Bright Star / Al/Hg/MeNH2 Questions

[Neron]

The hypothetical synthesis shown below is what I have combined out of Bright Star's excellent piece of work and Dr. Gonzo's awesome nitromethane route to the finished product.

Distillation of Sassafras oil to yield pure Safrole
Under vacuum, slowly raise heat until Safrole starts coming over; record temperature
Switch flasks and then heat to ~10° under where the Safrole came over

RXN: Wacker Oxidation of Safrole -> MDP-2-P
In a 500mL RBF, put 300mL DMF, 50mL H2O, 120g p-Benzoquinone, and 2g PdCl2
Start magnetic stirrer on slow
Mix 160g Safrole and 50mL DMF and drip into the flask over 30 minutes
Solution should turn a very dark red-orange
Continue stirring for 7 hours
Flood rxn mix with slightly acidic water and mix contents thoroughly
Decant organic layer and save
Wash aqueous layer with 2x100mL DCM and save
Combine organic layer and DCM washes and wash with 2x150mL 10% NaOH
Decant organic layers and save

Distillation of rxn contents to yield pure MDP-2-P
In a 500mL RBF goes the impure MDP-2-P and boiling stones
Weigh receiving flask and set up to vacuum distill
Turn up the heat to where the Safrole came over under vacuum
Release vacuum and replace receiving flask; start vacuum slowly
Maximum theoretical yield ~120g pure MDP-2-P (?)

RXN: Al/Hg/Nitromethane Amalgam of MDP-2-P -> MDMA
On a 2L 3-necked RBF, plug one neck and place a condenser in the center neck
Prepare 27.5g Al foil and add to flask
Dissolve 400mg HgCl2 in 750mL MeOH
Mix 25g MDP-2-P, 20g Nitromethane, and 25mL MeOH in addition funnel
Pour the MeOH solution into the flask and turn on the condenser
Open valve on addition funnel to about 1 drop a second
Stir briefly every minute
After the flask starts heating up, leave the stirrer on continuously
Adjust the flow rate of the funnel accordingly
When the rxn starts to slow down, add another 75mL of MeOH and let sit for about an hour
Mix 700mL H2O and 262g NaOH in a beaker
Dump the rxn contents into a 4L beaker (add MeOH to loosen sludge)
Add the NaOH solution to the beaker
Stir the mixture for about an hour
Add 500mL toluene and stir for a few minutes, then layer
Wash the sludge with 2x250mL toluene and save
Combine toluene layers
Wash 2x with saturated Sodium Bicarbonate, once with saturated NaCl, and once with H2O
Drain into an extremely clean beaker with 35g anhydrous MgSO4, stir, and let sit for 30 minutes
Filter into a very clean beaker and wash the MgSO4 with a little more toluene
Gas with anhydrous HCl until MDMA precipitates out of solution
When solution becomes cloudy, cover the beaker and place in the freezer for half an hour
Vacuum filter
Continue to gas the toluene until no there is no more MDMA precipitate
Chill, filter, and dry
Maximum theoretical yield ~90g pure MDMA (?)

I have a few unanswered questions, though.
Can I use Xylene instead of toluene?  Are there any other chems that I could substitute with more OTC products?  Any advice on the best way to get ice-cold water running through your condenser, instead of just cold tap-water?  I'm trying to eliminate variables so I can come up with a good 'hypothetical' yield the first time, so any corrections/additions/etc. would be helpful.

Any comments on this would be greatly appreciated.

[terbium]

Any advice on the best way to get ice-cold water running through your condenser, instead of just cold tap-water?

Any number of schemes would work such as a recirculating pump pumping the water from a bucket, through a copper cooling coil in another big bucket of ice and thence through the condenser.  Just a different type of condenser might be as effective as ice cold cooling water. A Friedrich
condenser is much better at holding back a strong reflux than a Liebig or Allihn condenser. A Friedrich condenser, though, should not be used in a vacuum distillation.

[DiethylEtherMan]

With the Benzo wacker...use MeOH. Its easier to get, for my grandmother, at least. And she's almost 80 now.

You don't need that much HgCl2...use 200mg.

Like terbium said, just get a 5 gallon bucket, fill it with ice and water, throw a pump from the aquarium, or whatever, in there, rig it up and bang, you all good.


Yes, Xylene works great. Make sure you chill it before you gas. The only drawback, is it takes longer for the xtals to dry, but who gives a shit. Toulene is getting hard to get nowadays. Somewhat!





If some of us were not so far ahead, the rest of you would not be so far behind!

[Neron]

With the Benzo wacker...use MeOH. Its easier to get, for my grandmother, at least. And she's almost 80 now.

So I would be replacing the 300mL and 50mL DMF portions with an equal amount of MeOH?

[VinnyC]

Well a little late (DOH!) but yes that is correct. It worked for SWIM!

Hey, what the frig happened? My post count got lost and I am a stranger again Stoni, any ideas? If this is it, thats ok, I usually have something to say, mostly nonsense but something atleast
Cheers!

"My arrival was poorly timed..." Fear & Loathing

[Neron]

A few more questions:

What's the optimum addition rate for the Safrole?

Will this entire mess stir in a 2L rbf with a 1-1.5" normal stirbar?

Also;

I've been looking into the Spiceboy SRV procedure, and one thing that tempted me was no use of p-Benzoquinone.  It seems that the metal catalysts would be resuable after this reaction, because the only reason they couldn't in the p-Benzo wacker was because it's too hard to separate from the hydroquinone afterwards.  Do any bees out there have any experience with this?

[VinnyC]

Honestly SWIM does not think its really matters all that much for the addition, just try to keep close to the 30 min mark. honestly I can't tell you for sure about the mix fitting in the rbf. SWIM used a 1 quart **rex measuring cup to do it in. He had no probs but the stirbar will be very slow (at times due to the solids building up) and jiggly ( he was in another room for the whole process and could just mute the tube to hear it and know it was still going )

Can't help you with the last ? though.... sorry.

Peace!

"My arrival was poorly timed..." Fear & Loathing

[dirtybastard]

Ol'ditry does a few different things, but nothing drastic

1. pre-stir the PdCl2 and the DMF overnight, in the AM add the benzo and the h2o. stir an additional hour
2. add the safrole over 1 hour. no sense to rush things.
3. apply heat (reflux) for 7 hours. seems to work well

Gonzo's shit
1. if you can find a 3L 3neck RBF use that. much more "relaxed" reaction, but 2L will work.
2. you'll find the need to add more MeOH the shit gets pretty thick. just add as needed. Unless you have an overhead mixer, odds are the stirbar wont be able to handle it at some points. Ol'dirty stirs by hand if needed.
3. let the NaOH and the rxn mixture cool down before mixing. NaOH will take an hour or two to cool.
4.ODB hates the Bicarb wash. just uses the water and the NaCl washes. Im sure he'll get flamed for doing that, but the results are magnificent.
5. ODB also finds that gassing can be difficult. suggestion is to seperate the dried toluene into smaller portions (1/5 batch sizes) that way if you fuck up, you can try again. Gassing is an art. swirl the gas stick around, pulling it in and out of the toluene until you can see the xtals, then keep it in. you'll notice on your 3rd or 4th gassing the xtals get yellow in color. just dump that crap then.

xylene will work. uses NaCl and ice in a bucket to get really cold water, then use a pump.

Ol' dirty thinks you have been doing your homework, you have all that you need, just remember to take your time, not to rush. Hurrying though a proceedure will surely kill you.

Oh and distilling the ketone is a motherfucker. ODB takes around 8 hours start to finish. when your oil bath is nearly in flames the ketone begins to come over (~220C)
if you have ever worked in a kitchen you'll be reminded of the hours you slaved over the deep fryer.

good luck and good eatin'

I have no data to actually back up what I say.

[Semtexium]

220C?!?  What the fuck!?!  If you cannot distill ketone at a temp of under 190C get a new source of vac.  Even a fridge compressor that costs like $15 can have your ketone coming over at between 135C-175C.  I don't think you've ever had the black snake of death show itself in your flask.  Imagine if you will, you are 5/6 of the way thru your ketone distillation and you can see a nice flask 2/3 full of freshly distilled ketone, then you turn your head for literally a MOMENT and turn back to see that your WHOLE distillation setup, from the boiling flask all the way to what was your flask full of crystal clear ketone is full of black foam carbon shit.  Not only ruining your goods, but requiring a substational cleaning with acetone to get your glass ware usable again.  Seriously, if you can't pull your ketone over at less then 190C get a new source of vac.  Aspirators and fridge compressors and vac pumps will all pull enough of a vac to do that, if yours doesn't, then get something else...

 

[dirtybastard]

thanks for the tip. I have seen the black snake. it blows. the crispy bastard climbs its way from my rbf into the distillation tube (im fucked up right now, what the hell is it called?) but fuck it, it obviously worked. Guess swim shoud spend some profit and buy a new pump.

god bless the hive!

I have no data to actually back up what I say.

[RoundBottom]

no, instead, follow MMs MeOH Benzo Wack.

http://rhodium.lycaeum.org/chemistry/wacker.benzo2.txt

[ChemReack]

Well yes you can just replace it like that, or like roundbottom said you can go the MM route.
Hey DEM ur granny is freaking ingenious...laughs

"I always tell the truth, even when I lie"
                                         Tony Montana

[DiethylEtherMan]

Yea...my grandmother would go along with the MM synth. As these two said, but then again, she's not familiar with the other. MM's has always worked great.

If some of us were not so far ahead, the rest of you would not be so far behind!

[Neron]

The only major differences I saw in Bright Star's vs. MM's is the extra washes and the addition of the ketone buffer.  I think I'm gonna stick with the simpler route.

Another question.  Say you have 3 fractions in a flask, and you need the middle one.  We'll say it boils at 100°C under vacuum.  The first and third fractions boil at 90°C and 110°C, respectively.  Would it be possible to heat to 100°C, collect the first and second fractions, then switch the flasks and heat to 90°C and distill off the first fraction, leaving only the 2nd?  Comments always welcome.

Oh, yeah, and seeing as how I'm pretty new to the Hive, I just want to congratulate all of you on a marvelous creation.  This is a great resource to all involved.

[foxy2]

Yes that is possible for your fractional distillation.

Or you could take the first fraction, change reciever flasks and then collect the second fraction while leaving the third in the boiling flask.

The sceme I outlined will proceed much smoother in real life as it only requires a quick change of reciever flasks.  Your method is more involved and in practice more difficult.

Do Your Part To Win The War

[Neron]

Or you could take the first fraction, change reciever flasks and then collect the second fraction while leaving the third in the boiling flask.

That would work fine, except I was dreaming about doing this in a situation where I won't know the exact bp's of the (more than three) fractions involved.  I think that would make my method easier, at least for me.

Are there any old bees out there who would be interested in proofing/revising this synth with me to try to create a kind of 'successor' to Bright Star's wonderful piece of work?  Minimum equipment and reactants with easy to follow instructions and good yields?  I think I have this synth worked out to only 6 chems that you wouldn't find at your local hardware store (MeOH, MeNH2, p-Benzo, PdCl2, HgCl2, and DCM).  Any comments are always welcome.  Thanks.

[foxy2]

Well you don't need to know exact temps.  How would you know when to switch the flasks with your setup???
They are the same.

How to know
There will bee a pause in the distillation(distillate flow rate), the temperature at the head of your column will rise and then a new fraction will begin to come over.  You switch recievers at this pause/temperature shift.

Do Your Part To Win The War

[Neron]

Good call.  Sorry, I just kinda misunderstood your post.  I got it now, though   .

[Neron]

<From MM's Benzo Wacker>

Don’t try to recycle the PdCl2, as it is too difficult to separate from the hydroquinone to be worthwhile.

Is there a way to separate the two at all?  There has to be something hydroquinone is soluble in that PdCl2 isn't...

[VinnyC]

Hey Semtex... I absolutely agree with you about the temp. SWIM got lucky that time. He also feels that he did not do a very good job at sealing the aspirator as best as possible. He would use something better, if some extra funds come around

Cheers!
"My arrival was poorly timed..." Fear & Loathing