Author Topic: Methylation: Eschweiler-Clark  (Read 4199 times)

0 Members and 1 Guest are viewing this topic.

Z_Hound

  • Guest
Methylation: Eschweiler-Clark
« on: March 31, 2002, 12:42:00 PM »

In this reductive methylation method formic acid serves as a reductunt;
anyone else trying it with tryptamine?
See:
[1] Moore, M.L. Org. React., 1949, 5, 301
[2] J.C.S., 1342 (1950)
[3] J. Org. Chem., 50, 1110 (1985)
[4] J. Org. Chem., 51, 5169 (1986)
[5] Joseph Casanova and Praveena Devi, Synth. Comm., 23(2), 245-251 (1993)

Procedure below is taken from ref. [5]:
5 mmol of prime amine is dissolved in minimal amount of ether and placed in a 3-neck rbf equipped with a reflux condenser and a magnetic stirrer.
Solution is cooled to 0 C followed by addition of formaldehyde (38%, 9 mL) and formic acid ( 85%, 10 mL)
(Authors in [5] report that reaction is exotermic upon addition of formic acid,
in the case tryptamine it was not that obvious to me.)
After the addition the mix is heated at 80 C for 10 hrs
Cooled to RT
Ether was added (50 mL), mix was neutralized with 20% NaOH and stirred for 10 min.
Extracted with ether, -combined organic layers were dried over MgSO4. and the solvents removed.
------------
DO IT NOW!

Z_Hound



Any Possession is a Demonic Possession!

Z_Hound

  • Guest
damn these carbolines
« Reply #1 on: March 31, 2002, 12:53:00 PM »
Well, seems it is good with synthesis of betacarboline at least.

Still, the residue after evaporation, far from pure on TLC (I suspect mixture of dmt and carboline, and may be some 2- methyl);
 gave sweet 1-hr
mild trip with break through into Plato realms,
when bioassayed (vapor)
also, I believe, 2-Methyl substitute was present

How would I avoid formation of carbolines? I ll do low tempr, and reduce time.

Z_Hound


Any Possession is a Demonic Possession!

Lilienthal

  • Guest
beta-Carboline formation can't be avoided
« Reply #2 on: March 31, 2002, 01:18:00 PM »
Unfortunately it's impossible. beta-Carboline formation can't be avoided under acidic conditions.

Z_Hound

  • Guest
should be ok with 2-sdbstitutes
« Reply #3 on: March 31, 2002, 01:33:00 PM »

PolytheneSam

  • Guest
beta-Carboline
« Reply #4 on: March 31, 2002, 02:18:00 PM »
There's a lot of hits for beta-Carboline when UingTFSE.

http://www.geocities.com/dritte123/PSPF.html
The hardest thing to explain is the obvious

Z_Hound

  • Guest
yeah, those damn carbolines are everywhere!
« Reply #5 on: March 31, 2002, 03:03:00 PM »

foxy2

  • Guest
active?
« Reply #6 on: April 01, 2002, 12:11:00 AM »
Are tryptamines with a saturated indole ring double bond active?

Those who give up essential liberties for temporary safety deserve neither liberty nor safety

cilliersb

  • Guest
Just a shot in the dark
« Reply #7 on: April 01, 2002, 03:23:00 AM »
How about boiling your final product in Ethanolamine.

Might just do the trick?? ;)

Lilienthal

  • Guest
Foxy: As far as it is known they are inactive.
« Reply #8 on: April 01, 2002, 07:53:00 AM »
Foxy: As far as it is known they are inactive.
cilliersb: Ethanolamine - huh?! No way...

PolytheneSam

  • Guest
reference
« Reply #9 on: April 01, 2002, 07:03:00 PM »
Note reference here

Post 276458

(PolytheneSam: "Benzothiophene analogs", Tryptamine Chemistry)


http://www.geocities.com/dritte123/PSPF.html
The hardest thing to explain is the obvious

obia

  • Guest
i guess one way to use formic acid/ formaldehyde ...
« Reply #10 on: April 04, 2002, 04:23:00 AM »
i guess one way to use formic acid/ formaldehyde is to reduce the indol double bond first with cat h2. do the methylation, then oxidise with Mno2. the reduction of tryptophan to dihydrotryptophan is used in on of the lysergic acid synths.