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Concept for the formation of betacarbolines from tryptamines Options
 
AlbertKLloyd
#1 Posted : 1/4/2012 2:11:21 AM

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In a paper about one pot microwave synthesis of betacarbolines from tryptamines
4-nitrobenzaldehyde was reacted with tryptamine hcl on a silica gel for about 10 minutes in a 100W microwave oven designed for synthesis reactions.

This got me thinking that one might attempt something similar, using a different aldehyde. The most likely candidate for this is cinnamaldehyde, cinnamon oil is largely composed of this aldehyde.


I am interested in candidate aldehydes and the structures that would result but do not know enough about the topic. I sure could use some help on this.

The goal is to have a potential method for a microwave reaction that can produce betacarbolines and isoquinolines from PEA and tryptamine precursors.
from a wiki page:
Quote:
The original Pictet–Spengler reaction was the reaction of β-phenethylamine with the dimethyl acetal of formaldehyde and hydrochloric acid forming a tetrahydroisoquinoline.

the dimethyl acetal of formaldehyde is:
http://en.wikipedia.org/wiki/Dimethoxymethane
Quote:

It can be manufactured by oxidation of methanol or by the reaction of formaldehyde with methanol. In aqueous acid, it is hydrolyzed back to formaldehyde and methanol.


So right now i am considering oxidation of methanol and or ethanol as a potential source of aldehydes.

There are some microwave assisted oxidation methods using a catalyst, in one case colloidal silver is used, but it is put on a silica sphere support. I wonder if one could use a silica gel and colloidal silver to create an effective catalyst to create a formalin solution? Could a formalin solution work to create betacarbolines?

I have zero formal training in chemistry so really need some help with this.
 

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benzyme
#2 Posted : 1/4/2012 2:19:20 AM

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you don't need a metal catalyst for pictet-spengler, the acid is the catalyst.
also, the reaction isn't simply a cyclization reaction, it's also an addition reaction...using cinnamaldehyde, your product would have a phenylpropyl group at the 1-position (on the nitrogen) of the beta-carboline, and the molecule would likely have too much steric hindrance at receptor cites to be active.
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AlbertKLloyd
#3 Posted : 1/4/2012 3:20:35 AM

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That makes sense about the functional group attached to the aldehyde, so using formaldehyde seems more promising.

The metal catalyst is for the oxidation of methanol to make a formalin solution.

Using formaldehyde to do the reaction would result in what at the 1-position (on the nitrogen) of the beta-carboline?

Thanks!
 
benzyme
#4 Posted : 1/4/2012 3:38:01 AM

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a methyl

I won't say any more about this stuff, it's treading into synthesis territory, which is a violation of forum rules. you may want to edit your entries
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AlbertKLloyd
#5 Posted : 1/4/2012 4:01:19 AM

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I had intended it to be a conversion method, but the line between synth and conversion is a fine one, one i don't fully understand.

If you take a molecule and change it, then is that a synth or a conversion? Both, i would think. So converting an oxide to a non-oxidized form counts as a synthesis as well as a conversion.

I don't want to violate the rules of the forum, but really don't understand where the line i am not supposed to cross is.

Basically it seems that the conversion i am discussing is happening unintentionally and resulting in a common artifact. I wish to understand that artifact better through creating it deliberately, if this is in violation of the rules would someone please just let me know and i will take whatever action is appropriate regarding my posts.

Thanks!
 
nen888
#6 Posted : 1/4/2012 4:13:34 AM
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..after years of fooling around i'm beginning to think that simply prolonged boiling of tryptamines in strong acetic acid will create larger quantities of ß-carboline, though obviously not a full conversion..
 
Dozuki
#7 Posted : 1/4/2012 5:42:49 AM

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@nen- you may be on to something there, from my understanding its the double bonded carbon of an aldehyde that creates the cyclization. It looks as though acetic acid has that quality, much like formaldehyde which has been used as the reactant in the Pictet–Spengler.

I too would like to know if this is indeed breaking forum rules. I think this is important information with relation to the beta-carbolines and if they are by products of extraction procedures and analysis methods. Specifically in regards to 2MeTHBC and 6MeOTHBC which could be cyclized from their respective tryptamine compounds and used as standards.

I feel that this could further some of the research that is going on. It would be nice to have a forum to discuss this without having to discuss it at some other forum.


-D.
 
AlbertKLloyd
#8 Posted : 1/4/2012 5:54:55 AM

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I think we can talk about the theory behind it without having to propose or encourage any synthesis in practical terms.

I too think heat and acid results in the artifact and also think that the artifact does not have the same solubility that DMT has and it might occur in larger amounts but only come across as a low percentage impurity because that is the amount making it into solution.

 
endlessness
#9 Posted : 1/4/2012 9:56:11 AM

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The rules regarding no-synthesis talk are not black and white. For example DMT N-Oxide to DMT is in a way a synthesis, or the supposed LSA to LSH, but they are allowed.... The basic questions to ask is:

Does it require very dangerous/watched chems or proceedures? Is the end product something for commercial exploitation?

I dont think the formation of betacarbolines is something that will interest most people, it's much more an investigation of a subject that is related to some of the analysis we're doing. Formaldehyde may be carcinogenic, but so may DCM which is often used in extractions, or chloroform.

In my opinion if there are disclaimers and if potential dangers are outlined, if it keeps in this non-commercial purely scientific line, this discussion could continue. If anybody else (mods or otherwise) disagree, feel free to voice your opinion.
 
Shaolin
#10 Posted : 1/4/2012 10:59:46 AM

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Dozuki, is the creating that (theoretically) somehow unique to acetic acid (and not phosphoric or hydrochloric)?
Got GVG ? Mhm. Got DMT ?

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benzyme
#11 Posted : 1/4/2012 12:50:35 PM

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no

again, an acid only acts as a catalyst. it's represented in the reaction as H+;

and the reaction isn't specific to acid-catalyzed addition either; mass spec determinations of thermolytic decarboxylation of tryptophan product, using ketone catalysts with no acid involved, have also shown the production of beta-carbolines. this reaction is driven by heat (~ >165C), and the quaternary ammonium intermediate is so susceptible to oxidation that the ketone will be added to the cyclized product, depending on the ketone used.
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endlessness
#12 Posted : 1/4/2012 1:04:57 PM

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Benz, as nen quoted in the jungle spice analysis thread, someone told him that cyclization of NMT would form 1,2,3,4 Tetrahydro-B-Carboline (tryptoline?). Do you think that is correct? And what would be the product formed from the cyclization of DMT? Could it be 2MTHBC? Could it form as an artifact in GC-MS analysis?

nen mentioned in another thread that he thinks b-carbolines may be formed with simple extended boiling of tryptamines in acetic acid.. Dennis Mckenna mentioned something similar when discussing the presence of b carbolines in virola:

"The low levels of b-carbolines detected in the pastes, and the failure to detect similar compounds in the source-plants used for the drugs, also leaves open the possibility that they may be formed as artifacts either during the cooking and concentration of the Virola resin or during the work-up of the alkaloid extract. This possibility has also been raised by Holmstedt et al. (1980). Tetrahydro-bcarbolines of the type found in the paste samples can be readily formed from tryptamine derivatives such as NMT by aldehyde condensation followed by cyclization (Taborsky and McIsaac, 1964)."

(mckenna et al 1984)

Im attaching the Tarborsky and McIsaac paper

Here's the Holmstedt paper
 
AlbertKLloyd
#13 Posted : 1/4/2012 6:30:24 PM

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endlessness wrote:
And what would be the product formed from the cyclization of DMT?

When I asked this same question of K Trout he responded in the affirmative that 2meTHBC was the DMT product in question.

I'd like some more information about the solubility and properties of this betacarboline. What type of extractions would be specific for it, and what would not be? Do the standard methods of extraction work well to obtain it or would one have to use another route? Maybe an alkaline precipitation method would crash it out of solution?

And what color does this molecule glow under black light if it does indeed glow in the visible spectrum?
 
Dozuki
#14 Posted : 1/4/2012 6:48:26 PM

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AlbertkLloyd wrote:
And what color does this molecule glow under black light if it does indeed glow in the visible spectrum?


According to Frahn and O'Keefe (1971): Alkaloid 1 [2MeTHBC] was crystallized from heptane:ethyl acetate (10:1) or benzene. m.p. 216 - 218. Using a Hanovia "Chromalite" UV lamp [254 nm] it showed a blue flourescence on PC. It gives a pink color with xanthydrol reagent and no-to very little reaction with Ehrlich's reagent. TLC on SG in acetone:ammonia (75:1) gave an Rf .57

If DMT is cyclized to 2MeTHBC, then what of MMT (IE:NMT)?
 
endlessness
#15 Posted : 1/4/2012 6:50:06 PM

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If anybody can find a legitimate source for it (I think CAS number is 13100-00-0 ), I can buy through our organization and make all these tests... It is a legal substance but I could not find it through any of the typical suppliers (sigma aldrich, etc).

Another option would be to find the plant with highest known content of it (any clues what plants have high 2mthbc content?) and do a column work to isolate it.
 
endlessness
#16 Posted : 1/4/2012 9:13:52 PM

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Thanks! Im sending them an email, as well as to another couple of companies that might have it. Another option is purchasing tryptoline from sigma aldrich which isnt expensive, and synthesizing 2MTHBC from it, which apparently isnt too hard (would have to ask some chemist friend to do it... )

Ill keep you guys informed if there's any developments from my side
 
InMotion
#17 Posted : 1/4/2012 9:26:58 PM
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The most interesting use of the pictet spengler reaction in my opinion would probably be,

tryptamine + formaldeyde + H+ --inert atmospere-->pinoline

I believe this discussion is allowed, as anyone with access to inert gas, and a suitable reflux apparatus should know how to handle a trivial compound such as formaldehyde or paraformaldahyde.

As Benzyme has stated oxidation is a very common way to spoil these reactions. Tryptamine itself is easily oxidized. Work-up may also not be very intuitive and characterization would be necessary.

One must be very careful playing with beta-carboline analogues in my under educated opinion. This isn't a tryptamine back-bone(though they are indole based). Betacarbolines are accepted readily at a variety of receptor sites. Some have even been found to form adducts with DNA. As far as their ability to mutate DNA, I'd say look at something as simple as harmane(which is endogenous and found in meat), but also listed as a carcinogen and toxin(IIRC). Making these types of analogues very iffy and unpredictable.
 
benzyme
#18 Posted : 1/5/2012 1:22:47 AM

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Dozuki wrote:

If DMT is cyclized to 2MeTHBC, then what of MMT (IE:NMT)?


endlessness wrote:
that cyclization of NMT would form 1,2,3,4 Tetrahydro-B-Carboline (tryptoline?)


^^


I've inadvertently made 2MeTHBC before, starting from tryptophan. it's weakly active when vaporized, lasts about 8 mins.
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nen888
#19 Posted : 1/5/2012 6:39:29 AM
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..the ß-carboline fraction chromatographed from an acacia extract (possibly 2meTHBC or 1,2,3,4-tetrahydro-beta-carboline ) was mildly active at 20-30mg vaporized..

..the only other byproduct of NMT that the chemist can think of is N-hydroxy-N-methyltryptamine..(HMT)
certainly NMT darkens with time/exposure, and has no oxide...
 
Dr_Sister
#20 Posted : 1/6/2012 11:06:24 PM

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Here is an interesting paper on the synthesis of beta carbolines. Acidic conditions are not required, in fact yields will be much higher without the use of an acid. It is the electrophilic double bond of the imine which drives the cyclization.

All one needs to do is form an imine with tryptophan or tryptamine and an aldehyde.
 
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