Author Topic: KrZ DMT syntheses experience  (Read 5959 times)

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freakyDMT

  • Guest
KrZ DMT syntheses experience
« on: May 23, 2003, 02:14:00 PM »
I would like to know what the experiences are with the KrZ
NaCNBH3syntheses,how is the yield,i see that there are a lot of disinformation about this DMT route.

Rhodium

  • Guest
DMT from Tryptamine/NaBH3CN/37% HCHO
« Reply #1 on: May 23, 2003, 04:57:00 PM »
If you UTFSE in this forum for "nabh3cn or cyanoborohydride", you will find almost exclusively posted procedures which involve reductive amination of various tryptamines with formaldehyde and NaBH3CN - all of them have yields of 60% or more.

KrZ's synthesis in particular is not optimized, he runs the reaction for a far longer time than necessary, and in the first procedure he posted he used far too little formaldehyde for the reaction to go to completion. Try the procedure below instead, if you don't have any silica gel for chromatography, then you can try repeated recrystallization instead to purify the product, either from hexane (petroleum ether), ethyl acetate (EtOAc) or am mixture of both.

DMT by reductive methylation of Tryptamine with 37% Formaldehyde and NaBH3CN in Methanol
Synthesis according to a general procedure in

J. Med. Chem. 37(19), 3029 (1994)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/reductive.tryptamination-2.pdf)


Tryptamine (1.12g, 7 mmol), Sodium Cyanoborohydride (0.88g, 14 mmol) and Glacial Acetic Acid (2ml, 35 mmol) was dissolved in 110ml Methanol at 0°C, and a solution of 37% Formaldehyde (1.4 mL, 18.5 mmol) in 15ml Methanol was added dropwise over 20 min, and the resulting solution was allowed to stir for 20 min at 0°C and 2.5h at room temp. The methanol was evaporated under reduced pressure, and 80ml 25% aqueous potassium carbonate was added and the solution extracted with 2x125ml EtOAc, the extracts washed with 2x40ml brine, dried over MgSO4 and the solvent evaporated under reduced pressure to give an amber oil, which was purified by flash chromatography on 30g silica gel using a gradient of EtOAc:MeOH to give an oil, which was crystallized from boiling hexane to give N,N-Dimethyltryptamine as colorless waxy crystals, weighing 0.9g (69%).

freakyDMT

  • Guest
Thank you,RHODIUM,you realy helpt me ...
« Reply #2 on: May 23, 2003, 08:34:00 PM »
Thank you,RHODIUM,you realy helpt me out,thanks!!
by the way,what about the use of sodiummethoxide,what is the use of that and does it give it a higher yield?
a second question what is the exact purpuse of the acetic acid,does it control the pH or is it to make the tryptamine/DMT solvable?

Rhodium

  • Guest
acetic acid & sodium methoxide
« Reply #3 on: May 24, 2003, 02:55:00 PM »
The acetic acid will probably change the pH to an optimum level, but may also contribute to form some acetoxycyanoborohydride species in solution, which probably has other reducing properties than plain cyanoborohydride. I don't know which of these two effects is the most important here.

I don't see any sodium methoxide in this procedure?

freakyDMT

  • Guest
What i mean is see post 285474 03-20-02 were...
« Reply #4 on: May 25, 2003, 03:12:00 AM »
What i mean  is see

Post 285474

(Rhodium: "Tryptamine -> DMT w/ formaldehyde/NaBH3CN", Tryptamine Chemistry)
were they also use sodiummethoxide in the synthese.

ClearLight

  • Guest
Cyanoborohydride required?
« Reply #5 on: May 25, 2003, 08:43:00 AM »
Is the Cyanoborohydride required for this reduction or could NaBH4 be substituted?  If it is a yields question I can live/ that.


Rhodium

  • Guest
Reductive methylation of tryptamine
« Reply #6 on: May 25, 2003, 09:10:00 AM »
I'm not sure about the reason for the sodium methoxide in that procedure, maybe another pH is desired when working with a cyano-substituted tryptamine. This procedure uses tryptamine/cyanoborohydride/acetic acid/formaldehyde in a 1/2/5/2.5 ratio while the other one uses a 1/2/3/2.5 ratio (plus one equivalent of sodium acetate, which forms from 1 eq of acetic acid and 1 eq of sodium methoxide). There is no real difference but the final pH of the solution. The yields are erssentially the same anyway (even though the method with NaOMe hasn't been tried on DMT yet).

No, sodium borohydride cannot be used in this case, the formaldehyde will be reduced to methanol by it before it has had a chance to form an imine with the tryptamine.

Here is some more reading on acetoxyborohydrides and tryptamine:

Post 243844

(Rhodium: "Tryptamine reductive alkylation with NaBH(OAc)3", Tryptamine Chemistry)

freakyDMT

  • Guest
tryptamine v. tryptamine HcL
« Reply #7 on: May 25, 2003, 11:29:00 AM »
Rodium is there a diverence between tryptamine and the HcL form in use in the synthese,and what i read is it so hard to get cyanoborohydride,is it a controlled substance,were i live you can order it whitout any questions.

Rhodium

  • Guest
Methoxide Mystery Solved
« Reply #8 on: May 25, 2003, 12:19:00 PM »
You have a good eye for details! Then of course the sodium methoxide is added to deprotonate the 5-CN-Tryptamine HCl to its freebase, and there is only the 4 vs. 5 equivalents of acetic acid that differs. I really wonder if the active reducing species is a cyanoacetoxyborohydride or id it is free cyanoborohydride which does the job. NaBH3CN is stable down to around pH 3, so if the final reaction mixture isn't more acidic than that, then we can be pretty sure that it is free cyanoborohydride.

NaBH3CN is easy to aquire in many parts of the world, it is only in the US it is watched closely.

freakyDMT

  • Guest
Rodium,i think the sodiumcyanoborohydride is...
« Reply #9 on: May 25, 2003, 01:48:00 PM »
Rodium,i think the sodiumcyanoborohydride is in its free form,because i always messure the pH at the end of the reaction and the pH is normally around pH 5-5.5.
by the way what does the word bookmark mean?

Rhodium

  • Guest
pH & bookmarks
« Reply #10 on: May 25, 2003, 03:42:00 PM »
During a NaBH3CN reduction, the pH of the solution becomes progressively more basic, so you should rather measure the pH when you initiate the reaction to be able to tell for sure, but I agree with you that it is probably above 3 in the beginning too.

Bookmarking a post will add it to you personal list of favorite posts at

https://www.the-hive.ws/forum/favorites.pl?Cat

= (accessible by clicking "Show bookmarks" in your private area) so that you easily can go back to certain posts you want to read again without having to UTFSE for them every single time.

Chimimanie

  • Guest
Great DMT synth
« Reply #11 on: May 25, 2003, 03:54:00 PM »
Rhodium I like this DMT synthesis, it is great!

So simple and yet effective!

DMT easy way...

ClearLight

  • Guest
Acetic acid and trioxy?
« Reply #12 on: May 27, 2003, 07:22:00 PM »
Hmm, Rhodium,  this post indicates addition of acetic acid in the reaction, and in the post you linked to above using triacetoxyborohydride, they indicate that acetic acid would cause things to go bad quickly...

  Is there a modification of this method that would enable triacetoxyborohydride  to be substituted for the NaCNBH4 and not require acetic acid?  I really like the idea of using triacetoxyborohydride  since it seems to be easily made...


Rhodium

  • Guest
2 mL HOAc is ok...
« Reply #13 on: May 27, 2003, 07:43:00 PM »
The thing which made things go bad was when they used acetic acid as the solvent. There is a big difference between that and only 2 mL HOAc in 125 mL methanol... And don't worry about it, this procedure is used in almost a dozen articles on dimethyltryptamines over the last decade. It will not produce the indoline.

Lego

  • Guest
Please UTFSE
« Reply #14 on: May 28, 2003, 02:59:00 AM »

Is the Cyanoborohydride required for this reduction or could NaBH4 be substituted?  If it is a yields question I can live/ that




No, cyanoborohydride is not required, plain sodium borohydride can bee used, too.

A quick search with TFSE will tell you this  ;)

The search string is almost in your post, perhaps you have to try an abbreviation but the hit will lead you to the right post.

Hint: The post you are looking for is quite new........




raffike

  • Guest
cyanoboro is way too expensive to play with.
« Reply #15 on: May 28, 2003, 11:59:00 AM »
cyanoboro is way too expensive to play with.

Post 431982

(Lego: "Article on DMT derivate synths", Tryptamine Chemistry)



ClearLight

  • Guest
thx
« Reply #16 on: May 28, 2003, 12:02:00 PM »
For that indirect reference to the article you posted  :) !

  I downloaded the article and read your synopsis.   I'm afraid my theoretical understanding does not make the leap from the journal article to a practical synth from what was described. (Rhod let me know if you want the pdf of the tetrahedron original). I don't want compount 11b i would like the NN DMT variant.  A little clearer explanation of how YOU would adapt this procedure to produce elf spice would be appreciated!


raffike

  • Guest
think moles not grams
« Reply #17 on: May 28, 2003, 12:16:00 PM »
think moles not grams
PS you want 9b without that sulfonylmethyl group


ClearLight

  • Guest
right raffike
« Reply #18 on: May 28, 2003, 10:06:00 PM »
but when i read that synth i can't see HOW that sulfonylmethyl group got in there in the first place, since none of the reagents listed carry a sulfur atom..?  So this is where I go "What am I not seeing here???!!!"


Lego

  • Guest
What am I not seeing here?
« Reply #19 on: May 29, 2003, 03:17:00 AM »

but when i read that synth i can't see HOW that sulfonylmethyl group got in there in the first place, since none of the reagents listed carry a sulfur atom..?  So this is where I go "What am I not seeing here???!!!"



Check Scheme 2 of the article. They use a 4-sulfonyl derivate of aniline. So the sulfur is in the molecule since the beginning of the synthesis.





The procedure for DMT would go like this:


A solution of 35% formaldehyde (35 mL, 416 mmol) in MeOH (35 mL) and a solution of NaBH4 (5 g, 132 mmol) in H2O (70 mL) were added dropwise, simultaneously, at 15°C to a well-stirred solution of tryptamine (4.166 g, 26 mmol) in MeOH (150 mL). The mixture was stirred at 15°C for 0.5 h, 2N aqueous HCl was cautiously added to bring the pH to 3, and the resulting mixture was stirred for 10 min. Then, the pH was adjusted to 6.5-7 with saturated aqueous NaHCO3, MeOH was evaporated, and H2O (50 mL) was added. The mixture was washed with EtOAc (2x150 mL), basified with K2CO3, and extracted with EtOAc (2x130 mL). The organic extracts were dried, filtered, and concentrated to give DMT.




All italic words are modifications of the original procedure.
The modification of the original procedure is quite simple, calculate the molar weight of tryptamine (either by hand or Merck Index or with a computer programm) multiply it with the molar amount and you get the weight of tryptamine you have to use. That's all, now try it yourself..........


Yields should be similiar to the original procedure (88%, about 4.3 g) but expect rather 2-3 g than 4 g if you do it the first time.

Good luck!  8)