[AlphaScent]

I am making vinyloxirane (3,4-Epoxy-1-butene), by way of a bromohydrin produced from butadiene.  My query lies during the first steps workup. The succinimide by product is soluble in the organic layer and after removing solvent, it calls for a distillation.  The yield is affected though by the succinimide being present during the distillation of the bromohydrin.  Could this succinimide be removed with 1 N HCl wash?  I am told though that the bromohydrin is not miscible with water, but appreciably soluble.  Seems like either way I am going to lose material. 

Thank you in advance : )

[discodermolide]

I am making vinyloxirane (3,4-Epoxy-1-butene), by way of a bromohydrin produced from butadiene.  My query lies during the first steps workup. The succinimide by product is soluble in the organic layer and after removing solvent, it calls for a distillation.  The yield is affected though by the succinimide being present during the distillation of the bromohydrin.  Could this succinimide be removed with 1 N HCl wash?  I am told though that the bromohydrin is not miscible with water, but appreciably soluble.  Seems like either way I am going to lose material. 

Thank you in advance : )

Succinamide is not soluble in CCl₄. So dissolve , or suspend your reaction mixture in CCl₄, cool, filter and wash with cold CCl₄. Repeat if necessary. (measuring the dry weight of succinamide will give you an indication of your yield and how good the purification has been.

[AlphaScent]

^^ Hey disco thanks a lot.  The only problem is that I do not have access to carbon tet, nor do I have chloroform.  I could have the company order one of them.  Would DCM work?  Dissolve the crude material in DCM and let the succinimide crash out?

[discodermolide]

^^ Hey disco thanks a lot.  The only problem is that I do not have access to carbon tet, nor do I have chloroform.  I could have the company order one of them.  Would DCM work?  Dissolve the crude material in DCM and let the succinimide crash out?

No it should be CCl₄. This, in my time, was a standard work-up for NBS brominations to remove the succinamide.

[AlphaScent]

Yeah I figured as much.  I will ask my boss if we can get some CCl₄.  Thank you for your insight.  Very much appreciated sir.

[discodermolide]

Yeah I figured as much.  I will ask my boss if we can get some CCl₄.  Thank you for your insight.  Very much appreciated sir.

My pleasure.

[AlphaScent]

Was CCl₄ 295 bucks a liter from sigma aldrich in your time??  If it was cheaper, maybe it would justify getting it.  Im just going to have to be diligent with my distillation and not be cavalier at all about it.  Thanks again disco!

[nox]

Succinimide has a pKa of around 9.6, basically as acidic as phenol. If your stuff isn't terribly water soluble or sensitive to base, I would just wash it out with 1M NaOH.

Edit: Just re-read your original post, seems like aqueous solubility might be an issue. In that case, you could try back extracting the aqueous NaOH layer after washing out the succinimide with EtOAc or DCM. The succinimide anion should behave and stay in the aqueous layer without getting pulled into the organic extracts.

[discodermolide]

Was CCl₄ 295 bucks a liter from sigma aldrich in your time??  If it was cheaper, maybe it would justify getting it.  Im just going to have to be diligent with my distillation and not be cavalier at all about it.  Thanks again disco!

Nope it was cheap, but $295/Liter is not too bad. There are more expensive things, like your time!

[AlphaScent]

Nox,
    That seems like a great idea.  I knew about the Pka, but my problem is that the next step to get the vinyloxirane is to use NaOH as the base and then kicks out the bromine.  But as I thought about it, the reaction is done at about 120 °C.  So the washing with 1 N NaOH and then back extracting could work.  Thank you very much for the insight.

Disco,

You are 100% correct, my time is more valuable.  I can recover the CCl₄ aswell for future reactions.

[orgopete]

I think you will find the succinimide will become hydrolyzed to the carboxylate amide. If your product is sufficiently organic soluble, and I expect it would be, then you can simply extract it. By the way, does the bromination give the 1-bromo-but-3-en-2-ol? I might have expected the 4-bromo-but-2-en-1-ol. I believe bromination goes 1,4.

[AlphaScent]

Orgo Pete,

It goes through a bromonium ion, with water attacking the 2 position.  It is 1-bromo-3-butene-2-ol.  That is by my procedure, there may be some competitiveness though.  You think washing with 1 N NaOH will open up the succinimide huh..that is something to consider for sure.  Thanks for your response!!

[AlphaScent]

http://masterorganicchemistry.com/reaction-guide/formation-of-bromohydrins-from-alkenes-using-water-and-nbs/

[nox]

I doubt that succinimide will ring open with NaOH -- in fact you can react the anion with Br₂ to make NBS, which precipitates from solution and can be filtered off.

[AlphaScent]

I am doing production for a small company.  Using bromine may work, but how clean does that NBS come back?  Easily reusable?