PMA & MDMA; a new look at an old devil

PMA & MDMA; a new look at an old devil

News articles highlighting the dangers of ecstasy often claim PMA is a contaminant in MDMA. Paul Dillon was once quoted as saying PMA was produced from side reactions during synthesis, but no satisfactory explanation was offered which described how his occurred. Biscuit and I have argued against the idea that para-methoxy amphetamines could be produced from safrole via opening of the methylenedioxy bridge, as this would seem impossible with conditions normally employed in typical MDMA syntheses. Even if this did happen, no significant amount of PMA would be produced, as the amine used in producing MDMA is methylamine which would instead produce the N-methyl product PMMA.



However, unlikely as it is that PMA would be present as an impurity in MDMA, a recent article on establishing profiling parameters for forensic testing of Ecstasy indicates PMMA is a characteristic contaminant in MDMA. In fact, PMMA is a route-indicating impurity used by forensic chemists to determine such things as the method of synthesis and starting materials.

Optimization of extraction parameters for the chemical profiling of
3,4-methylenedioxymethamphetamine (MDMA) tablets
Pascal Gimeno, Fabrice Besacier*,
Huguette Chaudron-Thozet

Laboratoire de Police Scientifique de Lyon, 31 Avenue Franklin Roosevelt, 69134 Ecully, France

Received 9 October 2002; received in revised form 6 January 2003; accepted 10 January 2003

Full text article available atRhodium

Click to expand...

So where does the PMMA come from?


The answer is that it simply comes from sassafras oil - principle source of safrole - via another constituent of the oil known as anethole. Although distillation is required to separate the safrole from the other components of the oil, it would be impossible to completely separate anethole from safrole with distillation, as the boiling points are too close.

Boiling Point of Anethole = 233-235 deg C

Boiling Point of Safrole = 232-234 deg C

Boiling Point of Isosafrole = 253 deg C


Look, it really does get through!


Besides the characteristic ring substitutions (red = methylenedioxy for MDXX & blue = para-methoxy for PMXX) Safrole is also different to anethole in that safrole has a terminal double bond involving second and third (end) carbons in the alkyl chain, whereas anethole has the double bond between the first and second carbons of the alkyl side chain like isosafrole. With routes to MDMA involving the ketone, it is usually required that the safrole be first isomerised to isosafrole. Any anethole present at this stage would sit quite comfortably through the safrole isomerisation process.



What about purification of Isosafrole?

Isosafrole is to MDMA what Anethole is to PMMA, but as stated anethole has a boiling point around that of safrole which means most should be removed by fractional distillation of the isosafrole. This explains the absence of anethole in the commercially produced ketone.
Impurities in Commerically available MD2P2



However, if during an MDMA synthesis the isosafrole was not sufficiently purified (as could be expected with some clandestine labs) any anethole would then be processed via the same routes intended for the isosafrole, with the PM products passing through purification processes to produce PMMA as part of the final product. Of course if MDA was made instead of MDMA, the corresponding paramethoxy amine produced from the anethole would be PMA


But how dangerous is all this?

To keep things in perspective, even if techniques were very sloppy, it is not thought the total amount of PMMA or PMA synthesised would amount to little more than a small percentage of total amine produced (% IMO). While literature lists anethole as one of the major constituents of sassafras oil, the actual percentage is low compared to the active ingredient safrole. I would then think it unlikely that levels of PMMA found in street MDMA would be high enough to be of great concern to immediate health, but I couldn’t say for sure on this.

Other Goodies

PMMA is only one of the commonly found contaminants in MDMA. Another allyl-benzene present in safrole produces 3,4DMMA. This compound is also probably active, but would not be thought to be present in large enough quantities to cause any effect.

In all, mixtures of any of these compounds – including many toxic, non-active chemicals - are present in all MDMA. Although they should only be present in very small amounts, one can’t help but wonder if the roll is ever affected by them.



Open to all scrutiny

phase_dancer



Other References ;

http://sun.ars-grin.gov/cgi-bin/duke/chemical.pl?ANETHOLE

http://www.erowid.org/library/books_online/pihkal/pihkal055.shtml

-(thanks to Rhodium for the forensics article)-

Fantastic post phase_dancer, excellent reading and very informative

another excellent analysis phase_dancer!

nice post!
Just out of interest, was or is anethole used in the flavouring industry as iso/safrole was?

^ Unfortunately yes and yes. Such sources no doubt also provide a *safer* way for low life PMA producers to purchase the precursor. Safrole, once widely used, was removed from use as a flavouring due to it being classed carcinogenic. Piperonal was (and possibly still is) used as a synthetic vanilla flavouring. Isosafrole was also listed until quite recently, although it would be tightly regulated. It's also likely that a suitable synthetic replacement for isosafrole is now employed, as it too has recently been suspected of being carcinogenic. This happened with safrole/sassafras when Double Sass was taken off the market following the listing of safrole. Some years later when an effective synthetic sassafras flavouring had been developed, the drink returned to the shelves. Odd though, I've never been able to find out what this new sass flavour is. I have my suspicions, but enough said...

Other starting materials including benzaldehyde (almond flavour) and anisaldehyde (aniseed flavouring and another PMA precursor) are also listed in current flavourings and fragrance catalogues, but it's also quite reasonable to think that someone somewhere is monitoring large orders/imports of these compounds to new, or outside the industry companies.

In short many flavourings are listed as watched chemicals and those selling them are highly encouraged to report suspicious or unusual orders. But as with all such commodities, in a practical sense, complete regulation is all but impossible.

Brilliant post and I do agree with the entire analysis.

And to re-emphasise the point, whilst all these related compounds may be watched, the sad thing is isosafrole will send off fire alarms all over the country. The antheole probably a clock alarm in one persons house. The former makes MDMA the latter makes a killer.

Great work phase_dancer, interesting read.

^: Great post, Phase_dancer!!!

BigTrancer

Phase_dancer you are a champion! Thank you!!

agreed!

Good stuff!
Is powdered MDA hard to find because PMA can be produced as a contaminant in a synth? Although this would be in insignificant quantities yes?

Yes there would only be likely to be a very small amount of PMA if MDA was produced as described above. I think the reason MDA is less common in powder form is simply because there is less demand for it than for MDMA and so less is probably imported.

So could this explain why you can get two pills each with the same amount of MDMA could give you a good feeling with one, and a dirty feeling with the other? Could the quality of the peak be related to the level of contanimation from PMXX. ie would x-score have taken the time to completely isolate the anethole from the safrole by a complex and long process, yet a cheap back yard op will not bother?

I think Timmmy brought up a good point in another thread that a good pill may not be a factor of the perfect blend of chemicals, but the purity of the chemicals used. This is my personal opinion.

It would seem that any amount of PMMA or PMA produced from anethole as outlined would be too small to cause noticeable affects. Without comparing known differences in levels (say 70mg MDMA /1.5mg PMA to 70mg MDMA /2.5mg PMA) its impossible to say and I definitely wouldn't be prepared to suggest that this alone accounts for the variation in effects from pills of the same or different batches. There are just too many unknown variables involved.

As for the x scores; like many produced via commercial sized operations they were produced from MDP2P (see microgram- April) As mentioned above, commercially sourced MDP2P is not (to my knowledge) reported to contain anethole as a major impurity i.e. anethole is not present in amounts >0.1%

In regards to purity etc and impact on effect; when the first wave of Mitsubishis came out in Europe they were possibly the first pills mass produced from commercial PMK or MDP2P. Although the MDMA was pure and chemically no different from MDMA produced from safrole or piperonal, the purists claimed the *feel* of the high was less natural than the old safrole pills. Perhaps the impurities from the safrole route produced a better stone? Who knows, but technically the only differences between a product produced by different routes should be the types and amounts of contaminants (apart from specific isomer selective processes).

In the end it's all guess work when you can't evaluate each and every pill thoroughly. Let's just hope that's not too far away.

A bit off topic, but i used to know this really bizarre guy who only slept once a week (with or without drugs), anyway he used to hate MDMA/MDA but he LOVED PMA, he had a pma dealer and thats the only pills he ever took. He was a strange bloke though, but he said MDMA gave a bad comedown but PMA wore off real smooth for him.