05-21-01 21:44
No 196056
Before SWIM tries to make some honey, he wants to make sure that he has a good procedure to follow. He thinks, "I'll post it to the Hive and the nice bees there will point out the bad parts and hopefully add some good ones". Feel free to post any comments/suggestions.
SWIM plans on using an oil bath through this procedure. Just thought I should mention that.
Synthesis of MDMA
RXN: Wacker Oxidation of Safrole -> MDP-2-P
In a 2L flask, add 400mL MeOH and 2g PdCl2 and stir for 2½ hours
Add 120g p-Benzoquinone and 50mL dH2O and continue to stir for 1 more hour
Mix 160g Safrole and 50mL MeOH in an addition funnel and add over 1 hour with continuous magnetic stirring
Solution should turn a very dark red-orange
When the reaction is finished, heat to 70°C for 3 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
Wash with 2x200mL each 10% NaOH, saturated NaCO3, and saturated NaCl
Dry with 50g anhydrous MgSO4
Combine organic layers in a 500mL RBF
Vacuum distill the MDP-2-P
To further purify, vacuum filter through activated charcoal a few times
Theoretical yield ???
RXN: Al/Hg/MeNH2 Amalgam of MDP-2-P -> MDMA
On a 2L RBF, place a Claisen(?) adapter fitted with an addition funnel and a condenser
Add 400mg HgCl2 dissolved in 750mL to the flask and turn on the condenser
Turn up heat to boiling, then let cool and add 33g prepared (according to the Dr. Gonzo photoessay) Al foil
Start magnetic stirrer
Mix 31g MDP-2-P, 25g MeNH2, and 50mL MeOH in an addition funnel
Open valve on addition funnel to about 3 drops a second, or enough to maintain a steady reflux
When the rxn starts to slow down, add another 75mL of MeOH and let sit for 1 hour
Mix 700mL dH2O 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 NaCO3, once with saturated NaCl, and once with dH2O
Drain into a clean beaker with 35g anhydrous MgSO4, stir, and let sit for ½ hour
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 ½ hour
Vacuum filter the precipitate and repeat process until no more MDMA is produced
Dry crystals
Theoretical yield ???
Synthesis of Precursors:
HgCl2 synthesis
Measure 20g Hg and place in a 100mL conical flask with an exhaust tube
Add 60mL conc. H2SO4 to the flask
Bubbles of SO2 will rise from the H2SO4/Hg interface
Maintain a vigorous bubbling of SO2 by adjusting the heat
A white crystalline deposit of HgSO4 will appear
The Hg should be completely reacted after about 30 minutes
Allow the reaction mixture to cool and pour off the acid
Pour the crystals into 750mL hot dH2O and filter
Slowly add this solution to 500mL saturated NaCO2 until red-brown precipitate forms
Filter off the precipitate
Repeat until there is no more precipitate
Wash precipitate with dH2O
Place in a 500mL beaker and create a suspension with 20mL dH2O
Make up a solution of 20mL HCl in 100mL dH2O
Add this to the suspension in small quantities with good stirring
Stop HCl addition when the precipitate color changes to white
Neutralize solution
Cool, filter, and dry crystals
Recrystallize from boiling dH2O to purify
Theoretical Yield 19.37g HgCl2
(I'll be trying a scaled down version of this with 1.2g Hg that I recovered out of a broken thermometer since you only need <1g anyway)
Benzoquinone Synthesis
In a 500mL Erlenmeyer flask, place 23g hydroquinone
Add 17.5mL 93% H2SO4 in 250mL dH2O with low heat until hydroquinone dissolves
Plunge flask into an icebath and stir vigorously to obtain a crystal suspension
Remove the flask and add 35g K2Cr2O7 in 60mL dH2O over 10 minutes while swirling
Keep reaction temp under 25°C
The green-black quinhydrone complex will precipitate, then change to yellow-green
Cool mixture to 5°C and filter Benzoquinone crystals
Wash with a small portion of ice cold dH2O
Theoretical yield 14g
I have a few questions:
Any ideas on the theoretical yeilds?
Is Benzoquinone the same as p-Benzoquinone? If not, how can I convert it?
I know that Xylene can be used in place of Toluene. Are there any other solvents that can be replaced?
Does anyone see any difficulties that may be involved in this? Any improvements that I missed?
trancendence through neurochemistry
(Newbee)
05-21-01 22:44
No 196065
>Any ideas on the theoretical yeilds?
I know nothing about theoretical yields, but practical yields for Safrole->MDP2P (wacker oxidation) should be high. (in your example, over 100g would be average)
>Is Benzoquinone the same as p-Benzoquinone? If not, how can I convert it?
Yes, same thing. Search for posts by spric and others on how to convert hydroquinone->benzoquinone.
>I know that Xylene can be used in place of Toluene. Are there any other solvents that can be replaced?
Yes, other some organic solvents in theory, but xylene is ideal and OTC. Learn the standard route before you try mussing with it.
>Does anyone see any difficulties that may be involved in this?
Yes. The DEA doesn't approve.
>Any improvements that I missed?
"Mix 31g MDP-2-P, 25g MeNH2, and 50mL MeOH in an addition funnel"
Is this really what you meant? (in your reductive amination rxn)
Search for Methylman, ritter, others and nitromethane. (Hive and on Rhodiums page also)
When converting hydroquinone->benzoquinone consider using KMnO4 instead of KCr2O3. (and then write it up success OR failure, cuz nobody has verified it to my knowledge)
It's nice to see you took some time writing this. Make sure you take enough time learning what exactly is happing each step of the way. And remember that even your precursor synths are toxic. (Hg, KCr2O3, even safrole of you drink it by the gallon) Disclaimer: I skimmed your writeup. Don't think just because I only commented on these things, the rest must therefore be ok.
-quicksilver-
But what do I know, I'm a newbee.
(Hive Addict)
05-22-01 06:03
No 196106
>Any improvements that I missed?
"Mix 31g MDP-2-P, 25g MeNH2, and 50mL MeOH in an addition funnel"
Is this really what you meant? (in your reductive amination rxn)
What's wrong with this? It's a perfect 1.25X scale-up of MM (except for the MeOH in the addition funnel). Works fine for my friends...
z
"And if we don't get some cool rules ourselves, pronto, then we'll just be bogus too!"
(Hive Bee)
05-22-01 11:47
No 196181
Yes, this procedure is for using nitrmethane, MeNO2. If you use MeNH2, methylamine, you should use 31 cc of aq solution or 30 grams of the hydrochloride and the equimolar amount of NaOH no release the amine, everything mixed with the ketone in the reaction flask, and about 16 grams of Al should be enough.
(Hive Addict)
05-22-01 12:11
No 196188
Damn! I didn't even catch that he wrote MeNH2 instead of MeNO2.
I'm sure he meant to write the shorthand for nitromethane as he mentioned the Al prep was per Dr. Gonzo's writeup. Also, as I mentioned before, the ratios are a perfect 1.25x scale up of MM nitromethane route."And if we don't get some cool rules ourselves, pronto, then we'll just be bogus too!"
(Stranger)
05-22-01 17:26
No 196268
Damn! I totally missed that one also. Yes, I did mean to write MeNO2, not MeNH2. Whoops, sorry about the confusion.
trancendence through neurochemistry
(Hive Bee / Eraser)
05-23-01 02:32
No 196394
The nitro part looks great, the 2 washes with bicarb are unnecessary just use H2O, but the the NaCl wash is a must. I usually make that my 3 rd wash, then I cap it off with another H2O wash. Cant comment on the wacker, I dont dont go there.
Godisnowhere.
(Philanthropist)
05-23-01 14:34
No 196534
It is always a good idea to write down the compete path you choose to 'dream of'. This will cement it in your head and there will be much less confusion during the procedure ... however, 'less' is the key word here.
My advise would be to read as many different procedures as you can get your hands on. Assuimg they all work as read, and are by 'respected' chemists. ('respected' ... now thats humor) See what they did, and see how their methods differ from yours ... This will give you a better idea to what is really important.
Good Luck, and try SMALL batches first. You will not waste valuable precursor when you fail ... and I promise many do on the first try. But do not give up, because success is closer with experience.
PS - Most of the 'washes' are unnecessary ... just vacuum distill the whole mess.
Good Luck
http://rhodium.lycaeum.org/chemistry/mdm
(Stranger)
05-23-01 15:06
No 196541
That's what I tried to incorporate into this synthesis. The very first thing that sparked my interest in organic chemistry was _your_ writeup for MDMA. After I read it, I realized that I wanted to learn so much more. Then I found Rhodium's site, and learned more than I ever expected I would. After devouring the information posted there, I found the Hive. I was instantly amazed and entranced. Since I found this site, I've been scrounging all the boards, reading until the wee hours of morning until I am finally overcome by sleep. The method that I've tried to produce here is nothing new or earth shattering, but is the final result of trying to write a synthesis using the least amount of chemicals, the most developed and tried methods (according to people like Methyl_Man, yourself, Rhodium, Osmium, baalchemist, Antibody2, and others), and easy enough for someone like me (with little prior chemistry experience) to understand and reproduce.
If you look piece by piece at everything listed there, you'd find each step posted somewhere on this site. I claim no credit for the methods involved, just in the compilation of the total synthesis. I tried to make it easy, and I think I've made it quite OTC, also (not too many ingredients). If I'm successful with my honey-making procedure, I'm going to make a detailed photoessay (ala Dr. Gonzo), or maybe just an edited (for obvious reasons) video of the entire procedure (or at least the important parts). Anybody who feels like contributing is more than welcome to do so, and any help would be greatly appreciated.
Well, that's my goal for starting out in organic chemistry. I figure that if I can start out in here making something that will help a lot of bees, than my mission will be a success, and I'll be well on my way to being a 'respected' chemist :-)
trancendence through neurochemistry
(Newbee)
05-24-01 22:48
No 196867
If you're still interested in learning about solvents, don't forget to check out the Solvent faq on Rhodium's site. (if you haven't already)
http://rhodium.lycaeum.org/chemistry/otc
Just so you know, I wasn't trying to split hairs with the methylamine/nitromethane thing. Just wanted to make sure you had it straight in your head.
-quicksilver-
(Stranger)
05-25-01 10:22
No 197039
Thanks for the link. I remember seeing that page before but I didn't remember it being on Rhodium's site.
I'm glad that you corrected me, it always helps the learning process.
Anyway, I wish I could get some more input on this synth. I know there are more people out there who can share their cooking experiences here.
trancendence through neurochemistry
(Stranger)
05-30-01 22:01
No 197547
Ahhh!!! The thread is dying!!! Must ask more questions
!!!Mix 160g Safrole and 50mL MeOH in an addition funnel and add over 1 hour
Is this the optimum addition rate? Faster? Slower?
Flood rxn mix with slightly acidic water and mix contents thoroughly
Kapten suggests adding DCM at this point. I'm assuming Toluene would work just as well, or better. Doesn't DCM have a tendency to absorb small quantities of water? Or am I just trippin'?
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
If I'm using a 2L RBF with an egg-shaped stirbar, will this mess stir? Or should I find some way to ghetto-rig an overhead stirrer?
As always, any help is appreciated.
trancendence through neurochemistry
(Hive Addict)
05-31-01 04:31
No 197581
Referring to:
------------------------------------------------ -------- -------- -------- --------
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
------------------------------------------------ -------- -------- -------- --------
If I'm using a 2L RBF with an egg-shaped stirbar, will this mess stir? Or should I find some way to ghetto-rig an overhead stirrer?
SWIK Dumps their sludge into one of those big 2 gal. pourable kitty litter jugs, slowly pours in ice-cold NaOH soln, and then 15 minutes later adds toluene and a stir bar, caps it, and sets it on the floor. Then this chick goes about cleaning up her lab, and every time she passes the jug, she shakes/vents it. By the time tha lab is cleaned and ready for the first tol seperation, the sludge is pretty well extracted. She repeats with a second and third extraction, each being half the volume of tol as the last.
z
"And if we don't get some cool rules ourselves, pronto, then we'll just be bogus too!"
(Stranger)
06-04-01 12:10
No 197605
Will be having another crack at this in a couple of weeks. Made good ketone last time but failed to convert it into desired amine.
(Stranger)
06-04-01 22:03
No 197756
Just curious: is there any reason to use both DCM for extraction and toluene for the crystallization? Why can't you just use toluene for both? It's easier to get pure than DCM here, so I figure, why not? Any suggestions?
Oh, and could someone point me in the right direction on the optimum addition time to shoot for in the Safrole addition?
Another one: How stinky is this dream gonna be? SWIM plans on getting a fume hood (well, making anyway...) anyway, but is just curious...
trancendence through neurochemistry
(Hive Bee)
06-05-01 10:34
No 197792
Of course you can use toluene for both. DCM is better if you do a acid wash of product, due it is in bottom. Toluene is better for xtallization, it gets very little water and salts are less soluble in it.