Does anyone know where I could find IR spectra pictures for THH, harmine and harmaline? I have the numbers from TIHKAL but they don't seem to correlate with what I'm seeing in my scans. I've tried searching the forums and a Google search but can't find the THH spectra. Thanks in advance.
-Treehouse

What numbers are you getting and can you share how you are doing your IR tests exactly?

Also, what was the method for extraction/synthesis of the harmalas? Do you have access to any other analytical method to confirm their identity?

From a quick search:

FT-IR Spectra for (A) Harmaline Standard and (B) Harmine Standard and (C) P. harmala Seeds Extract:

http://ijbiotech.com/26501.pdf

http://www.researchgate....e/50463522d78db6f1ef.pdf

http://www.cheric.org/PDF/AC/AC12/AC12-1-0101.pdf

Clarke's Analysis of Drugs and Poisons
Harmine:
Infrared Spectrum Principal peaks at wavenumbers 1165, 817, 1629, 1200,
1282, 1239 cm –1 (KBr disk).

None of those links have IR spectra for THH.

I honestly don't know that much about IR, my chemistry mentor is a toxicologist and master of the IR but she wasn't around today, so I had to ask another professor (a plastics chemist). My mentor had told me IR would be good for ID and to check the fingerprint region and see if it matches Shulgin's description, but I'm not too good at reading them and the other prof doesn't work with drug-like compounds so he wasn't much help. His advice was to find a picture of the spectra and compare.

Harmaline was obtained by making P harmala seed tea, A/B extraction several times w/ lab paper filtering, Manske salt precip x3, separation from harmine by careful pH manipulation (several times redissolved and pH slowly raised to wash out harmine), touched up with activated charcoal, and recrystallized from methanol/ethanol x2. Checked this with TLC, was mostly harmaline with a very faint (but real) dot of harmine at the top.

15g of this harmaline was put in a 250ml flask with some zinc (a couple of 'mossy' chunks and some powder), and ~150ml 3M Acetic Acid. Dropped in a stirbar and allowed to mix for the weekend 48+hr (occasionally adding more powdered zinc and extra 3M AcH when the bubbling slowed down). After the weekend, added concentrated NaOH which resulted in a bunch of clay-like white precipitate, which was filtered and air dried. This white clay was extracted 2x with dried IPA (91% store-bought, dried with MgSO4), which gave a deep brownish red color solution. This was filtered and concentrated in a distillation setup (to recover the IPA) to about 250ml, which was allowed to cool and then placed in the freezer. ~12hr later there was a precipitate of snow-white crystals (assumed to be THH), which were filtered out and washed with a little room-temperature IPA to remove the last of the reddish colored solvent. Yield was ~6g from ~15g (40%). I evaporated the rest of the reddish solvent to see if any more would come out, but when the solvent finished evaporating it was just some dark blackish-brownish-red goo.

I took half of it (3g), dissolved in warm IPA, added some concentrated HCl, and allowed to sit for a day (Shulgin's process for converting THH to THH HCl), and it behaved pretty much exactly how he described (sat around in solution doing nothing, even after being put in freezer a few times, then after 24hr just spontaneously dropped out all at once).

As for the IR spectra, at the advice of the plastics chemist, I took the background spectra of the air and whatnot, dissolved my sample in acetone, poured a little on the crystal plate and allowed it to dry directly on the surface, then ran the scan. The computer had recently been replaced and the printer wasnt set up yet, so I had to take pictures of the screen. I ignored most of the stuff in the higher range because both Shulgin and my mentor focus on the "fingerprint" region for ID, and the plastics chemist was pointing out groups not in the molecule (>2000 range), like "oh that is CO2 from me blowing on it, oh that's a small carbonyl bump possibly from acetone vapors still bouncing around." So my pictures are of the lower region. This is all I know.

IR is the only method of ID I have other than anecdotal stuff like the time it takes to dissolve/precipitate. All we have at my college is IR and a GC that I'm not allowed to use. The lab coordinator is very suspicious of me so I can't do much in the labs there unless I am with a prof, and my mentor is rarely there. I will be transferring to a proper university with well-equipped labs in the fall, but I would like to get a positive ID before then. I contacted a couple analytical labs but they have to buy reference samples of harmine, harmaline, THH, and anything else that might be in the mix, so their quotes were all like $1k+ to get a couple samples tested.

I attached the pictures I took of the IR reading, they are both of the same reading. One is the full spectrum that I just took a picture of part of. The other one I made the reading just from like 600-1500 range and took a pic of that. Same scan, just one is stretched out.

I know THH from Caapi shows up yellow on TLC plates while the synthed (racemic) shows up blue, but Shulgin says the IR spectra are the same for both, I just can't find an image of it. TIHKAL says "IR (in cm-1): 789, 804, 816, 838, 1033, 1160. "

Thanks again,
-Treehouse

Oh and the harmaline TLC and THH IR spectra were done with the freebases, I only included the HCl conversion thing as evidence of identity.

Thanks for the thorough description. I´ll get back to you on that this weekend. I´m not experienced with IR but I can see if I find anything of interest out.


One question though, did you do a TLC with the hopefully THH? You can use 100:2.5 methanol:25% ammonia as eluent. If you haven`t seen this yet, it might help.

Thanks, I'll check back later. I have run HPTLCs plates on a couple test batches (microscale reactions that were not allowed to run to completion due to time restraints) and they looked almost identical to the harmaline controls, except the harmaline spot appeared to be trailing a little bit.

My chem mentor said that it looked like two different chems trying to separate, but to me it looked like a harmaline dot that was trailing a bit. I haven't run TLC of this particular batch (this one was allowed to go to completion) because my extracurricular lab time at the school has been cut short, and I don't have any plates at my house.

I'll see if I can get some plates in and try your solvent method, seems simpler than what I was using (if i remember right i was using an EtAc/MeOH/NH4OH carrier solvent).
-Treehouse

I know, I couldn't find one.

You could scan your harmaline and tetrahydroharmine and compare both spectra.

<total guessing here>
The difference between both molecules should be only a C=N double bond if I'm not mistaken. So both spectra should look fairly identical with the C=N double bond (@ 1650cm-1) being prominent compared to the C-N bond (@ 1200cm-1). </total guessing here>

Btw, you can make screenshots by pressing the print screen key and paste them in MS paint via ctrl+v.

Hmm there looks to be one around 1630 and there is also a decent dip at 1200 (this might still be strong from the C-N-C of the inner 5 member ring?). I'm not sure, the harmaline IR in the link you posted also has a dip at 1630 (well, 1626.12), and there isn't another bump @ 1650 on the sample I tested.

I dunno, I'm really clueless with IR and need someone experienced to take a look. I worked a few sample problems when I took O chem last year but never any practical work and I haven't really looked at it since then. I'll see if my mentor can decode it (hope she's working today). I'll let ya know if she comes up with anything. Oh and the IR comp can take screenshots, but it isn't connected to the net so you can't send it to anyone from there. The plastics chemist left and I couldn't get it to print, so I just took a picture and bounced before the lab coordinator could come ask a bunch of questions

-Treehouse

A bunch of questions deserves a bunch of answers.
You want to develop novel β-carbolines against dementia and alzheimers. Isn't that a noble goal one should support?

Anyway, good luck with your identification process and keep us updated. The Nexus Wiki def. lacks a good THH IR spectrum.

No luck, she was out of the office today. Will try again tomorrow.

Or its anti depressant use. For example Callaway reference for THH increasing serotonin transport platelets etc.

TreehouseChemist, if you can post pics of your TLC plates that would help. Does your plate have fluorescence indicator? With what wavelenght light are you visualizing spots? Are you using any reagent on top? Are you waiting a few hours and looking again at the plate?

All these sort of things may help with identification. Also, sometimes trailing can be related to too low ratio of ammonia, might want to experiment on that.

You're right. I'm going to go back up and ask the lab coordinator if I can run a quick TLC test. I have results from earlier but I want a direct comparison from my harmaline to my reaction sample. I'll post the old TLCs when I get back, and hopefully have the new one (my phone broke, using an iphone and the camera lens is cracked) We'll see.
-Treehouse

Well, here we go. I ran a new TLC plate with the starting harmaline and the product of the reaction. Again, the lens on this cam is cracked so everything is a bit blurry. I alternated the harmaline/potential THH, and just made them more and more concentrated as I went down the line. There are only 2 samples on this plate, just spotted multiple times in diff concentrations. There are images of both short and long wavelength UV light, I don't know the exact numbers. I labeled it with what I think they are.

Endless, as for the old plates, those are here https://www.dmt-nexus.me...m=534087&#post534087 I believe you helped me with those too. I have some more pics from a diff set of reactions, but the results look similar.

Anyway, let me know what you think. Definitely had a reaction.

-Treehouse

Lovin' all this feedback xD

Looks like you got it down very well, looks like a clean conversion

Congrats, let us know how the bioassay goes if you try it out!