improvement to iso-ketone via peracetic method

[wacko_reaco]

Firstly let me begin by saying that if you were running a factory making this shit any improvement that cut down processing time without hindering yeilds, quality or costs negatively would be pursued. What i am about to disclose may rankle some people here because it is not exactly in keeping with good laboratory practise, but who cares, it is good factory practise and good process practise to save resources.

Start with sassafras, stir this in a stainless pot on a heating plate, add 10%by weight KOH dissolved in MeOH or EthOH (normally a 20% solution). Heat whilst stirring well until the solvent has boiled off and the temperature has risen to over 200C, turn the heat off and continue to stir until the solution of gunk is cool. If you cannot do this outside or in a fume ghood i suggest a flask with a distillation condenser attached as the sassafras fumes are quite strong.
Let the pot settle for a few hours then decant the mix off the top, there should be a large chunk of black gunk in the bottom, leave this. Place your medium brown mixture into a vessel and add 10times its volume in DCM. Now wash the solution with water twice.
The resultant  brown isoafrole can be now processed via peracetic without consequence. I have performed it three times and found the only variation is that a clear fraction comes over before the ketone in the distillation that never did previously, it however is about 2% of the ketone fraction.
This method will most likely also work with the performic if that is your game.
So there is one vacuum distillation saved, now the process only requires two (or one if you don't distill your freebase)
That is all
wacka wacka wacka

[Rhodium]

I wouldn't reccommend doing this.

What is your yield with this variation, compared with a standard run with distilled isosafrole? Do you fractionately distill your MDP2P, and have you tested it with TLC to identify possible contaminants?

[wacko_reaco]

That is a legimate question, yes the ketone was frac distilled, my yeilds were a couple of percentage points down (52% normally-50% with this method)  on normal but that should have been expected given my stated observations.
Rhodium has never tried this method and suggests you don't try it: I have tried it successfully three times and suggest you do, and i know the correct use of a semi-colon. But hey if a useless several hour vac distil is your idea of a good time then knock yourself out, hell triple vac distill all your solvents.
The purity question is irrelevant as there are two further vac distils post this step and all the common reactions have the co-reagants in excess.
The standout feature of the per-acid methods are they are pretty bomb-proof. In fact post DCM distillation the glycol seemed no different to when the iso was vac distilled. In reality you probably destroy an equivalent fraction vac distilling than the miniscule drop in yeild that is experienced.
Please some-one else get 50g of sass and try this and then we can all shutup about it and we can all stop vac distilling the iso.
wacka wacka wacka

[Chromic]

You should be getting a 65% molar yield of ketone using the peracetic (if you fractionally distill, under vac). What is the purity like? Did you test with bisulfite to get a good idea on that?

The yield from safrole -> isosafrole is ~98% when done properly.

And most sassafras oil is only 70-90% safrole to begin with... I think anything under 95% needs purifying... and most chemists here would say my standards are low.

[Rhodium]

What I suggest will remove unreacted safrole, which when run through the peracid oxidation may yield MD-phenylacetaldehyde and/or MD-phenylpropionaldehyde, neither of which is easily separated from MDP2P through distillation. Both of them will aminate in the Al/Hg reductive amination to form the corresponding phenylalkylamines, which then will contaminate your final product.

They will be inactive at the concentrations they will appear in, but they are still undesirable contaminants in my opinion.

[wacko_reaco]

Come on rhodium, do you really think there will be fuckall reacted safrole intermediate in the final product after distilling the ketone and the freebase and re-crystalising, given the distilations are performed properly?
I have never gotten over 55% yeild with ths method even with distilled iso, don't know why, my performic yeilds where always down on expected as well. Also witht his isomerisation method there is practically no safrole forerun in the distillation anyways.

So Rhodium, if assuming this method works you had to recommend to someone to either use this method, and re-distill the freebase or distill the iso and  not re-distil the freebase  (as almost every fucker here does) what would you say. I predict you would asert the former would be a more desirable.
I must again state here that this is production logic and methodology over lab methodology. If you have run these rxns many time then you are a production chemist and should start behaving like one.
Lastly i have posted here many times, both under this name and under 'startinout', i always tend to state my assumptions carefully and not profess success until is it confirmed. i do not post for ego massaging, but rather to help out. Someone try it quickly (preferrably with the performic) and confirm my results for everyone else.

wacka wacka wacka

[Rhodium]

Come on rhodium, do you really think there will be fuckall reacted safrole intermediate in the final product after distilling the ketone and the freebase and re-crystalising, given the distilations are performed properly?

The freebase distillation won't change things much, as the boiling point difference between the possible amines is negligible, recrystallization of the hydrochloride salt afterwards will however be effective, provided that it is performed correctly, and doesn't constitute "crashing out" the crystals.  You did not mention performing both a freebase distillation followed by recrystallization to compensate for the skipped isosafrole distillation.

I have never gotten over 55% yeild with this method even with distilled iso

Overall yield of MDMA.HCl, or the performic oxidation? If the latter, then you really need to review your procedure to find out where the other 15-20% went, as you should at least get 65-70% yield in that step.

Also with this isomerisation method there is practically no safrole forerun in the distillation anyways.

Not usually, but how would you know that will be the case during your next run if you don't distill the isosafrole to confirm complete isomerization? Some unexpected quirk might one day leave 25% of your safrole unreacted, which you then unknowingly will plug into the performic oxidation and propagate all the way to the hydrochloride salt. A single recrystallization will not remove THAT much impurities.

So Rhodium, if assuming this method works you had to recommend to someone to either use this method, and re-distill the freebase or distill the iso and  not re-distil the freebase  (as almost every fucker here does) what would you say.

I'd say that bad lab practice is better than really bad lab practice, so yes - failure to purify the final product is worse than not doing it with one of the intermediates.

I must again state here that this is production logic and methodology over lab methodology. If you have run these rxns many time then you are a production chemist and should start behaving like one.

Yes, certainly, but in the role of a production chemist you should then switch to another form of quality control to ascertain purity, such as running a TLC on your crude isosafrole before oxidizing it (production chemists usually analyze each batch with GC/MS to verify purity, but for hobbyists TLC is a fully ok substitute - it is not only dirt cheap, it is also way faster than a GC/MS).

i do not post for ego massaging, but rather to help out. Someone try it quickly (preferrably with the performic) and confirm my results for everyone else.

I do not doubt that your method will have an appearance that differs little from the proper procedure, as in the yield not being lessened by a noticeable amount, or the appearance of the final product being different. What I worry about is mostly the things that you don't see with the naked eye, such as the purity level of your final product.

If you do analyze your product after each run, and find it to be indistinguishable from runs made according to proper protocol, then there is no reason whatsoever for you not to take shortcuts like this.

However, suggesting others to take shortcuts without at the same time provide any kind of proof that it makes no difference, or suggest how they can ascertain the purity of their product despite skipping a purification step is something that I will never tolerate here without contesting it.

[Chromic]

Recommending to others to take shortcuts before they are able to confidentally take the shortcuts themselves, is a HUGE MISTAKE. The worst thing that I've seen in many good writeups is where quick, easy tests of the intermediates are not taken on each and every step.

It is also very important to recommend these check-points in each reaction, so newbees can tell where they are making the mistakes.

[Osmium]

> This method will most likely also work with the performic
> if that is your game.

I assume you meant distilling the formic acid out from the glycol?
I did that once, many years ago since the vacuum available to me at that time was really shitty. Resulting yield: 0%
There is a reason why everyone says to do it under strong vacuum and T preferrably kept below 40°C.

Or were you talking about using the crude ketone for the amination reaction?
I did that once too, when I made my first batch and didn't have any vacuum available, and since the batch size was so small. The resulting stuff was dirty and wouldn't clean up, although it produced the desired effects.

> So there is one vacuum distillation saved, now the process
> only requires two (or one if you don't distill your freebase)

Production chemists who obviously make more than a few grams by definition should NOT take such shortcuts. While nobody gives a shit if you fry your own brain with your own candy, this stuff is meant to end up with unknown consumers, most of which are probably stupid kiddies who shouldn't do any drugs in the first place.
While your clients usually deserve to be fucked since they rarely want to pay the desired price and will try everything to get the stuff cheaper to maximise their own profits it is still unethical towards the end user to save time and produce dirty shit.

When someone is into production they should learn how to multitask. There's no reason whatsoever why distillations need a babysitter most of the time. Especially distillations like sassafras require not much attention at all once the forerun is out, the temp has stabilised and the safrole is coming over. All you need to do is checking it every 5-10 minutes or even less when doing really big amounts. One person can easily start a performic reaction and perform some time-consuming extractions, clean lab glass and maybe even recycle some solvents.
Once people have gained the required confidence in their abilities to do so and the knowledge of how long each step will usually take they can get quite some work done each day.
If I tried to do some big scale work I'd rather do it right and use big lab glass, long ass columns and slow unattended distillation etc. Sure, it would take me a week to distill 50 liter sassafras from the 5L flask requiring to run constantly, but since every other step would be performed the same way and in parallel those distillations wouldn't slow everything down by much. Just have a 'production line', e.g a big long U-shaped table with each step being done in its own area, with everything needed in place.
The glass and pumps etc. are an expensive one time investment, but I still like it better than rigging some old oil barrels to process the same 50 liters of sassy all at once. I'd rather maximise my yields AND purity (usually exclusive either/or) by being able to recycle and keep foreruns etc apart to be processed separately, optimise my reaction conditions and be able to shift production slightly in case some equipment fails, than doing it all with improvised reaction containers one step after the other.

I'm not fat just horizontally disproportionate.

[scram]

"Both of them will aminate in the Al/Hg reductive amination to form the corresponding phenylalkylamines, which then will contaminate your final product."
...ahh, this must the famous inactive 'mystery powder' obtained on 3 occassions due to not distilling.

Does anyone have the denity of the aldehyde?

[wacko_reaco]

All points taken, i assumed everyone was performing the tests anyways.
My tests are
1-after the isomerisation take a small representative sample to heavy boiling, then turn off the heat, the tempertaure at which all boilning ceases should be above 242C otherwise there is significant safrole contamination
2--ketone, we all know how that is tested
3-freebase, i don't test the freebase once distilled, the distillation temperature and conditions are indication enough for me, the recrystallisation i only ever perform to stop browning in the final product but if you think it removes the primary amine imputies then all the more.
The point about making things too simple for all is interesting as these reactions simply don't work if you fuckup a step, which in my book is the best safeguard of all.  At the end of the day maybe this post was irresponsible, i had always thought there was some conspiaracy here to keep things more complicated than they need to be, but my perhaps it is justified, i guess i always assumed people wouldn't try this crap without an education.
Finally if you perform a known reaction on any scale over and over again you are a production chemist, regardless if you are doing 100mg, 1000kg or 100g.

Now can everyone chill the fuck out, we are working together
wacka wacka wacka

[Rhodium]

i assumed everyone was performing the tests anyways

i had always thought there was some conspiaracy here to keep things more complicated than they need to be

i always assumed people wouldn't try this crap without an education

Unfortunately, none of these assumptions are true at all, just trust the elderbees. We are here to help you!

[placebo]

I just wanted to say I like Rhod's and Osmium's posts and their responsibility and integrity.
Remember... people are going to eat this shit, there is no length you should not go to for 100% purity. It is the half-stepping, short-cutting mother fuckers who bring the attention on this industry. Belt up or get out!!
Intelligence is not the recall of knowledge, but the ability to use it. (Rainman was a retard)

[wacko_reaco]

that is it is a valid process improvement in my book, but hell you are all still probably vacuum distilling your sassafras oil, think about the planet, don't use energy you don't need to (that was a joke for all those americans who don't understand sarcasm)
wacka wacka wacka

[hellman]

Good work, wack,

Getting closer!
This is a great timesaver, I believe that the only issue preventing this method having unparralelled mind numbing success, is the different purity levels of the starting sasafrass material,.

-but this CAN BE OVER COME BY FREEZING THE SASS!

It is an interesting argument, what rhodium is trying to say, and wacko,
I see both sides,
but what kind of slides the scales into the favourable region in the pro {no iso distilation} is the time saving, and that means less chance of legal proceedings,
We are the ones that supply this, we are the ones taking the risk, to play outside the game,.
therefore I am all for it,

- i am sure there will be more e, for the consumer and the manufacturer, when methods like this are tested thoroughly, logically speaking that is,.

This is great, this has huge significance,


hellman


- al new sideproducts, can be removed, so don't be anal,.
jems that come like this, are always, brownnosed by the higher community,
expect this, that's how you know you are on to something,.

But extraordinary breakthroughs, do need extraodinary proof, keep that in mind.

[Osmium]

> - al new sideproducts, can be removed, so don't be anal,.

Yes, the thought of a bunch of lazy, shortcut taking wannabee chemists trying to clean up a off-coloured, sticky and fragrant product mixture containing 50 components really appeals to me.

Care to share your wonder cleanup procedure?

> jems that come like this, are always, brownnosed by the higher community,

What's so special about doing a rushed, poorly performed, half-assed job?

> expect this, that's how you know you are on to something,.

May you develop ulcers from the phenolic toilet disinfectant-like impurities.
Hint: maximise your yield so you can buy the new stereo by omitting the cleanup steps. You will see, you might end up with 10% more yield. Never mind if it has the consistency of chewing gum and colour of dog vomit.

> But extraordinary breakthroughs, do need extraodinary
> proof, keep that in mind.

Extraordinary my ass! Can't wait to read more about your sloppy "improvements" and "breakthroughs" in clandestine chemistry. You guys make me all giddy inside. It's so exciting to witness history to be made!

[Protium]

Polymerization is not a good thing  

[yellium]

Os: You shouldn't be so negative to those good-meaning bees.
Just because you happen to be a good chemist is no reason to
speak badly about other clandestine chemists, who have more limited
resources (in terms of glassware, chemicals, and intellect). After all,
these guys do all the best they can, and isn't that what it's all about?

Plus, every idea, how stupid it may be, might be helpful to other bees.
There's no need to downplay other helpful bees, especially since they are
so willing to invest so much of their copious free time in typing in al
this so-called 'nonsense'. It might be nonsense to you and me, but if even
one bee is enlightened, who are we to condemn those bees?

Plus, saying bad things about stupid ideas of other beas is considered
37143 behaviour, which is seriously frowned upon among grownups. Instead,
you should give positive, constructive comments.

Another thing I noticed in your reply is that you tend to insert a lot of
very subjective value judgements, which might be considered as personal
judgements. You should refrain from that, and instead use more neutral, or
preferably politically correct terms for that.


So, for instance, you shouldn't say


'Yes, the thought of a bunch of lazy, shortcut taking wannabee chemists
trying to clean up a off-coloured, sticky and fragrant product mixture
containing 50 components really appeals to me'


but instead you might consider replying
            
   
'Well! That is a very good idea! I have given your suggestions much thought
and did a few trials in my own lab. Of course, I wasted a lot of valuable
precursors on your unclear suggestions, but that shouldn't matter. And that
the end product contained more contaminants than the usual route followed
doesn't matter also: it is about intentions, and the users will surely
appreciate that while this product might be more unclean than the product made
earlier, it does contain more good intentions than before. So, actually, it
is a BETTER product!!. Anyway, I have to clean up the lab now; I hope to hear
from you soon.'

   
Note that the second reply is much longer, thus giving your opponent more
attention, and a longer time for the message to sink in. For completeness,
add some incomprehensible raving and spelling typo's to approach them more
at their intellectual level.
   
   
   
And now I'm off to bang the heads of a few lusers against the wall.

[X_Stacy]

It is great when a fellow bee finds a shortcut that clandestine chemists who don't have access to fancy lab equipment can use. But when you are talking about distribution, especially concerning MDMA, you really need to consider how the shortcut affects the product. I know this is like the fifth post in this thread with the same message, but I don't think it can be stressed enough:
The contaminents found in crude MDMA can really fuck you up, NOT IN THE GOOD WAY!
If you want Parkinson's, then just test your crude unpurified product after every batch.
Not to say that the shortcuts aren't viable, just that YOU REALLY NEED TO TEST YOUR FINAL PRODUCT before distributing the info to the hundreds of non-chemists and beginning chemists that will try it.
It's only an unethical business because of ignorance.  

[Triton]

So what contaminents would make it through ketone distillation, an A/B extraction followed by distillation of the freebase?