Sciencemadness Discussion Board

Tryptamine degradation?

GreenD - 12-7-2011 at 08:44

I see that tryptamine is not very stable in atmosphere, it degrades to something - but what?

The interesting thing is;

When psychoactive tryptamnes are allowed to fully (I'll make an assumption and say oxidize) oxidize in air, activities do not change. I read that from a forum - not a scientific study.

I know amines can creat Amine-Oxides, which are the zwitterion ion of (+)NR3-O(-).

But I'm wondering, if - since they retain their psychoactive properties - they can retain most of their chemical properties as well?

What I'm eventually getting at is if it is possible to alkylate an amine oxide.

Vogelzang - 12-7-2011 at 13:01

One time I tried decarboxylating tryptophan by heating it in glycerine (after reading the Bull Soc Chim Fr. on amino acid decarboxylation). I think I put in some lab or reagent grade acetone as a catalyst, but can't remember. After heating it for a couple hours, it was cooled and mixed with water and an off white ppt. separated out. I figured that it was relatively pure tryptamine or its imine, if I used a ketone catalyst, and to test it I tried boiling it in water to see how soluble it is (tryptophan is soluble in water). What I discovered is that the product turned into a black syrupy liquid and when cooled was a black tar. Apparently, boiling it in water seemed to decompose or polymerize part of it.


http://www.fileden.com/files/2008/8/24/2063601/chemistry/LaD...

http://www.fileden.com/files/2008/8/24/2063601/chemistry/LaD...


[Edited on 12-7-2011 by Vogelzang]

GreenD - 13-7-2011 at 13:17

Interesting it percipitated in H2O - perhaps ice cold H2O is slow enough in the degredation to safely isolate and store tryptamine. Any further analysis of the products or further attempts?

Vogelzang - 15-7-2011 at 12:48

I only tried it once. I didn't think enough precipitated out to be worthwhile. Extraction might work to get more out of the water/glycerine solution.

antibody - 16-7-2011 at 08:20

I don't know if you can alkylate the oxide or not, but I usually recrystallize my tryptamine from boiling EtAcO and then slowly add pet ether to crash out the tryptamine.

The tryptamine is tryptophan decarboxylated in acetophenone and then extracted with dilute HoAc.

If you convert your tryptamine to a salt, it will be more stable.

GreenD - 21-7-2011 at 08:48

I went on with the decarboxylation of tryptamine without any acid to salt it with.

The decarboxylation went well, as I noticed bubbles that were clearly not at reflux, and nothing was condensing - so decarboxylation was taking place. [this was done following Student on the hive archives with spearmint oil and turpentine]

After about 4 hours solid remained. A few more drops of spearmint oil were added and the solution refluxed for an additional 5 hours. After which the solution was quickly cooled in RT water, so as to be warm enough to handle with hands, capped, and placed in a normal food freezer for approximately 5 days.

A thick dark sludge accumulated on the bottom after taking out, with a brown solution on top. Hunig's base and ethyl bromide were added and the solution stirred for nearly 24 hours at which point the stir bar became lodged in the gunk at the bottom, and let sit for another 24.

The solvents were evaporated and the "DET" was worked up according to shulgin to yield a very small amount of very viscous orange goo. At certain times smelt of tryptamines, but overwhelming was the smell of hunig's base.

This was allowed to sit in a freezer [still] and will be addressed in the future, but little hope is found currently for any desired product.

If done again, the salt form will be sought after.

I do have a question though... why is fumarate salts so common? Why are things like tartaric and citric not often used for salting tryptamines?

It is odd to me that tryptamine degrades so readily, yet any alkylated tryptamine can stand at RT for years without any noticeable decline in psychoactivity. Perhaps some type of cyclization or ring-opening reaction is occuring... as I think was said above. Even more interesting is that the body decarboxylates tryptamine to make serotoning, which obviously does not break down very readily within our aqueous bodies!

Interesting compounds.

jon - 21-7-2011 at 10:04

Mr. green could you tell me if hunig's base is mandatory for this reaction and why, if so?
if not, can something more common like potassium carbonate be used?
could the technique be adapted to say; (add the alkyl halide dropwise to prevent quaternization?)

and fumarates of dialkyltryptamines give better crystals don't ask me why i just know it to be the case.




[Edited on 21-7-2011 by jon]

[Edited on 21-7-2011 by jon]

[Edited on 21-7-2011 by jon]

GreenD - 22-7-2011 at 15:29

Quote: Originally posted by jon  
Mr. green could you tell me if hunig's base is mandatory for this reaction and why, if so?
if not, can something more common like potassium carbonate be used?
could the technique be adapted to say; (add the alkyl halide dropwise to prevent quaternization?)

and fumarates of dialkyltryptamines give better crystals don't ask me why i just know it to be the case.


The idea with hunig's base (as far as I understand it) is that it is basic enough to extract the proton from a primary and secondary amine (tryptamine), allowing for the SN2 reaction between the tryp[amine] and the ethyl bromide to occur.

However, it is so sterically hindered that it cannot possibly, itself, take place in the SN2 reaction. (giving the ethylated-hunig's base).

Using another base will undoubtedly cause quaternary formation, because due to the fact of dissociation of the base, you are allowing for NR4(+) / X - salt to form.

Hope this makes sense. Good question - I hadn't really thought about it until you asked.

jon - 22-7-2011 at 16:22

one would think the reaction would just take longer if you used kalium carbonate.
then again n-alkylating secondary amino ketones is a no go without a strong base like naoh.
that is if you use phenylethylbromide for example, if you used alkyl iodides you could get better success no?


[Edited on 23-7-2011 by jon]