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Benignium
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[*] posted on 11-12-2020 at 02:52
Methaqualone


There is something delightfully attractive about things that are prohibited or otherwise challenging to obtain. Exclusivity. Perhaps the desire to feel special. I guess if you know you know. Oftentimes it is very motivating to work towards a product that you can't simply buy from any chemical supplier.

So here's me making drugs.

Reference.

9.63 grams of o-toluidine, 14.19 grams of anthranilic acid and 9.00 grams of glacial acetic acid were combined in a 250 mL Erlenmeyer. With strong stirring, 90 grams of hot polyphosphoric acid was added in 10-20 gram portions using a glass syringe. The mixture was heated to and kept at 185 degrees Celsius for three hours.

Degraded, stored-for-a-while o-toluidine.


PPA <--> o-T + AA


After adding all of the PPA.


Reaction taking place.


Cooled reaction mixture.


Once sufficiently cooled, the reaction mixture was poured in 400 mL of water and, after filtration, the solution was made basic using sodium carbonate. A grotesque mass separated from the aqueous solution and floated to the surface. The liquid was discarded and the solid(ish) mass melted and dried in the oven at 110 deg. C. This was then dissolved in in acetone and sufficient concentrated hydrochloric acid was added to precipitate out the product as the hydrochloride salt.

Reaction mixture being poured in water.


Some initial garbage caught in the filter.


Apparently, some people consume and even smoke this stuff.


Melted and sufficiently dry.


Precipitate containing crude methaqualone hydrochloride.


The crude product was collected by vacuum filtration and dried. At this point it looks deceivingly clean and weighs 9.63 grams. The solid was dissolved in minimal methanol, filtered and dried. Once dry the solid was washed with anhydrous acetone. This was then dissolved, dried and washed two more times in the same manner.

Crude product vacuum filtered.


Crude product dried.


Impurity exposed after redissolving and drying.


The now cleaner product was dissolved in acidified boiling water and treated with activated charcoal. There was some improvement. The treated solution was made basic, filtered and the solid base dried. The melting point range was determined to be 106-110 deg. C according to an interrupted alcohol-based thermometer. Actual melting point was likely a few degrees higher.

Product being dissolved in acidic water.


Hydrochloride solution before charcoal treatment.


Hydrochloride solution after charcoal treatment.


Methaqualone base.


Melting point test.


Melting point test. Still impure.


The product was once more converted to its hydrochloride salt. Recrystallization from the aqueous solution was attempted revealing more garbage. The solids were washed with acetonitrile, whose performance was very similar to that of acetone, dissolved in methanol, dried and washed with acetone.

Hydrochloride recrystallized from acidic water.


Getting there.


Finally, when no more color seemed to come off with acetone, the product was dissolved in minimal boiling methanol. An equivalent volume of MEK was added and much of the methanol was boiled off. At about the original volume of methanol, the still clear solution was taken off heat and a dash of acetone was added. This method of recrystallization is somewhat unreliable but affords decent crystals.

No matter what I tried - and I tried a lot of different things - some color always remained. Here are some of the purest crystals I could manage:






The whole project was a bit of a mess but I am still immensely happy with the fact that I managed as well as I did. All the reagents for this project, except for the phthalic anhydride which I purchased off Ebay, were sourced OTC which makes it all that much more special to me.

And now for a small rant. The workup was extremely frustrating. There was an incredible amount of colored impurity that followed the product everywhere and had to be leached out bit by bit. This is all well and good, but methaqualone has an incredibly obnoxious tendency to dissolve in solvents that it isn't soluble in if there is even a drop of water, alcohol, etc. in them. This makes it really hard to purify everything as you often have to go back a step and reclaim whatever you lost to unexpected dissolution. I might revisit the preparation and workup at a later date to see if using cleaner reagents and utilizing acetic anhydride makes for a cleaner product. For now, though, I've definitely had enough.




[Edited on 11-12-2020 by Benignium]
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mackolol
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[*] posted on 11-12-2020 at 09:14


Generally this forum is not about drug making. It's even prohibited to do it here. There may be some exceptions if it actually teaches something about chemistry. I'm curious how will admins react to this. I like the workup though. It's great
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stoichiometric_steve
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[*] posted on 11-12-2020 at 09:22


Of course the subject of this post is a scheduled substance, but nonetheless the presentation is far beyond anything cookery related.

Great presentation, Benignium. Thanks for sharing!
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Corrosive Joeseph
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[*] posted on 11-12-2020 at 09:38


Quote: Originally posted by mackolol  
It's even prohibited to do it here.


This is not technically true.... Drug chemistry is acceptable, as long as it is discussed in a scientific manner.
I actually think the OP has done excellentl here and has provided a well done and tasty write-up.

Ludes went out of fashion with flares and platform shoes (the first time), I don't think anybody would be particularly interested in consuming the goods, or at least they shouldn't be.



/CJ




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mackolol
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[*] posted on 11-12-2020 at 09:50


Quote: Originally posted by Benignium  

The crude product was collected by vacuum filtration and dried. At this point it looks deceivingly clean and weighs 9.63 grams. The solid was dissolved in minimal methanol, filtered and dried. Once dry the solid was washed with anhydrous acetone. This was then dissolved, dried and washed two more times in the same manner.
[Edited on 11-12-2020 by Benignium]

I don't really understand this part, you have a HCl salt at this point and you said that you dissolved it in methanol. And then you just filter it from what? Do you mean recrystallisation or suspending it to wash the crude salt with methaqualone?

I wonder if it could be purified with good old A/B extraction though. Dissolving the salt in water and washing it with DCM. This shit works almost every time. Not sure about these type of compounds.
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mackolol
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[*] posted on 11-12-2020 at 09:57


Quote: Originally posted by Corrosive Joeseph  


Ludes went out of fashion with flares and platform shoes (the first time), I don't think anybody would be particularly interested in consuming the goods, or at least they shouldn't be.
/CJ

I wonder why. It's so easy to make them, yet practically nobody does so.
Of course there are now lots of different benzos and they're even legal (prescription drugs) and easily accessable. But I would always think of qualuudes as about this original drug producing big euforia, very addictive, irreplaceable. That's how they're described at least.
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[*] posted on 11-12-2020 at 10:03


OP
Quality post sir. Thank you.
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Corrosive Joeseph
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[*] posted on 11-12-2020 at 10:19


Quote: Originally posted by mackolol  

I wonder why. It's so easy to make them, yet practically nobody does so.


I can only guess, but if there was a demand, somebody would be filling it. They are a historical curiosity and I don't think many of todays youngsters have even heard of them.



/CJ




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mackolol
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[*] posted on 11-12-2020 at 10:25


Unless they've watched wolf of wall street :D
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[*] posted on 11-12-2020 at 12:34


Some real work done. Sweet. :-)

A few remarks:

- A reaction equation would have been nice.

- How thoroughly could you check the properties of the target compound? Do you know its solubility in various solvents? Could it be e.g. steam distilled? Sublimated? (You mentioned people used to smoke it. Well, it may be a good candidate for sublimation.)

- Have you tried to remove the colourful contamination with something slightly polar (pentane/hexane/diethylether/whatnot) ? If they worked: great, if not: not a big deal, they evaporate quickly and don't interfere with the later stages of purification.

- What is the melting point of the pure methaqualone? How the various "semi-purified end products" converged to this value?

- I don't even mention TLC. :-)

All in all, the synth was very interesting, I could almost "feel" the pain of some of its stages based on the appearance of things on the photos.



[Edited on 11-12-2020 by Pumukli]
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[*] posted on 11-12-2020 at 13:12


I'd love to know what your method for producing polyphoshoric acid is, and where you choose to stop the heating and finally use it. This is a reagent I'd love to try in a lot of different syntheses, particularly in inorganic chemistry.

Also, can I assume you made the o-toluidine the usual home chemist way by mono-nitrating toluene, reducing everything with a metal and acid, then steam-distilling?

Beautiful pictures and some very good chemistry on show in this post. This is the kind of scheduled substance post I can actually get behind.
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[*] posted on 11-12-2020 at 16:26


Great presentation! ( I don't intend on repeating this), but very informative and well presented.

Unrelated to anything, but the first image of the o-toluidine looks kind of like mercury if you don't look at it too closely




Nuclear physics is neat. It's a shame it's so regulated...

Now that I think about it, that's probably a good thing. Still annoying though.
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[*] posted on 12-12-2020 at 11:03


Very good publication!
But why haven't you put this into prepublication directly?
It is more than worthy for this.

Also, a personal opinion, I consider the product rather boring and would always prefer thalidomide to which I grew a certain fondness over time :)
This does also not have the certain possible impurities that ruin the experience with their harmfulness... bladder cancer is a big issue with clandestinely produced methaqualone or so, I've heard.
Due to possible toluidine residues.

It might make for an interesting next project for you to try the preparation of thalidomide?
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[*] posted on 12-12-2020 at 12:38


Quote: Originally posted by Amos  
I'd love to know what your method for producing polyphoshoric acid is, and where you choose to stop the heating and finally use it. This is a reagent I'd love to try in a lot of different syntheses, particularly in inorganic chemistry.

Also, can I assume you made the o-toluidine the usual home chemist way by mono-nitrating toluene, reducing everything with a metal and acid, then steam-distilling?

Beautiful pictures and some very good chemistry on show in this post. This is the kind of scheduled substance post I can actually get behind.

There is also a DCM nitration route to making almost purely o-nitrotoluene. Chemplayer has a video on it and it is a very interesting reaction in my opinion. I wish there was a similar way to get the para product since I would prefer p over o for a benzocaine synth. I failed isomer separation last time due to lack of equipment that I wanted to dirty :I




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[*] posted on 14-12-2020 at 14:49


Yup. Once upon a time, I might have done such a thing. Not now.

There was a time, when purification of the final product, might have been easy.

That time, was before, you started the reaction sequence.

Simple vacuum distillation of your crude O-toluidine, should have delivered a more-or-less colorless starting material. And, probably a less colorfully contaminated product.

Also, of interest.... I have used PPA on occasion. Depending on reaction conditions, it may produce cruddy
charred-like products. Can other, milder reagents, perform your cyclization?

Amos. PPA is expensive, and not generally over the counter available.

The question is: What is PPA?

Well, it is dehydrated, or "Polymerized" Phosphoric Acid.

Seems to me, you can formulate a reasonable grade of PPA by microwaving phosphoric acid under vacuum.

Or, adding Phosphorus Pentoxide to Phosphoric Acid.

There might be some discussions found, in Pre-publication.

Maybe 5 to 10 years ago? I'll check......

OK, I found a link.....

https://www.sciencemadness.org/whisper/viewthread.php?tid=73...



[Edited on 15-12-2020 by zed]

[Edited on 15-12-2020 by zed]

[Edited on 15-12-2020 by zed]
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[*] posted on 14-12-2020 at 15:13


Man. Memories memories. In my high school daze we called 'ludes Gorilla biscuits. I've eaten the RORER ludes, before Lemmon bought them. (I'm 57)

And yes, very nice write up.




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[*] posted on 14-12-2020 at 16:43


Quote: Originally posted by zed  


OK, I found a link.....

https://www.sciencemadness.org/whisper/viewthread.php?tid=73...




Very cool..... I presume this also works with diammonium phosphate, or at least it should, very readily available as yeast nutrient at the brew shop.


/CJ




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[*] posted on 19-12-2020 at 22:38


Quote: Originally posted by karlos³  
Also, a personal opinion, I consider the product rather boring and would always prefer thalidomide to which I grew a certain fondness over time :)
This does also not have the certain possible impurities that ruin the experience with their harmfulness...


Thalidomide: As in the substance which caused this? https://helix.northwestern.edu/article/thalidomide-tragedy-l...
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[*] posted on 21-12-2020 at 17:08


Excellent synthesis. The fact that this is all mostly OTC makes me question why street methaqualone is not more common than it is.



Please check out my latest video: Synthesizing Nitrobenzene, and the last one:
Making Nitric Acid.
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[*] posted on 21-12-2020 at 18:45


Quote: Originally posted by thors.lab  
Excellent synthesis. The fact that this is all mostly OTC makes me question why street methaqualone is not more common than it is.


Likely due to it just being a virtually extinct drug. Plus continuous users would be at high risk for bladder cancer since most street level cooks will just half ass the entire thing and leave loads of o-toluidine impurities in there. Plus I am sure that the majority of people don't want to go through the entire trouble of making anthranilic acid from scratch, then making o-toluidine from scratch, buying or making (I rarely hear of success and never see a true write up) polyphosphoric acid, and then they have that super messy reaction to go through, AND to top it off there is likely loads of impurity issues that need to be resolved on top of that.

Just doesn't seem to be a fun type of thing overall.




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Benignium
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[*] posted on 27-12-2020 at 13:36


I would like to thank everyone who replied! I'm incredibly grateful for the positive response.

mackolol - To be frank I wasn't really too sure of this myself, but my interpretation was such that as long as my focus is on the chemistry it would be fine. I wish to keep posting here but in the future I will no longer make it as obvious if the subject is controversial. I've grown very attached to Sciencemadness and I would hate to do it harm.

As for your question, and I'm truly sorry it took me so long to get around to replying, the filtration in question was done just to get rid of any insoluble impurities that may be present.

I actually did try out the A/B approach but the line of inquiry took me a long time to finish. It worked out quite well and could in fact be used to significantly cut down on labor.

To some of the crude hydrochloride that was precipitated from acetone and redissolved in methanol, an approximated slight excess (2 grams) of oxalic acid dihydrate was added. The solution was concentrated for as long as it remained clear and water was added until no more precipitation was observed. The solution was decanted off and filtered. Dark brown solids remained in the beaker and on adding NaOH it was evident that no methaqualone was present.




The filtered solution was extracted once with 10 milliliters of DCM, which turned out to be enough to extract very nearly everything. The extract was stripped of solvent, redissolved in water and the aqueous solution made basic. Methaqualone base was filtered off and washed with water. The solid was dissolved in water by adding 48% hydrobromic acid dropwise. The water was removed by evaporation and the solid hydrobromide salt was recrystallized from minimal boiling methanol.



The hydrobromide salt seems to crystallize more readily and with significantly less impurity, affording very pale crystals even from a strongly colored mother liquor.

Pumukli - Steam distillation is a brilliant idea! I will definitely try it some day. Different melting points are reported for methaqualone ranging from 113 (Wikipedia) to 120 (PubChem) deg. Celsius. I have since repeated the melting point test with a proper thermometer and it seems consistent, with a sharp melting point range at 113-116. TLC plates are something I've been meaning to buy for ages now, but since it has not really been necessary until recently, I've just kept putting it off. Definitely going to need TLC going forward. Thank you!

Amos - I actually made a small post on the preparation of PPA. Perhaps you have already found it, but in any case here you go! You're absolutely correct on the o-toluidine - I followed ChemPlayer's procedure.

karlos³ - Thank you so much! I'm going to have to look into the prepublications as I'm still unfamiliar with the concept. I like the idea of synthesizing thalidomide. I recently learned that thalidomide very nearly made it so I would not be born. It is an interesting compound.




[Edited on 27-12-2020 by Benignium]
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[*] posted on 8-1-2021 at 13:24


Deleted - I asked about TLC, but I see you already answered that in your reply to Pumukli. Sorry :-) Ignore this.

[Edited on 8-1-2021 by SuperOxide]
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[*] posted on 9-1-2021 at 03:19


All right, one more example, that proves universality of A/B extractions.
It's good to do it, because of what Karlos have said about the toluidine impurities. Nobody wants to poison themselves, right?
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[*] posted on 17-1-2021 at 10:00


Quote: Originally posted by Benignium  

Degraded, stored-for-a-while o-toluidine.

How long did you store the o-toluidine for in order for it to degrade this much? I plan on making some o-toluidine, but I may not be able to use it for a while, so if it degrades that quickly then perhaps I should wait til I can work on the project for a few consecutive days in a row.
Also, did you purify the degraded o-toluidine before you used it? Or did you use it as is?

[Edited on 17-1-2021 by SuperOxide]
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[*] posted on 17-1-2021 at 11:28


I believe the salts of toluidine are stable, so you could form for example the HCl salt and store it as a water solution. Before use you then freebase it, extract with a solvent, dry with sodium sulfate and evaporate the solvent.
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