Unknown Product

[goiterjoe]

OK, so SWIM had some ketone that for some reason or another had to be buried offsite for a while.  He didn't bury it below the frost line, so the ketone was exposed to temperature fluctuations throughout the summer and extremely warm winter.  He finally decided it was time to aminate the oil 6 months later with an Al/Hg nitro reaction.  everything went like it supposedly should have through the reaction.  At the end, the product was basified, extracted with 500ml + 200ml + 150ml xylene, washed 4x with 300ml dH2O, 2x with 300ml NaCl solution, and then dryed with baked epson salts and filtered.  A gassing apparatus was then used to gas out the oil.  At first, gas went in and turned the NP slightly yellow.  Crystals then started to form and immediately drop to the bottom, and then SWIM overgassed his product and the xylene turned red.  A couple of minutes later, the crystals turned into a red oil and dispersed throughout the xylene.  So SWIM added 75ml dH2O and shook in a separatory funnel to reclaim the crystals, and proceeded to evaporate them out.  He was left with a red tar that upon repetitive acetone washes produced a little under 6g of extremely light powder that's not very crystalline in nature, has no noticeable smell over the acetone, and has no taste!  Do anyone have any ideas what he might have?  He thinks it could possibly be a problem with the ketone being stored so long, since it had a somewhat different smell than it had originally and was a darker yellow than before.

Sed quis custodiet ipsos custodes?

[Chromic]

I doubt the ketone "went bad" if it was distilled before it was stored, I've stored distilled ketone in a air tight container at room temp for months. By what method was the ketone produced? Did you do a bisulfite test before you went to aminate?

I doubt the crystals that formed when you gassed were MDMA.

[sunlight]

Make a home mp test, make a capillary with a glass tube and a flame, put a miligrams of product, join it to a thermometer, inmerse them in sunflower oil and heat it slowly, a few seconds/degree till see the product melting, if it melts in the range 147-151 it's MDMA. But if they have not taste, it's not a good new.
If ketne was stored so much time and was not very pure may be it was very degraded, and god knows what you got.

[goiterjoe]

SWIM got a second opinion, and they do have a delayed taste of MDMA after a polymer taste similar to that of sudafed gakk.  another point he should probably mention is that after gassing, the glass tube that was used to gas had the taste of MDMA.  SWIM is wondering if the extremely acidic conditions that the product was exposed to could have polymerized it, and if that is why he reads of so many people acidifying with HCl in IPA.
Sed quis custodiet ipsos custodes?

[Chromic]

But, GJ:

1. How was the ketone made?
2. Did you verify that it was ketone?

[cheeseboy]

GJ:
  cheese had similar problemo a long time ago. cheese tried gassing for first time, over gassed and got the red slime.
This was obviously due to OVER gassing and product was wrecked. Re-Basifying wouldn't help it (tried 3 times)Acetone did fuck all either.
  cheese learned that it was possible to hydrolize by just dripping the HCl 8 in non-polar/freebase, shake hard and freeze the MDMA/MDA out. This works beautifully and if you're worried about losing product to water in HCl, just evap everything once all product has been dripped out. Just remember, 6 drops HCl per gram expected, but always drip in less to avoid over acidifying. Over acidifying will produce product by "oiling out" on the bottom, this oil can be crystalized  with acetone. it's all good.
May The Source Bee With Yous

[goiterjoe]

Chromic, the ketone was produced from peracetic oxidation. 

Now,  when you say you've stored ketone at room temperature after distilling, does that mean you stored it inside in a somewhat controlled environment?  The said ketone was stored in an area that was exposed to 100F weather for almost a month, followed by 80+F weather for another three months.  To make matters worse, the ketone was not fractionally distilled, but merely distilled from the post reaction mixture.  SWIM says he will continue to enjoy his vacation for a little while longer, and then report back with his findings.  happy holidays everyone.
Sed quis custodiet ipsos custodes?

[Bandil]

I've had the exact same problem using the peracetic route aswell... Tried just about everything to reclaim my crystals, but alas nothing.

[Chromic]

Nope, just in a well-sealed bottle away from direct sunlight. (ie no air-conditioning, temps ranged from 20-30C).

If your product "oils out" (ie does not crystallize, and forms a viscous tar), extract the "oil" with water and acid to get it acidic, then do an A/B with DCM, evap the water, you'll likely still see a clear tar of sorts, but just go ahead and freeze until it crystalizes (takes a while), then break it up fine, and wash with acetone.

The only time that I've seen this happen is if the A/B extraction has not been performed and significant amounts of alkene or ketone remain in the post amalgam rxn.

Btw, you guys always should be using indicators like methyl orange or litmus so you can tell when your organic has been gassed or when you've added enough hydrochloric acid to extract all the product.

... and ... I've got a feeling that the peracetic oxidation requires amounts more in line with what I gave in my most recent writeup (due to equilibrium reasons, which I've explained in other posts). In that writeup, nearly all of the alkene was converted.

[baalchemist]

Let me shed some new light on this subject, overgassing
cannot happen if the gas is DRY & the freebase/toluene DRY.
The Hcl will form salt as long as base is present, after that it simply dissipates through the solution doing nothing, then exits. The 'red-oil' is actualy a small amount
of un-reacted ketone causing the trouble, and it doesnt take much for it to happen. The first clue was the
'yellowish toluene', it should be crystal clear prior to gassing. That 'yellow tint' is your un-reacted ketone culprit. An A/B will clear that up in a hurry and save the day. Gassing it with the tint can be done, but it has to be done slow, and in 2-3 seperate gassings & use super cold toluene/mix. The freebase will take up the Hcl quickly while the freebase concentration is high, then once the  freebase becomes sparse that ketone start getting attacked.
Toluene/slurry will suddenly turn from yellow to red in a split second at some point soon if gassing is continued, the gassing window is a very narrow one with dirty toluene. A quick A/B on yellow toluene, clear toluene is all systems go minus the A/B.
GODISNOWHERE

[LaBTop]

To avoid all these problems, gas f.e. 1 liter fresh toluene first until really saturated with HCl 99% gas (when the gas exits the toluene while vigorously stirring), then use this saturated Toluene/HCl solution in a sepfunnel above your toluene/freebase mix to titrate that mixture to pH 6. No reddish gums or strange sideproducts will and can form. Filter crystals.
One small acetone wash of your buchnerfilter will leave you with snowwhite crystals on the filterpaper.
Toluene is one of the best solvents to saturate with HCl gas, after several days standing in a closed bottle it wasn't changed at all, no colourisation or change when used again. LT/
WISDOMwillWIN