Thermal isosafrole epoxide rearrangement trials

[foxy2]

"Just look at my declining performance at my site (Over 100 new additions in October, 75 in November, 30 in december, and now in January only 11, of which fiveare just PDF/ZIP files, nothing I have written myself and put any work into!!). And I have not made any practical contributions either, other than taking pictures of ammonium nitrate crystals. If it continue like this, people will be bored with my site as not much new is happening, methods becomes obsolete as I haven't updated the documents with the latest breakthroughs, and I no longer have a purpose here..."


Hmmm
I wonder if Fractal Flowers beautiful breasts had anything to do with the recent slowdown???
 

Fully Informed Jury!

(http://www.fija.org/)

[Vibrating_Lights]

Noj, does 1 Lb of oxone have the capability to epoxidise 450gms of alkene. Very interested to hear of the ketone work up.
Also Chromic try to use phosphoric acid to make the tma crystals i hear the salt is less hygroscopic.
VL_

[Chromic]

I've tried it, the epoxide wasn't destroyed in the distillation. I didn't confirm that I made the ketone (although it seems likely I did), I'm looking for cleaner techniques to go from the epoxide to the ketone. I encourage others to try it tho.

[PoohBear4Ever]

What's so bad about the sulfuric hydrolysis?  Maybe the black crud that's left in the flask after distillation...

PB

[goiterjoe]

ethyl acetate is available by the gallon in most stores that sell fiberglass and other boat fabricating accessories.
If Pacman had influenced us, we'd run around dark rooms eating pills and listen to repetitive music

[Chromic]

I was referring to asarone epoxide.

[noj]

VL, sorry. It was 2Kg oxone. Let me run it again with detailed note taking and will let you know. I have written down 450g, 355x10 (yellow bottles) 2 gal (but recall adding some more) and 2Kg oxone. I'll make a new thread with an appropriate title when finished. This one is supposed to be thermal rearrangement, which I want to try yet.
Real men cook naked.

[uemura]

Hi Rhodium,
as Uemura has to agree today: never change a running system...
Another paper on the thermal rearrangement from Mannich ( the Mannich ) "Zu Studien über Adrenalinverbindungen" Ber. ??, ?? (have to check if you want) confirms Hörings statement (Mannich may have however just copied the results, you may know the scientific beesines...)

[Vibrating_Lights]

Make sure you vaccume distill the epoxide.  Swim promises that a flask full of crud will ensue with crude epoxide in a thermal rearrangement. did that 450gm batch work up right with those ratios.
VL_

[noj]

VL, was there anything left in the flask after the Atm distillation? And was the ketone more viscous?
there must be an answer for everything, if only you knew how to set forth the questions

[Vibrating_Lights]

Yes only from the atm distillation of the un distilled epoxide the ketone from the crude rearrangement did not aminate.  however the ketone that was produced with the previously vac distilled epoxide did aminate in 66% yeild.there was very little left over in the distillatio it was rubbery and brownish red it dissolved after a while in methanol.  the crud from the crude eopxide will still not coome out of the flask.
VL_

[noj]

Ok, swim has some fluid in the freezer that won't freeze. The H2SO4 hydrolysis was done, then tried a bisulfite adduct, which failed. Tried to aminate anyway, and it failed. So took what was left and distilled at atm pres, leaving a raunchy smelling brown fluid left in flask. I mean it was rank. The distillate looks the same as before though. It is not very visous, like ketones from experience. The blacklight didn't seem to do anything for me. Thermometer was broken, but the hotplate required max heat to get it to come over. I'm not sure what this is anymore with no way to check bp. It smells right, just not viscous. And refractive a bit. I hate to throw it away, since it can't be safrol or iso, and it is unlikely that it is epoxide.
there must be an answer for everything, if only you knew how to set forth the questions

[sunlight]

Rhodium , wich catalyst would you use ? LiI and wich else ? ZnCl2, silica gel ?

[Rhodium]

If I would rank the available alternatives, I'd begin with LiI (or the perchlorate or bromide), followed by MgBr2 (which is said to work satisfactorily, is inexpensive and non-toxic). Next, I would try the Bi(III) salts mentioned in that PDF journal article on my page, just because. My really last choiches would be the stronger lewis acids (FeBr3, AlCl3 etc) as they are probably going to misbehave and tear apart other things of the molecule which we rather would keep if possible (like methylenedioxy rings, methoxy groups, amines etc).

[backburner70]

Rhodium - Still use the ethyl acetate and nitrogen atmosphere and just substitute a molar amount of the salt?

[cheeseboy]

Does epoxide/diol/glycol freeze in a norml freezer? What is the temp for a thermal rearrangmetn under ATM? Guess a vacuum shouldn't be used for the thermal re arrangment so you can get the exact temp.Thanks
Cheeseboy-a whiteboy with Soul Like a black guy without soul
May The Source Bee With You Always.

[wacko_reaco]

Rhodium,
Can MgBr2 be prepared from Mg(s) and HBr(aq), if so i will give it a whirl, is there any OTC source of Lithium that i can convert to the halogen salt, am not connected to a lab anymore so getting these things involves pulling favours that i would rather save up for the present.
Have some AlCl3 though, any way of weakening it, it has a habit of cleaving ethers so it is worrisome, but i am rather experienced with it so who knows, if it could remain in the solid phase we would be able to control exposure times, i think it would co-ordinate equally well with the methylene ring though, however if mild hydrolysis conditions were used we might convince only the epoxide to rearrange/cleave.
the mag salt seems more promising though, have a think, my inorganic sucks
wacka wacka wacka

[Rhodium]

Yes, you can make MgBr2 by dissolving magnesium in HBr. Lithium is available OTC in Lithium batteries - a search in the meth form should reveal the details behind opening such batteries and getting the desired Li metal strip.

[psychokitty]

Noj, so which is it?  1 pound or 2 kilograms of oxone? (How you can confuse the two is beyond me.)   Did you add any buffer?  The advice about filtering out the potassium sulfate is great, BTW.  However, I'm still perplexed about your results.  Are you saying that the yield of ketone was misreported by you earlier in the thread? That the yields of ketone are NOT so good?  More information, please.

[cheeseboy]

Maybe the filtering out of the solids in the OXONE solution has something to do with noj's 'mystery oil' ?
Cheeseboy-a whiteboy with Soul Like a black guy without soul
May The Source Bee With You Always.