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Modern MDMA precursor is chiral (R) hence 'wrong'

I don't think there is a way to transfer chiralityity.all of the following reactions create racemic product.that was one of the major talking points among the scientific community from breaking bad. Q:how does Walter get pure d meth and not racemic meth using the P2P method? A: you can't, science doesn't have the answer other than it made for good tv.

You can with tartaric acid. P2p does give racemic but it’s not terribly difficult to separate the two. Problem then arises that you now have a ton of l-isomer meth.

If I’m not mistaken though it is possible to then turn that l-meth into a racemic mixture and separate again.

P2P to racemic then separating the isomers would technically be the better route for large scale production. P2P is easier to obtain large scale than E/PSE.

-GC
 
[QUOTE = "indigoaura, post: 14868200, lid: 120420"]
MehDMA lijkt pro-sociale effecten te missen, dus ik weet niet of R-MDMA past in het gerapporteerde effectenprofiel.
[/CITAAT]
ik was once tould pills contained inferiour product. Alll pills were DL-MDMA

He had capsules, with he filled with this super-MDMA, from a lab he said. Het effect differrt from usual pills. De come up was extreme slow. No stimulation and a very psychedelic edge. Worked longer also. But not like MDA would def diffferent.

Could these have been (r)MDMD
 
You can with tartaric acid. P2p does give racemic but it’s not terribly difficult to separate the two. Problem then arises that you now have a ton of l-isomer meth.

If I’m not mistaken though it is possible to then turn that l-meth into a racemic mixture and separate again.

P2P to racemic then separating the isomers would technically be the better route for large scale production. P2P is easier to obtain large scale than E/PSE.

-GC
That's how you seperate the isomers after there formed but there's no way to get P2P to only produce one isomer.
I've had the question of what to do with all the leftover l meth after seperation in the back of my mind for years now. I'm thinking deamination by diazotization with sodium nitrite and then whatever to yeild the alcohol which if oxidised further should produce P2P again but not sure it'll work on a secondary amine.
 
That's how you seperate the isomers after there formed but there's no way to get P2P to only produce one isomer.
I've had the question of what to do with all the leftover l meth after seperation in the back of my mind for years now. I'm thinking deamination by diazotization with sodium nitrite and then whatever to yeild the alcohol which if oxidised further should produce P2P again but not sure it'll work on a secondary amine.

Ah this is true. I’ve seen reports of labs being found with large amounts so I’m assuming some guys just stockpile it until they can find a better use for it.

-GC
 
So a major source of information is Breaking Bad, A series where the protagonist tried to dissolve a body in one of the weakest but most toxic mineral acids Hydrofluoric acid. YMMV on that one.

G-Chem you are correct, there are several ways to P2P from l-meth and also from pseudophedrine/ephedrine and there are also ways to racemize l-meth into d/l racemic meth and then resolve again. It has to be pointed out though that if chiral meth is the objective then starting from chiral ephedrine or pseudoephedrine is cheaper and easier and ephedrine/pseudoephedrine is readily available.

Chiral (enantiopure) meth can be made from P2P using chiral alphamethylbenzylamine as the amine or using chiral reductive amination or even chiral reduction to a chiral alcohol, of course there are other more indirect ways and other chiral amines which would be obvious to someone skilled in the art.
In those situations the chirality is coming from the chiral reducing agent or a chiral amine, something else (which by definition is chiral itself) is providing and transferring the chirality.

This is an important concept to grasp, it is actually a key idea. Making racemic and the separating the two enantiomers as diasteriomeric salts for example is not transfer of chirality from a chiral synthetic starting material, instead the tartaric acid in a resolution step is chiral and that provides chirality to the diastereomeric salt pair, because diastereomers have different physical properties, one diastereomer can then be separated from its mirror image.

Draculic acid look up N-Nitrosoamines for the answer to what happens if you hit secondary amines with acidified sodium nitrite in effect HONO. basic stuff.

Terminology is important, to understand what people are saying you need to be speaking the same language. this is the generally accepted use of one pot,
One pot does not have anything to do with whether stuff is distilled or not, one pot is where sequential reactions are carried out in one vessel (hence being called one pot) whether it is a glass lined reactor or a coke bottle.
With or without isolation of the intermediate products in that pot. so for example react step 1 crash solid intermediate product decant liquid, wash add new reagents react step 2 is a one pot with isolation, a one pot 2 step reaction.

Telescoped reactions are sequential reactions where the product is carried into the next step without purification to remove by products from the earlier step.

There is absolutely nothing wrong with one pot or telescoped reactions they are used all the time in Pharma API manufacturing because often they result in higher yields than more traditional approaches, they also prevent worker exposure to intermediates. In Pharma though the chemists actually know and understand the chemistry, the by-products and carefully manage the whole scheme.

On the original topic chiral PMK glycidate to chiral MDMA requires chirality transfer from the PMK glycidate to the product and to remain chiral that position basically it needs to remain tetrahedral, sp3 hybridized. If the chirality is not transferred from the PMK glycidate then it is irrelevent whether the starting glycidate is chiral or not.

Perhaps we need to wait for Clubcard to explain the mechanism of the fantastic(al) chiral PMK glycidate to chiral MDMA route.

this is most likely remains a total red herring because commercial Ethyl Chloropropionate (and Methyl) most certainly is not all enantiopure some is some isn't. if racemic ethyl chloropropionate is used in a Darzens reaction to make PMK glycidate then the glycidate is also racemic.
 
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Well I am sure that people will appreciate that the glycidate esters are synthesized using a Darzen's Condensation. Consider the cheapest source of the halo-ester. The chlorination of methyl lactate, the cheapest source of which is lactic acid. (R) methyl lactate is significantly cheaper than (S) methyl lactate. So that is why the glycidic ester is chiral. Check Ali Baba.

Now it seems that people are presuming that this pre-precursor is decarboxylated back to BK-P2P but it if that route is followed, their is a significant amount of BK-P1P formed. In fact, BK-P1P is used as a marker to detect if the glycidate ester was a precursor. In some cases it is seen, in others it is not. The EMCDDA has been monitoring this anomaly.

But their is obviously a chiral epoxide in the glycidate ester. A search of recent literature will uncover a direct glycidate ester to amine reaction. More specifically, it has been researched in the synthesis of amino acids. But if you are going on to decarboxylate the amino-acid, you get a chiral amine.

I don't think I'm suppose to write up exactly how it's done but it does not take a lot of searching to spot that others have ALSO noted that those high-dose MDMA tablets ARE chiral.

I admit that it was initially guesswork but I was confused by friends noting the huge doses of MDMA in some pills and yet also noting how little activity they seem to have.

All I can say in my defense is that I have a LOT of experience in how Chinese suppliers really will do anything they can to keep costs down. Back in about 2012 I reread a Ken Kesey quote on AMT. He said it was 'The Rolls Royce of psychedelics with a 12 hour duration'. Back then I remember that the guys I worked for sold AMT and while it seemed popular, it wasn't THAT special. That is why I specifically asked for AMT to be resolved so I could test both enantiomers. Having very pure powder, I could vape it. It did not take long for me to work out just how different the (R) & (S) isomers are. As for the 7-Me derivatives, well McNeil patented them in the mid-1960s. I do not know if people are aware of this but their are almost NO novel RCs. In almost every case, the data was gleaned from patents. I mean, Diphenidine had been patented in the 90s and as I have said elsewhere, it turns out that the N-isopropyl analogue that is MOST MXE-like and interestingly (to me) shows that the QSAR of the 1,2-diarylethylamine class has a QSAR more like PCP than MXE. So yes, the N-isopropyl is novel, but the overall structure is not.

i admit that it was years ago when I really spent the time dotting the i s & ctossing the t s and it's just another fact that most of the people found in speed and/or MDMA labs are 'cooks'. They can only repeat what they have been shown. Again, the EMCDDA will bear me out. There have been a couple of dozen big speed labs that are nigh on identical such as using stainless steel rather than glass and more specifically using those large SS vessels larger is delivered in being used as reaction vessels. Whoever is behind it has a 'formula' for a speed lab. Maybe they can weld SS? I don't know. I just know they are SCALE and that nobody with any experience of industrial chemistry has ever been arrested.
 
Oh - I should point out that (R) AMT is that 'Rolls Royce' but then (S)-AMT is much more like MDMA.

All of those etactogens were produced and tested. I was concerned that the 4-carbon analogs might have MAOI activity (and Dr. Dave didn't know) and also the precursor 7-methyl indoles are not cheap. They are not commercially available and the synthesis requires rather complex routes.... but the important thing is that a lot of compounds are MDMA-like. For those interested, we could not get KOCN to cyclize the amino-alcohol precursors of the AR series and while we found someone who would make it cheap, I knew that they were not working safely with BrCN and I cannot speak for others but I could not deal with the possible outcome.
Now I DID notice that ring-substituted phenyloxiranes + NaHNCN is supposed to work. It isn't a simple class to make at scale BUT one thing I know is that while 4MAR derivatives have MAOI activity while MAR derivatives do not (or Dr. Dave said so - good enough for me). Oddly, pynazolam is a serotonin released which I suspect is why nitrobenzodiazepines are used as hypnotics. The reason pynazolam is not a hypnotic is that the 4-ring benzos have no a1 affinity.

I will finish by noting that the 7 position of the indole system overlays the p-position of PEAs. 7-Me DMT is just as active as it's parent but you have to remember that it was the per-Kg price that people were interested!
 
Well I am sure that people will appreciate that the glycidate esters are synthesized using a Darzen's Condensation. Consider the cheapest source of the halo-ester. The chlorination of methyl lactate, the cheapest source of which is lactic acid. (R) methyl lactate is significantly cheaper than (S) methyl lactate. So that is why the glycidic ester is chiral. Check Ali Baba.

Now it seems that people are presuming that this pre-precursor is decarboxylated back to BK-P2P but it if that route is followed, their is a significant amount of BK-P1P formed. In fact, BK-P1P is used as a marker to detect if the glycidate ester was a precursor. In some cases it is seen, in others it is not. The EMCDDA has been monitoring this anomaly.

But their is obviously a chiral epoxide in the glycidate ester. A search of recent literature will uncover a direct glycidate ester to amine reaction. More specifically, it has been researched in the synthesis of amino acids. But if you are going on to decarboxylate the amino-acid, you get a chiral amine.

one DOI or reference and people can see for themselves,
If you don't want to publicly post it then PM it.
I think nucleophilic attack on the glycidate ester epoxy opens the ring the wrong way and gives primarily benzylamines not phenethylamines.
 
So mdp1p is formed also from the decomposition of glycidate to mdp2p?
If so what percentages are formed 1%,5%,10% or more?
I read propiophenones don't form bisulfite adducts like phenylacetones which says if that's showing up in samples they really don't give a shit about quality, purification or the fact that if they took the effort to seperate them they'd get better mdma.
 
So mdp1p is formed also from the decomposition of glycidate to mdp2p?
If so what percentages are formed 1%,5%,10% or more?
I read propiophenones don't form bisulfite adducts like phenylacetones which says if that's showing up in samples they really don't give a shit about quality, purification or the fact that if they took the effort to seperate them they'd get better mdma.

No, 30 years ago the makers cared about quality because a lot of small producers were involved. Now it's cheaper to use 'cooks', make a bad product and sell for less.


General and Synthetic Methods: Volume 10 p160-168 is a good primer.

It's a Perkins Transactions papers so no DOI. I am just sifting through it now. It's one of those rare things (like the use of PyBOP to make LSD), someone actually took a paper and developed it.
 
No, 30 years ago the makers cared about quality because a lot of small producers were involved. Now it's cheaper to use 'cooks', make a bad product and sell for less.


General and Synthetic Methods: Volume 10 p160-168 is a good primer.

It's a Perkins Transactions papers so no DOI. I am just sifting through it now. It's one of those rare things (like the use of PyBOP to make LSD), someone actually took a paper and developed it.

hmm that is not relevent at all from scan reading it. It contains some stuff to do with glycine sythons in amino acid and a nucleophilic opening of an oxirane with an azide

This chirality preserving one pot chemistry looks pretty mythical at this point.

What is the nucleophile that opens the ring? and why doesn't the nucleophile add to the benzylic position primarily? the electronic configuration of the oxirane (epoxy) ring favours benzylic substitution.

The one pot chirality preserving PMK glycidate to MDMA cook route looks mythical because there is a lack of plausible mechanism, and an equal shortage of papers detailing anything that opens the phenyl oxirane rings the right way, apart from that single paper that uses Indium threobananadine sesquichloride to destabilize the intermediate cation, which you must already be famimilar with, but that would never be commercially used because it consumes stoichiometric amount of ITS-Cl which is much more expensive than MDMA and ITS-Cl doesn't work catalytically.

PyBOP LSD wasn't ground breaking, merely substituting one peptide coupling agent for another. Where the chemistry it did was exactly the same as every other single acid activating coupling agent. There was already plausible chemistry and in addition to PyBOP there are others that work just as well or even better.
 
Oh - I should point out that (R) AMT is that 'Rolls Royce' but then (S)-AMT is much more like MDMA.

Where did you get this info? I love amt and am pretty sure i have experience with the racemic compound (if thats something the CASnumber can indicate. I looked for a place to buy more amt and only found (R) aMT. In low doses its like you would expect, with energy and a general tryptamine feel. Id love to have more info on amt isomers and related subjects.
 
Where did you get this info? I love amt and am pretty sure i have experience with the racemic compound (if thats something the CASnumber can indicate. I looked for a place to buy more amt and only found (R) aMT. In low doses its like you would expect, with energy and a general tryptamine feel. Id love to have more info on amt isomers and related subjects.

Jacob Szmuszkovicz spent the 1960s working on indole alkylamines for Upjohn. There are a LOT of patents but 7,a-MT & 7-methyl a-MT & ET are listed as antidepressants.


Vector - maybe it was a bad example but the point I was trying to make that until Nichols did it, it was LIKELY to work but had not been triad with that specific precursor. This is a similar idea. Someone applied a reaction in a novel way. I'm going to go through those Perkins Transactions.... so I'm just going to go down the list as I did a few years ago but you will have to read through vide infra. If memory serves the epoxide is converted to the aziridine which is then opened. It's not an easy one to find. But I will. I do not intend to waste your time or mine.
 
Vector - maybe it was a bad example but the point I was trying to make that until Nichols did it, it was LIKELY to work but had not been triad with that specific precursor. This is a similar idea. Someone applied a reaction in a novel way. I'm going to go through those Perkins Transactions.... so I'm just going to go down the list as I did a few years ago but you will have to read through vide infra. If memory serves the epoxide is converted to the aziridine which is then opened. It's not an easy one to find. But I will. I do not intend to waste your time or mine.

great.
I would be fascinated if it did exist, but I rather think something really simple heating with acid to give the ketone PMK then reductive amination is going to win hands down in terms of cost and ease of synthesis.

epoxide to to aziridine is usually epoxide to 1,2 amino alcohol conversion of the alcohol into a leaving group like OTs OMs or ONs then base catalysed aziridine formation, the very old methods use sulfuric acid to do it and are terrible.
or epoxide to 1,2 halo alcohol then conversion of the halo to amine either directly or through the azide or direct nucleophillic ring opening of the epoxy with azide and then activation of the alcohol and ring close with reduction to the aziridine. Any reaction with an azide intermediate is likely to give a N-H aziridine except in special cases.

V
 
high-dose MDMA tablets ARE chiral.
Could this explain the supposed super MDMA I got at times that had no kick, took ages to come up and felt bordering a psychedelic rather then an Amphetaminergic.

All I can say in my defense is that I have a LOT of experience in how Chinese suppliers really will do anything they can to keep costs down. Back in about 2012 I reread a Ken Kesey quote on AMT. He said it was 'The Rolls Royce of psychedelics with a 12 hour duration'.

Know that quote, and the smelly mothball powder, which I bought. Which most prob is racemic, never got beyond being a Fiat Panda with legs.
 
Serious, this needs some explaining. How come there was MDMA available, lab tested. That had an totally different effect then the mayority of the commercial pills. Which were also just pure MDMA. Little to no adultrants over here.

The differences were an delayed come up. Akin to a psychedelic during this. No peak, just slow waves. And no fiending.

My opinion on these caps, it was MDMA but it missed the rush and kick. Weird shit, as they did contain MDMA nothing else.
 
Serious, this needs some explaining. How come there was MDMA available, lab tested. That had an totally different effect then the mayority of the commercial pills. Which were also just pure MDMA. Little to no adultrants over here.

The differences were an delayed come up. Akin to a psychedelic during this. No peak, just slow waves. And no fiending.

My opinion on these caps, it was MDMA but it missed the rush and kick. Weird shit, as they did contain MDMA nothing else.

Were the dosages comparable? The most popular pills in Europe are ~250mg these days.
 
Were the dosages comparable? The most popular pills in Europe are ~250mg these days.
Hazy memory but this was around 2000 I guess. Pills at that time were on average between 80/ 120mg. Once in a while a high dose pill turned up.

But these were not better or more specteculair. The press or stamp said more about the experience then the dosage.
 
Hazy memory but this was around 2000 I guess. Pills at that time were on average between 80/ 120mg. Once in a while a high dose pill turned up.

But these were not better or more specteculair. The press or stamp said more about the experience then the dosage.

Are you comparing pills to capsules in 2000, or the MDMA available today to the pills you had in 2000?
 
@emkee_reinvented,
How come there was MDMA available, lab tested. That had an totally different effect then the mayority of the commercial pills. Which were also just pure MDMA. Little to no adultrants over here.

We have literally been trying to figure this out for 260 pages and several years in the other thread. Many, many, many people have commented on it and encountered this "Meh-DMA" with subpar effects, longer comeup, lack of peak, "no kick" as you said. Many people have sent samples to labs, and the results are MDMA. We are trying to figure it out, believe me.

 
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