Anethole epoxide from oxone

[backburner70]

I found this scrawled on a piece of paper in the trash. Thought I should pass it on to the elder bees and see what they say.

"29.6 grams of anethole was subjected to treatment with oxone per standard procedures. The reaction proceeded in the exact fashion described in the writeup. After 5 hours the look and smell was perfect. The solution was acidifed with 125mls of 31% HCl and all solids were dissolved. Everything was loaded into the sep funnel and upon standing a few minutes separated into 2 components: urine yellow on top and a darker reddish/gold/yellow oil on bottom. The darker bottom layer was in proportion to the expected epoxide yield so it was decanted and saved. Subsequent DCM extractions (3x75ml) were quick to separate, only slightly discolored, and no emulsions formed with shaking. The DCM was distilled off and only a few more mls of epoxide were obtained. These extra few mls were added to the original decanted bulk.

All in all, it just seemed too damn easy.

So the question: Is this reddish gold oil ready for an H2SO4 bath? It seems like it should need a brine wash or something(!) first. Will it matter if some pot bisulfate or sodium bicarb get thrown in with it? This whole exercise is just for education, not for consumption. The bee in question isn't really concerned about yield or viability, just getting a feel for oxone."

BB 7.0

[pickler]

https://www.thevespiary.org/rhodium/Rhodium/chemistry/oxone.epoxidation.html

[Chromic]

If you buffered it as I wrote in my document, I would recommend that you carefully distill the epoxide at atmospheric pressure (skip the H2SO4 rearrangement and distill it, it worked beautifully for anethole epoxide).

Raise the temperature past 200C slowly! (or do the H2SO4 rearrangement, but it's more work than just distilling the epoxide)

You'll get anethole ketone which will react perfectly. Test it by: 1) adding a drop to water, watch it sink (anethole floats) 2) check by doing a bisulfite test 3) try aminating 5g of PMP2P per MM to get a feel for the reductions. Taste PMMA if you dare, don't do over 80-120mg, trust me, it doesn't get better with higher doses.

[humidbeing]

Does the atm distillation epoxide> (higher temps)>ketone
as well?

 This hasn't been made clear yet.
singel wite intejunt male

[Chromic]

Yes, I am 100% certain that it works.

I rearranged anethole epoxide to anethole ketone and got PMMA in good yields. I also rearranged isosafrole epoxide to isosafrole ketone and got MDMA in poor yields (I blame this on my technique during that specific run, I accidentally added aqueous base to the foil before it had completed amalgamating...)

[backburner70]

pickler - Seen that doc, read it numerous times, thanks though!

Chromic - Many thanks for the reply. That other oxone thread is getting crowded, so a few more questions if you don't mind.

>If you buffered it as I wrote in my document,
Yeah, 45g of bicarb slowly added, had an initial pH of about 6.8.

>I would recommend that you carefully distill
Do you remember what temps did you were seeing for the epoxide to distill over? I know you mention the 200 degree mark. Did you heat first, then distill? Or did you just slowly crank it up until the ketone started coming across?

>Taste PMMA if you dare
Dare seems an appropriate word here. That's why the comment was made above about not being concerned about yield. The bee in question might not even bother to aminate. Who really needs 10g of PMMA.HCl in their life?

This does bring up a larger question though: Psychokitty mentions trying to acidify the post reaction mix with H2SO4 instead of HCl. This naturally leads one to consider the possibility of a one-pot oxone/rearrangment (using iso-saf of course). After 5 hours of oxone, add sulfuric, reflux, extract with DCM, and distill. Although I guess if thermal rearrangement of iso-saf turns out to be viable it will be a moot point anyway. Just thinking out loud.

BB 7.0

[LaBTop]

I would be interested to see ANYBODY repeat that oxone isosafrole thingy with heating/distilling at normal pressure, and then aminating the obtained product the right way, to see real yield. JUST CURIOUS. LT/
WISDOMwillWIN

[humidbeing]

Chromic and terbium have said that they've done it, why
wouldn't it work?

I'm sorry, you said REAl yeild. What does that constitute?
I crave..I YEARN

[Sinistar]

Is PMMA deathly dangerous like PMA is?

[Chromic]

LT: me too.

Temperature for distilling anethole epoxide was well over 200C, likely around 300C. I don't have a high temperature thermometer (ie markings stop at 260C) so I can't tell you exactly. I don't think Terb's done the thermal rearrangement, but I do believe that Ueruma and twodogs have.

[LaBTop]

MDP2P boiling point at normal pressure should be around 281°C, IIRC. The epoxide, can't find any figures on that, practice must give them. LT/
IIRC=ifIremembercorrectly
WISDOMwillWIN

[uemura]

Chromic,

, but I do believe that Uemura and twodogs have.

Just for the bees who still don't want to believe! Yes, the anethol expoxide thermal arrangement works very well, it works also for the crude epoxide.

The temperature of the boiling epoxide/ketone was 265-270DegC. Vapour temp about 5DegC less.

Let uemura add another evidence test for anethole ketone: Put into the freezer (-20DegC), the ketone should cristallise after some time if it's pure enough.

Carpe Diem

[backburner70]

Uemura - thanks for the info! Will give it a try and report back.

Everybody - Nobody cares to comment on the one-pot rearrangement idea?

BB 7.0

[Chromic]

Backburner, the correct sequence, which I performed, and which succeeded is:

Perform buffered oxone reaction, extract with DCM, distill with no vacuum to get your ketone.

It's that simple.Cleaning your distilling flask will be a bit harder...

[backburner70]

Chromic - I understand that part perfectly. And SWIM will try it out on anethole epoxide. The end product will get hit with some bisulfite to see if it is legit.

For clarity, let me re-state what I am asking: Assume for a second that some bee decided to perform an oxone reaction with iso-saf, and that same bee was a little paranoid of scorching their precious MD-P2P with those high (281!) temperatures.  Further assume the bee is lazy and at the end of the oxone reaction instead of dissolving the solids back into solution with HCl, they decide to add an appropriate ammount of H2SO4. Since their mix is already in a decent sized flask fitted with reflux condenser and is sitting on a hot-plate stirrer, they decide to do the 2 hour reflux right then and there, without ever isolating the epoxide from the oxone reaction mix.

Realize that I am just asking. I have not done this, I do not advocate it, I doubt it will work, and it is probably just a Plain Stupid Idea (tm). Is it lazy? Well yeah. Is it really that difficult to isolate the epoxide? Well no. Even if it had a remote chance of working, wouldn't it require a fair amount of tinkering to get it right? Probably. But always strive for efficiency, whenever and wherever possible.

Necessity may be the mother of invention, but laziness is her half sister.

BB 7.0

[Chromic]

The huge volume will be a pain if you don't extract the epoxide.

[Vibrating_Lights]

For the  thermal rearrangement of the isosafrole epoxide to be high yeilding the epoxide must first be vac distilled to remove the impurities that catalize the polymerization at high temps.  with vac distilled epoxide there is only small ammounts of polymerization.

[twodogs]

What makes you say that?

[Vibrating_Lights]

observed trial and error.  why do you people quit doubting and try it your damn self.

[twodogs]

Vibrator, I have tried thermal rearrangement of isosafrole glycol (got 60% ketone) and isodillapiole epoxide (got about 50% ketone.) It is just that when I saw your post using words like "impurities that catalyse the polymerization" I thought oooh he's a scientist. So.. what were your results from distilling crude epoxide and what did you get after vac distilling?