useful tryptamine methods

[C_Nemo]

a good bunch of methods is collected at

http://hyperlab.org/syn/dmten.html

i would greatly appreciate any comments, improvements or alternative routes.

Sincerely, CN

[Lilienthal]

Check my references page

http://www.fortunecity.com/westwood/storey/116/index.html

for the (nearly) complete literature onto that route to tryptamines.
There you will find a more convenient route to the acetal compound. The cyclization is a bit tricky - the educts have to be added to only moderately warm (< 60°C) 4% H2SO4 solution. Otherwise the yields will drop dramatically.

[C_Nemo]

hrm... my reference said "boil 2h", and i suspect that means >100°? SWIM made that procedure (w/ dioxolan instead of dimethylacetal) and it really produced a poor yeld, but we think that w/ acetal it'll be OK...

and thanks, your page's great =) lemme submit a small ref.? that's about imporvement to PCC procedures:

http://jchemed.chem.wisc.edu/Journal/issues/1999/Jul/abs974.html

Yours, CN

[Lilienthal]

The dioxolan should not be the problem. Its the heat I think. In the JOC original publication they heated to 50°C, added the educts over 30 min (while cooling to room temperature?), and then brought to boil (slowly?). It is very mistakable in their description. But I heard that this seemed to be the key. At higher temperatures the intermediate imine possibly splits off the respective aniline. Maybe lower temperatures would work even better (e.g. RT -> 50°C). I also heard that this type of reaction seemed to be fast even at 60 - 70°C.
Could you post experimental details for your preferred legal derivative here later?

[C_Nemo]

they heated to 50°C, added the educts over 30 min (while cooling to room temperature?)

but what the order of addition should be then?

I also heard that this type of reaction seemed to be fast even at 60-70°C.
Could you post experimental details for your preferred legal derivative here later?

of course. i'll try to convince that FOAF to try lower heat level next time and send me a report. meanwhile i'm askin him about a complete account of that low-yeld (1,3-dioxolan) procedure. will publish it ASAP.

Yours, CN

[Rhodium]

How did your friend synthesize/aquire 4-chlorobutanal? I feel its synthesis is the greatest obstacle to this promising method. There is only two suppliers of this compound in the world, one in france (Lipha Chemie, referenced in the JOC article, and a japanese online company that doesn't answer their email).

http://rhodium.lycaeum.org

[C_Nemo]

he did it from 4-clorobutanol (wich was made from THF) with PCC oxydation as described in Tetrahedron, 50(40) Post 1994 (not existing) 11665-11692, and reproduced on dmten.html, with yeld ~60%.


With sincere respect, CN

[C_Nemo]

don't you think it's watched anyway?

[Rhodium]

No it would definitely not be watched. Expensive perhaps. Could someone with Fluka catalog access check out its price?

http://rhodium.lycaeum.org

[C_Nemo]

PCC doesnt suit you, Rhod? =) or you're short in THF? =)

okay, i'll post the procedures i've promised right here as soon as i'll get 'em... i'll edit this msg...

Yours, CN

[Rhodium]

Chlorobutanol and PCC are expensive, and one would also have to make that acetal. Why start from scratch if you don't have to? Do a websearch for Lipha Chemie in France, and buy the chlorobutanal diethylacetal directly from them. As they are probably making at least hundreds of kilos of this reagent, it shouldn't be much more expensive than chlorobutanol itself, max $1/g.

Rhodium (Spoiled brat)

[Rhodium]

The document mentioned in

Post 17677

(C_Nemo: "useful tryptamine methods", Tryptamine Chemistry) can nowadays be found at my page:

One-step Synthesis of Substituted Tryptamines

(https://www.thevespiary.org/rhodium/Rhodium/chemistry/dmten.html)

Also, here follows the full alcohol oxidation article which was mentioned in

Post 17704

(C_Nemo: "Fisher @60°??", Tryptamine Chemistry):

A Facile Oxidation of Alcohols Using Pyridinium Chlorochromate/Silica Gel
Frederick A. Luzzio, Richard W. Fitch, William J. Moore, and Kelli J. Mudd

J. Chem. Educ. 76, 974 (1999)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/pcc-sio2.alcohol.oxidation.pdf)

Abstract

An efficient and convenient adaptation of the pyridinium chlorochromate (PCC) oxidation for an organic chemistry student exercise is based on the employment of reagent-grade silica gel, which simplifies workup and purification of the product. The procedures include the oxidation of 4-tert-butylcyclohexanol to 4-tert-butylcyclohexanone and d,l-menthol to d,l-menthone.

[cilliersb]

Hope this proves more financially viable!!

[Rhodium]

cilliersb: That picture is not working...