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Halogenated Hydrocarbons.

Migrated topic.

Heulas

Rising Star
So, i've found a solvent that claims to contain:

Hydrocarbons C6 isoalkanes, <5% N-Hexane, >30% Alifatic Hydrocarbons, isoalkanes, 5%/15% Halogenated Hydrocarbons.

I have some spice extracted with this solvent, i noobly used it as it was commercially named as another i always used without problems, but this batch just evaporate with residue and leaves it a grossy goo (probably the residue + plant stuff) on the dish even with freeze precipitation.

As far as i know, everything is fine, except for the "5%/15% Halogenated Hydrocarbons" which is the only compound i can't find people talking about here on the Nexus, could be this compound the problem?
 
could be this compound the problem?
That describes a mixture of compounds, of which there are numerous possibilities. Typically, halogenated hydrocarbons as solvents might be trichloroethylene, trichloroethane, DCM or (as described in the other thread) tetrachloroethylene. Maybe chloroform. Any of these would be a 'better' solvent than the light naphtha described in the rest of the contents. Thus it will pull more gunk from your extraction mixture.


I just wish I had taken the chance to avail myself of at least one of those bottles of trichlorotrifluoroethane when I had the chance.
 
I see, thank you.

Anyway i discarted the product, as it leaves residue upon evaporation.

I also discarded the spice, as after one week of drying it still smelled of solvent and i couldn't find a way to remove the smell/traces, nor with re-x, nor with mini A/B, the problematic residue would inevitably go into the new NPS and manifest itself everytime.

Considering my chemistry ignorance: better safe than sorry.
 
You should wash your base phase with a decent, pure NPS in such circumstances. Always a shame to ditch spice.


Anyway i discarted the product, as it leaves residue upon evaporation.
The product left residue? Surely that's the extra gunk pulled by the unusual solvent?

How do you perform your recrystallisations?
 
downwardsfromzero said:
Surely that's the extra gunk pulled by the unusual solvent?

Could have been, but after further re-x with hexane it still remained and smelled like solvent, or at least very similar to it.
Edit:
About re-x, i follow the very basic method: dissolve with minimum amount of solvent heated in water bath, throw in the freezer.

Could have been some other form of spice, or other spice at all, but i couldn't find a way to test it.
 
Unfortunately, discussing the nature of odours over the internet is fraught with difficulties. Are you fully familiar with the odour variants of DMT and the various comparison substances? I find highly refined DMT to smell faintly floral and almost sweet. Cruder material might resemble naphthalene mothballs and/or veer towards somewhat faecal.


Re-x: slower cooling makes bigger crystals, on the whole.
 
downwardsfromzero said:
Unfortunately, discussing the nature of odours over the internet is fraught with difficulties. Are you fully familiar with the odour variants of DMT and the various comparison substances?

Thaaaat's one big thing.

Anyway, the problem was that the solvent iteslf evaporated leaving residue, so there are still some risky variables about the nature of that residue.
 
Heulas said:
Anyway, the problem was that the solvent iteslf evaporated leaving residue, so there are still some risky variables about the nature of that residue.

:?:
Could you evaporate some of the unused solvent to test whether it leaves any residue? Or is that what you meant by: "the solvent itself evaporated leaving residue?"

Here's why I ask: I have been interested in the potential of the halogenated hydrocarbon chloroethane (ethyl chloride) as a solvent for mescaline and related alkaloids. At first glance it seems to have similar qulaities to choloroform, DCM (low boiling, sparingly miscible with water, low polarity), but unlike these EtCl is readily available at the consumer level in medical grade and, most important to me, seems to be less toxic* at the level of exposure I predicted for my cactus extractions.

My understanding of organic chemistry is very basic so I looked for any research that would shed some light on the use of EtCl as a solvent for phenylethylamine fb and salts. Notably I found the study "The Action of Ephedrine on Halogenated Organic Compounds" (published c. 1940) in JOURNAL OF THE AMERICAN PHARMACEUTICAL ASSOCIATION (links: sciencedirect, jpharmsci, DocSlide download).
Steldt said:
The fact that ephedrine base reacts with chloroform to give ephedrine hydrochloride was first pointed out by Peterson in 1927 (1). To date no other organic compounds have been reported to have a similar reaction with ephedrine, although a priori it would seem possible. In order to test the validity of this idea, the present investigation was undertaken.

The article gives the reaction times and reaction products of ephedrine base (pKa = 9.6 for eph whereas pKa = 9.56 for mesc) to associated salts in common halogenated hydrocarbons (precipitated as residue?).

9TJnxFk.png


I don't know how applicble this is to DMT but I thought I'd offer that data. Good luck.
*
 
One of the reasons why using ethyl chloride is not practical is its low boiling point: 12 degrees centigrade.

Another reason is that is is more commonly used as an alkylating agent than as a solvent. You would be ending up with some N-ethyl mescaline or even N,N-diethyl mescaline.

The publication that you quoted seems to hint at the alkylating effects of the clorinated solvents on freebase amines. The reaction forms HCl as byproduct, which in turn reacts with the freebase amine to the HCl salt. It is a bit curious that the formation of alkylated amines is not reported in the article. Perhaps one of the resident chemists could chime in on the details here?
 
someblackguy said:
Heulas said:
Anyway, the problem was that the solvent iteslf evaporated leaving residue, so there are still some risky variables about the nature of that residue.

:?:
Could you evaporate some of the unused solvent to test whether it leaves any residue? Or is that what you meant by: "the solvent itself evaporated leaving residue?"

Here's why I ask: I have been interested in the potential of the halogenated hydrocarbon chloroethane (ethyl chloride) as a solvent for mescaline and related alkaloids. At first glance it seems to have similar qulaities to choloroform, DCM (low boiling, sparingly miscible with water, low polarity), but unlike these EtCl is readily available at the consumer level in medical grade and, most important to me, seems to be less toxic* at the level of exposure I predicted for my cactus extractions.

My understanding of organic chemistry is very basic so I looked for any research that would shed some light on the use of EtCl as a solvent for phenylethylamine fb and salts. Notably I found the study "The Action of Ephedrine on Halogenated Organic Compounds" (published c. 1940) in JOURNAL OF THE AMERICAN PHARMACEUTICAL ASSOCIATION (links: sciencedirect, jpharmsci, DocSlide download).
Steldt said:
The fact that ephedrine base reacts with chloroform to give ephedrine hydrochloride was first pointed out by Peterson in 1927 (1). To date no other organic compounds have been reported to have a similar reaction with ephedrine, although a priori it would seem possible. In order to test the validity of this idea, the present investigation was undertaken.

The article gives the reaction times and reaction products of ephedrine base (pKa = 9.6 for eph whereas pKa = 9.56 for mesc) to associated salts in common halogenated hydrocarbons (precipitated as residue?).

9TJnxFk.png


I don't know how applicble this is to DMT but I thought I'd offer that data. Good luck.
*

there is actually a similar paper that specifically pertains to DMT reacting with methylene chloride, there are a couple threads on the forum about it already.

They found that solutions of DMT in DCM when stored for long periods forms crystals of the quarternary salt as an alkylation product between dcm and dmt.


DMT is slightly different in this respect, it is a tertiary amine, but its actually more nucleophillic. Basicitiy tends to increase with alkylation of amines, which plays an obvious role in nucleophlicity however in the case of DMT it is not significant. Dimethyltryptamine is particularly nucleophilic not only due to low steric restrictions, but due to inductive electronic effects from the N-methyls.

This is why it is so difficult to avoid overmethylation to the quartnary salt with methyl halides, it is difficult with even longer chain alkyls but methyl in particular, the rate of reaction is extremely fast in comparison. Understanding this, it is not too surprising to see DCM as just the methylating agent given enough time.

So this doesn't necessarily correlate to mescaline, a primary amine. You'll note in that paper that DCM (and chloroform) isn't listed. DCM is relatively inert, it is still used all the time to solvate amines in synthesis, even as a reaction solvent. Still, It is bad practice to leave out freebase amines in organic solvent anyway, typically they degrade fast. So especially regarding this, do not leave them out in halogenated solvents.

In the paper you posted the reaction product observed is just the hydrochloride salt, which is nothing to worry about, since you would be extracting the alkaloid as the salt anyway if you are using halogenated solvents. It appears to be an elimination reaction of the halogenated solvent promoted by the freebase amine.

In my experience, I used DCM to solvate both dmt and mescaline. I never saw any evidence of the quartary salt, but the freebase DMT is never in contact with the DCM for longer than 5 or 10 minutes since I salt it out immediately after extraction. It is bad practice to leave out freebase amines in organic solvent anyway, typically they degrade fast. However I never found any trace of the DCM alkylation product by NMR, nothing a recrystallization couldn't handle. Always recrystallize fumarates anyway for asthetics.

With mescaline, I actually salted it out of DCM directly as the sulfate salt, which gave BRILLANT crystals, heheh, and not a trace of anything by HNMR, but NMR is only useful down to the 1/100th and 1/1000th range, benzyme ran a mass spec on this same sample, which can detect down to the picogram 10^-12, as it was synthetically produced he mentioned it was more pure than the extracted mescaline, but i wonder if you could see an alkylation product if you went looking.. im sure its possible considering he had problems with plasticizers in the spectrum from the caps of the solvent bottles.

---

regarding your residue, keep in mind some of your chlorinated solvent will be very high BP and not easily evap. It may smell sickly sweet, characteristic of chlorocarbons. Don't evap. Salt it out.
 
Thanks for that. :thumb_up: Sorry for the sidetrack; I should've studied Heulas question in the OP before I took up half the loving page.:roll:

Heulas said:
As far as i know, everything is fine, except for the "5%/15% Halogenated Hydrocarbons" which is the only compound i can't find people talking about here on the Nexus, could be this compound the problem?

I dunno.

pitubo said:
One of the reasons why using ethyl chloride is not practical is its low boiling point: 12 degrees centigrade.

I'll vouch for that, as demonstrated in my first, and so far only, experiment with EtCl as a solvent and a safer (?) route to Mescaline HCl (?) without the need for the added muriatic or dreaded HCl gassing. I'm good with the H; it's them Cl- what makes me nervous.

It was A/b of potent cactus with ethyl acetate as my organic phase (if that makes sense, sorry I'm in over my head here. I'm more conversant in the humanities, "right brain", associative, unqualifyingly qualitative, metaphoric social science slice of the entheogenic pie... y'know: nonsensical bullsh&%). Anyway I wanted to see if EtAc would be a useful addend to my cactus extractions (for the same reasons, not safe but not as dangerous as some other chems, and a possible route to mescaline acetate as the ester broke down (hydrolyzed?) into EtOH and acetic acid, also not safe per se but not as dangerous:)?: ?) as some solvents... On a whim I decided to combine two experiments in mescaline freebase solubility in unknown solvents: first pulling with ethyl acetate out of basic layer and then further refining by dissolving the EtAc extract into our halogenated hydrocarbon, EtCl. (thoroughly unscientific hackery I know). I decided to use the can of poppers I'd snagged on a trip to the Castro's sex shops for its labeled purpose: as a solvent, to selectively :)?: ?) pull actives out of a dirty EtAc extract resin—as one has wont to do.

"Well...Ok then." I thought as I read the words on the label of "Slam N. Mann Brand: Hog Wild II" or some ridiculous who-are-we-kidding name. "100% Ethyl Chloride: Solvent" the label proclaimed of its compressed liquid contents in perhaps the most paper-thin ploy at plausible deniability perpetrated on the public since "for tobacco use only.", SWIM, "medicinal" cannabis infused jalapeno-lime corn crisps, with a branding that rivaled JLF "Poisonous Non-Consumables" in its show of straight faced CYA.
"Solvent. Yeah, I guess it is..." I said, musing at the prospect of being perhaps the only hippie-queer from the Hill to Castro and Church who would actually be using his poppers as intended, as stated by the manufacture, Slam N. Mann, not as the dissociative anesthetic/smooth muscle relaxant inhalant that was the rocket fuel for the most consciousness-expanding, soul melding moments of transnational sex over a year long affair with a beautiful Arab man-bear-pig who sought political asylum in the US... *sigh*... This can of Hog Wild II ethyl chloride—what I presume is the sequel ("II"?) to the popular Hog Wild solvent—would instead be used as directed as solvent, in this case, for a mixture of water insoluble cactus alkaloids, fats, volatiles, chlorophyll compounds, and residual plant waxes... (Turns out ethyl acetate pulls a lot of that gunk out of the basic phase, along with an apparently moderate share of freebase alkaloids compared to d-limo, a small portion of which extract was redissolved into the EtCl.)

sigh... حبيبتي. I miss my sexy-pig. :|

Long story short... the EtCl "clean up" experiment had mediocre results, resulting in a precipitate that crashed out over 12 or so hours in a manner analogous to that described in the ephedrine experiments of Steldt (1940). But god-only-knows what the hell I actually ended up with:

someblackguy said:
The ethyl acetate did not seem to pull much at all from the cactus, only a disappointingly faint, urine colored broth that evaporated leaving chlorophyll and some kind of yellow oil. The precipitate that formed after this was dissolved in EtCl (chloroethane poppers) did not appear in the EtAc and may be an insoluble salt remnant from the initial extraction or an artifact of the interaction between the haloalkene and the amine—the HCl salt of some alkaloid.

Overall disappointing but hopeful that some actives are present ether in the greenish liquid or the white precipitate... bioassay will follow soon.

meh...:|

And I can't whiff of the stuff without remembering the guy that kicked my heart. But he was a whooole lotta fun.


In both cases the solvent precipitated more problems than it solved.

I used an ice bath to keep it liquid. This whitish sandy cloud precipitated
lOwb8Rl.jpg

IgX3nkM.jpg
 
Mindlusion said:
It is bad practice to leave out freebase amines in organic solvent anyway, typically they degrade fast.

This bit got me worried. Some freebase dmt has been left dissolved in xylene for over 2 months now as there hasnt been time to salt it out, for various reasons. Will it have degraded badly by now? Would this just result in less product available to salt out, or will there be undesirable by-products formed in the solution?
 
ijahdan said:
Mindlusion said:
It is bad practice to leave out freebase amines in organic solvent anyway, typically they degrade fast.

This bit got me worried. Some freebase dmt has been left dissolved in xylene for over 2 months now as there hasnt been time to salt it out, for various reasons. Will it have degraded badly by now? Would this just result in less product available to salt out, or will there be undesirable by-products formed in the solution?

DMT is relatively stable in comparison to most freebase amines, it might just turn yellow and some will oxidize, it will salt out just fine, worst case it comes out as a goo
 
Pedantry alert!! For the general entertainment of organic chemists:

someblackguy said:
[...]ethyl acetate as my organic phase[...]
Anyway I wanted to see if EtAc

In the accepted protocols, "Ac" represents - probably more often than standing for "Actinium" - an acetyl group CH3CO. So "EtAc" would represent MEK (2-butanone, CH3CO.C2H5). For ethyl acetate I would write "EtOAc" as this is structurally consistent (CH3CO.OC2H5). But it's transparently clear what you meant here and in any case MEK is the standard term for, er, itself.

OK, I've stopped 😁


On a more useful note, DMT freebase survives for years although I wouldn't leave it for that long in a chlorinated solvent.

Get a solvent that evaporates clean, or carefully distil out the most volatile components and use those.
 
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