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pbenz0o · Psychonaut Joined: 29 Aug 2007 Posts: 26

Hi all,

I've tried out a few times (3 times actually) to make my own MDP2P from safrole using the Dr. Drool method. I bought some nice and rather expensive equipment, reviewed my high school chem lessons and started.

The described method is the Wacker oxydation process using pbenzoquinone / PdCl2 in methanol. I managed to get some really messy crap, but I couldn't get my MDP2P. First time I tried, I left my pbenzo/methanol/safrole/PdCl2 mixture stirring for 8h refluxing methanol (temp 65°C). The result was that, after DCM extraction, the NaOH wash made a really nasty, impossible to separate "mayonnaise". I tried to ditill my MDP2P, but I got apprx half of my safrole back. Next time I tried without applying any heat, same shit.

Has anyone tried this method successfully? I would like to try with DMF instead of methanol, but DMF is really hard to get for me. Next time I'll try the KRV / CuCl2 method...

Thanx

spice · Psychonaut Joined: 22 Dec 2006 Posts: 861

These are the reactions I studied the most out of all my time at the hive.

Where you messed up is by following a non referenced process. I brought some of the (if not the) first successful pd-wacker synth reports to that place in 1997 and the res say;

Use DMF when using benzo.

Use methanol when using SRV w/ O2.

benzo=85% yields

O2 wacker = 80% yields, but cleaner and easier, not as demanding on your organic chem technique.

There are problems with extracting mdp2p from the reaction mess, as hydroquinone extracts over with the mdp2p....its red, and must bee washed w/ 5% NaOH.....

Better yet, save your pd till you get some experience, and use modified #109....w/ peracetic acid subbing for performic.

Works every time.

pbenz0o · Psychonaut Joined: 29 Aug 2007 Posts: 26

Hi

thx for your answer. DMF is kinda hard for me to get, but i'll figure out how to deal with it. The thing with the 5% NaOH is that it makes a sort of messy "mayonnaise" that is rather hard to separate... does it matter to distill the whole stuff even though there's some hydroquinone left? it's boiling point is higher than the MDP2P, so it shouldnt be a problem...

I havn't tried the KRV for now, but i'll tell if it works.

ComposMentis · Posted: Wed Sep 19, 2007 17:12 Post subject:

DMF?
SRV?
What do those stand for?

pbenz0o · Psychonaut Joined: 29 Aug 2007 Posts: 26

DMF dimethylformamide
SRV/KRV pressurized reactor

spice · Psychonaut Joined: 22 Dec 2006 Posts: 861

It doesn't make the mayonaisse when you use the dmf variation. This is what I meant when I said this is where you messed up.

We used different solvents sometimes toluene, sometimes dcm, depending....just extract the reaction mess with a non polar, and dsitill, then wash, then distill again. This removes a lot of the hyroquinone, for the most part.

I'd give the O2 Wacker a serious looking at, if I were you.

spice · Psychonaut Joined: 22 Dec 2006 Posts: 861

Also, the very fact that you recovered half your safrole means that this
'variant' doesn't work very well. The whole wacker reaction is a cycle, based on the fact that palladium chloride, copper chloride, oxygen and safrole form, under the correct conditions, what is called a co-ordination complex....this coordination comples is then busted up, with HCL, which then yields ketone, aka mdp2p.

When this cycle is set up correctly, ALL the safrole reacts, with ease....when there isn't enough oxygen present, safrole is isomerized to isosafrole, which is a competing by product. This is not that unusual if you examine the ways in which safrole is normally isomerized; with a strong base. Well alkenes can also be isomerized in various other ways,
and acidic media is one of them.

So, if you're SURE you have safrole, not isosafrole, then the mayo is the least of your issues. This reaction is not working at all.

My intuition is that most of this is the methanols fault.

For instance, when you use the SRV, with methanol, a little known secret ( which I disclose fairly regularly here, btw) is that you MUST pre-dissolve the pd and the copper salts for 24 hrs in methanol, then add it to the reaction.

When you at least get the cycle set up correctly, the worst thing that will happen is you'll at least get isosafrole back, which then can bee recycled into the peracetic epoxidation (#109 pihkal)....

Dr. Drool came around after many of the luminaries at the hive were gone. I can't advise you as to his reliability.

When you have unknown references unsupported by legit ones, you're on shaky ground.

SRV in methanol- JOC34 1962 Gulf oil patent

Per-acid PIHKAL

or even the old bromosafrole....which is referenced....

pbenz0o · Psychonaut Joined: 29 Aug 2007 Posts: 26

Thanx for your advices... One more thing, I have read through the Wacker KRV recipes on erowid. There are different variations on the KRV process.

The first method shows that the mixture has to be flooded with some (500ml) distilled water after shaking/pressurizing before DCM extraction. The DCM part is then fraction-distilled. Does the DCM need to be washed with NaCl, NaHCO3, NaOH? or can it be distilled right away?

In the second method (spiceboy variation), they flood it with dilute acid wich produces HEAVY RED OIL to fall out to the bottom. It doesn't say anything about (DCM?) extraction. The oil is filtered and then distilled... Not very clear to me if this can be working...

If I use more PdCl2, does it improve the yield? Can I recycle my PdCl2 by cleaning (rince off CuCl2 with distilled water for example) the stuff I Buchner-filtered?

Thx

spice · Psychonaut Joined: 22 Dec 2006 Posts: 861

There isn't much of a difference in the two, actually. Ketone (the guy who was the 'k' in the krv) assumed that the media was acidic after the reaction was over, which is supposed to be true. Spiceboy (me)
followed the reference to the T, and used dilute HCL. The function of the acid is to bust up the coordination complex and 'release; the mdp2p, which IS the red oil which falls to the bottom. By all means extract the water which remains with dcm, but 90% of it is on the bottom already.

Yes, wash the dcm extracts with a weak sodium bicarb solution to remove carryover acid.

The reason I filtered it is because it'll coat your distillation flask with scorched pd, which is hard to clean.

Recovery of pdcl2 is possible, but only realistic when larger amounts are used.

You ask if using more pd will improve yield?

Yes, and no.....if the pd is the 'limiting reagent' , then increasing it will improve yields....but if you follow the REFERENCES, instead of some internet phantom, chemists have already worked out the optimum conditions and ratios, and in that scenario, your answer is no, it wont help the yields, but there will BE yields.

spice · Psychonaut Joined: 22 Dec 2006 Posts: 861

I have recieved messages from some of you who are interested in the SRV/KRV but are worried about the use of a 2 liter coke bottle.

Don't be.

I researched this concept thoroughly before testing it, then I personally tested it over twenty times without a failure of the bottle.

An engineer at coca-cola told me that eighty psi of carbon dioxide is what EVERY 2 liter bottle of coke comes from the bottler containing.

The cracks I reported were generally caused by a good sized eggbar I had chucked in there to help with agitation....

The ONLY thhing I invented was the shaker. The ratios that yield 80% safrole was worked out by chemists at gulf oil, and I can testify to the validity of these, in particular;

1 g pdcl2
4 g cucl2
100 g safrole, clean
350 ml methanol

45 psi O2

shake two hours with 6 repressurizations

MDP2P

ComposMentis · Posted: Wed Sep 26, 2007 17:42 Post subject:

Sitting in chem class learning about acids and bases and skimming the forums...
I might be just missing something dumb, but how exactly do you pressurize a coke bottle?

spice · Psychonaut Joined: 22 Dec 2006 Posts: 861

By creating a SRV, ComposMentis.

This is why the srv rocked, its a 2L coke bottle with no physical modification at all. The ONLY mod is a tire valve, like the ones on our cars.

If you picture a tire valve (out of the tire) it is shaped like a bowling pin.
Fat on bottom, slim on top. The bottom is soft rubber. Engineers made it this way so it could deform and create a seal at high pressures.

If you squeeze the base of a tire valve, you'll discover that it easily deforms with finger pressure. Take a 2L bottle and take the top off, set it aside, but save it.

Take your tire valve, deform it w/ finger pressure until its an oval shape...insert one end of the oval into the opening of the 2L...
push it through, while holding the stem by the very end. Get the whole base of the tire valve IN the bottle while holding onto it. Its not hard. Now pull the valve straight up, 'corking' the bottle FROM BELOW.

Coke designed the necks perfectly for this.

Now, take the original 2L cap, and drill a hole in it that is roughly equal to the size of the tire valve base above the neck opening.

You're going to put the cap OVER the valve and screw it back on,
which acts as a retainer for the valve and holds it.

Never had a failure with the cap.

So, for less than 5 dollars you can make a 2000 dollar pressure vessel.

you're welcome.

phalaris · Posted: Thu Sep 27, 2007 13:55 Post subject:

Nice practical use of a coke bottle as pressure reaction vessels; especially the tire valve solution.

I wonder.. would PET bottles be suitable as pressure hydrogenation vessels as well ?.. I'm not sure the PET provides enough of a barrier to H2 gas.

A transparant reaction vessel would be of an advantage.. at least a psychological one.

pbenz0o · Psychonaut Joined: 29 Aug 2007 Posts: 26

Hi all,

plastic coke bottles are designed to resist to more than 140 psi...

Is it best to use pure O2 at 45 psi or air at this same pressure (about 10 psi O2 partial pressure)?

spice · Psychonaut Joined: 22 Dec 2006 Posts: 861

yes.

45 psi of O2, not air.

6 Repressurizations in 2 hours, with constant shaking.

Believe it or not, the most negative feedback I ever got for these reactions had to do with the shaking, nothing else. This reaction really is the highest yielding mdp2p synthesis, period.

Methanol isnt a good enough solvent when using benzoquinone. The reason they use dmf is because of its superior properties as a solvent.

Examine the parameters of the reactions;

SRV uses methanol, safrole, miniscule amount of two salts and oxygen. Your solvent doesn't really have to do much 'solvating'.

Anyone who has ever handled benzoquinone knows its nasty. Its a stinky green poisonous powder, and it's somewhat dense and sticky.
Its a pain in the ass, generally, but its the chemical source of oxygen and a precursor for the highest yielding ketone synthesis that there is.
Coming in right behind, hot on it's heels is the O2 methanol version of the wacker.

Actually, a chemist named sunlight did work with methyl nitrite and pd salts that yielded in the 80's %-wise.....but thats still a wacker. Same reaction, different parameters.

There is a lot of flexibility within the parameters of the wacker, and many different ways to run it, but the way I advocate is the simplest, in my opinion, and it works, if done as I sadi I did it, last century.

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