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Phenethylamines as tryptamine analogues

fastandbulbous

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Phenethylamines as tryptamine analogues

The fact that tryptamines constitute one distinct group of psychedelic agents, and phenethylamines another, at first seems quite strange as they are seperate chemical structures, with the only apparent common feature being that they are basically an aromatic nucleus connected to an ethylamine side chain. Examination of their structures though reveals that they are both part of a grander scheme, best exemplified by the ergoline LSD.

59655phens_and_tryps-med.JPG


What appears strange at first glance is that with optically active phenethylamines (ie amphetamines) the most active is the (-) / R isomer, yet with optically active tryptamines (such as AMT and its 5-methoxy derivative) the more active isomer is the (+) / S isomer.

59655Optical_active_isomers.JPG


With both the R amphetamine and the S alphamethyltryptamine, it can be seen that the hydrogen on the alpha carbon are both above (ie if the planar molecule is in the plane of the paper) the plane of the molecule. This implies that the configuration having the hydrogen below the plane of the molecule is in some manner 'getting in the way of binding' (in other words, steric hinderance). This is effectively what abolishes the activity of alpha-ethylphenethylamines, as both isomers, due to free rotation of the ethyl group (or more precisely, the methyl group at the end of the ethyl), which causes spacial problems.

Accordingly, the dragonfly series of compounds are not dissimilar to tryptamines, in that one of the furan rings occupies the same region that the pyrrole ring of the indole. As both are dependant upon hydrogen bonding of the lone pair electrons (1 with nitrogen, 2 with oxygen) to the amino acid residue of one of the receptor subunit proteins, it is not improbable that the two are almost fully interchangable (although the oxygen cannot be further substituted, as the nitrogen can with alkyl or acyl groups). In the entry in TIKHAL for alpha-methyltryptamine, Shulgin mentions that of the other positional isomers for the 2-aminopropyl group, only the indole with the group in the 5 position is active, and then only as a long lived stimulant; from the above notes, it should be that a further substituted indole nucleus, with the 2-aminopropyl group attached at the 4 position should be active. Equally, substituting the 2-aminopropyl group into the 3 position of benzofuran derivatives should also give a series of active compounds.

Below is the metamorphosis of DOM to 5-methoxy AMT

59655PEA_to_tryptamine.JPG


Again, these are only speculation based on models of how phenethylamines and tryptamines bind to the 5HT2a receptor, but the given structures do fit all the criteria so far discovered.


For refs, see list given for Acid, dragonflies and the 5HT2a receptor, with additionally

NIDA Research monograph 146 – Hallucinogens, an update

Patricia A. Palumbo and J. C. Winter: Stimulus Effects of Ibogaine in Rats Trained With Yohimbine, DOM, or LSD; Pharmocologv Biochanistry and Behavior, Vol. 43, pp. 1221-1226, 1992
 
So all of those compounds should be active right? Compound 4 looks interesting... couldn't you turn the cylco hexane into it's fully aromatic form, and keep the whole thing even more planar?
 
well laid out thoughts. Who knows, some of these might be the psychedelics of the next generation.
 
3 & 4 have question marks over thir activity. The structure 4 without the methyl group attached to the aromatic ring is active (it would be interesting to see if 3 was active, as it would be a non-tryptamine indole - a bit of a first).

Making the cyclohexyl ring fully aromatic alters the electronic configuration of of the amine group so it wouldn't bind correctly to the a.a. residue of the appropriate protein sub-unit (wish it didn't as it would open up aminonapthylenes as potential 5HT2a agonists)
 
Ah, MGS.. always about the nomenclature.. ;)

FnB... I'm confused about the stereochemistry issue. Surely the opposite isomers (S DOM and R AMT) can also have the hydrogen above the plane of the molecule - just that the carbon and nitrogen would be reversed in the pictures you have drawn. I'm guessing that there's something about the configuration thats necessary for binding...

S.
 
No, the other optical isomer has the hydrogen below the plane of the molecule. The carbon atom that is the chiral centre is sp3 hybridized, so that the bond angles all point towards the apexes (is that the correct plural) of a tetrahedron (a three sided pyramid), the mirror image of one configuration cannot be superimposed over the other, no matter how you rotate them. The S-isomer of DOM and R-isomer of 5-methoxyAMT are also active compounds, but because of their shape about the chiral centre, are hindered in their binding to the receptor which translates through to having less potency (for DOM, the S isomer is about a qyarter the potency of R-DOM)

MGS.
It does have a name that has something to do with bufotenine I think. If you want, I'll look at the IUPAC rules to give it its (nightmare!) organic chemistry name.

At a quick guess for the (non-IUPAC) name, I think 5-methoxy-3,4-(2-aminotrimethylene)indole (for the molecule 4 - with methyl group, it would be 5-methoxy-7-methyl-3,4-(2-aminotrimethylene)indole). The activity report for 5-methoxy-3,4-(2-aminotrimethylene)indole and 3,4-(2-aminotrimethylene)indole were in a book called 'The Encyclopaedia of Psychoactive Compounds', that was in the library of my old Uni. It gave references as to activity assays, but all I can remember is the actual molecular structure of the two compounds (there was something on the Hive, but sadly that's now gone).
The compound without the methoxy or methyl groups has the same stereochemistry as the A, B & C rings of LSD, and is like a cyclic version of AMT.

Compound 3 is 5-methoxy-7-methyl-4-(2-aminopropyl)indole, and is really a true hybrid between tryptamines and phenethylamines. It fulfils all the criteria for 5HT2a receptor binding, but as to its activity, who knows (unless someone out there knows different).

Using the dragonfly molecule as a starting point (and the way it is known to bind to the 5HT2a receptor), I'm really curious as to whether 3-(2-dimethylaminoethyl)benzofuran and 5-methoxy-3-(2-dimethylaminoethyl)benzofuran are active compounds, as the onlt change between them and DMT/5-methoxyDMT is the replacement of the indolic nitrogen with an oxygen atom, which, as the dragonflies have shown, is quite capable of replacing the hydrogen bonding function of the indolic nitrogen

See attached jpeg
 

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FnB, I understand the bond angles describe the shape of a tetrahedron, and that the optical isomers can't be rotated so one fits over the other...

what i was trying to say was that since the bond between the alpha (chiral) and beta carbon CAN rotate, allowing the hydrogen to be above the plane?

eg, R AMT would look exactly like you have drawn S AMT, but with the NH2 and CH3 groups on the alpha carbon the other way round... with the H still sticking up above the plain...?

If I am being thick, sorry! It's been a while since I studied chemistry..
 
This is a profound philosophical idea at the top of this thread that uses LSD as a test-bed to overlay the pharmacophoric elements of various hallucinogenic tryptamine and phenethylamine derivatives.
 
specialspack

in the posistion where the S isomer of DOM has the hydrogen above the plane, the amino group isn't in the best posistion for binding to the amino acid residue of one of the protein subunits, therefore lower affinity.

I might have explained myself better now I don't have other more immediate things pressuring me!
 
You can make the whole thing aromatic, because then the Pi system will extend onto the nitrogen right?
 
Yes, but that's what you don't want to happen to the nitrogen equivalent to the one at position 6 in the LSD molecule, as aniline (amino group attached to benzene ring) is a much weaker base than the analogous cyclohexylamine, so an aniline NH3+ group wouldn't form as strong a hydrogen bond with the COO- group of the amino acid residue as a NH3+ group that wasn't attached to an aromatic ring.

The ring is pretty flat anyway due to the restrictions of bond angles of carbon atoms attached to the aromatic indole nucleus (only the carbon the amino group is attached to is capable of being in a position other than in the plane of the aromatic rings)
 
Indeed, I am enjoying this thread, I wish for pics!

Also, some of the chem in tihkal and pihkal goes over my head, is there a basic chem book that someone can recomend to me? Or any other books.
I am not going to pretend to devote all my time to this stuff, but I am very interested in it as a hobby, so a few more books can't hurt.
 
nuke said:
McMurry - Organic Chemistry

Will that cover things like, the difference between AcO and HO (acetoxy and hydroxy?) (just a simple example), other naming stuff? what isomer means, different examples of this and such. stuff along those lines. I want to read and understand these books, I don't actualy want to go out and create the stuff, interested in whats going on inside my head and how it gets there more than anything, I want to be more educated in my quest into the research chems world.

I'll try find above mentioned book in the library and see for my self I guess, although a bit more verbose discussion with some options would be great, eh here I am thread hijacking again!
 
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