Cleaning-Up Isosafrole

[Bwiti]

In my dreams, a squid-like alien creature contacted me. It said that communication while humans were in a dream-state was easier, because our disgusting egos get in the way less than when we are concious. It said that it would help us abolish drug-control by giving all federal employees rectal cancer if I can help it with a chemistry problem. Here's what it said:

"I added calcium oxide/KOH to sassy oil, then refluxed for a few hours, and now it's time to clean-up the isosafrole, which is a uniform light tan color. I've done several dH2O washings on this, and even tried washing with HCl, but it's the same damn color. Besides distillation, what else can I do to clean this stuff up? Without a vac-pump, I'm afraid to distill, so I have to make the best with what I have. Yes, I'm a poor alien; spent all of my cash on fixing up my ship, and various interesting drugs. I want to put my tentacles into your brain, so you can see the world as I do....."
Love my country, fear my government.

[Belial]

Vacuum filtering is very effective in cleaning up the product of this isomerization. SWIM follows her Eluesis devotional bible and vac. filters then distills. Although you state that you dont have vacuum! so this could be a set back. and why are you afraid to distill? Atmospheric is fine here

[humidbeing]

Bwiti, just run room temp water through the condesor
 and runn stirring to avoid bumping, then just distill
at atmospheric.
 The tan color worries me though. Should be much darker.

CG I miss you sweety, I really do.

[cheeseboy]

Yes, the color of Isoasafrol from the isomerization is a dark brown. Maybe the CaO does something to the color.
May De Sorce Bee Wit Chu-Always

[metwurst]

Bwiti, was isomerization performed on sassafras oil or on safrole distilled from sassafras oil? If the alien used plain sassafras without any form of clean-up, this would probably explain the difference in color, and almost undoubtedly has negatively effected yield.
Isomerizations carried out on fractionally distilled safrole using KOH and CaO in this neck of the woods all yield a dark brown oil. When this is vacuum filtered, the resultant oil could be called "dark tan", but one's first choice of a name for the color would be brown.
TFSE suggests vacuum isomerization with anhydrous KOH yields better than CaO/KOH isomerizations.
You should distill your isosafrole to purify it, separating unreacted safrole from isosafrole, and leaving behind reaction by-products. Proceeding without distillation would seem to be undesirably "ghetto", and is going to throw stones in your path.

[Bwiti]

"was isomerization performed on sassafras oil or on safrole distilled from sassafras oil?"

  Well, at least it was washed with a solution of NaOH, then dried with Mg-sulfate. Also, I'm slightly color-blind.
Love my country, fear my government.

[zooligan]

Perhaps living underwater your squid friend overestimates STP (standard temp/pressure).  However, on the crunchy crusty surface of the planet, with only the atmosphere exerting its force upon our bodies and distillation rig contents, a STP distillation of iso is nothing to be scared of.  Peanut oil as a buffer will result in crystal clear iso from fractional distillation, with all the brown yummy scuzz left in the buffer oil.

No shit.  Really.

z
"No one can build his security upon the nobleness of another person." -- Willa Cather

[Bwiti]

Peanut oil? Is this watched?  Alright, he'll give that a shot. He'll also add some broken chips of glass to give it a more uniform boil, so oil won't splatter all over the kitchen again.  
Love my country, fear my government.

[Rhodium]

I thought we all agreed in a recent dicussion (UTFSE) that buffer oil was unnecessary, and just an urban legend started by Eleusis?

[riobard]

The peanut oil people bring up can be found near the turkey fryers in that Orange Warehouse everyone goes to for home related items in the US, at least in SWIM's market in the south. It is completely unnecessary though, but i guess one could eek out every last drop of non polymerized isosafrole and safrole forerun by using it to drive out the lower boiling good stuff. Your reaction color seems like bad news to me. Swim's atmospheric without Cao was dark brown, almost black. With the CaO, you should get that dark color with even more insoluble crap in the bottom of your flask. The KOH makes the color, the CaO takes up the moisture to ensure reaction progress. Distillates should be clear in color, and can be done at atmospheric pressure.

[goiterjoe]

Buffering essential oils for distilling has always spelled disaster from my experiences.  I was never able to reclaim my attempt at TMP2P due to buffering, and my only botched peracid synth came about after buffering the ketone and then trying to vacuum distill.  Maybe it was because of the oil I used, but it seemed to hold the oil in for an extra 30C or so without letting it distill.

[Chromic]

Agreed, use no buffer oil.

Rhod, you should update

https://www.thevespiary.org/rhodium/Rhodium/chemistry/peracid.html

to reflect that... where it says:

Dry organic phase over 50g of anhydrous MgSO4 (made by baking epsom salts at 300°C for a couple of hours, let cool, then grinding into a powder) making sure to filter off the MgSO4, and washing the filter cake with a small amount of DCM. The solvent is removed and kept for a later run, the resulting residue is combined with 100ml of vegetable cooking oil and distilled under vacuum to yield ketone (>200 grams) [That is a 56%+ yield].

It should read:

The DCM is quickly distilled off with no vacuum and kept for a later run, the resulting residue is then distilled under vacuum to yield ketone (>200 grams) [That is a 56%+ yield].

There's no reason to dry DCM before distilling (water is azeotropically removed), and there is no reason to add a buffer oil to ketone (if it's polymerizing, that's because your vacuum sucks).

[Rhodium]

Sure - I'll remove the cooking oil part - but what about that azeotrope? Composition/bp? I am very fond of always drying my non-polars before evaporating the solvent in all reactions - are you saying I'm wasting my time?

[Osmium]

No! Dry it!
The DCM/H2O azeotrope contains only very little water. When you distill ketone without drying there will invariably be water present, which will cause the usual problems (bad vacuum until it is all gone).
I'm not fat just horizontally disproportionate.

[zooligan]

I dunno, maybe it is unnecessary, but it sure helps when it comes time to clean out the flasks.  It holds any leftover crap in suspension instead of polymerizing/carbonizing it on the flask walls...

z

"No one can build his security upon the nobleness of another person." -- Willa Cather

[goiterjoe]

There isn't anything left over after distilling ketone that a couple washes of acetone won't cure.  If you still have some gunk at the bottom of the flask, KOH in IPA or just hot NaOH solution soaks will finish up the job.

[Bwiti]

Thanks for the heads-up folks! In my dreams, I was into PCP-analogs for so long that when a technique was questioned in the phenethylamine world, I wasn't there.
Love my country, fear my government.

[dr_ruthenium]

I understand the use of a buffer oil to try to avoid scorching/carbonization/polymerization and the cons.  Any idea if using safflower oil as buffer could f'up the ketone?  Could this be cause of my failed amination?

[Rhodium]

Yes, possibly. The buffer oil is not necessary at all - the only thing it might help with is easier flask cleaning, while the problems it may cause are unknown.

[dr_ruthenium]

Has anyone experienced failed amination with ketone distilled with buffer oil while keeping all other parameters from successful aminations constant?  Rhod, PLEASE check out my post "Amination Failure" in Newbee Forum.