Lilienthal (Moderator)
08-28-01 17:21
No 208020
       You can't dimethylate tryptamines with MeI or DMS  Bookmark   

You can't dimethylate tryptamines by simply reacting them with methyl iodide (MeI) or dimethylsulfate (DMS) due to overalkylation to quaternary salts.

Post 126957 (Lilienthal: "Breath of Hoax? / PTC tryptamine alkylation on the test bench", Tryptamine Chemistry)

trimethyltryptamine quaternary salts to dimethyltryptamines (e.g. using ethanolamine):
Post 67812 (smiley_boy: "Re: Melatonin->5-MeO-MET", Tryptamine Chemistry), Post 6376 (Teonanacatl: "Re: Yield, schmield", Tryptamine Chemistry), Post 17344 (foxy2: "Quant Salts", Tryptamine Chemistry), Post 126976 (Lilienthal: "Re: Breath of Hoax? / PTC tryptamine alkylation on the test bench", Tryptamine Chemistry), Post 17344 (foxy2: "Quant Salts", Tryptamine Chemistry)

smile 		 
 
 
 
    jim
(Hive Bee)
08-28-01 21:24
No 208054
       Re: You can't dimethylate tryptamines with MeI or DMS  Bookmark   

You can dequaternize the salts using ethanolamine however... 		 
 
 
 
    sunlight
(Hive Bee)
08-29-01 00:14
No 208111
       Re: You can't dimethylate tryptamines with MeI or DMS  Bookmark   

Can anyone describe a working procedure to demethylate a quaternary salt with ethanolamine ? 		 
 
 
 
    Lilienthal
(Moderator)
08-29-01 01:47
No 208130
       Re: You can't dimethylate tryptamines with MeI or  Bookmark   

A while ago I found some papers on it, unfortunately I can't find them again (sorry Rhod. It's because I'm a bit chaotical smile). But I think the refs are somewhere here at the tryptamine forum. 		 
 
 
 
    lugh
(Hive Bee)
08-29-01 02:36
No 208139
       Re: You can't dimethylate tryptamines with MeI or  Bookmark   

See Post 126976 (Lilienthal: "Re: Breath of Hoax? / PTC tryptamine alkylation on the test bench", Tryptamine Chemistry)smile 		 
 
 
 
    jim
(Hive Bee)
08-30-01 02:53
No 208463
       Re: You can't dimethylate tryptamines with MeI or  Bookmark   

Does a dialkylation with a isopropyl halide and a PTC work?  How about some other alkyl halide? 		 
 
 
 
    foxy2
(Hive Addict)
08-30-01 11:05
No 208576
       Re: You can't dimethylate tryptamines with MeI or  Bookmark   

Thanks Lilli!!!! Post 67812 (smiley_boy: "Re: Melatonin->5-MeO-MET", Tryptamine Chemistry) is the shit!!!!
laugh

I really wanted the ref's for ethanolamine and you served em up, now why was my UTFSE unsuccessful, guess its time to go back to beginner bee FSE training.

I think Shulgin successfully diisopropylated with isopropyl iodide.  Look at one of his synths.
Do Your Part To Win The War 		 
 
 
 
    Lilienthal
(Moderator)
08-30-01 16:59
No 208652
       Re: You can't dimethylate tryptamines with MeI or  Bookmark   

Higher n-alkyl halides work well. 1-branched alkyl halides may cause problems due to steric hindrance (monoalkylation) or dehydrohalogenation (zerohalogenation). 		 
 
 
 
    Rhodium
(Chief Bee)
09-06-01 21:39
No 210832
       Re: You can't dimethylate tryptamines with MeI or  Bookmark   

The long awaited reference on ethanolamine dequaternization of a quat salt from J Med Chem 13, 254 (1970):

Edit: The text is found in the post below 		 
 
 
 
    PoohBear4Ever
(Junior Service Representative)
10-11-01 13:42
No 223131
       Re: You can't dimethylate tryptamines with MeI or
(Rated as: excellent) 		 Bookmark   

"4,N,N-Trimethylbicyclo[2.2.2]octan-1-amine Hydrochloride (19). A mixture of 13.2g (95 mmol) of 9, 95g (0.7 mol) of MeI, 26.2g (0.31 mol) of NaHCO3, and 150ml of MeOH was stirred and refluxed for 16hr. The solid salt, A, that precipitated was collected and the filtrate, B, was evaporated to dryness. The residue of B and the solid A were extracted with boiling CHCl3 and the CHCl3 extracts evaporated to give 30g of the quaternary salt. The salt was refluxed with 57g of ethanolamine for 15min and then poured into 200g of ice (H2O). The resultant solution was extracted with Et2O in a continuous extractor for about 16hr. The Et2O extract was dried (NaOH) and distilled to give 11.2g of amine. The amine was dissolved in Et2O and treated with HCL(g) and the precipitate recrystalized from i-PrOH-C6H6 to give 12.0g of 19 with the properties given in Table IV."

What the hell did I just transcribe...?

PB 		 
 
 
 
    Rhodium
(Chief Bee)
10-11-01 16:18
No 223166
       Re: You can't dimethylate tryptamines with MeI or  Bookmark   

How to use ethanolamine to convert a quaternary amine to the tertiary amine. Useful for converting N,N,N-ttrimethyltryptammonium iodide (from the reaction of tryptamine with MeI) to DMT. Thanks for the transcription, now I can remove that image from my site. 		 
 
 
 
    picloud
(Stranger)
10-13-01 23:03
No 224109
       Re: You can't dimethylate tryptamines with MeI or  Bookmark   

It would appear, from the above, that the original (primary?) amine was restored from the quaternary by the ethanolamine.  Did I misread this? 

picloud
Cheers,

picloud 		 
 
 
 
    Rhodium
(Synaptic Cleft Mountaineer)
10-14-01 03:18
No 224228
       Re: You can't dimethylate tryptamines with MeI or  Bookmark   

No, the N,N,N-trimethylammonium iodide is turned into a N,N-dimethylamino compound.