i'm definitely going to scrap EtOH in favor of MeOH next time and increase the volume and concentration of the NaOH solution as well, it'll be awhile but i'll post the results when i run it

you're right the combo of relaxation (mdma) and stimulation (mda) is incredible.  reminds me of a much milder version of a candyflip, the relaxtion (mdma) and stimulation (lsd) combine to give you bodily sensation unlike anything else, the negative aspects of both are canceled out by one another and seems like you only get the positive effects plus unique new facts you don't get with either by themself. 

You don't have to let the oxime crystallize, but yields will be slightly slower.  Wash it with 1M HCl, this should help.

Any ideas why the oxime is a real pain in the crystallizing ? I've noticed that even Chromic who ran many many trials didn't always adopt the exact same strategy after reflux...If I'm not mistaken, the reaction is REALLY REALLY sensible to ketone purity. Damn the oximation part suclks. I'll have some numbers the day thins crystallize/dry 

yeah the oximation is actually the most finicky reaction that exists for our ketone that i'm aware of (that and adduct formation are both very picky about pure ketone, nice shardy adduct crystals only come from really pure ketone, whereas other ketone gets chicken fat crystals).  ketone purity is critical for the oximation.  chromic and madpro both talked about how it took so long for the oxime to solidify.  the h oxime solidified over the course of one day for me, but the mdp2p oxime took like a week.  i only did one thing differently, after the oximation, i washed the h oxime with 20% AcOH, then washed it with distilled h2o to remove residual AcOH.  for the mdp2p oxime i skipped the 20% AcOH wash because i found it unnecessary, the oximation procedure i followed stays at a ph of 7 the whole time so i saw no need for acid or base washes.  now akcom recommends for you to wash with HCl and that makes me wonder if there is some logic i'm missing with the use of acids to wash the oxime.  all's i know is i washed the h oxime with 20% AcOH and it solidified the same day piece of cake.  next time i run this reaction (won't be for a little while), i'll wash with 20% AcOH again and see if it makes a difference

Hey sorry guys, didn't get back to ya sooner.
No idea why it works, but it helped my MDP2P oxime crystallize significantly quicker.  Hours instead of days

nice write-up RoidRage!  didn't have time to try the acid wash on the oxime this time around?  next time i do this reaction i'll try an acid wash per akcom's recommendation b/c i noticed the same thing (oxime drying faster/easier) except with a different oxime, probably won't be for another 1.5-2 months before i give it a shot though.

nice work, 78% w/w is a great yield, that's better than any of my nitro al/hg yields

Still early a bit to tell, but seeding the post-reactio content with some dryed oxime seems to REALLY HELPS with crystallization. Didn't get to wash with the acid this time since it dried pretty fast. I will post another small write-up once it's completely dried. But it seems good again; 35.9g oxime from 40g ketone, and there is still a second crop of about 2-4g which is currently drying  

Oxime has been dried...40.5g dryer-than-usual oxime from 40g ketone I'm starting to believes that this path to MDA is not that bad afterall

nice work, 100+% w/w yields on the oximation mean some good technique is being employed
if you unlock any new tips on the reduction let us know.  at some point later this year i'd like to use this route for apiole and/or myristicin

Been a long time since I haven't posted anything but it doesn't I'm not doing any work

 Below are my last and biggest oximation + 2 reduction runs. Gonna resume them since the procedure used is exactly the same than for the run I posted a detailed write-up for excepting for minors modifications While I seriously hated this damn reaction 3-4 months ago, I've come to the point that I've actually optimized it enough to always get great and reproductible yield. On top of that, the reaction isn't really capricious and runs smootly. I've also noticed that the reaction doesn't need to be refluxed for 3 hours. So far, I've tried doing it for 2h30 and yields aren't hurt. Only downfall is that It uses a ridiculous amount of aluminium but I've noticed that even after basifying the post-reaction mixture and letting it sit for hours, there is still a a lot of unreacted aluminium so there is probably a lot being overkill. Chromic probably used that much initially to be sure that the oxime is fulled reduced to MDA. At this point, I could still optimize the reaction by following the reaction with TLC to know what the outcome of the reaction is depending on the amount of aluminium used. In the end, if N-Hydroxy-MDA is EXACTLY the same as MDA, the reaction should be ran with the minimum amount of Al required to completly reduce the oxime. I also think that the two 5% NaOH washes of the non-polar solvent Chromic used are totally useless. Only reason I see he did that was too neutralizes the remaining acetic acid but I'm 100% positive it's already completely neutralized by the post-reaction basification. The toluene phase can be washed with distilled water or more brine.


EXPERIMENTAL RESULTS



OXIMATION

40.0g Ketone +  19.6g Hydroxylamine HCl + 17.6g Sodium Carbonate + 170ml MeOH + 34ml dH20. 2 hours reflux.  Added ??ml H2O.

YIELD AFTER DRYING FOR A WEEK:  40.5g Isosafrole Ketoxime (97% Theorical / 101% w/w)




FIRST REDUCTION

30.0g Oxime + 43.0g Aluminium Foil + 118g Glacial Acetic Acid + 500mg Mercuric Chloride + 585ml MeOH + 118ml H2O. BASIFIED with 423g NaOH + 940ml H2O. EXTRACTED with 1x  400ml +  1x 250ml Toluene. WASHED with  1x  700ml 5% NaOH + 1x 700ml Brine.  ACIDIFIED with 12ml HCl + 150ml H2O

RAW YIELD:  24.5g MDA Hydrochloride  (71% Theorical / 82% w/w)




SECOND REDUCTION

30.9g Oxime + 43.0g Aluminium Foil + 121g Glacial Acetic Acid + 500mg Mercuric Chloride + 650ml MeOH + 140ml H2O. BASIFIED with 436g NaOH + 1000ml H2O. EXTRACTED with 1x  400ml +  1x 250ml Toluene. WASHED with  1x  7? ?ml 5% NaOH + 1x ?ml Brine.  ACIDIFIED with 12ml HCl + 150ml H2O

RAW YIELD:  23.0g MDA Hydrochloride  (67% Theorical  / 74% w/w)

Was the 500mg HgCl2 a typo?  That seems like a lot.  Have you tried using less?  Anyway, awesome results.  Nice to see some solid info on here!

very nice work!  i'm going to follow your suit and use MeOH next time i do a run.  have you tried washing the oxime with 10% AcOH yet?  i did this with a different oxime awhile back and complete drying of the oxime came easy as akcom stated.  i'm going to do a wacker this month and later this month or next month i'll prepare the isosafrole ketoxime and test the AcOH wash on it, see if it dries faster like the oxime did.

one thing to keep in mind if you want to lower the amount of al foil and shoot for MDOH is that i heard freebase MDOH is a solid, so it's possible it might precipitate out as a solid in certain solvents.  i'm not sure what it's soluble in (probably nonpolars just like mda freebase), but there's a chance it might precipitate out of the reaction solvent and basified water possibly.  i really have no idea what it's soluble in but i figured i should let you know that it's a solid at RT just so you know to keep an eye out for that in case it actually does precipitate out and you wonder WTF is going on lol.

i've only done this reaction once and i wouldn't recommend you follow my parameters because as you know from my post on page 2, my yields left something to be desired.  you can lower the amount of aluminum though because per my calculation you're using a 10.26 molar excess of aluminum compared to the ketoxime.  when i ran the oxime reduction i had a 8.59 molar excess of aluminum to ketoxime and at 40 min's into the reaction (40 min's after the addition of the ketoxime) all of my aluminum was pretty much gone there was only a very little bit left which remained until i basified with 10% NaOH solution (next time i'll use a more concentrated solution to change the alcohol/water layer's density because separation of toluene when doing extracts took awhile to separate).  but anyway, this dilute solution was enough to get it to ph 14 and took care of the minimal amount of aluminum that was left.  on the topic of the amount of hgcl2, yeah you can use less.  you used a 0.0118 molar equivalent of hgcl2 compared to ketoxime.  i used a 0.0046 molar eq of hgcl2 to ketoxime.  i also noticed you used a ~12 molar excess of AcOH to oxime, I thought only 10 molar excess was needed?

just in case you don't have this data, here is some info in case you need to do molar calculations:
Isosafrole Ketoxime = 193.215 g/mol
MDOH freebase = 195.22 g/mol
MDOH HCl = 231.68 g/mol
MDA freebase = 178.7 g/mol
MDA HCl = 215 g/mol

quick question, do you do an a/b?  the one run i did, i skipped the a/b and titrated in IPA, reduced the IPA, then flooded with acetone and vac filtered followed by some acetone washes.  this usually gives me white odorless mdma when doing the nitro al/hg with no a/b.  however the mda i got was pink/red, very impure.  i had to recrystallize it for it to be acceptable.  do you just titrate in water and evaporate it with a fan?  i think i'll either have to do an a/b in the workup for the oxime reduction or i'll have to titrate differently due to the impurities having apparent different solubility than the impurities from the nitro al/hg.  also i wonder if the reflux is necessary at all, madprossor got good yields by stirring for 5-6 hours instead of refluxing at all.  chromic played around with reflux vs no reflux also, notes on the first page.  but your yields are golden, i don't think there's anymore optimization you can do aside changing variables to make the reaction even easier to run.  the only thing gained by reducing the amount of aluminum and playing around to see how necessary the reflux is, is just to make the procedure easier.  as far as yields go, you got it nailed.  feel free to drop your amount of aluminum to 10 molar eq instead of 10.26, that won't make much of a difference i know, but if you drop it much further down to like 5 molar eq then keep in mind what antibody said.  he said sure you can drop it down to get a larger ratio of MDOH and lower ratio of MDA but he also said that overall yields of product is higher at 10 molar eq compared to lower amounts.  he got 72% w/w yield of MDOH when using 5 molar eq of aluminum compared to 81% w/w yield of MDA when using 10 molar eq of aluminum.  i wouldn't change a whole lot of variables in one go, otherwise you won't be able to pinpoint the reason for the change in yields - if there is one.  if you want to drop the amount of aluminum then maybe you shouldn't play around with the reflux, reflux it the same as you've been doing, and just drop the amount of aluminum.  that way troubleshooting is easier if the necessity for it arises.  whenever i do my next run i'll be sure to post the details here as well but it probably won't be for a month.