I watched the crazy old man with the dark trimmed glasses go at it again. This time he fucking amazed me! I saw him do something like 125ml MeOH, 25mL H2O, pinch HgCl2, stirred. 8.9g Al, stirred ~20 mins. Added 6.4g isosafrole ketoxime, added 25g HOAc. ~3 hours pass with mag stirring (flask is only warm to the touch). Slowly added 90g NaOH dissolved in 200mL ice-water. Extracted with 80ml, then 45ml toluene. Washed with 150ml 5% NaOH, filter, 150ml 5% NaOH, 150ml brine. Titrated to pH 4 with HCl in distilled water with stirring. Evaporated water. 5.9g MDA.HCl yield (before recrystallization). (83% crude yield!!!)

The reaction ran HOT and FAST. It was over and done in about two or three hours. The yields are FUCKING STELLAR.

Antibody gets two thumbs up for this procedure!!!

Things learned (this is his third run of ketoxime reduction, btw):

1) you can use MeOH instead of EtOH, which is good news
2) you can amalgamate all the Al before hand and in situ as MM does (very good news!)

This definitely paves the way for OTC MDA.HCl in high yields! (or is it really MDOH.HCl? ahh, who really cares!)

HAPPY, HAPPY, JOY, JOY!!!!!

Btw, the bioassay on the MDMA that the man produced that I wrote about in other posts was predictably good.

How can the statements "flask is only warm to the touch" and "The reaction ran HOT and FAST" be superimposed onto each other? The former being a description of what the flask felt like after 3h?

pinch HgCl2
Shudder!!! You probably shouldn't say it like that. Too many people here are likely to interpret this literally.

I'd say I used about 50mg of HgCl2. It was the smallest sizeable bit that comfortable fits on the small end of a spatula tip. The reaction ran hot during the first hour, with a healthly reflux, then petered out quickly. It was over by two hours and was warm to the touch by the third hour. 83% yield is the highest yield I've ever gotten with an Al/Hg. I can't believe it happened with a ketoxime reduction...

The MDA/MDMA mixture is phenomenal!

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The MDA/MDMA mixture is phenomenal

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Was the mix 75mg MDA/75mg MDMA ?

"Balls to the walls" right!

Yes, it was 75/75... it included dreaming while awake, long-lasting buzz, full pupil dilation, intense euphoria... all round it's highly recommended!

After success forming MDA & PMA with the peracetic... the next target is using asarone to form TMA-2. Stay tuned! The reaction is running right now and everything looks very promising!

*excited*

How do you plan on hydrolyzing the post peracetic results?  Acid hydrolysis fucks it up.

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All paths are the same: they lead nowhere

I used H2SO4 rearrangement. What happened was a viscous canary yellow asarone glycol acetate was turned into a light brown viscous sludge. When the sludge is put into bisulfite, I think some crystals form (it's hard to tell -- it's nothing like the bisulfite reaction with PMP2P or MDP2P). I hope to form the oxime to purify it up a bit. I know that distillation without a vacuum leaves nothing worthwhile behind. Distillation of asarone epoxide does not give TMP2P either. (maybe if it's done with a mild  vacuum?)

The sludge can be aminated to TMMA-2 with an methylamine Al/Hg, but since TMMA-2 is worthless (nearly inactive), I hope to form the oxime.

Yes, the yield via this route SUCK, but if I even got a 10% yield of amine from the 150mmol reaction that would be 3.4g of TMA-2 and I'd be jumping for joy!  

Try LiI, MgBr2, BF3*Et2O, BiOClO4 or Bi(OTf)3 for the rearrangement of the epoxide...

Sounds like a good idea... I think the peracetic in DCM gives the epoxide if it's fully buffered and run at a cool temperature.

Anyways, I'm going to give this a try first. Hopefully I'll be able to form some oxime from the impure crap (and then find a way to purify it). It's just so bloody hot right now... ugh! Too bad I can't work in an air-conditioned lab.  

No oxime crystallized.  

This doesn't mean failure (I never would give up so easily), but it sure isn't a good sign. I guess what I'm forced to do is flood with water, then extract with DCM, boil it off, then scratching the tar to crystallize it. Perhaps even that won't work, in which case the project will be abandoned. (with the final saying, "TMP2P  can be made via the peracetic, but in low yields and the clean up is problematic")

I hope not to repeat that sentence anywhere in this thread.

I isolated a beige sludge. I'm wondering if I should aminate it or not, might just be a waste of time.

I threw 5g of the sludge into an AcOH Al/Hg. I'll have the results tonight or tomorrow. I'm really expecting failure. I'll work the Al/Hg up just the same, but, this story looks to have a sad ending. I really don't believe that asarone glycol or asarone epoxide can be turned into asarone ketone with anything more than very modest yields with H2SO4...    

Besides nitroalkenes and wackers, are there any other techniques for making asarone into a ketone? Or in my desire for another molecule, should I find another alkene to try the peracetic on?

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Besides nitroalkenes and wackers, are there any other techniques for making asarone into a ketone?

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The classic method of making asarone ketone is via the dichloride/dibromide; it's been mentioned here (FSE) and now at:

https://www.thevespiary.org/rhodium/Rhodium/chemistry/mdp2p.dibromide.html

That 5g of sludge that was thrown in, was assumed to be 2.5g pure stuff (and ab2's ratios adjusted). Well, the AcOH Al/Hg went along fast & hard as usual... cooled down... then when it came to extracting, I titrated with dilute hydrochloric acid (using methyl orange as the indicator) then distilled water, then boiled that off. I had ~2.5g of stuff. Then I added about 20ml of MeOH, and boiled it to dissolve the crystals. Then poured off the boiling MeOH (leaving behind some traces of white salts) into an evaporating dish and put it onto the hot plate. Well, I fucked up and spilled about a third of the MeOH onto the hotplate... oops. Heh... my hands are a bit shaky from trying to quit GHB... anyways, I finished evaporating it down, sat it in 10ml of acetone, filtered it and was left with 1.4g!

I don't know about you, but that makes me really happy. I want to make sure everyone hears this:

TMA-2 can be made via the peracetic oxidation & oxime reduction! (*)

I suppose I should bioassay this stuff first, eh? I think my head has had enough amphetamines for a while, so it might take some time to find someone who's willing to sample 100mg of it or so....

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(*) Yes, the yields suck in this example. But understand a few things: 1) the ketone was not vacuum distilled 2) the oxime was not properly crystallized 3) the batch size was small, while the glass was big 4) some boiling meoh with amine was lost to the ground

Congratulations! Yet another pioneering synthetic route... And we have struggled with this off and on for five years to no avail. Now something has finally happened! All that's left is to push the yields over 50% and after that most people should be satisfied.

TAKE AWAY THESE HALLUCINATIONS!

arrgh... they're over powering... it's a definite +3 and I wasn't ready for this kind of trip tonight!