12-23-03 21:36
No 478712
I'm not entirely sure this is the right place to post this, i've just been asked by someone about whether it would be possible to separate the different tryptamines in an organic extract, or more to the point, how to separate the 5-meo and 5-OH dmt from the NN dmt.
My first thought in this direction was using recrystallisation purification. in the merck it says this about crystallising dmt freebase:
Crystals, mp 44.6-46.8. pKa 8.68 (ethanol-water). also reported as plates from ethanol and light petroleum, mp 46 (fleming, woolias). bp 60-80. pKa 8.68 (ethanol-water). Freely sol in dil acetic and dil mineral acids.
is this saying that a mix of ethanol and light petroleum (naptha? toluene?) can be used to recrystallise dmt?
some more info from the dmt entry in tihkal:
In principle, DMT is contained in the filtrate along with NMT and tryptamine itself. The tryptamine can be removed based on its ether insolubility and the NMT by its conversion to the benzamide with acetic anhydride or benzoyl chloride. The remaining basic material is largely DMT which can be further purified as the picrate salt.
okay, this information is of some use. tryptamine is sometimes present in plant sources, so being able to eliminate it is handy, but not all *that* useful. Removing nmt is more interesting however, as this material is inactive, well, virtually inactive, and often in high proportion to the dmt as it is an intermediate in the methylation. it's dead weight in the material, more smoke to inhale that's not getting you anywhere.
Now, the last thing is to be able to eliminate the 5-substituted tryptamines that we may or may not want or perhaps want to separate. I have only two ideas about how these will be separated.
The solubility of 5-meo and 5-OH dmt is diferent to each other and different to the dmt. one has an alcohol group, the other has an ether. perhaps the right combination of solvents would permit selectively precipitating the desired or undesired material from the solution. The solubilities of these materials could be enumerated in a wide range of solvents, and then tailor a mix that favours one or more over the other materials to become insoluble.
How can we change the solubilities of these even more so because of the presence of their particular functional groups, through a gentle chemical process which does not damage the rest of the alkaloids? In the case of the bufotenine, could we esterify it? that would make it less polar (?). acetic anhydride was suggested to remove the nmt in that synthesis, what would it do to 5-meo dmt and 5-OH dmt?
After removal of the solvent from the pooled extracts, the residue (an amber oil, 1.04 g) was distilled at the KugelRohr. A white oil distilled over at 130-140 °C at 0.1 mm/Hg, and crystallized spontaneously. This distillate weighed 0.77 g, and was recrystallized from boiling hexane after decanting the solution from a small amount of insolubles. There was thus obtained 0.40 g of dimethyltryptamine (DMT) with a mp 67-68 °C. The distillate contained about 3% of 2-Methyl-1,2,3,4-tetrahydro-b-carboline (parent peak mass 186, major peak mass 186) as an impurity which was lost upon recrystallization.
i have observed that recrystallisation out of a boiling pentane/heptane mix (shellite) of acacia obtusifolia extract there formed two major different substances, which would form inclusions if cooled quickly but the slower cooling was done (a cooling/warming process was used to substitute for insulated containers etc). there were cubic crystals of a semi-translucent white material, and a semi-liquid yellow which was fluid enough when removed from the crystals, which were attached to the glass, simply by swirling and loosening it first and then quickly decanting the mother liquor, a little wash with a pipette of ice cold naptha useually was enough to get it to the point the material was a very faintly offwhite colour.
In the case of these alkaloids, this is not enough to separate them in any way, i figure that the crystalline material is actually a mixture of nn dmt, nmt, 5-meo and possibly some tryptamine. knowing how to selectively remove these chemicals with some kind of process that does not damage them would be very useful to make the utilisation of high bufotenine content plants more possible. it would also permit the separation of the nn from the 5-meo which would be good for experimenting with them separately or reblending them in different proportions.
also, the other point about the quote just above is that dmt can be distilled. although, is that other chemical mentioned a side product or an oxidation product? also, what level of operator skill is required to run a kugelrohr?
To obtain the HCl salt of DMT, the residue was dissolved in anhydrous Et2O and saturated with anhydrous hydrogen chloride. The resulting crystals were recrystallized from benzene/methanol to give N,N-dimethyltryptamine hydrochloride with a mp of 165-167 °C. The yield from 14 g of the amide was 13.3 g of the salt.
heh, the old hydrochloride salts thing again... recrystallised in benzene/methanol... would toluene/xylene and ethanol substitute okay? maybe if it was all freshly dried solvents?
but digressing onto another sidebranch, what about salt solubility differences. and can other of the tryptamines crystallise as salts... (no don't answer that, i'll go and find out and post the info)
(Stranger)
12-23-03 22:36
No 478721
in the bufotenine page of tihkal, there is this:
There was thus obtained, after filtration, Et2O washing, and air drying, 0.53 g (87%) bufotenine mono-oxalate as pink needles, with a mp 93-94 °C. A mp of 178 °C in the literature may be of the bioxalate. The free base has been reported to have a mp of 125-126 °C or 146-147 °C.
so mono and bioxalates can be crystallised from bufotenine. i wonder what changes that would make to the whole mixture, the dmt and nmt and meo? careful recrystallisation would probably result in one or another precipitating out (preferably one that crystallises :)
there was obtained 1.22 g (70%) of N-methyltryptamine as a white oil that spontaneously set up to white crystals of the free base. These rapidly darkened on exposure to air. The infra-red spectral fingerprint was (in cm-1): 740, 1018, 1103, 1132, 1161. The literature mp is 90 °C. A 0.22 g sample of darkened base in 1.0 g IPA was neutralized with concentrated HCl (using external moistened pH paper as a titration guide) with the development of an intense blue-green color with the addition of each drop of acid. The acidified solution (now a stable blue-green color) was diluted with diethyl Et2O (about 1 mL). This cloudy solution, upon scratching, set to crystals which, upon removal by filtration, Et2O washing, and air drying to constant weight, weighed 0.18 g and had a mp of 178-180 °C.
so it says that dissolving the nmt.hcl in IPA and adding a little diethylether (i think it's reasonable to suspect that toluene/naptha could be substituted as this is clearly a two solvent recrystallisation)
After reviewing all of this information, i think that the isolation of the different tryptamine fractions is not really going to be difficult.
according to my (maybe ill-concieved) concept of polarity, i would say that the least polar tryptamine would be dmt, followed by 5-meo, then 5-oh and nmt... which would be more polar? probably 5-oh, since that makes it an aminoalcohol.
so, if one had a solvent on either end of the scale, say dH2O and toluene, which would precipitate first out of each, the freebase, and the HCl salt, and other salts?
well, in the case of the HCl, according to my scale of relative polarities, the dmt will be the least polar, and the 5-oh dmt will be the most polar, which means the dmt.hcl will precipitate out of the water first, followed by 5-meo, followed by nmt then last of all the bufotenine.
in a dual solvent system with ethanol and toluene, one would be more able to control the exact polarity of the solution, and in that situation, the addition of toluene to the HCl salts dissolved in alcohol in small portions, until clouding occurs, then heat until it clears, scratch the sides of the glass and let it cool, subsequent increases of the amount of toluene and clearing the precipitated solids should gradually elute the alkaloid salts according to their polarity, and the first fraction will be dmt HCl. The 5-meo.HCl will crystallise, so the appearance of crystals will indicate that the 5-meo is crystallising. likewise, the 5-oh dmt will also crystallise, however the NMT may not crystallise
(Moderator)
12-24-03 00:33
No 478729
Bufotenine has a phenolic OH group which should deprotonate under basic conditions (NaOH) to form the hydrophilic phenolate. Work fast, work under protecting gas, and/or add antioxidants to prevent possible degradation under these conditions.
(Stranger)
12-24-03 02:05
No 478745
how long does it take and what temperature should be used. ascorbic acid would be a suitable antioxidant to use? perhaps even use it as the acidifying agent in the acidic extraction and this reaction performed just before extracting the freebase. should it be stirred?
(Stranger)
12-24-03 18:26
No 478853
The 2-methyl-tetrahydro-beta-carboline mentioned above might be the result of extracting DMT-base with dichloromethane as this has reaction has been observed to happen. Better use MTBE, avoid chlorinated solvents.
DMT in its freebase form isnīt so easy to purify from other alkaloid impurities as recrystallization of DMT-base from alkanes is prone to precipitate most of the material again and there are not many solvents to choose from.
Recrystallization of the hydrogenfumarate salt of DMT with ethanol (best anhydrous) or isopropanol has been proven to be a good way for purification with acceptable small loss of the material (about 7 to 8% loss after each recrystallization from about 10 times its amount of alcohol).
2-methyl-tetrahydro-betacarboline could effectively removed with two to three recrystallizations and there is a good chance that it will work for other alkaloids too.
I wouldnīt count on being able to recover any bufotenine from alkaline extraction unless you work in a sophisticated environment (inert gas).
Just an idea: Reacting the crude alkaloid extract with an acid anhydride should also esterify phenolic -OH. If enough care is taken not to saponificate the sensitive phenolic esters and the acid is "heavy" enough a careful distillation should leave the esters in the distillation residue and yield a reasonably pure material.
.
(Stranger)
12-24-03 19:45
No 478871
About distilling DMT freebase:
A Kugelrohr is not needed. Simple vacuum distillation under a good vacuum (best < 1mbar) will do. Immersing the flask in a heating (oil) bath will minimize loss due to "reflux" on unheated surface.
Kugelrohr is useful for small quantities of solvent free material.
A simple Kugelrohr can be made out of a two (or three) roundbottom flasks (50ml, NS14 for quantities up to 3g) and a tinbox (cooky jar) into whose side a hole has been cut. The hole should be large enough to accomodate the ground glass socket of this flask.
Place the flask charged with the material to be distilled in horizontal position in the hot air bath and place the lid on the tinbox. The receiver is a modified flask of the same size to which an extra NS14 ground glass neck has been attached on a short (+/- 2cm) tube protruding from the bottom of the flask. Connect the receiverīs neck (horizontal position) from the outside to the socket of the flask in the air bath (secure with clamp). Connect the socket of the receiver to a vacuum pump. The flasks are held in position from a support on the receiver (and the not too big hole in the tinbox). Start the vacuum pump. Carefully heat the airbath (tinbox) - if no more solvents are present, this may be done with a bunsen burner - and cool the receiver on the outside with some wet glasswool (wear protective goggles!). Actually you may even put two receivers in a row before the pump, in case the flask closest to the heated airbath gets too hot. If the glass joints are greased well enough, this should give you the option to revolve the receiver with the sump flask attached to it slowly with your hands as distillation starts. Otherwise some small pebbles in the sump may prevent spattering.
A temperature measuring device inserted from the top into the cooky jar to about the level of the distillation flask is a good idea.
Usually distillation takes only few minutes with fair results. Repeating often gives excellent results.
The product is washed out of the receiver by putting the receiver on top of a flask with a suitable solvent (in case of DMT petrol ether/ n-hexane may do). Heat to reflux (receiver flask serves as condenser) and let the refluxing solvent dissolve your product. On cooling the product separates from the solvent.
Costs for having one or two 50ml flasks customized: 20 to 40$.
(Moderator)
12-25-03 13:46
No 478971
It should be possible to extract the bufotenine phenolate without substantial losses if you basify, extract, and acidify fast enough (i.e. a few minutes). At least it's worth a try...