Author Topic: KrZ DMT syntheses experience  (Read 5696 times)

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freakyDMT

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NaBH4 in H2O?
« Reply #20 on: May 29, 2003, 08:09:00 AM »
you say in the synthese to drip simultaneously a solution of formaline in MeOH and a solution of NaBH4 in H2O (70 ml),is this correct or do you mean MeOH instead of H2O?

raffike

  • Guest
No i think it meant H2O.H2O doesn't hurt ...
« Reply #21 on: May 29, 2003, 10:28:00 AM »
No i think it meant H2O.H2O doesn't hurt NaBH4.Formalin used also contains water so process isn't anhydrous anyway,why should it be?MeOH could/should be substituted with EtOH or IPA imo cuz NaBH4 reacts with MeOH


ClearLight

  • Guest
Right out of the abstract.
« Reply #22 on: May 29, 2003, 11:02:00 AM »
That NaBH4 in H20 is right out of the article.. raffike is right about MeOH as well...  That is not an error.


raffike

  • Guest
But all that makes synth of DMT out of ...
« Reply #23 on: May 29, 2003, 11:15:00 AM »
But all that makes synth of DMT out of tryptophan worth considering.Whole process doesn't even need vacuum distillation apparatus.Tryptophan,which is bought for pennies,is easily decarboxylated to tryptamine.Sodium borohydride might be bitch to get but raf could get it quite easily as it's not watched over here.Other chemicals are cheap and available also.This just might become raf's next project.


Rhodium

  • Guest
Reductive Methylation
« Reply #24 on: May 29, 2003, 06:02:00 PM »
If you prepare an aqueous solution of NaBH4 immediately before putting it into an addition funnel and use it in this reaction, then it will keep long enough - just not several hours.

The article, which now can be read in its entirety at

Tetrahedron 57(6), 1041-1048 (2001)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/tryptamine.nabh4.methylation.pdf), references the sodium borohydride reductive methylation of tryptamines from

Patent ES2084560

, where the procedure is largely the same.

Why can the authors of this article now succeed where so many have failed, and use the lowly and unselective reducing agent NaBH4 for the reductive methylation of tryptamine, and in addition to that even get yields of 80-90%? The answer lies in their use of low temperatures (-15°C, attainable with a cooling bath filled with sodium chloride/crushed ice in a 1:3 ratio), as well as the fact that they are adding the formaldehyde and NaBH4 solutions slowly, simulataneously and separately.

By performing the reaction cold, they are weakening the reducing power of NaBH4 so that it might reduce imines slightly faster than aldehydes, and by introducing both the aldehyde and NaBH4 slowly and in parallell they are insuring that as much as possible of the added formaldehyde manages to react with the tryptamine (and/or the intermediate N-methyl-tryptamine, NMT) to form an imine before the NaBH4 reduces the formaldehyde to methanol. All this is logical, but I couldn't imagine that it was possible to make it work that good by playing with the reaction conditions...

ClearLight

  • Guest
Amazing...
« Reply #25 on: May 30, 2003, 01:05:00 AM »
Chemistry is truely amazing!!! thx! rhodium for the goodies..


Barium

  • Guest
Strange
« Reply #26 on: May 30, 2003, 02:46:00 AM »
What I find peculiar is that the imine formation is so much faster than the aldehyde reduction at that low temp. Since the yield of the N,N-dimethylated tryptamine is in the 80-90% range the imine must be formed immediately. When for example methylamine and benzaldehyde is reacted one is still recommended to let them react for an hour or so to allow the reaction to go to completion. Here the reducing agent is added simultanously with the carbonyl compound and the yield is sky-high.


freakyDMT

  • Guest
+15 or -15 ?
« Reply #27 on: May 30, 2003, 05:06:00 AM »
it has to be -15°C instead of 15°C,doesn't it? there is is a major difference between those to, see

Post 436291

(Lego: "What am I not seeing here?", Tryptamine Chemistry)

raffike

  • Guest
Actually the article says 15 C not -15 ...
« Reply #28 on: May 30, 2003, 05:10:00 AM »
Actually the article says 15 C not -15 C.Anyways wouldn't it be better to add formaldehyde first and then NaBH4?Probably no,even though raf's non-chemist brain says it might as it would leave imine some time to form.


ClearLight

  • Guest
Someone plz test this...
« Reply #29 on: May 30, 2003, 01:19:00 PM »
It's SUCH a no brainer w/ these simple chems could someone please test and report?  ( I can't get to it immediately or I would  :( )


raffike

  • Guest
It would take at least a month to get all...
« Reply #30 on: May 30, 2003, 11:03:00 PM »
It would take at least a month to get all needed chemicals if raf had money,but at the moment he's nearly broke.But raf hopes to check this out in near future.


L42L

  • Guest
Shiff base shite
« Reply #31 on: September 09, 2003, 12:11:00 PM »
Building from Raffike's 'non-chemist' thoughts and what Barium finds 'piculiar', would it be wize to promote imine formation before the reduction? If so, maybe we could microwave the tryptamine/formaldehyde over clay to form the imine first before moving on to the reduction? Would formaldehyde behave in the microwave(B.P.?)?

See the microwave chem section at rhodium, the sodium borohydride on wet clay (tetrahedron 54 6293-8) for the imine formation i'm yakin about.

Lurk

koalaa

  • Guest
NaBH4 in water?
« Reply #32 on: February 26, 2004, 09:24:00 AM »
The opportunity to try the tryptamine/formaldehyde/NaBH4 DMT synthesis has presented itself.  The procedure is (from Lego, 5/29/03):

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.

There are a series of concerns with this, however.  First, formaldehyde reacts with methanol, and the only available formaldehyde is in water solution.  So the procedure will be attempted with 37% formaldehyde in water, rather than methanol.  The second concern is with the NaBH4 in water.  NaBH4 reacts explosively with water, so how can a solution of 5 g in 70 mL be safely made?  Instead of making a water solution, an IPA solution is being considered.  Would there be an undesirable difference between the two solvents?  The last question concerns the statement 'The mixture was washed with EtOAc (2x150 mL), basified with K2CO3, and extracted with EtOAc (2x130 mL).'  The pKa DMT is something like 8.86, so to what extent is the basification with K2CO3 taken?  pH 9, 10, 11?  Also, should concentration of the organic extracts be conducted with rotovap?

These two modifications, if valid, don't really change the reaction extensively.  Using water/formaldehyde and NaBH4/IPA would be essentially the same, upon mixing with the tryptamine/MeOH, as MeOH/formaldehyde and NaBH4/H2O, the only difference being presence of IPA.

Some comments on these ideas would be welcomed.  Especially before the procedure is eXecuted, circa 1 week from the present.

Lilienthal

  • Guest
The link to Lego's post is Post 436291 :-P...
« Reply #33 on: February 26, 2004, 09:33:00 AM »
The link to Lego's post above in this thread is

Post 436291

(Lego: "What am I not seeing here?", Tryptamine Chemistry)
 :P

This is a hypothetical procedure and I'm very very sure that it doesn't work because of cyclization (UTFSE). At least it's nothing for a beginner without adequate analytical methods to determine the products of this synthesis.

Lilienthal

  • Guest
NaBH4 doesn't react explosively with plain...
« Reply #34 on: February 26, 2004, 09:37:00 AM »
NaBH4 doesn't react explosively with plain water (without a strong acid), it's a pretty slow reaction.  Formaldehyde in methanol shouldn't be a problem because the reaction is reversible.

koalaa

  • Guest
Successful synthesis, reduced yields.
« Reply #35 on: April 14, 2004, 09:30:00 PM »

elfspice

  • Guest
pretended
« Reply #36 on: April 15, 2004, 04:51:00 AM »
one went to all that effort to write a nice atemporal apersonal report and sticks just one (although i was a little cursory in my perusal) personal attribution of activity and intent (mind you, it was a little to broad in the scope that it introduced to be pretending really) it just ruins everything... the info in there is good, please repost with more careful editing.

Madog

  • Guest
please repost SWIY's experiance edited, SWIM...
« Reply #37 on: June 01, 2004, 06:32:00 PM »