Xicori (Hive Bee)
03-02-03 11:34
No 413120
      Dialkyltryptamines from Tryptophol  Bookmark   


swim needs some help again...

In his dream he found 20g of tryptophol in his fridge... the tryptophol told swim that it would be much happier it it would get converted to DIPT, DET and DMT...

so swim wants to help the tryptophol to fulfil its wishes...

On Rhodium swim found 2 methods:

1. Brominate with PBr3 to get 3-(2-bromoethyl)-indole. This compound can be reacted with the amine to get the dialkyltryptamine.


Into a flask fitted with a Dean-Stark recieving trap were placed 0.1 moles of tryptophol [2-(3-indolyl)-ethanol], 0.1 moles of a secondary amine [dimethylamine for DMT], 4ml of skeletal nickel [Raney Ni] suspension in water and 100ml of benzene or xylene [I assume toluene is good too]. The reaction mixture was refluxed, and the condensed water collected for four hours, the hot solution filtered and the catalyst washed repeatedly with benzene or xylene [or toluene] and the mother liquor concentrated under vacuum. The product was either distilled in vacuo or isolated as the hydrochloride by acidifying with an equivalent of hydrogen chloride solution [they are probably referring to a non-aqueous HCl solution here]. The yields were in the 82-98% range.

Now there are a lot of open questions to swim, he hope some bee finds some time to help swim...

ad 1) The Bromination shouldnt be a problem at all, the yeilds should be quite good. The reaction should take place at room temperature - so just stir the Tryptophol and Phosphortribromide in Ether overnight, ad water, dry the organic phase and evaporate.

The second step could be a pain - Dimethylamin is only available in watery solution....wouldthis work? Swim has no chance to do pressurized reactions, Would it be ok to let the thing just react at room temperature for some days?

any experiences with that synthesis?

ad 2) This synthesis seems to be very promising, but some bees noticed that the solubility of the amine in boiling Toluene gant be great, and experience reports arent available at the hive... any ideas on that? maybe some russian bees?

would homemade raney-nickel suffice for that purpose?

some helpful answers would be great ;)

many thanks!

Edit: Post 407891 (Rhodium: "o-Iodoaniline + Butynol -> Tryptophol -> DMT", Tryptamine Chemistry)

...this route looks also very promising...but i think mesyl chloride may be hard to get.... But even in the paper cant be found reaction details... can anyone help out here?

03-02-03 13:12
No 413152
      #1 would probably work in alcoholic aqueous...  Bookmark   

#1 would probably work in alcoholic aqueous solution as long as your precursor dissolves and you have excess (> twofold) amine.

Think about the boiling point of dimethylamine in combination with an open reflux apparatus... #2 wouldn't work without modifications.
(Hive Bee)
03-04-03 09:24
No 413724
      thanks to our chief bee ive read the ...  Bookmark   

thanks to our chief bee ive read the following 2 posts

Post 336537 (Cyrax: "Tosylate and friends", Chemistry Discourse)
Post 102978 (Ritter: "Re: MDMA via Tosyl Chloride Intermediate?", Chemistry Discourse)

and worked out the following procedure:

1. tryptophole methanesulfonate

In an round bottom flask, immersed in an ice bath were 5g (0,031mol) of Tryptophol, dissolved in 50ml of DCM treated with 4,5g (0,045 mol) of Triethylamine. With stirring and cooling ad dropwise 4,5g (0,04 mol) of Mesyl Chloride. The mixture is stirred at room temperature for several hours. the organic phase is washed two times with 50ml of water, followed by two washes with NaHCO3 Solution, followed by a final water wash. The organic phase is dried with sodium sulfate, and the DCM evaporated to leave the product (tryptophole methanesulfonate)


The product from step 1 is dissolved in THF and an 3-fold excess ammount of secondary amine is added (Dimethylamine aq. 40% for DMT, Diisopropylamine for DIPT, Diethylamine for DET), and the mixture is heated to 65C for 3 hours.
After cooling down the reaction mixture was diluted with Et2O, washed with aq. sat. NaHCO3 soln, brine and water, then dried with anhydrous K2CO3.  Then the solvent is distilled off to leave the crude amine which should crystallize slowly. The HCl-salt is made by dissolving in anhydrous ether and gas with HCl.

any comments on that?

best wishes,

03-04-03 12:13
No 413761
      Maybe you should include an acidic extraction...  Bookmark   

Maybe you should include an acidic extraction step at the end.
03-07-03 12:45
No 414658
      Sn2 reactions require polar, aprotic solvents.  Bookmark   

Therefore, use DMF, DMSO, or ACN in the last step (the one where the dimethylamine is used to nucleophilically displace the bromide ion) for best results.