Need help from a Chemist

[Schafschaf]

Dear Nexians,
somtimes my harmala extracts smell strongly of n,n dmt...:surprised
And since it is possible to make weird beta carbolines from dmt, by overheating it, could it be possible to crack open the third ring of the beta-carbolines, to pruduce dmt without the use of nasty chemicals?

Schaaf

 

[DreaMTripper]

I'm no chemist but logic tells me if it could be done then it would be well published.

 

[An1cca]

I've been doing a lot of harmala extractions and never experienced this, weird.

Can it have something to do with the process you employ for extracting the alkaloids? Solvents?

Harmine and harmaline are quite heat-stable op to 200 degrees Celsius, then they quickly break down while some of it sublimates.

Synthesizing dmt from harmala's would seem to be a greater enigma than the conception of ayahuasca itself...:?

 

[Schafschaf]

i use uncrushed seeds, washed multiple times with hot water and acetic acid then base warm with lye...
i`m at the moment trying to repeat the effect, but there semms to to be a factor, i`m not aware of, so the smell doesn`t always occur :surprised

 

[pitubo]

Lab contamination? Are you sure that your glassware and tools were clean?

I've noticed a funny smell when baking freebase harmalas dry in an oven (still well below sublimation temperatures) but it doesn't really resemble the smell of dmt very much at all. When I smell dmt vapor, my smell memory gives me a visceral reaction. Harmala vapor doesn't do that.

 

[Nathanial.Dread]

Extremely unlikely for a number of reasons.

1) Targeted cleavage of a C-C bond is difficult. Not impossible, but way beyond the capabilities of pretty much any kitchen chemistry set up.
2) Most harmala alkaloids have functional groups in the 6 position (MeO or HO groups), so even if you could do the ring cleavage, it still wouldn't be DMT, as IIRC, functional groups on the 6 position generally inhibit activity.
3) If you look at those 3rd rings, there's nowhere you could actually cut that would produce DMT. Most of those amine groups are do not have three unique atoms attatched to them (except hydrogen in the case of THH), so if you did manage to cleave the ring, you're not going to get the classic dimethyl tail, but rather, something like ethylamine.

A lot of indoles smell flowery, it occurs in natural and artificial perfumes.

Blessings
~ND

 

[entheogenic-gnosis]

I'm a chemistry student, but I think I may have some insight here:

When you were referring to beta-carbolines being produced from tryptamines, this is generally carried out by what's called the "Pictet-Spengler reaction".

In a Pictet-Spengler cyclization, a tryptamine undergoes condensation with an aldehyde or ketone, generally with an acidic catalyst, and the reaction mixture heated, yielding a beta-carboline cyclization product from the β-arylethylamine starting point...This reaction can also be applied to phenethylamine compounds for production of tetrahydroisoquinoline compounds.

Ok, now to the rest of your question:

You were asking if you could "brake" beta-carbolines to form tryptamines, no?

I've never really thought about that very much...

Look into Abramovitch–Shapiro tryptamine synthesis, this is where tryptamine is synthesized from beta-carboline...or look into its modifications or similar reactions...

-eg

 

[pitubo]

Look into Abramovitch–Shapiro tryptamine synthesis, this is where tryptamine is synthesized from beta-carboline...or look into its modifications or similar reactions...

That does not apply to harmala alkaloids. These have a methyl group where the Abramovitch–Shapiro substrate has a carbonyl. Without the carbonyl exactly in that position, the decarboxylation after the ring cleavage cannot happen.

OP, IMHO you either have contaminated equipment, contaminated plant material (unlikely) or you confuse harmala smell with dmt smell (is that at all possible?)

 

[entheogenic-gnosis]

Look into Abramovitch–Shapiro tryptamine synthesis, this is where tryptamine is synthesized from beta-carboline...or look into its modifications or similar reactions...

That does not apply to harmala alkaloids. These have a methyl group where the Abramovitch–Shapiro substrate has a carbonyl. Without the carbonyl exactly in that position, the decarboxylation after the ring cleavage cannot happen.

OP, IMHO you either have contaminated equipment, contaminated plant material (unlikely) or you confuse harmala smell with dmt smell (is that at all possible?)

Thank you.

I suppose I should have been focused on harmala alkaloids rather than the broader beta-carbolines...

(Below I posted a depiction of harmala alkaloids as well as a depiction of Abramovitch–Shapiro tryptamine synthesis. )

-eg

 

[Mindlusion]

Yeah no, this wont open up in an extraction.

That image you took from Wikipedia is wrong by the way eg, it seemed weird that they used PPA (a dehydrating agent) for a reaction that ADDS water, so I checked the paper, the hydrolysis step uses ethanolic KOH (typical) , the preparation of that keto-carboline is what uses the PPA. (which makes sense)

So never trust wikipedia. Check the literature. (Though the literature can be wrong too.. Hah!)


If the ring contains an imine, like harmaline does, another way to open it by reversing the tautomer by acylating it, and then hydrolyzing the imine.. but again this won't happen in extraction. Just a fun fact

In your case, you said you used lye. When you freebase plant matter with lye it gives off a sweet soapy smell, rootbark especially you must know this smell. Perhaps you are mistaking this smell of basic plant matter for the smell of DMT.

Also, what I think is just as likely, when I first got into DMT, I would smell the stuff everywhere, at the grocer, trying on new nikes, outside in the garden, sometimes in my food.

It seemed to be random, though some smells seemed to trigger it more than others.. Like a ghost scent.. Strange, but I know other members who have had that same effect.

 

[downwardsfromzero]

IMO eg could be right. Traces of the alkaloid harmalacidine, or 1-hydroxynorharmaline, occur in Peganum harmala. This alkaloid has a keto group at position 1, instead of the usual harmala methyl group. For harmalacidine the Abramovich-Shapiro reaction would be possible, producing 6-MeO-T which would go some way towards explaining the indolic smell. I've noticed this same indolic smell from basified harmala extractions but it's distinct from DMT despite the similarity.

Harmalacidine is mentioned in the attached document.

 

[Schafschaf]

Thanks a lot guys

Pitty i doesn´t seem to work, but it opened my imagination quite a bit

And i think you´re right, its the indolic smell, i most likely mistook for n,n, since my chaliponga extraction didn´t smell anything like that.

I´ll have a look at the literature and maybe, even learn somthing

Schaaf

 

[entheogenic-gnosis]

http://www.nanoniele.jp/cgi-bin/nanoniele.cgi?inputsite=nanoniele_top&serieskey=Name_Reactions

The image of the Abramovitch–Shapiro tryptamine synthesis came from the site above, which is great for reaction formulas.

My advice was:

Look into Abramovitch–Shapiro tryptamine synthesis, this is where tryptamine is synthesized from beta-carboline...or look into its modifications or similar reactions... -eg

Still good advice if you ask me, if you are interested in performing certian chemical feats, why not start your research with known and related reactions?

here's a second depiction of the Abramovitch–Shapiro tryptamine synthesis from a separate source, though it's exactly the same as the first depiction...

-eg

 

[Mindlusion]

http://www.nanoniele.jp/cgi-bin/nanoniele.cgi?inputsite=nanoniele_top&serieskey=Name_Reactions

The image of the Abramovitch–Shapiro tryptamine synthesis came from the site above, which is great for reaction formulas.


-eg

Nice website, thanks for the link.

However, their image is still incorrect.. The process simply doesn't make sense. Maybe THEY got it from wikipedia too

If you still don't believe me,
This is a quote from the 1956 paper written by Abramovitch and Shaprio


The ring opening step...

Tryptamine-2-carboxylic Acid.
-The following are the optimum conditions found for this
ring-opening. The carboline (0.5 g.) was boiled under reflux with 2N-potassium hydroxide
in 50% ethanol (10 c.c.) for 5 hr.

and for the generation of the actual carboline from the corresponding phenylhydrazone ( 3-Dioxopiperidine 3-phenylhydrazone)

1,2,3,4-tetrahydro-1-oxo-beta-carboline-
-By use of polyphosphoric acid
The phenylhydrazone (1 g.) and polyphosphoric acid (5 c.c.) were slowly heated in an oil bath with stirring.
When the internal temperature reached ca. 105O the solid dissolved, and the internal temperature
rose to 120-125° (bath-temp. 105") and was kept there for 5 min.

In one step you are removing water, in another you are adding it (hydrolysis).

--

and yeah of course traces of Harmalacidine can certainly react to give the ring opening. I was speaking about the harmala alkaloids that were suggested. Though I haven't heard of the stuff before, it must be present in a pretty low concentration. I would hesitate to say that it is alone the cause of the smell. Since the basified cyclic ones can have the indole smell too. Though I haven't really noticed it myself.

But lets say it is, I've always used sodium carbonate which isn't really a strong enough base to do the ring opening, especially at room temp. Remember the actually ring opening involves refluxing with concentrated ethanolic KOH. So simply adding aqueous NaOH isn't going to open up all of the Harmalacidine, maybe 10% of it to be generous.
Maybe the smell is stronger when you use NaOH to basify? So ring opened tryptamines smell stronger? I dunno its a longshot without much evidence.

edit:

Just took a whiff of both freebase THH and harmaline in their respective vials, both definitely smell indoley, faint, not as obvious as DMT, but nice and floral

 

[pitubo]

and yeah of course traces of Harmalacidine can certainly react to give the ring opening. I was speaking about the harmala alkaloids that were suggested. Though I haven't heard of the stuff before, it must be present in a pretty low concentration.

The 1988 Siddiqui et al. paper elucidating the structure of harmalacidine suggests that it is not very water soluble. The authors made an extract of rue seeds with ethanol and evaporated the ethanol. The residue was split between a fraction soluble in 5% acetic:hydrochloric 1:1 and the remainder. Harmalicidine was found in the latter fraction.

I doubt that there is much harmalacidine in a dilute acetic extract of rue seeds.

BTW, schafschaf, you state in your OP that overheating dmt creates betacarbolines. This is news to me. Do you have more information about such reactions?

 

[Jees]

...somtimes my harmala extracts smell strongly of n,n dmt...

Say again? :shock:

Meaning: my whiffer never did , likely never will.

I do remember to smell THC in the most unreal unexpected occasions, in times long ago when I used to blow my mind inside out on a habitual daily pattern. Stopping blowing like that, this effect stopped too. Strange things can be noticed while not actually there.

 

[Godsmacker]

Regarding the scent, I believe your question would be better answered by a flavoring-agent chemist. DMT & Beta Carbolines both share the indole functional group; this group gives off the unique smell of DMT, especially so as a freebase. Harmalas are also indolealkylamines which contain the same functional group. Considering that both compounds contain a similar ligand (indole group) for the olfactory glands (the sensors in your sinuses/nasal tract which pick up smells), I would hypothesize that these molecules would smell somewhat similar due to either a)impurities or b)a shared functional group which produces a distinct scent.

 

[Jees]

There's not much to hypothesize when your able to stick your nose in a pot and actually sniff.

Well I gave it another chance and I must now admit, having sniffed much deeper than ever that I could imagine a resemblance because this resemblance was put out here. But not 'strongly' like OP seems to notice, noses/material might differ.
So I must partly stand corrected, the smell never occurred to me before and I would never have noticed it without mentioning.
:thumb_up: