Author Topic: Question on A/B extraction of PSE  (Read 754 times)

embezzler

  • Subordinate Wasp
  • ***
  • Posts: 228
Re: Question on A/B extraction of PSE
« Reply #40 on: December 10, 2010, 06:42:54 PM »
I would have to concur with prepuce here that as far as I can remember the distinction made between a weak and strong acid was the completeness of the dissociation into protons and their respective anions in aq. solutions. The proton in HCL and the first proton in H2SO4 should easily be completely liberated in water (second may be slightly more difficult but not too much would be my guess). I would really appreciate correction on this point if I am wrong as this was learned when I initially started learning chemistry and remained a fast rule which was not reexamined??? Is this not the case?

Perhaps both myself and Prepuce are off beam slightly and Sedit you are referring to the attraction between the amine and the hydrochloride entities? That is an interesting suggestion but I doubt, considering the established history of the PSE molecule in medicinal preparations, that there is any amine left as a freebase when an excess of the acid is present. Worth looking into though, good suggestion! 8)

More likely to impact proceedings in terms of association and dissociation is the interaction of the PSE from the polymer units. A sacrificial molecule here may displace the PSE from these polymers. 
All that we see or seem is but a dream within a dream...

Prepuce

  • Mighty Bhagwan
  • Subordinate Wasp
  • ***
  • Posts: 100
Re: Question on A/B extraction of PSE
« Reply #41 on: December 12, 2010, 04:55:45 AM »
Some of what we've been discussing is awfully reminiscent of a method used several years ago, the name of which I no longer recall. I used to wonder how it worked and how the person who thought of it came to have the inspiration. I think I more or less understand it now, and it agrees with much of what I've read as well as what's been said so far in this thread.

This is from memory so it's unlikely to be completely accurate, but I think it's pretty close.

A small amount of tetrachloroethylene was added to the powdered mass from which PSE was to be extracted, and given a minute or two to swell the polymers. No one put it in those terms but it was visible. The mass was then added to a solution at room temperature of NaCl, citric acid, weak acetic acid (white vinegar), salt, and a layer of naptha. This mixture was slowly heated and at the same time base was added, until at last the solution was strongly basic and boiling. At that point the naptha was separated from the rest and chilled to let the PSE freebase crystallize out.

The procedure worked very well for some time, and I no longer recall what was eventually added that caused it to fail. But if you take a step back you can see the logic. It took the pillmass through a sweep of both temperature and pH. If it was allowed to dwell long enough at the isoelectric point of the polymers, most of the pse would have migrated into the hot naptha along with little else.

One of the most difficult aspects of the problem as it stands today is, IMO, identification of additives. Certainly polymers are still in the mix, sometimes acrylics, maybe Eudragit, and the whole range of metal salts, sugars, cellulose derivatives, etc. Several people have stated their preference for discussing specific compounds in this thread and I couldn't agree more. But how are they to be identified? The fact that this information is generally not available is a big part of the problem.

As a recent example, it has been reported that over the last year a substance not previously seen in this context has apparently been added to the mix of most pills. It is indistinguishable from PSE through most phases of an extraction, and only if heated in a non-polar does it take on a pinkish color. Isolated and dried, it's a pink wax. Whatever this is, it seems to attach itself to the PSE and is able to follow it around through nearly any operation that can be performed. It interferes with a reaction although it is not reported to stop or completely poison it. It continues to follow the compound of interest through steam distillation and recrystalklization, only showing up again when vaporized, where it shows up by taking on a tan color. It opposes crystal formation as the melted product cools, turning it instead into an amorphous looking mass.

Does anyone have any ideas on what it might be?

PP
Support the never ending quest for new and better hedonicants. Send your gift today to:

 N & B H Foundation, Attn. Bhagwan SP
 University of Massachusetts at Los Angeles
 PO Box 6.02 X 10^23
 Houston, MD 884411

zzhuchila_clocker

  • Subordinate Wasp
  • ***
  • Posts: 167
Re: Question on A/B extraction of PSE
« Reply #42 on: December 13, 2010, 10:09:41 AM »
Prepuce, i think any stronger chelating agent would break complex with PSE/EPH.
What it could be among OTC reagents, im not sure but i suppose :
glutamic acid(in basic solution)(that is widely used as sodium glutamate seasoning for chinese food),
thiosulfate(solution for infusion on pharmacies) that reduces Cu(2) to Cu(1) with further formation of thiosulfate complex of Cu(1)
maybe ammonia (not sure, pH may also play a role as 2+ charged PHE/EPH complex is less stable then 0 charged(the one that is possible to extract), and it may form either in neutral pH, or only in alkaline, i dont know, so better to use not too high pH).
Maybe diols like sorbitol or sugars in alkaline media also.
The indication of complex destruction(it is still quite stable, not all chelators may suit) could be the docolorizing of organic layer(coloured complex with amine) with some chelating agents that form insoluble in organic phase chaletes(glutamic acid, ammonia, thiosulfate, maybe citrate etc). At the same time amine would be transferred to organic layer
« Last Edit: December 13, 2010, 10:11:59 AM by zzhuchila_clocker »
Who stuff the banks? Who staff the party ranks? More for Gore or the son of a drug lord?
None of the above, fuck it, cut the cord!
Lights out.. guerrilla radio
Turn that shit up

Prepuce

  • Mighty Bhagwan
  • Subordinate Wasp
  • ***
  • Posts: 100
Re: Question on A/B extraction of PSE
« Reply #43 on: December 17, 2010, 09:14:54 PM »
zclocker,

That's an intriguing suggestion. It's a subject almost totally unknown to me, and I confess I've skipped over it in the past for no good reason that I can recall. Thanks.

PP
Support the never ending quest for new and better hedonicants. Send your gift today to:

 N & B H Foundation, Attn. Bhagwan SP
 University of Massachusetts at Los Angeles
 PO Box 6.02 X 10^23
 Houston, MD 884411

jon

  • Foundress Queen
  • *****
  • Posts: 1,883
Re: Question on A/B extraction of PSE
« Reply #44 on: December 17, 2010, 09:59:35 PM »
i think that additive you are talking about is a polymer known as poly vinyl pyrollidinone
it is nitrogeneous and bears a ketonic oxygen.
so in basic conditions it will form a shiff's base with the amine and in acidic conditions it is protonated and water soluble.
hence it "follows the amine around wherever it goes" as you stated.
so the strategy would be to get rid of the polymer by boiling it in perchloethylene first, then extract.
maybe the state of the art has changed over the years but that was once of the main strategies employed.
perchloroethylene is preferable overr dcm and chloroform because the amine hcl is soluble in both due to polarity issues.
« Last Edit: December 18, 2010, 01:42:41 AM by jon »

zzhuchila_clocker

  • Subordinate Wasp
  • ***
  • Posts: 167
Re: Question on A/B extraction of PSE
« Reply #45 on: December 18, 2010, 10:04:42 AM »
Prepuce: this infomation was also new for me. I think metal complexes are bearing a big potentail for home chemists and are neglected undeservingly. As for using complexes in PSE/EPH extraction, i am not sure it is a good option because usual extraction would give same result. But for purification, identification and qualitaltive analysis of propanolamines in pills it may be promising      
Quote
is nitrogeneous and bears a ketonic oxygen.
so in basic conditions it will form a shiff's base with the amine and in acidic conditions it is protonated and water soluble.
not exactly, PVP is an amide, amides differ greatly from ketones and amidines(corresponding "shiff bases" of amines) are not formed that easy..
btw, wiki claims that PVP is water soluble
Quote
Polyvinylpyrrolidone (PVP), also called Polyvidone, is a water-soluble polymer ...
 if solubility is low, concentrated urea may probebly increase it, as due to its ability to break down the water's hydrogen bond system it generally increases solubility of low soluble compounds , for instance: http://www.faqs.org/patents/app/20090105312
« Last Edit: December 18, 2010, 10:30:56 AM by zzhuchila_clocker »
Who stuff the banks? Who staff the party ranks? More for Gore or the son of a drug lord?
None of the above, fuck it, cut the cord!
Lights out.. guerrilla radio
Turn that shit up

jon

  • Foundress Queen
  • *****
  • Posts: 1,883
Re: Question on A/B extraction of PSE
« Reply #46 on: December 18, 2010, 08:41:13 PM »
why not ion exchange resins?

Prepuce

  • Mighty Bhagwan
  • Subordinate Wasp
  • ***
  • Posts: 100
Re: Question on A/B extraction of PSE
« Reply #47 on: December 21, 2010, 07:01:14 AM »
jon, thanks  for the tips. Although I know that perchlorethylene has been tried without success, it will still be a big help if you're right about the unknown substance. If nothing else it gives me another avenue to research.

zclocker, as I said the subject of complexes is very new to me. I've never had a need to understand them before. But from what I read in the pdf you posted the copper forms a covalent bond with the nitrogen in the PSE molecule. (It's still a mystery to me why this needs a special name, unless it's because you would normally expect copper to form ionic bonds.)

I'm afraid I tend to use the term extraction more or less synonymously with purification, but youj're correct. Purification is the challenge.

The test mentioned in the pdf has been successfully used to identify PSE. This alone is beneficial, since previously there was no commonly known way of identifying the substance.

The copper ion bonds with the same nitrogen that the HCl attaches to in the salt, and that's obviously why one of the test reagents is NaOH, since the freebase is needed. It seems as though a strong base would again serve to form the freebase and be rid of the copper, but I'm not sure about that. In case it wasn't clear, the ultimate objective would be to have fully purified pse at the completion of purification.

Would any of the chelaters you listed leave the PSE as a freebase? Unless we can back to that point nothing has really been accomplished, since ultimately we probably want the replace the HCl in that position.

I hope at least some of this is making sense. I'm getting tired, and although it makes sense to me at the moment I'm not sure my opinion will be similar tomorrow, so I'll stop for now. Thanks to everyone who has responded. It's all interesting.

PP
Support the never ending quest for new and better hedonicants. Send your gift today to:

 N & B H Foundation, Attn. Bhagwan SP
 University of Massachusetts at Los Angeles
 PO Box 6.02 X 10^23
 Houston, MD 884411

zzhuchila_clocker

  • Subordinate Wasp
  • ***
  • Posts: 167
Re: Question on A/B extraction of PSE
« Reply #48 on: January 03, 2011, 04:09:43 PM »
Quote
It seems as though a strong base would again serve to form the freebase and be rid of the copper, but I'm not sure about that.
no, base won't do that. acid - yes, as you said base is used to generate a free base, but as you can see the complex is being extracted into ether, that means it is not charged. That means, base also deprotonates 2 OH groups to make them O-, so the total charge of complex is 0. This may require a very high pH, like 13+, or it may be taking place at pH just above 8, i dont know.
Who stuff the banks? Who staff the party ranks? More for Gore or the son of a drug lord?
None of the above, fuck it, cut the cord!
Lights out.. guerrilla radio
Turn that shit up

Prepuce

  • Mighty Bhagwan
  • Subordinate Wasp
  • ***
  • Posts: 100
Re: Question on A/B extraction of PSE
« Reply #49 on: January 14, 2011, 05:19:14 AM »
Happy New Year everyone.

ZC, you've really lost me in this one. You say that

"That means, base also deprotonates 2 OH groups to make them O-, so the total charge of complex is 0. This may require a very high pH, like 13+"

Where would the second OH group come from? PSE only has one. Hopefully mine is a fundamental misunderstanding here. Otherwise I may have to ask more questions.  ;D
PP
Support the never ending quest for new and better hedonicants. Send your gift today to:

 N & B H Foundation, Attn. Bhagwan SP
 University of Massachusetts at Los Angeles
 PO Box 6.02 X 10^23
 Houston, MD 884411

zzhuchila_clocker

  • Subordinate Wasp
  • ***
  • Posts: 167
Re: Question on A/B extraction of PSE
« Reply #50 on: January 14, 2011, 04:05:27 PM »
yeap you are right, but chelate may consist of 2 PSE molecules, PSE ligands make it more hydrophobic, and OH deprotonation provides a neutral charge, so it can be extracted with ether  
Who stuff the banks? Who staff the party ranks? More for Gore or the son of a drug lord?
None of the above, fuck it, cut the cord!
Lights out.. guerrilla radio
Turn that shit up

Prepuce

  • Mighty Bhagwan
  • Subordinate Wasp
  • ***
  • Posts: 100
Re: Question on A/B extraction of PSE
« Reply #51 on: January 21, 2011, 04:25:31 AM »
ZC, sorry it's taken me so long to respond. It sounds like you're quite knowledgeable on the subject of chelates, and I'm having a hard time keeping up with you. Let me see if you agree with my summary.

PSE combined with copper forms a complex with a charge of zero, which should release it from the grip of any polymers/surfactants or the like. This complex is soluble in ether, and that would be the preferred method of extraction. Once extraction is complete, the complex would need to be treated with monosodium glutamate to break the PSE bond with copper, which would form another compound that wouldn't interfere with separation of the PSE.

Further questions that I haven't found answers to include the following. What defines a complex? Does the Cu actually form a covalent bond with the PSE, or is something else happening. What are the chances of breaking this bond without damaging the PSE in some other way? How likely is it that all of the Cu can be removed from the PSE? It wouldn't do to have traces remaining.

You've supplied a lot of information and it's much appreciated. This is such a new area of chemistry to me, however, and information seems to be so sparse, that anything additional you can supply would be much appreciated.

Jon: I didn't mean to overlook your comment on ion exchange resins. I know that someone has been working on that over at the other board. I need to look in to see how it's coming. At last check it looked promising. I was going to look into it but couldn't find the suggested resin. From there it kind of went on the back burner.

PP
Support the never ending quest for new and better hedonicants. Send your gift today to:

 N & B H Foundation, Attn. Bhagwan SP
 University of Massachusetts at Los Angeles
 PO Box 6.02 X 10^23
 Houston, MD 884411

zzhuchila_clocker

  • Subordinate Wasp
  • ***
  • Posts: 167
Re: Question on A/B extraction of PSE
« Reply #52 on: January 22, 2011, 07:30:30 PM »
Quote
PSE combined with copper forms a complex with a charge of zero
Yes, there are probably also 2+ and 1+ charged chelates at lower pH, but at high pH charge becomes 0
Quote
which should release it from the grip of any polymers/surfactants or the like.
yes
Quote
This complex is soluble in ether, and that would be the preferred method of extraction.
Yes, it is soluble in ether but in water it is soluble too. The resolution value(or how it is called in extraction, i dont remember exactly) that is a ratio between concentrations in organic layer and water, may be not that high for this complex. If it is even 1/5 (ether:water), or even 1/25, it is sufficient to colorize ether layer, so for analysis it is ok. But for you it means using gallons of ether for complete extraction. I dont know what this resolution value can be even approximately, maybe it is sufficient enough and the substance can be fully extracted with several portions of ether. There should be data on resolution values for inner-complex compounds(chelates charged zero) in literature, but i am not sure PSE or EPH complexes are there. You may probably use similar hydrophobic structures to estimate resolution value. But the best way is to do it experimentally, by changing an ether layer for a new portion of clear ether. If resolution value is high enough, the colour would be much less then in previous portion. You can also add saline compounds to increase a resolution value. Still if there is no possibility to extract the chelate completely, it does not mean using it for isolation is impossible. For example, this can be used to get rid off other amines by extracting them at pH values when PSE complex is charged 1 or 2+ and thus not extracted.
Quote
Once extraction is complete, the complex would need to be treated with monosodium glutamate to break the PSE bond with copper, which would form another compound that wouldn't interfere with separation of the PSE.
Yes, this hopefully can be glutamate. Zero charged complex is still quite stable, maybe more stable then glutamate, better to try at pH values at which complex is charged 1 or 2+. You can try to find data on these complexes stability in books, if there is no such data on PSE - you can assume that stability of monoethanolamine copper chelates is quite similar. Btw, monoethanolamine, if you can find it, would definitely release PSE. Edetic acid as well.
      
Quote
What defines a complex? Does the Cu actually form a covalent bond with the PSE, or is something else happening. What are the chances of breaking this bond without damaging the PSE in some other way? 
There are plenty of books about complexes, or having chapters dedicated to complexes. Better to start with inorganic chemistry books(basic theory, nature of bond, geometry(for inorganic ligands mostly) and analytical chemistry(chelates and their stability, inner complex compounds, resolution value etc). The bond is donor-acceptor, it is not covalent(otherwise, how valency of copper can be 4?). No chances of breaking down unless you use extreme conditions. Moreover, in complexes, ligands generally become more chemically stable then without metal, this should be fair for PSE as well. Of course there are exceptions, but without harsh conditions and oxidizers nothing should happen.
Quote
How likely is it that all of the Cu can be removed from the PSE? It wouldn't do to have traces remaining.
This is quite possible. That should depend on a method of breaking down copper complex, and a ligand used for that. If the difference between stability of these chelates is quite big, like 10^5, then there would be small trace of copper, if it is not that high (like 10^2) you can get about 1% of copper chelate in your PSE if you use equimolar amount of chelator. If you use 2 fold excess, then it should be 0,01% of copper chelate. But maybe simple recrystallizing can diminish it even more then using excess of chelator. Of course, better is not to administer such PSE or EPH or ephedrone, unless an appropriate analysis of copper presence is not been done(maybe flame analysis? it is having a rather low threshold of determination of copper if i'm not mistaken, better to inquire in literature what can be used). Otherwise it may be hazardous, maybe not that hazardous as Mn, but this should be inquired. Good question.   
« Last Edit: January 22, 2011, 08:08:19 PM by zzhuchila_clocker »
Who stuff the banks? Who staff the party ranks? More for Gore or the son of a drug lord?
None of the above, fuck it, cut the cord!
Lights out.. guerrilla radio
Turn that shit up

Prepuce

  • Mighty Bhagwan
  • Subordinate Wasp
  • ***
  • Posts: 100
Re: Question on A/B extraction of PSE
« Reply #53 on: February 07, 2011, 05:36:33 AM »
Well, ZC, I think you're right. I'm going to have to hit the books about this. I can't believe I haven't run into complexes before, since it's not like it's an obscure topic. But I don't believe I learned anything about them in school, and I've evidently been flipping by the subject in books. It actually sounds quite interesting as well. (I've never heard of a donor-acceptor bond either.) Maybe I've missed the subject because I'm always reading about preparative chemistry, and seldom analytical.

At any rate, I'm glad you brought it up.

Cheers,
PP
Support the never ending quest for new and better hedonicants. Send your gift today to:

 N & B H Foundation, Attn. Bhagwan SP
 University of Massachusetts at Los Angeles
 PO Box 6.02 X 10^23
 Houston, MD 884411