One year ago Drone posted a reaction for a phase transfer catalysis assisted amino dimethylation of tryptamine, yielding N,N-dimethyltryptamine (DMT). This reaction remains still obscure:
- People from the hive and the DMT site were not able to reproduce this reaction. If I remember right, only one confirmation appeared shortly after Drones message.
- I found no single reactions of this type in the Beilstein database or through intensive classical literature search,
- nevertheless, drone stated "... it's based on a procedure found in the literature, but honnestly, I cannot divulge my source.".
- Drone stated several times that his reaction resembled reactions from THIKAL, which is wrong.
- Drones posted long literature lists to the DMT site to corroborate the possibility of practical PTC-ionic and SN2 amine dimethylations. Most of these sources either show the opposite or have nothing to do with this special reactions.
- the pKA for the indolic N-H is lower (if I remember right) than for a substituted amine. Indeed the conditions he gave are the standard conditions for indole-1-alkylation and 1-acylation, many examples exist for that in the literature.
- Drone did not see any overalkylation to quaternary ammonium salts, even if he used an excess of methyl iodide ("Actually, its even better to use a larger excess, and no, quaternization is no problem..."). But the non-PTC SN2 alkylation should be an serious competing reaction.
- Drone never answered the doubts posted here and at the DMT site.
A friend of mine, which I trust in chemical things, did this reaction to show that no DMT will be produced. He analyzed the products by TLC, color reagents, and comparison with non-prohibited standards. The protocols from his experiments are given below.
His results show that the main product is the quaternary N,N,N-trimethyl-tryptamine salt, together with unchanged tryptamine. Only traces of the intermediate N-methyl-tryptamine were visible.
This is in accordance with a very normal SN2 reaction mechanism, which leads to quaternary ammonium salts. This is because the reaction rate increases with each single alkylation due to the electron donating effect of alkyl groups and the low steric hindrance of methyl groups.
I am not totally sure about the reasons for these discrepancies, so I would be interested to hear the practical experience of other bees (and newbees from the DMT site 
) with this reaction and, especially, a statement from Drone.
Lilienthal
Experimental Part
________________________
Reaction
This reaction closely follows Drone's "breath of hope" recipe, scaled down to 1/50. In a test tube with small magnetic stirring bar 128 mg NaOH (finely ground, 40.0 g/mol, 3.2 mmol, 5.2 equ.), 6 mg benzyltriethylammonium chloride (227.8 g/mol, 0.026 mmol, 0.04 equ.), and 3 ml methylene chloride were combined, ultrasonificated in a ultrasonic bath for 15 s, and allowed to stir at room temperature for 15 min. 100 mg of tryptamine base (160.2 g/mol, 0.62 mmol, 1.0 equ.) was added and the solution was allowed to stir for 1 h. 0.1 ml methyl iodide (141.9 g/mol, 2.28 g/ml, 0.228 g, 1.61 mmol, 2.6 equ) was added and the mixture was allowed to stir for 15 h at room temperature.
Work up and thin layer chromatography
0.1 ml of this suspension was added to 0.4 ml methylene chloride and 0.4 ml ammonia solution and the mixture was thoroughly shaken. The clear phases were separated and extracted with 0.4 ml ammonia solution and 0.4 ml methylene chloride, respectively. The organic and the aquous phases were combined and chromatographed on 0.25 mm silica gel plates with UV indicator with 10% ammonia solution in methanol as solvent. The plates were stained by immersion into Dragendorff's reagent and van Urk's reagent and subsequent heating in a stream of hot air. The following standards were used: tryptamine, N-methyl-tryptamine, N,N-dipropyl-tryptamine, and benzyltriethylammonium chloride.
Color reagents (vol% for liquids)
Van Urk's / Ehrlich's reagent for 2-unsubstituted indoles: 8% HCl conc. and 1% para-dimethylaminobenzaldehyde in methanol.
Dragendorff's reagent for substituted amines (staining intensity: quaternary > tertiary > secondary > primary amines): 12.5% acetic acid, 0.85% BiONO3 (basic bismuth nitrate), and 20% KI in water. Diluted 1 + 12 with 17% acetic acid in water.
Results
The tryptamine base dissolved very slowly in methylene chloride over 45 min. 1 h after the addition of methyliodide the fine suspension became flocculent and light brown coagulated masses settled. Over the next hours these masses were suspended to yield a thick white milky suspension.
The organic phase gave only one UV absorbing spot of Rf 0.52 (tryptamine), which was strongly stained by van Urk's reagent. Additional very faint van Urk positive spots were seen at Rf 0.04 (N,N,N-trimethyl-tryptamine salt?), Rf 0.39 (N-methyl-tryptamine), Rf 0.72 (?), and Rf 0.95 (?). None of these spots were seen if stained with Dragendorff's reagent.
The aqueous phase gave only one UV absorbing spot of Rf 0.04 (N,N,N-trimethyl-tryptamine salt?) which was strongly stained by van Urk's reagent and Dragendorff's reagent. Additionally a faint van Urk positive spot of Rf 0.52 (tryptamine) and a faint but sharp Dragendorff positive band of Rf 0.95 were seen.
Rf values and staining properties
_Rf__UV__Drag.__Urk_________________
0.95__?____+_____-___?, product in aqueous phase, yellow after heating
0.95__?____-____(+)__?, very minor product in aqueous phase
0.95__?____+_____+___N,N-dipropyl-tryptamine standard
0.72__-____-_____+___?, very minor product in organic phase
0.52__+____-_____+___tryptamine standard / unchanged educt in organic phase
0.43__+___(+)____+___N-methyl-tryptamine standard / very minor product in organic phase
0.08_(+)__++_____-___benzyltriethylammonium chloride standard
0.04__+___++_____+___N,N,N-trimethyl-tryptamine salt?, main product in aqueous phase
- no staining, (+) faint staining, + staining, ++ strong staining
