Author Topic: Dr Drool method Viable? (Read 2303 times)

QBall · « **on:** September 12, 2012, 11:03:12 AM »

I recently came across a post by Spice stating the BS method was the only easy method that worked for MDMA synthesis. (I'm just starting to read "Total Synth 2")

Does anyone have experience using Dr Drools or BS method with success?
www.erowid.org/archive/rhodium/chemistry/mdma.drdrool.html

Also found was a modified version...
http://www.scribd.com/doc/16630697/AKIRA-Guide-to-MDMA-Synthes

Everyone seems to have trouble converting the Safrole to Ketone using the Dr Drool method..... lots of emulsion...

If using the method Spice posted below, would Dr Drools method be viable way of making MDMA from the Ketone?
A typical scheme:

1 g PdCL2
4 g CuCL2
100 g distilled safrole
~350 g methanol

predissolve salts for 24 hrs w/ vig. stirring.. add all to srv process w/ shaking for two hours. Rest breaks of 5 mins every 20 mins or so are OK then back to shaking. Re pressurize per instructions, etc..

after a couple of hours, flood the rxn mix w/ water acidified to ph 5 w/ HCL and extract w/ DCM 3X.

distill for ~80-84 g of MDP2P as a pale yellow oil w/ a very slight tinge of green possibe.

Any info would be greatly appreciated! Btw... I am completely a noob and have been doing research for the past few weeks as I have had the time. Hope to be dreaming of honey soon!

QBall · « **Reply #1 on:** September 13, 2012, 06:44:11 PM »

After reading through the forum a bit it seems to me I was trying to run before I could even crawl..... Good way to waste money and product.

I am off to keep reading, glad to hear so many ppl are actually able to dream away with a few tries, gives me some serious hope.

Thanks to certain members I have found info all over, thanks for all you guys contribute, I will have some questions in the future I'm sure. Need to cure this insomnia

Wish I would have started like 15 years ago when things where a lot more chill, but at least I am here now.

Sneak · « **Reply #2 on:** September 13, 2012, 09:41:36 PM »

Sit back, relax and chill. It's a long hard rough road. Running is only a quarter of the way. To do this shit properly you need to be a marathon runner and have won at least 2.

Haha.

I've been reading for a good year. Iv got loads to go. But that's just me...

Wraith · « **Reply #3 on:** December 02, 2012, 06:41:45 AM »

Viable - Tested, tried and true for years now

Don't recommend scaling up, smaller batches run better ... I'm told

pbinteger · « **Reply #4 on:** December 04, 2012, 07:13:17 AM »

Why don't more people use the buffered performic oxidation of isosafrole to yield the ketone?
It allows one to avoid purchasing very expensive, and somewhat watched chemicals (Pdcl2, p-Benzoquinone). The yields of ketone seem slightly better, and the workup is easy...

nigluhS · « **Reply #5 on:** December 04, 2012, 09:56:50 AM »

as a wise bee once told me "you better believe mdma is'nt easy to make"

reading helps a bunch, but practical application teaches best.

pbI, was this what you were referring to?

A solution of 65 grams of isosafrole in 100ml of acetone was added in one
portion to a stirred solution of 60ml of 35% H2O2 in 300g of 85% formic acid in
a 1000 ml beaker situated in an ice-bath (both solutions was pre-cooled to -20°C
in the freezer). Some ice was added to the reaction mixture to prevent the temp
from rising above 40°C, (three ice-cubes was needed until the temp stabilized).
The mixture was allowed to stir for 16 hours, whereupon it was poured into 1500ml
of cold water. The cloudy solution was extracted with 3x100ml CH2Cl2, and the
pooled extracts was freed from solvent by distillation. The dark red residue was
taken up in 120 ml of methanol, and added to 700ml of 15% H2SO4 (w/v), and the
solution was slowly refluxed for three hours. The reaction mixture was cooled and
extracted with 3x75ml CH2Cl2. The extracts were washed with 250ml of water and
250 ml of 5% NaOH solution. The organic phase was dried over MgSO4, filtered with
suction, the filter cake washed with a little CH2Cl2, and the solvent was removed
by distillation. The black residue was distilled with aspirator vacuum, to give
~30 ml of a yellow-brown oil (bp 115-170°C), which was redistilled to give 31g
(44%) of an intensely yellow oil (bp 140-150°C) which gave a single spot with TLC.

fractal · « **Reply #6 on:** December 04, 2012, 03:19:33 PM »

That's not buffered, he means this:

Isosafrole (230g, 1.42 mol) was dissolved in 550ml dichloromethane in a 2000ml round-bottomed flask (equipped with a reflux condenser and an addition funnel), and 71g (0.82 mol) NaHCO3 was added to the solution. Then, a solution of performic acid which was prepared one hour in advance by mixing 220g (2.25 mol) 35% H2O2 and 290ml (350g, 6.45 mol) 85% HCOOH, was added dropwise to the isosafrole solution during 2h, causing the solution to evolve carbon dioxide and reflux slightly. The mixture was allowed to stir at room temperature for 16h, and was then poured into a 2000ml separatory funnel. The bottom organic layer was tapped off and the top aqueous layer was washed in the funnel with 100ml dichloromethane, that DCM extract also tapped off and added to the organic layer, which then was washed with 2x200ml water and 150ml brine (concentrated aqueous sodium chloride). The light yellow aqueous extracts were backwashed with 75 ml dichloromethane, and the organic phases were pooled and stripped of solvent by distillation on a water bath.

The residual orange oil was dissolved in 400ml methanol and lightly boiled in a 2000ml round-bottomed flask with 1400ml 15% H2SO4 for 2h with good stirring. The solution was allowed to cool, the dark bottom layer drawn off, and the aqueous layer extracted with 3x200ml diethyl ether. The pooled organic layers was washed with 3x200ml water, 300ml 5% NaOH and 200ml brine, and dried over MgSO4 and filtered. The ether was distilled off and the residue vacuum distilled at aspirator vacuum (~15 mmHg) to yield 174g (68%) of yellow MDP2P (bp 130-150°C)

pygmalion · « **Reply #7 on:** December 04, 2012, 03:50:08 PM »

People like the benzo PdCl method because it is easy, scales up just as easy, high yields, and clean up- guess? - easy. Those chems are quite easy to get . The only bitch is the cost once you figure the ins and outs , and it is still is morenthan worth it IMO. For the layman a purer ketone might be gotten from the performic.

Yes, it takes a lot of work. Reading, reading, and trial and error.

fractal · « **Reply #8 on:** December 04, 2012, 07:40:51 PM »

The clean up from the performic oxidation is much easier. Not a bunch of hydroquinone to filter out. The wacker oxidation doesn't scale up just as easy either. The amount of solvents needed gets to be a bit much among a few other issues discussed a lot already.

myhero · « **Reply #9 on:** December 05, 2012, 10:54:59 AM »

SWIM s a fan of the buffered performic in DCM. It's easy to perform. The only drawback is that it takes more time overall from safrole to ketone. But if time isn't an issue ....

pbinteger · « **Reply #10 on:** December 19, 2012, 01:16:43 AM »

I just attempted my first buffered performic oxidation and I don't think it ran...

myhero: can you report on the color of the organic layer post reaction? Mine is just pale yellow. Also in the write up it mentions the organic layer being on the bottom and mine was on the top... Perhaps my stoich is off or perhaps my isomerization didn't run. The isomerization looked successful -- color change to brown -- distilled off a water white oil -- but that could just be safrole...

I'm going to run some tests in ethanol using conc h2so4, but was just curious if someone w/ experience on this rxn had much different results.

Thanks,
_Pbinteger_

jon · « **Reply #11 on:** December 19, 2012, 03:50:39 AM »

the fumes off formic acid are something else.

myhero · « **Reply #12 on:** December 20, 2012, 09:05:55 AM »

post reaction should be yellow/orange color, once DCM is distilled off a reddish color should remain. SWIM had a deep orange color since he had unreacted isosafrole due low concentration of H2O2.

SWIM's issue the first time was in fact the concentration of the H2O2. you should check that in some way.

I suggest you follow this procedure

http://parazite.nn.fi/hiveboard/newbee/000528375.html

About the isosafrole, it boils at a different temp so you can check it yourself on a sample at atm pressure. If it is iso it should start boiling around 243°C or more depending on the isomer mix

pbinteger · « **Reply #13 on:** December 21, 2012, 01:23:30 AM »

So...

My isomerization is failing and I'm hoping one of you has some insight.

myhero: I had already begun another isomerization when you posted that write up. I fractionally distilled it this AM under strong vacuum, and I got back 74g of safrole and 4g of isosafrole -- tested boiling points in both and the safrole began to boil at 219c while the isosafrole boiled at 235c... This is also confusing because the listed boiling points (wikipedia) for both of those are different -- but I would assume the 74g fraction that has a higher refractive index, smells more intense, and came through the fractionating colum at a lower temperature 110c.. is safrole.

I only ran this reaction with stirring on heat until I noticed a change in boiling point. I saw a change in the reflux ring so I stopped it, but I let it sit overnight...

Here are the things I did not do, that are listed in the write up you posted, because I was not aware of them yet:

1.) I did not boil off the water for an hour
2.) I did not keep the reaction at 140-150c for 24 hours...
3.) I only used 1.25% 99% KOH
4.) I DID add about 10g of CaO to the mix while it was stirring
5.) I only ran the reaction with heat and stirring for 30 minutes until I noticed a drop in the reflux ring.

Why did this reaction fail? Are any of the items listed above reaction killers?
Thoughts?

_Pbinteger_

lugh · « **Reply #14 on:** December 21, 2012, 02:14:34 AM »

The entire buffered performic reaction sequence is explained in great detail by LT/:

https://the-collective.ws/forum/index.php?topic=9873.msg153357#msg153357

including Osmium's vacuum reflux which if studied thoroughly should prove enlightening

The end results from the effort applied

LilDookie · « **Reply #15 on:** December 21, 2012, 07:14:06 AM »

Quote from: jon on December 19, 2012, 03:50:39 AM

the fumes off formic acid are something else.

Don't thy decompose to CO in the presence of a strong acid, like H2SO4?

myhero · « **Reply #16 on:** December 21, 2012, 09:34:47 AM »

SWIM has never tried isomerising with CaO, but in theory it should work. In your case it should be done at atmospheric pressure afaik. What SWIM did was the long process with water elimination (heat or vacuum) and much longer reflux at around 140-150°C.

I believe if your safrole is boiling at 219°C then it's not safrole. If your iso is boiling at 235°C then it's most likely safrole since safrole boils at 232-234°C.

i believe you had a look here:

http://www.erowid.org/archive/rhodium/chemistry/isomerizafrole.html

Isosafrole starts boiling around 245°C

You should test it by boiling a little sample, a few ml, and measuring the vapor right over the liquid. SWIM does this tests in test tubes.

Are you properly distilling you sassy oil first?

pbinteger · « **Reply #17 on:** December 21, 2012, 05:28:50 PM »

I am vacuum distilling the safrole -- perhaps my probe is a little off. I'm using a metal temp probe with a max of 400c that's attached to a heidolph hot plate / stir plate to measure temp because I don't have a mercury thermometer that goes up past 200c -- i was running the boiling point tests in beakers on the hot plate, but I will re-run them in test tubes -- seems more apt glassware for the test.

It is also my understanding that even slight impurities can change boiling points / melting points so they aren't the most reliable test methods.

If I go by what was in the write up you posted, the stuff that boils at the higher temp is iso -- it smells weaker and has less refractivity. Also what else could this 74g distillate be? A crystal clear oil that smells like rootbeer perfume and has a high refractive index. I don't think a reaction with KOH could have produced such a large amount of something elimination product.

There's also a test you can run with conc h2so4 -- you dissolve some safrole and some isosafrole in ethanol at the exact same concentration and drop it onto concentrated h2so4... safrole should be dark purple -- isosafrole should be much more in the red..

I've tested my safrole and it's dark purple -- I need to test this iso.

I'll re-run the bp tests and report back.

_Pbint_

myhero · « **Reply #18 on:** December 21, 2012, 06:45:37 PM »

Maybe it was the probe then. It makes much more sense.

pbinteger · « **Reply #19 on:** December 21, 2012, 06:55:57 PM »

Yay! My new glass thermometer just came in -- it goes up to 360c

going to re-run the tests -- I know this therm will be much more accurate.

_Pbint_

Author Topic: Dr Drool method Viable? (Read 2303 times)

QBall

Dr Drool method Viable?

QBall

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Sneak

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Wraith

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pbinteger

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nigluhS

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fractal

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pygmalion

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fractal

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myhero

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pbinteger

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jon

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myhero

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pbinteger

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lugh

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LilDookie

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myhero

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pbinteger

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myhero

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pbinteger

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