, 02:36:00 PM »
DMSO and DMF are both dipolar-aprotic solvents (don't ask), so the chance is high that they might be interchangeable. Dunno if the yield will be affected or not.



Only one way to find out  ;)

improv_chem

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Re: electro MD-P2P with DMSO vs DMF??
« Reply #2 on: March 28, 2001, 05:41:00 PM »
Actually i think i answered my own question.  On Rhodium's page there is something on this method and in reading it i noticed that the people who were doing the research indicated that you could use DMSO.  There wern't any examples using DMSO in the writeup but i believe that it will work. 
One other question which has been bothering me:
Why do they use the LiI and ethyl acetate to rearrange the epoxide instead of just using the standard 15% H2SO4 reflux like in the peracid synths??  I thought that the epoxide would rearrange into the diol and then to the ketone in the acid reflux. 
Wouldn't it be much easier to just use the acid reflux then messing with LiI and ethyl acetate?
If the epoxide could be changed to the ketone with simple H2SO4, this synth would be made much more otc.
This one might just be a winner!
--improv :)


--Preventing odors from escaping to nearby noses is essential.....

Osmium

  • Guest
Re: electro MD-P2P with DMSO vs DMF??
« Reply #3 on: March 29, 2001, 03:16:00 AM »
LiI/EtOAc rearranges the epoxide directly into the ketone. This is a very clean, selective and high-yielding reaction. The H2SO4 reflux is not. Yields will be lower, and purity too.

improv_chem

  • Guest
Re: electro MD-P2P with DMSO vs DMF??
« Reply #4 on: March 29, 2001, 07:51:00 AM »
But it should work to produce the ketone right?  The yeild shouldn't be too much worse than with the performic method.  SWIM thinks that this might be a way to start until SWIM can find some LiI and ethyl acetate. 
Thanks for the help Osmium!!
:) --improv


--Preventing odors from escaping to nearby noses is essential.....

Dr_Sister

  • Guest
Re: electro MD-P2P with DMSO vs DMF??
« Reply #5 on: April 02, 2001, 08:25:00 AM »
dunno bout the LiI but EtAc is available otc from beauty supply wholesalers, as a nail polish remover.  :P

Gen_Washington

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Re: electro MD-P2P with DMSO vs DMF??
« Reply #6 on: April 03, 2001, 07:14:00 PM »
With absolutly no chem understanding of the above stated, could you use DMSO in the Bright Star synth instead of dm(formamide)?  Is it hygroscopic?  I know Methyl Man has a sub for formamide~his meoh synth~but you need a pressure equalized sep funnel (or at least a ground joint one), and a 3 neck 2000ml flask~all about $250