Reduction of Tryptamine using STAB. Advice?

[Rabidreject]

Okay so I’m doing an aminative reduction of tryptamine to yield various different primary active tryptamines.
I will be using the method that is on video, filmed by Hamilton Morris - not the one where HE makes MEO, the one with the weird third eye guy lol
I’ll be making sodium triacetoxyborohydrite, made in situ at the time of reduction. I have everything I need but the tryptamine (quite an essential component) but it looks as if iv solved that now.
I guess my question is, do you have any advice, experience or knowledge on this RXN?
I’v said it many times but I’m not looking to sell the world (or anyone) DMT or anything else I make.
if I poison myself, that’s on me…I have TLC equipment to be able to check what’s going on to some degree.
I think I’ll also spring for some dry ice to be able to keep It cool easier. Or maybe not actually I don’t know the temp but I’m pretty sure it can’t exceed 0c but I’d have to relook at the literature I have saved.
I am also wondering if anyone can tell me why they need to use 4A Mol seives and not 3A? Obviously when you use them for the remaining 2% of alcohol, you use 3a so why, if they are both soaking up water molecules does it need the 4a? Also what’s the difference? Are they just bigger meaning they can absorb more?
I can’t express how glad I am to have found somewhere and people to discuss this stuff with!
Iv resorted to buying tryptamine because Christ I can’t decarb it for shit! It don’t know why, maybe it doesn’t like cyclohexanone as a catylist….I dunno I just either got Goo or a liquid that’s dark and won’t re-x. Anyway I’m done with that!
im hoping the reductions are slightly less messy!

 

[HerrHaber]

I'm curious wether in situ formed STAB would do just like the commercial solids (I still have couple of grams of both STAB and tryptamine) but also previous hands-on experience on tryptamine prep work so I will find the right moment to do some alkylations not keen on making a big mess for no results. in theory NaBH4 + 3 M eq. HOAc gl. should result in STAB but in literature for some reason solids are used in this regard (at least last time I documented it).

 

[CCL4 huffer]

yeah it would i think the only downside of using stab is the water sensitivity so ull have to generate the formalin insitu with for example the bisulfite and formaldehyde adduct and triethylamine also its not compatiable with methanol so id just use a aprotic solvent with it.

 

[Rabidreject]

Ah thanks for your reply - tbf I think I’m going to try the NaBH4 animatics reduction route first.
I did try it but it’s summer here and I only had a normal water/ice/salt bath and didn’t add everything sufficiently slowly…
Am going to get some dry ice, try it again and also ACTUALLY make use of TLC this time also, most likely.

I must admit, iv been a little distracted trying to gather up the reagents to my next planned RXN - it involves reclaiming a few of them by distilling impure products to obtain the nitroethane/nitromethane I need to start working on phenethylamines.
Now that iv actually studied for 6 months or so, its REALLY obvious and has been for a while, that phenethylamines seem to be an easier jumping off point - in terms of not needing as many things that cost! I,e - I have everything I need but the dry ice and heptane to re-x from.
When I get £40-50 I shall try the reductive amination again - I also thought about adding the NaBH4 to some methanol maybe in order to be able to constantly drip it in really slowly or if it won’t dissolve in methanol and work that way, at the very least just add everything s-l-o-w-l-y. Although tbf with dry ice /acetone it shouldn’t matter as much.
I assume by the way the methanol that’s left over from my last round flows under UV, the equilibrium was pushed the wrong way due to high temps and maybe closed off that ring to make a beta-carboline.
I could be wrong and I may have done it correctly but I still need blooming hePtane and not f**king heXane!!
In the mean time I shall be distilling the hard to obtain chems I need to start working on different aldehydes to make phenethylamines and/or the corresponding amphetamine (in the case of the tri-substituted aldehydes - I would only make small amounts of each anyway however the psychedelic amphetamines would be used less by me than the corresponding PEA but hey ho!
This is the issue when you have a lab and yet don’t sell anything you produce! It takes a long time to gather up the actual supplies you do need and you have to have more than one project on the go at once - not physically but the gathering of materials never really stops!

 

[CCL4 huffer]

i mean if u want heptane u could fractionaly destill gasoline its a bit tedious but its possible

 

[Rabidreject]

lol it’s okay I have the heptane now!
Am I meant to end up with a yellowy/brown sort of oil at the end stage? Just before re-x’ing with boiling heptane?
I kept the oil from the rxn I did with a normal ice bath but I didn’t really pay close attention to the temp. I know it was MAINLY below 0 but I didn’t pace myself adding the NaBH4 or even the formaldehyde so it may have risen to 5c for a few mins.
Also not having the correct end solvent was an issue I won’t lie!
I was going to give it one more shot with normal ice and salt baths and then I’m just going to order some dry ice.
Can you tell me if you freeze precip the end crystals out of the heptane or do you evaporate the heptane?

 

[CCL4 huffer]

just evaporate it and then recrist it

 

[Rabidreject]

Ah okay. Should it be taking a lot of the oil created in the last step by removing the DCM with it when you do the first re-x?
I did try a freeze precip purely because I used a pipette to draw up the hot heptane and it instantly went cloudy so I assumed something was happening. I did get a few crystals via freeze precip but most of it just melted back to a clearer goo - I shall try to re-x that and see where I get.
Does it take quite a bit of heptane? Given the literature says it’s only slightly soluble when boiling…
Thanks for your help - I feel like I’m almost there….is v frustrating!

 

[CCL4 huffer]

thats organic chemistry for ya just save all ur solutions and try aggain and recover what u can

 

[Rabidreject]

To be fair, all went much as the synth said, other than me stupidly adding the reagents to quickly and not having the correct alkane at the end…..
Having said that, iv not found the ‘oil’ very EASY to re-x as it states - even from boiling heptane.
I think I should just try it again tbf

 

[Rabidreject]

I am nail bitingly close now lol iv done the final few attempts of re-x.
Experimented by using pure heptane for one, and another using 1:9 chloroform:heptane so I guess we will see.
The last time I freeze precipitated out the DMT I got a few beautiful white x’stals around the edge and then the bottom looked like it was pure DMT but then when I drained off the heptane and put it in front of a fan, it unfroze and most of it went back to oil (but a clearer oil).
Now iv done it again and I have a vacuum chamber and pump and everything to make it work tomorrow - something iv been wanting / needing for ages. When you need it you fucking need it right?
The write up did say from the beginning that i needed one…painful to pay for though…lucky I’ll have a lifetime supply of DMT and Hopefuly, if I can work out the syntheses some other tertiary amines. I’d love to synthesise DET.
How do you get those ethyl groups on there instead!!

 

[CCL4 huffer]

To a solution of 1.6 g tryptamine base in 20 mL isopropanol, there was added
5.5 mL diisopropylethylamine and 2.3 mL ethyl bromide. After stirring at room temperature for
36 h the volatiles were removed under vacuum on the rotary evaporator and the light brown
residue (5.17 g) was treated with 5 mL of acetic anhydride and heated in the steam bath for 5
min. After coming to room temperature, 3.5 mL ammonium hydroxide was added, and the
exothermic reaction was allowed to return to room temperature. The reaction mixture was
suspended in 150 mL 0.5 N H2SO4, and washed with 3x40 mL CH2Cl2. The pooled washes
were again extracted with 150 mL 0.5 N H2SO4 and the aqueous phases again washed with
CH2Cl2. The aqueous phases were combined, made basic with 6 N NaOH, and then extracted
with 3x40 mL CH2Cl2. The pooled extracts were stripped of solvent under vacuum, and the
residue (1.49 g of a dark oil with a sharp smell) was distilled at the KugelRohr. The product,
N,N-diethyltryptamine, distilled at 175-185 °C at 0.05 mm/Hg to yield a white oil weighing 1.02
g, which spontaneously crystallized. This product was dissolved in 20 mL boiling hexane,
cooled to room temperature, and seeded. There was thus obtained 0.72 g of a white waxy
crystalline material melting at 84-87 °C. IR (in cm-1): 741, 804, 970, 1018, 1067, 1090 and
1120. MS (in m/z): C5H12N+ 86 (100%); indolemethylene+ 130 (6%); parent ion 206 (1%). The
hydrochloride salt (crystallizing spontaneously from an IPA solution of the base treated with a
few drops of concentrated HCl) had a mp 169-171 °C, and the following fingerprint: IR (in cm-
1): 717 (br.), 759, 847, 968, 1017, 1110. This salt appears to be unstable, darkening with time.
- from tihkal
or yk just use that other method starting from indole

 

[Rabidreject]

Yes I have read the shulgin method, I have the book in front of me. Was just curious if there was a way using acetaldehyde in place of the formaldehyde.
Iv heard a few people talk about it and saw some very basic notes on it but havnt expressly heard anyone state it works.

With regards the DMT synth - I didn’t use STAB in the end and just used NaBH4.
I just tried it again over the past couple days and to be honest, I appear to have gotten a much better result this time, after following a few pointers from other people who similarly do not have access to rotary evaporators or even reduced pressure for long periods as the pump is too loud!
I think i was just exposing the final oil you re-x using heptane, to too much heat and air - basically taking too long!