C_Nemo (Stranger)
06-15-00 04:29
No 17677
      useful tryptamine methods     

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
(Moderator)
06-15-00 06:01
No 17700
      Re: useful tryptamine methods     

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 (< 60C) 4% H2SO4 solution. Otherwise the yields will drop dramatically.

 
 
 
 
    C_Nemo
(Stranger)
06-15-00 06:23
No 17704
      Fisher @60??     

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
(Moderator)
06-15-00 07:42
No 17713
      Re: Fisher @60??     

The dioxolan should not be the problem. Its the heat I think. In the JOC original publication they heated to 50C, 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 -> 50C). I also heard that this type of reaction seemed to be fast even at 60 - 70C.
Could you post experimental details for your preferred legal derivative here later?

 
 
 
 
    C_Nemo
(Stranger)
06-16-00 02:33
No 18022
      Re: Fisher @60??     


they heated to 50C, 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 60-70C.
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
(Chief Bee)
06-17-00 13:01
No 18296
      Re: Fisher @60??     

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
(Stranger)
06-19-00 03:02
No 18814
      4-chlorobutanal     

<edited>
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%.
</edited>

With sincere respect, CN
 
 
 
 
    C_Nemo
(Stranger)
06-19-00 10:27
No 18961
      4-chlorobutanal     

don't you think it's watched anyway?

 
 
 
 
    Rhodium
(Chief Bee)
06-19-00 14:53
No 19039
      Re: 4-chlorobutanal     

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
(Stranger)
06-22-00 11:15
No 20135
      Re: 4-chlorobutanal     

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
(Chief Bee)
06-22-00 13:45
No 20208
      Re: 4-chlorobutanal     

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
(Chief Bee)
09-09-03 16:32
No 458004
      Facile Alcohol Oxidation using PCC/Silica Gel
(Rated as: excellent)
    

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 (../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) (../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
(Hive Bee)
09-12-03 05:35
No 458641
      4-Chlorobutanal synth     



Hope this proves more financially viable!!

wink
 
 
 
 
    Rhodium
(Chief Bee)
09-12-03 11:41
No 458711
      dead link     

cilliersb: That picture is not working...