Molar excess means using more than the theoretical 1:1 ratio of NMT to aspirin. Different molecules each have their own molecular weights (MW) according to the numbers and types of atoms they contain (as you probably know). A 1:1 molar ratio of NMT to aspirin for 'x' mg NMT would require:

'x' *(MW[aspirin]/MW[NMT]) mg aspirin (Let's call this equation 'A' for the moment) So, that's divide the MW of aspirin by the MW of NMT and multiply by the mass of NMT to be used.

- I'll let you do the maths. Remember to take the mass of the counter ion (e.g. fumarate, acetate) into account if weighing an NMT salt.

I'm not sure if the 1.2 molar excess means to use 2.2 times the theoretical 1:1 amount - i.e. 1 part NMT to 2.2 parts aspirin, or merely 1:1.2, I'll look back and check. Anyhow, to get the correct amount of aspirin required for the reaction, multiply the result of equation 'A' above by 2.2 (or 1.2).

EDIT: I've been and looked back through the thread. The original post refers to the 1.2 molar excess and there's no further clarification, so I'd take it to mean 2.2 times the theoretical amount of aspirin. In particular this greater amount of aspirin would drive the reaction nearer to completion.

Thank you so much, downwardsfromzero! I really appreciate you taking the time to explain that to me!

When I tried the aspirin thing, I didn't use the appropriate amount of aspirin, and I didn't use the appropriate amount of alcohol. I used too much of each. Now that I have a little bit to work with, I'll try to reiterate the process using 1 gram of acacia alkaloids. I will use methanol, as it is the only dry alcohol I have right now, and try to minimize the amount involved.

DMT: 188.27 g/mol
NMT: 174.24 g/mol
Acetylsalicylic acid: 180.18 g/mol

If we assume 50:50 ratio of the alkaloids, we can average their molar mass.

181.26. So 1.0 g alkaloid mixture/181.26 then multiplied by the molar mass of aspirin (180.18 ).

0.994 g of aspirin. Then multiply by 1.2 for a 1.2x molar excess. 1.193!

So for one gram of acacia alkaloids, you want approximately 1.193g of acetylsalicylic acid, and barely any methanol or isopropanol. I will try it exactly like this and report here.

Once again, it does work. I used these exact ratios, and I got 300 +/- 30 mg. I think either I have low dmt content in the alkaloid extract or the process robs some DMT. I think the CO2 method might be the winner here, though I have yet to try that.

You will never get 100% recovery from a reaction mixture...

Sorry for not chiming in earlier, by a 1.2 molar XS Sister meant to multiply your tryptamine by a factor of 1.2

So if you have 1 mole of NMT or 174g
you would need 1.2 mole of acetyl salicylic acid or 216g

Mind you, a larger XS of aspirin will not cause any problems with this reaction. Also when calculating the weight of your aspirin, use only the active ingredient weight/dose/tablet, not the weight of the entire tablet, fillers and all.

Thanks for clarifying.

I suppose too much aspirin would hinder recovery from the reaction mixture somewhat. Someone here even suggests this was the case when they did so?

This post:

Shame xylene is a bit crummy to evaporate. Did you (lysurgeon) recover any NMT or its N-Ac derivative? Wouldn't bestine extract the N-Ac-NMT too?

Meanwhile, I'll check theories & practice of amide hydrolysis.

A large XS of aspirin should not cause problem with extraction.

Amides will be inert to hydrolysis, even with a strong base.

If the acidified post reaction mixture was initially extracted with Xylene, there will be very little of the amide remaining to be extracted into the Bestine.

The amide will be poorly soluble in Bestine in any event.

Lysurgeons write up doesn't indicate how many bestine extarctions were performed, nor the quantity or temperature of extraction solvent used, so it is difficult to say why the yield was low, whether due to poor feedstock, high NMT content, or poor lab technique.

Over the last 3 days I have tried the CO2 method twice. It really is a breeze in comparison to the aspirin tek. In fact I had to improvise a CO2 generator from a 500ml flask, a bathtub stopper, some vinyl tubing and a bit of silicone sealant. The classic vinegar/baking soda volcano mix was used, and even though I thought about putting some desiccant in the tubing, I decided to be as ghetto as possible and not dry the gas.

It rapidly precipitated the carbamic acid, leaving somewhat cloudy naphtha. When the naphtha was freeze precipitated, it resulted in mimosa-like crystals which dried to a very white powder completely lacking any stickiness. Bioassay is yet to happen but it will happen soon.

The whole point of this post being in this thread is to demonstrate that my feedstock has a very high NMT very low DMT profile. The two times trying aspirin and two times trying CO2 gas resulted in the same sadly low yield of DMT, and with both processes I was able to observe the high amount of NMT traveling to xylene or precipitating, and the low amount of DMT crystallizing as the end product.

Also, with using bestine, I don't really measure stuff during general extractions, but I know that there was more than enough bestine used to dissolve 500mg DMT, when 30mg precipitated. I think my issue is actually my source material. Also I noticed that HCl was needed to back-extract the xylene on my second attempt. Vinegar was not doing it. That NMT-acetamide must have some kind of attraction to DMT.

Thanks for coming back with your results Lysurgeon.

Following the inconclusive/incomplete information I had previously posted in this thread, here is a full write-up of this procedure.

An alkaloid extract of the Thoughtful Tree was isolated by standard A/B extraction, the details of which are commonly spread throughout this forum. The solvent used was hexane isomers with some pentane and cyclohexane as adulterants. Works just like naphtha for freeze-precipitation, hereafter referred to simply as hexanes. The extract is very gooey.

3 grams of this extract was added to a small beaker. To this was added the minimum amount of dry methanol at 27°C and stirred until it all dissolved. To another beaker was added 12x 325mg tablets of aspirin. These were crushed to a powder and the minimum amount of methanol was added and stirred to dissolution. The solution was filtered and the filter was washed with a little more methanol. These two solutions were combined in a flat-bottomed flask. The total volume at this point was 60-70 ml.

The flask was then heated in a 55°C water bath until methanol vapor evolved. This took about 10 minutes. The temp was held at 55°C for another 10 minutes. The flask was then cooled under running cold water until the liquid was at 20°C. About 50ml 31% HCl was diluted with water to an approximate volume of 220 ml. This was added to the cooled methanol solution resulting in a volume of 300ml. This was extracted with 3x 45 ml DCM, which turned yellow on the first extraction. The combined DCM was back-extracted with a small amount of HCl (about 45 ml). The combined aqueous layer had some junk floating around in it so it was filtered, resulting in a nice (disappointingly) clean looking aqueous solution.

The aqueous layer was basified slowly with concentrated NaOH until the cloudiness did not dissipate upon mixing. pH was measured at around 14. This solution, while at around 40°C, was extracted with 2x 75ml hexanes. This 150 ml hexanes solution was filtered and placed in the freezer. Crystallization immediately commenced, and results will be posted tomorrow.

The combined DCM solution was filtered and distilled leaving a very clean-looking white crystalline residue in the distilling flask. This was removed with acetone, and the acetone was evaporated on a steam bath with a fan, resulting in a white to slightly hi-liter yellow crystalline material.

There is 3.3g of this material, which I take to be a mixture of salicylic acid, acetylsalicylic acid, and N-methyl-N-acetyltryptamine. Its smell is both sour and tryptamine-like. It is soluble in DCM and acetone. A component of this mixture crystallizes from acetone similarly to DMT, with circular needle-like formations. Melting point is obviously much greater than 88°C, as at this temperature there is no hint of softening or melting.

It would be interesting if anyone had any information about N-methyl-N-acetyltryptamine. Likely a hydrolysis will be attempted and reported.

RESULT: 2.2g of the Good Stuff!
Upon collection and drying of the precipitated output of this procedure, it weighs in at 2.2g which is considerably more than I expected. The color of this material is blindingly white, and it is a bit waxy and slightly oily. It would appear that this material still contains some NMT, based on its texture being more waxy than crispy. The aroma is still a bit muted. Bioassay indicates however that everything is wonderful.

I think the next attempt at this procedure will feature a reflux in the alcohol so that temperature can be maintained longer. I am definitely happy with the result. It was easy to load into the pipe, and it had a pronounced and hard-hitting effect. The flavor is like MHRB extract only a little softer. Next time I try this I'll report on whether the refluxing has any effect.

Nice work. It will be interesting to see if you can hydrolyse that amide without wrecking the whole molecule. It must be fairly hard to resist the impulse to try reducing it

The amide will also cyclize quite readily to 1,2-dimethyl-1,2,3,4,-tetrahydro-β-carboline (2-methyl-tetrahydroharman).

Nice work!

By the sound of your work up, there would not be much leftover amide asa, or salicylic acid

Did you recover the amide separately? Dilute Hcl and bicarbonate washes of the original DCM will remove any dmt, nmt, asa, and salicylic acid.

It would be cool to hydrolyze to recover the NMT, but amides are dang rocks, even boiling in NaOH won't do it.

In my experiments hydrolyzing a very similar molecule, 5-meo-n-aceťyltryptamine (melatonin), typical methanolic NaOH did not work, neither ethanol or isopropyl. The rxn was just too slow, it would take around 6hr to complete, but boiling for that long causes decomposition of the tryptamine ( argon atmosphere would help) doing it in higher bp alcohols like butanol gave completion in only 1hr, a bit of antioxidant thrown in helps with decomp, I got decent yields of around 65%. Butanol is stinky though and hard to acquire, I'd like to test out ethylene glycol or glycerol, at 100C, they may work just fine.

This is why carbamates appeal to me too, it is much more reversible

Reduction of course, would be fun, but you have the problem of amide being stable as a rock again! Needs very violent reagents to reduce!

I'm trying my hand at this
One piece of the tek concerns and/or intrigues me though.[Emphasis added]
If the NMT were in the NP as the freebase alkaloid, recovering the solvent by distillation would probably work since NMT is high boiling and amines rarely form azeotropes.
Amides do form azeotropes. For instance, if you add the high boiling compounds acetamide or dimethylacetamide to xylene the mixture will distill over at a lower temperature than either the amide or the xylene boils at. Wont acetylNMT form an azeotrope with some/most of the solvents we are using and distil over with the solvent before the pure solvent distills over?
This could be a novel way to purify acetylNMT, assuming the azeotrope forms and contains significantly more than 0.1% acetylNMT. It could also complicate recycling of solvent unless you had a good fractional distillation setup and could see an unequivocal temperature spike when the acetylNMT azeotrope finished distilling over.
Since I dont have a GC/MS at hand any more I think I'll just try to hydrolyze the acetylNMT back to NMT by refluxing with 1M H2SO4 (aq).

I would not worry about this, at all.

The boiling point and volatility of acetamide and dimethylacetamide are far closer to that of xylene, compared to the boiling point and volatility of acetylated nmt. Xylene and acetylated nmt are not going to form an azeotrope. I haven't tested it, but I'm happy to bet my house on it.

On a side note, I have observed this procedure to work very well for separating nmt/dmt mixtures. It really is very useful if you have acacias. Good luck with it!

Good to hear your success with this

Your right in that xylene and acetylNMT boil at far distant temperatures, but as far as I know that doesnt technically negate the possibility of azeotropes. Though it almost certainly means if it does happen the acetylNMT will be a very minor component of the mix, certainly under 1% [and the mix will boil within a degree of the pure solvent].
Nicotine boils at 247° and forms an azeotrope with water [its how you separate nicotine from all other tobacco alkaloids], I can think of numerous other examples of the lesser component in an azeotrope boiling 150-200° hotter than the carrier. AcetylNMT would be even farther than that, I wouldnt bet my house either way though
In college we didnt go into depth on azeotropy, just basically 'it happens, here are the charts, this is why you cant distill goofy juice from denatured ethanol' can anyone recommend a text book on the dynamics of azeotropy, preferably something comprehensible to a normal lab rat rather than a chemical physicist?

Interesting to hear that about nicotine.
It makes you wonder how one would tell the difference between the occurrence of a nicotine/water azeotrope, vs steam distillation of nicotine from a water mixture. That is, I'm happy to bet my house and car that you can steam distill nicotine from an aqueous solution. The difference here is that, in the receiving flask, nicotine will be sitting on top of the water layer, unlike an azeotrope.
None the less, formation of azeotropes is largely a function of volatility, and volatility of nicotine is going to be sufficiently greater than that of acetyl nmt.

On a side note, on my to do list is the attempted steam distillation of Dmt.
Imagine this;
Put bark in a flask, add 2-3M naoh and set up still head and condenser. Distill. Keep adding water to flask as needed. Receiving flask contains water with largely dmt on top.
It's been talked about, but never attempted as far as I know.
Some indoles can be steam distilled, I know that much. Sorry, off topic.

That depends on the temperature. The phase diagram of the nicotine/water system is quite unusual.