hell yeah, congrats to you!  that's what i like to hear    i'm glad you went through with the al/hg, sounds like your red ketone was much more pure than mine was when i played around with red ketone.

the buffered is actually the preferred route because the excessively acidic pH in the unbuffered route is prone to side reactions like over-oxidation being the primarily one if i remember correctly.  the buffered peracid oxidation stops the oxidation at the epoxide/glycol stage whereas the unbuffered oxidizes further to the glycol/ester stage and a small percentage of ester gets oxidized further into a worthless compound, i can't remember the mechanism for the side reactions, so i can't get any more descriptive than that. i'm probably lucky to have remembered as much as i have. anyway both buffered and unbuffered work beautifully but the buffered peracid is the generally accepted route for "higher yields"

hopefully next time when you include basic washes after the pinacol rearrangement (and then brine washes after the basic washes) you hopefully should distill some yellow/green oil without the presence of the red but i'm very glad to hear it worked out.

the toluene smell that lingers on the gassed product, yeah this is something that perhaps isn't talked about but that is to be expected.  residual toluene is lingering on the surface of the crystals.  just chop it up and spread it thinly across a plate/etc/whatever so there is more exposed surface area to the air and sometimes a heat lamp is utilized but not necessary to drive off the lingering toluene.  if you ever gas in xylene you'll see that xylene is far worse than toluene, xylene lingers for what seems like ever.  it's good to keep in mind that there will be small amounts of solvent within those tiny little crystals.  whenever you crystallize, the crystals are formed in solution and a small amount of whatever solvent the crystals are formed in will be trapped within the crystal lattice.  more than a couple times i've had gassed product that has had its surface washed with acetone per usual and no longer smelled of toluene/xylene yet i allowed a sizable dose to dissolve on my tongue (gross i know but it was on purpose to test this) and there was a very slight burning on my tongue which signals that there was still toluene/xylene present.  i couldn't smell it and it had been washed with plenty of time to evaporate as well so perhaps it was that little bit that was present within the crystal lattice that gave the slight burning sensation upon the product's dissolving on my tongue.  so i recommend that if you gas, you recrystallize.  i recrystallize from a minimal amount of boiling anhydrous IPA, cover the beaker that has the dissolved product with minimal amount of IPA with aluminum foil and pinch the al foil around the edges of the beaker to prevent moisture in the air from being absorbed by the anhydrous IPA (cuz anhydrous IPA loves to suck up water from the air and you don't want that), let it cool until it's warm to the touch then add anhydrous acetone (4x volume of acetone in relation to amount of IPA used), then recover the beaker (or stopper the flask if you use a flask) and put it in the freezer.  after 30 min's you should see some crystal formation happening but i leave it in for 8-24 hours - i prefer 24 hours just to be safe.  then either decant or vac filter.  the reason for trying to keep water out of the IPA/acetone recrystallization is cuz the product is highly soluble in water as you probably know and the more water that is in the IPA or acetone, the more losses in yield there will be cuz it will stay dissolved instead of recrystallizing.  if you lose a large amount from the recrystallization then just evaporate the IPA/acetone that was used to recrystallize with, the remaining product will still be in there.  i usually just pour it into a pyrex pan and put a fan over it in a well-ventilated area with no ignition sources.  IPA and acetone are so volatile they will evaporate very quickly and you will yield the missing product although all the impurities will be with this reclaimed "missing" product so you will def have to further purify it if you reclaim it.  by recrystallizing you are removing other impurities as well but you are basically swapping the toluene being in the crystal lattice for IPA/acetone being in the crystal lattice.  of course you wouldn't drink IPA/acetone but those 2 are far more healthy to be in your body than toluene would be.

during the al/hg was the smell you mentioned like rotten tuna? if so it would be methylamine.  it sounds to me, from the extreme loss of MeOH and the ability to smell what's in the flask, that you had insufficient cooling or perhaps an insufficient condenser for the reflux or your drip-rate was just entirely too fast and your condenser couldn't keep up with the evaporation rate of the MeOH.  yeah the MeOH reflux will be pouring down like rain from the reflux condenser at the peak.  although on a few occasions, after being quite familiar with the reaction, was able to pace myself in a way so that the reflux never went over 2 drops per second and yet i still had plenty of time to add all the ketone and the yields were as they should be.  the al/hg is just one of those reactions you have to get a feel for, CheshireCat has some awesome al/hg-related posts over at the-collective, the website that lugh linked.  yes you're right don't be fooled by the calm beginning, there is a bit of a lag when the al/hg starts.  some people think that since it's calm they can go full throttle with the drip-rate and they add it too fast, only for the al/hg to eventually catch up with that drip-rate then it gets out of control.  the frothy solutions climbs up the condenser and spews out like a volcano all over the place - it's a highly flammable and very poisonous solution, not good!  if you use an oversized flask like you did and don't run the risk of the reaction's frothy solution overflowing into the condenser then what would happen instead is the MeOH would evaporate at an incredible rate and choke your condenser or start to escape from the top of the condenser into the room you're in.  with all the MeOH loss and all the MeOH that is constantly being evaporated, it can leave your al/hg too dry if not enough MeOH is present.  if the al/hg gets dry it will start to smoke and things can potentially get bad.  you definitely want to get the highest yield you can but faster isn't always better.  also if you're just learning the reaction then doing it too slow and having unreacted/wasted ketone is perhaps a better alternative to adding it too fast and turning your condenser into a volcano spewing that toxic crap or if you use a large oversized flask then as i said, the MeOH evaporating too fast and running the risk of the al/hg getting dry, smoking, etc.  it's actually best to start out with a slow drip-rate and stick to your guns, start out at like 1 drop per second once you notice the amalgamation is ready.  then you'll notice that eventually (patience!) the al/hg will become more vigorous and the reflux drip-rate will catch up with your addition drip-rate, once the reflux's drip-rate gets faster than your addition drip-rate then speed it up to match the reflux's drip-rate.  i wouldn't recommend over 3 drops per second though, some people do like BaalChemist and i'm sure many more, but ~3 drops per second is plenty sufficient for a maximum drip-rate IME.  so you only match the reflux rate up to a certain extent.  i've run al/hg's where i use the rule of matching the reflux's drip-rate but i match it with only 1/2 speed for the addition rate - ie: if reflux is at 2 drops per second then my addition was 1 drop per second.  just stick to one of those rules starting out and get a feel for how that changed the reaction compared to this last time you did it.  then the time after that perhaps try it a slightly slower or faster rate and see how that changes the al/hg.  basically the slower paced the addition rate is, the less vigorous the reaction and the slower the aluminum gets consumed which means you'll have a longer window of time to add in your ketone.  the addition rate directly determines the reaction rate when it comes to the al/hg.  another factor is the use of external heat, i definitely do not recommend using external heat unless you're running the al/hg in microscale or unless we're talking about kicking off antibody2's oxime al/hg for mda.  but with the MeNO2 al/hg at any scale of 10+g of ketone, external heat will make everything entirely too crazy and will make the aluminum be consumed at a much faster rate which will give you a much smaller window of time to add in all your ketone.

if the al/hg gets real wild/hot it's not damaging because since MeOH is the reaction solvent, the maximum temp is 65C - the bp of MeOH, unless it gets superheated.  the hotter it gets the more the MeOH just evaporates immediately so really efficient cooling and efficient condenser is real important for the reflux.  some bees run the al/hg as fast as they can without losing control, i used to do it that way starting out (getting up to 4 drops per second or so, it gets hard to count at that rate) and then progressed to a slower/calmer reaction (2-2.5-ish drops per second max, yet addition always finished in plenty of time, it's all about how you pace everything and how you let the reaction progress).  it's a little easier on the nerves and i found the yield to be the same if not slightly better.

regarding the gassing, most bees that i'm aware of gas twice but it just depends on how heavily you gas the solution.  when you see the solution start to turn yellow that means you've added far too much HCl and yeah it gets messy if there is product in there when it turns yellow.  it can stain the product and if you overgas even further it'll make your gassed product discolor even further as it oils out.  trying to get everything in one gassing session would be ideal but IME there is always at least a little bit left to precipitate from a 2nd gassing but it just all depends on technique.  titration is another option, it's all about personal preference b/c there are pro's and con's to both ways.  FYI if you plan to distill and re-use the toluene that you gassed in, for future use as an extraction solvent in the al/hg, then you'll want to do this:  gas the toluene until you've recovered all your product and vac filtered so now you're left with just the toluene with no goods in it (containing impurities still of course).  then wash the toluene with an NaOH solution, the concentration of the NaOH solution depends on how much HCl gas is in the toluene.  the NaOH wash is to neutralize residual HCl gas present in the toluene.  after you washed the toluene and neutralized all the acid then dry the toluene with a desiccant like you do before you gas it, then distill the toluene.  if you were to just distill the toluene as-is without the NaOH wash then you can potentially distill it with HCl still in the toluene distillate.  then when you go to re-use as an extraction solvent for the al/hg, the toluene is acidic so it might cause problems.  most likely, if you follow MethylMan's write-up then there is a large abundance of NaOH solution so the residual HCl in the toluene would form base salts (HCl + NaOH = NaCl + H2O) and there will still be a vast abundance of NaOH solution so no worries.  but just wanted to toss that in just in case.  some newbees are unaware of gasses being able to distill over along with the solution they were in originally.

get rid of that toluene smell and enjoy!     then if you have plenty of oil to work with and get bored, shoot for mda by running the mdp2p through an oximation then reduce the oxime via antibody2's al/hg.  the mda/mdma combo is just incredible.

good call, the first time i used to ever get ahold of a new compound i performed a mp test and reagent test as well.  certainly doesn't hurt.

the second gassed product, yeah one of the first couple times i gassed that same thing happened to me.  it was during the 2nd gassing as well, i overgassed and everything turned yellowish/orangish and stained the product that was in there.  it was a bitch trying to get the product back to white.

is that 87% yield w/w or molar?  the mdp2p made via peracid has a reputation is being high yielding in the al/hg, more-so than the benzo wacker because the benzo wacker produces more impurities and a good bit of isosafrole - the main competing side reaction in the benzo wacker to mdp2p oxidation is isomerization to isosafrole... the peracid route doesn't have that problem.  yep, gassed product in toluene or xylene gives way to incredibly tiny crystals that appear like a fine powder almost.  when dry in a pile you can see the crystalline nature (sparkle) of it.

yeah i dicked around with the same "more than 1 dog" method as well back when he first released that info.  at the time, the kinks were still being ironed out and to be honest i researched the reactions pretty well but never really pursued it with much motivation, only gave it 2 half-assed attempts and said fuck it.  i had been eyeballing the oxime reduction for some time and i just scrapped the melon stuff in favor of antibody's oxime al/hg because it was just so much more convenient.  scale your peracid up x2 in size, get your ketone and split up the vac distilled ketone into 2 portions.  1 portion for the MeNO2 al/hg and one portion for oximation then antibody's al/hg.  just so much more convenient imho.  not to mention the mda from antibody's method doesn't come out with questionable purity like i've heard from a few people about the uhhh melon-related choice.

yeah methylamine is a truly horrendous stench.  it smells like a dead hooker's pussy mixed with rotten tuna.  not a smell you would want getting into your clothes that's for damn sure lol

at the bottom of this paragraph is the url for the post that me and RoidRage started on antibody2's oxime al/hg.  you would just go through your normal procedure until you get to your vac distilled yellow/green ketone produced via peracid.  instead of tossing it in the MeNO2 al/hg you run the oximation, once you have a clean, dry oxime then you run antibody2's al/hg on the oxime.  that thread has progressed into a very long thread but the plus to that is that it should have everything you need.  the only thing you'll need that you probably don't already have is glacial acetic acid and hydroxylamine sulfate-or-hcl, doesn't matter.  the only thing that isn't included in that thread is the particular oximation i always preferred doing but there are several ways to run the oximation.  in fact if you have experience successfully running an oximation for the "more than 1 dog" route and if you got a solid white oxime from it, then you're good to go.  just follow that same procedure except substitute the ketone you get from peracid instead of the uh.. melon, just make sure the molar ratios stay the same.  the molar amount of your new ketone will have a different weight than the molar amount of the melon stuff.  but you can use the same exact procedure.  at any rate, here's the link http://127.0.0.1/talk/index.php/topic,1459.0.html

Melting point? Wide range..

that's a good yield all things considered.  if the product is still wet with toluene you may lose some weight as it dries.  the peracid produced ketone is possible of 100+% w/w yield, much better yields than what is possible from the benzo wacker.

as for dangerous by-products being formed, that's impossible for me to say for sure.  we'd have to know what the transmission fluid colored stuff is first.  maybe someone here has seen what you're talking about before and can chime in on that one hopefully.

about the oximation - no you don't want to use the melon aldoxime for the MeNO2 al/hg and you don't want to use the mdp2p ketoxime for the beckman.  if you did that i'd have no idea what the resulting compound would be.  i didn't mean to use mdp2p as the starting compound instead of the melon stuff then go through the beckman and hoffman.  also don't use the melon stuff or its oxime in any al/hg's.  what i meant was strictly for the oximation.  because the melon stuff's first reaction is an oximation.  unrelated to that, if you wanted to use mdp2p to get to mda you want to make the mdp2p oxime then follow antibody's oxime al/hg for mda.  there are lots of slightly different ways to pull off oximations out there.  i was just trying to make it easy by letting you know that since you have experience running an oximation to get from the melon to the melon's oxime, that you could apply that same procedure just replace the melon with mdp2p and you get the mdp2p oxime instead of the melon's oxime.  if you did that and got the mdp2p oxime then you're ready for antibody'2 al/hg for mda.  so if you took that oximation procedure that you used to use for the melon aldehyde and put it on paper.  then calculate the number of moles of melon aldehyde you used to use, then replace that molar amount of melon with an equal molar amount of mdp2p (ie: 1.25 moles melon would be replaced with 1.25 moles mdp2p), then calculate that molar amount of mdp2p into weight/grams (the melon and mdp2p would be the same molar amount but would have a different weight in grams cuz the melon stuff and mdp2p have a different molecular weight so 1 melon-stuff molecule weighs differently than 1 mdp2p molecule), if you work out that math and then scale it however you want - you now have your mdp2p oximation procedure on paper.  so you just basically modified the oxime procedure that you're used to and comfortable with from the melon days and adapted it to work with mdp2p to get you ready for antibody's al/hg - if that's something that interests you.

as far as the melting point of mdma hcl, that depends on the form of mdma hcl.  since you gassed it in a dry solvent with dry HCl gas i'd say you'd have the anhydrous salt but if there is moisture present it's possible you might have a hydrate salt of some kind.  hydrate salts contain water and add weight to the molecule so that changes the melting point temperature.  so depending whether your MDMA HCl is anhydrous or is a partial hydrate salt like 1/4, 1/2, 3/4 or a full hydrate depends on what the temp range will be.  the list below starts out with anhydrous MDMA HCl at top and full hydrate at the bottom.

MDMA HCl: 147 – 153°C
MDMA HCl•1/4H2O: soften 132°C; m.p. 135°C
MDMA HCl•1/2H2O: soften 92°C; m.p. 138-145°C
MDMA HCl•3/4H2O: soften 50°C; m.p. 90-132°C
MDMA HCl•H2O: soften 80°C; m.p. 107-133°C

As long as your freebase end product was properly base & brine washed, there should be zero harmful contams.

One had their repeatedly acetone washed salt tested by GC/MS and a purity of 99.9% was determined.

i remember Dr Gonzo, the guy who did the pictorial of MethylMan's MeNO2 al/hg, said he had his salt tested by GC/MS following the exact procedure he used in the pictorial and it was 99.9% purity.  i didn't get to see the actual analysis results though, i just read the post with the claim on it on the hive.

Hello Tox.

Not sure of a reflux ring in the column, but a decent amount of methanol did escape in gaseous form, judging by the smell and the lower level during the reaction.  Soonafter more methanol was added back in.  The best way to describe the condensor during its wild times, was "chugging".  If you can picture it condensing and wanting to drop back down, but getting a bit choked up, and than rising higher and higher.  It was released for a second, reset you could say, re-connected, and it started to breathe again.

Condensor consists of a west type (straight tube style), of the 24/40 size, and 400mm length pretty certain.  Small pond pump in ice water. 

To optimize this, it would seem to require a larger diameter tube, and longer maybe double in length or more.  Girth and length, oh oops thats something else 

After naoh added, and toleune extraction.  Washed twice with saturated nacl, and once with dh20.  The product was gassed, and no apparent odor of toluene remains.  No acetone wash is planned.   

-Interesting to hear what the red oil could be as Neil questioned as well, and what the possible products could be after amination?
-What happens if saf, or isosaf are run in the al/hg? 

87% would be with days of random drying/stirring/chopping.  This would seem pretty dry.

Yeah, column saturation can happen. In large booze distilleries they some times use choke rings spaced in the packing media to refocus the condensate towards the middle of the media and allow the lower density distillate to run up the outside.

Does your west condenser have some small inner fingers or nubs at the base to hold packing material in place? You really may want to try beads or Raschig rings and/or a cold finger just in case for future reference.

The idea of the coldfinger or dual condensors in parallel sounds good.  The coldfinger just looks bad ass  The assumption would be to place coldfinger first than the condensor.

Tox- the west condensor does not have any place to hold, just a lip where it goes in and the water surrounds.  For distillations, this leaves a little puddle that has to be titled to get that last fraction out. 

Dual condensors sounds nice too.  Instead of parallel, what about big one, than little one.  Less choking, but also limiting the gas from coming out the larger one...

Suppose it could be personal opinion or preference at this point. 

Toluene had a major excess of mgso4 added, so it can be presumed to be dry.  The gas could perhaps have moisture as h2so4+nacl is used with no Cacl dryer before gassing.  This may have to be added.  OR there is an impurity present? Maybe that is what happens with orange ketone...hrrmm.

Neil- you got PM.

in all honesty, it's notoriously difficult to dry a solvent in its entirety,

It's very simple to prepare adequately anhydrous toluene by simply fractionally distilling the azeotrope formed with water    When the distillate becomes clear it's free of water    Calcium chloride is recommended for drying toluene in Vogel's   Drying agents have differing efficiencies and capacities, it's best to consult the chemical literature when planning a procedure    The end results from the effort applied 

You can't use calcium chloride to dry toluene that has free base in it as it forms complexes with amines as documented in the attached abstract which was posted on the Hive about six months before it went offline   It can be used to dry toluene that is going to be mixed with dry free base oil for gassing    Bases such as sodium hydroxide work well as drying agents for amines