Which brings me back to my question: how would YOU rationalize the fact that when you combine an aldehyde or a ketone, DMF, 90% formic acid, and heat it at 190 deg C for a few hours, you get dialkyl tryptamines?
------------------
-the good reverend drone
Wizard X
Moderator posted 04-06-99 11:07 PM
--------------------------------------------------------------------------------
This is very similar to the
ESCHWEILER-CLARKE METHYLATION REACTION
The intermediate immonium ion +N=CH2 (produced by reaction of aldehyde or ketone with a formamide) is reduced with formic acid to N-CH3 + CO2.
Other reducing agents are NaBH4 or NaBH3CN
rev drone
Member posted 04-07-99 10:43 AM
--------------------------------------------------------------------------------
Yes, the Eschweiler-Clarke is simply an inversion of the Leukart-Wallach, but what my question is is pertaining to actual mechanism. Try drawing an electron-pushing diagram for systems involving dialkylformamides, and see what happens -- this isn't half that straight forward.
------------------
-the good reverend drone
Wizard X
Moderator posted 04-08-99 07:33 PM
--------------------------------------------------------------------------------
Drone : here is a Leuckart with dimethylformamide and formic acid I've used.
Mole ratios : 173gr (2.5 moles)dimethylformamide and 54gr (1 mole) of 85% formic acid. This is heated to 150-155 deg C
Over a period of 4-5 hour, a mixture of 1 mole of redistilled aldehyde, and 163gr (3 moles) of 85% formic acid through a dropping funnel. The water and formic acid which distil is discarded.
As for the mechanism I will send it to you as a jpg image file when I'm done.
Optimus Prime
Member posted 04-10-99 04:59 PM
--------------------------------------------------------------------------------
Include me also in the mailing please...
OP
Rhodium
Administrator posted 04-11-99 03:02 AM
--------------------------------------------------------------------------------
What kind of aldehyde have you used? 3-IAA?
rev drone
Member posted 04-12-99 12:40 PM
--------------------------------------------------------------------------------
So generally, how would you verbally describe the mechanism for this?
------------------
-the good reverend drone
Wizard X
Moderator posted 04-14-99 11:22 PM
--------------------------------------------------------------------------------
Hope the JPG images are OK !
Optimus Prime
Member posted 04-17-99 09:27 PM
--------------------------------------------------------------------------------
Here are some refs for you also Boss... I have no access to tett or Bull jap or I would have scanned them...
Lukasiewicz, Tetrahedron, 1963, 19, 1789;
Oba; Sekiya Bull. Chem. Soc. Jpn. 1976, 49, 2485...
I can get the japanese translated if you can get the article...
OP
All times are CT (US)
next newest topic | next oldest topic
Administrative Options: Close Topic | Archive/Move | Delete Topic
Hop to: Select a Forum or ArchiveList of Forums:General DiscussionAcquisition DiscourseChemistry DiscourseMethods DiscourseNovel DiscourseCrystal MethSerious Chemistry ForumThe Hive CouchSerious Tryptamine DiscourseAdmin Chill-out TentList of Archives:Couch ArchivesClassics!Law and OrderThe litter box.misc. PEAs
Contact Us | the Hive
Powered by: Ultimate Bulletin Board, Version 5.39a
© Infopop Corporation (formerly Madrona Park, Inc.), 1998 - 1999.