T + hydroxylate -> 4-HO-T
I find it interesting that you wish to isolate the hydroxylate enzyme. Is this feasible?
Or perhaps the enzyme pathway is more of a biomechanical process and not extractable?
If it is an isolatable compound can anyone define any of its molecular properties, please? If it functioned as proposed it would indiscriminatingly add a hydroxyl group to the 4 position of almost any tryptamine. Well, here's everything I know on the subject :
'The occurence and extraction of indole derivatives in six species from four genera of higher fungi were investigated. By using pure methanol for extraction of the mushrooms analysis revealed the highest concentrations of psilocybin and baeocystin. The psilocin content of the species was higher by using aqueous solutions of alcohols than with methanol alone but was an artificial phenomenon caused by enzymatic destruction of psilocybin. The extraction with dilute acetic acid yielded better results than with the water containing alcohols. The simlpe one-step procedure with methanol for the quantitative extraction is still the safest method to obtain the genuine alkaloids from funghal biomass.'
- Jochen Gartz, Journal of Basic Microbiology, 1994, Vol 34, Extraction and analysis of indole derivatives from fungal biomass.
http://www.erowid.org/plants/mushrooms/mushrooms_journal1.shtml
Now, as their concern was a
genuine analysis of alkaloids, rather than the isolation of psilocyn, it would seem (though I cannot prove) that the T-4-OHase enzyme would be included in similar soluability; So, for suspected known properties, we have :
High molecular weight (ain't seen a simple enzyme yet).
Soluable in water
Insoluable in MeOH.
Less soluable in acetic acid solution :
'The problem with wet alcohol is that the enzymes which dephosphorylise Psilocybin to the instable Psilcin are also extracted from the biomass. This also occures with acetic acid but to a smaller amount and does not occure at all with pure methanol (ethanol?).'
'course, it's all a stretch.
But, a moderately reasonable one - it but remains for experimentation to decide whether to kick our arses or not.
Now as to the T-4-OH enzyme, all I know comes from Shulgin :
'Normally, this mushroom species dutifully converts N,N-dimethyltryptamine (DMT) to psilocin, by introducing a 4-hydroxyl group into the molecule by something that is probably called an indole 4-hydroxylase by the biochemists. You put DMT in, and you get 4-hydroxy-DMT out, and this is psilocin. Maybe if you put Mickey Mouse in, you would get 4-hydroxy-Mickey Mouse out. It is as if the mushroom psyche didn't really care what it was working with, it was simply compelled to do its sacred duty to 4-hydroxylate any tryptamine it came across. It was observed that if you put N,N-diethyltryptamine (DET, not a material found in nature) into the growing process, the dutiful and ignorant enzymes would hydroxylate it to 4-hydroxy-N,N-diethyltryptamine (4-HO-DET) a potent drug also not known in nature.'
Now, he's speaking of live culture - but, let's just say that this particular enzyme - and this part probably is a 1-step enzymatic process - is also water soluable (likely, though not guaranteed, for reasons outlined above).
This would indicate that any tryptamine alkaloid popped into a water-based 'shroom juice is coming out 4-hydroxylated, neither more nor less.
Hmm..
Oh, forgot that last link...
http://www.erowid.org/library/books_online/tihkal/tihkal16.shtml
TCl + IPA + Cl -> TCl + IP? + HCl -> iPT + HCl +OCl
iPTCl + IPA + Cl -> IPTCl + IP? + HCL -> DiPT + HCl + OCl
If this is possible, I find it profound. In theory you could substitute methanol to yield a methyl radical [CH3] and end up with DMT, no? Or how about t-Butyl Alcohol to a [C1(CH3)3] Tert-butyl radical to form DiTert-ButylTryptamine? I don't think Shulgin really mentions this analogue in his book.. maybe something neat, massive CNS stimulator? 5-MeO-DTBT might be tempting, like Foxy plus. Hmm... it does sound rather interesting... I'll have to look up my analogue n-chain info. Maybe get a predictive effect.
The theory behind what I put down above, though, is the concept behind alkyl halide alkloxylation - most commonly found in the MeI + R-OH -> HI + R-MeO. Mmm... methoxy, I love you...
It should hopefully work 'backwards,' using the halide salt of tryptamine...
...it's a bit more conventional in the hydroxyacetylation, though...
(T - H) + CH3 -> NMT
(NMT - H) + CH3 -> DMT
(DMT - 2H) + 2CH3 ->DET
(DET - 2H) + 2CH3 -> DIPT
(DIPT - 2H) + 2CH3 -> DTBT
If you could find a way to methylate DMT's N group, from CH3 to C3H7 [CH1(CH3)2] forming DIPT with a couple methyl radicals I'd truly think you're an alchemical saint. I think, though I'm not certain, that it's easier to do it in a one-step... but that's not too likely unless one is swapping nitrogen, if one's starting material is DMT. I reckon, if one were to continue to use the haloalkylation method, that one would have to oxidize and swap... find a way to make DMT into DMeOHT, and then hit it up with whichever alkyl halide one wishes...
hmm... I'm not certain it wants to oxidize, there... maybe if the oxidizing agent were attracted to the amine tail... maybe...
...'till then, there's always strong acid to create indole-ethylene, removing the amine (good luck
), oxidization with sulfuric acid to create indole-2-ethanol, further oxidation with ammonium nitrate to swap it to indole-2-ethanone, and a reductive di-whatever-amination... or, for that matter, one would probably get better yields with such a tail going back to our friend, alkyl halogenation... and skiping the ammonium nitrate step... 2 DiXylaneAmine Iodide + indole-2-ethanol. 1/2 your DXAI is now HI and free DXA, and the other half should be forming DXT...
...but I'm hoping that, say, Rhodium will take me to task, for better or for worse, on each little piece - 'cause I try to avoid trusting theory 'less I have to.
acetylene + chlorine -> acetylchlorine : + 4-OH-T -> 4-Ac-T
This is what preservative dreams could be made from. You could clean up your psilocin to something as stable as psilocybin. The 4-HO compounds degrade rapidly in exposure to air, the phosphate form gives psilocybin an outstanding shelf life. It can't be this easy? If we use 4-HO-T in the isopropyl radical method instead of T, the Cl will probably instigate degradation, actually looks like a "polymerization" of two molecules at the 4 position, but maybe the acetyl form could hold out? Hmm... that's a thought, and a damn good one at that. Me, I was all certain, 'till now, that one had to diisopropylate the amine before the 4-hydroxylation... but if one was already sitting there with a 4-acetyl-tryptamine (something I'd like to eat once, anyways), it could very damn well be safe!
Thanks for the point! BTW, off the top of your head, what would you expect CFl4 + 5-OH-T -> 5-Fl3MeO-T to do when eaten?
...just curious.
'fraid I gotta go, now, though...
Rev. Psi Locybe, insane alchemist.
