Author Topic: MDA with Ritter Reaction  (Read 260 times)

Oerlikon

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MDA with Ritter Reaction
« on: September 04, 2011, 10:14:46 PM »
Quote
This reaction utilizes safrole to directly form the formamide (or acetamide) of MDA which is then hydrolyzed to MDA. The following procedures are adapted from procedures used to produce amphetamine from allylbenzene and other amines from their corresponding tertiary alcohol or alkene.

 A fume hood is required for this procedure due to use of cyanide which can easily be released from acidic solutions as a gas. A mixture of 25ml acetic acid, 34.2g safrole (0.2 moles, 29.5 ml), and 11g (0.2 moles) of 90% sodium cyanide is placed in the flask of the apparatus shown in the picture.

To the separatory funnel is added a mixture of 50g (27.2 ml) of concentrated sulfuric acid and 25 ml of acetic acid. This is dripped into the flask over 30 minutes. Shake the reaction mixture occasionally or stir the solution with a magnetic stirring bar. Remove the separatory funnel and still head and allow the mixture to sit overnight. Add a solution of 120g of NaOH in 250 ml water to the mixture. The mixture will heat up and neutralize the acid. A few boiling chips are added and a condenser is fitted into the top of the flask for refluxing. The mixture is refluxed for five hours. The mixture is allowed to cool and the amine and unreacted amide are extracted with ether (or toluene etc). The ether is washed three times with water and the MDA is precipitated by a stream of HCl gas. Filter and let dry.

Acetonitrile can be used in place of sodium cyanide to form the acetamide. The acetamide would need to be hydrolyzed with hydrochloric acid though. Refer to Ritter's article under N-(benzylmethylcarbinyl)-acetamide. Substitute the allylbenzene for 32.4g of safrole.


Used from: http://www.erowid.org/archive/rhodium/chemistry/tcboe/chapter7.html
(You can find aparatus picture there.)

Anyone had any luck using this reaction!?
What about yields!?
In the same page you can find method to prepare MDA using NH4Cl and Al/Hg reductive amination with cca 70% yields.
I find this hard to believe.
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lugh

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Re: MDA with Ritter Reaction
« Reply #1 on: September 04, 2011, 11:20:47 PM »
The Ritter reaction won't produce safrylamine from safrole, no matter what the author says  ::)  Many members have decorated their ceilings attempting to get this procedure to work, only to conclude it's a waste of safrole  :P  An isoquinoline results, as was published in the attached article authored by John Ritter  ;)  It's simply a matter of if it sounds too good to be true, then it almost certainly isn't  8)
« Last Edit: September 04, 2011, 11:22:34 PM by lugh »
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Oerlikon

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Re: MDA with Ritter Reaction
« Reply #2 on: September 05, 2011, 12:47:44 AM »
Thank you lugh! Good to know.  It's weird that Erowid/Rhodium posts such misleading papers. ???
And what about getting MDA using NH4Cl and Al/Hg reductive amination with cca 70% yields!?   :o
That also sounds to good to be truth especialy when guy used amalgation process and cleaning
of post rxn mix in very similar fashion like Dr. Shulgin.
(too much effor to remove Hg salts,too much acid/base conversions and washes etc.)
Dr. Shulgin himself said it's possible but yields are small but he didin' said how small.
Anyone here actually tried it!? I would say 30-40% or less.

I had an idea to actualy have some MeAm.HCl/NH4Cl mixture for this reaction to get
MDA/MDMA in one pot but MeAm is more basic and will react much faster than NH3 if I am not mistaken...
This is probably a reason why NH4Cl reacts poorly in this case.
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lugh

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Re: MDA with Ritter Reaction
« Reply #3 on: September 05, 2011, 01:30:09 AM »
That book was written before the advent of the Hive, which was where most of those methods were exposed as being very low in yield  ::)  Reduction of the oxime is generally the best route to safrylamine from the ketone, unless one can get sodium cyanoborohydride  ;)  There's pretty good discussions of that route on the internet, but of course it's widely scattered since the diaspora of the swarm   8)
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Oerlikon

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Re: MDA with Ritter Reaction
« Reply #4 on: September 05, 2011, 01:36:18 PM »
I wasn't member ot The Hivem,thanks for the help!
Sodium cyanoborohydride is next to impossible to get here,oxime route looks good,RoidRage posted short write-up here
with great yields but I can't get more details on crystal formation which is said to be very tricky.
Never understood why people just don't reduce lipophobic oxime syrup,russians use filthy reactants and have great ressults!  :)
Pitty I only understand a little bit...
Other than that,jon's method sounds good if you have acess to dry ice and patience to put peaces of the procedure together.
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Wizard X

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Re: MDA with Ritter Reaction
« Reply #5 on: September 06, 2011, 02:03:32 AM »
Production of amphetamine from allylbenzene: Fujisawa and Deguchi, Chemical Abstracts, 52, 11965 (1958)

A problem with the Ritter reaction is the necessity of an extremely strong acid catalyst in order to produce the carbocation.

However, other methods have been proposed in order promote carbocation formation, including photosensitized electron transfer[16] or direct photolysis.[17]

http://en.wikipedia.org/wiki/Ritter_reaction



Page 16 of http://www.columbia.edu/cu/chemistry/groups/synth-lit/NR/2008_08_08-LAmbrosini-Ritter.pdf

Page 1 of 2008_08_08-LAmbrosini-Ritter.pdf Only works for species that can form a stable carbocation.

As the benzene ring becomes more substituted, like safrole, the promoted carbocation formation is unstable, and rearrangement to isoquinolines results with further extensive decomposition when exposed to standard Ritter conditions.
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