eugenol to MD(M)A

[boppesz]

T read the following somewhere:

Eugenol is refluxed with
HCl to give catechol-2-chloro-propane.  This is easily converted to the alcohol and then methylenated to give MD-P2Pol. The alcohol is oxidised to ketone which is then reductively aminated with MeNH2 to give MDMA.

Skip everything but the catechol-2-chloro-propane preparation. The only thing left to do is methylating the 3,4 dihydro and forming the amine. I read that methylation is possible with catechol etc with a PTC & DCM, but is it possible too with the 2-chloro compound? Could the chloro provide some other problems? (polymerization??) But suppose it'll work, than it has to be no problem to make our lovely compound out of this. I suggest we first swap the Cl for an I with an acetone/NaI solution. Than treat it with ammonia or methylamine and eureka?? Dikke pillen?

[Rhodium]

An alkyl halide with an exposed phenol (or even worse a catechol) in the same molecule would be very prone to di/polymerization in my opinion. The same reaction that would be used to form the methylenedioxy ring would probably also make the 2-chloro-alkyl side chain couple to the phenol, making an useless dimer.

Look at the eugenol subheader in the MDMA section at my page, there you will find more proven ways of turning eugenol into worthwhile precursors.

[UTFSE]

couldn't there be some kind of extreme reaction conditions that (perhaps) prevent polymerization?


just glad to bee here-----he he he

[Rhodium]

That is possible, but you will have to find out for yourself what those reaction conditions are. One suggestion is to use Diiodomethane (CH2I2 , very reactive) to form the methylenedioxy bridge, and to only use a weak base (like aqueous carbonate) to deprotonate the catechol, and react it all at relatively low temperature. That would favor the MD bridge formation over dimerization. I don't know exactly how selective this would be though.

[boppesz]

Isn't it possible to swap Cl for I first, then make the amine and at the last step make the methyelene dioxy?

[Rhodium]

No, because then the methylene chloride (or whatever you make the MD bridge with) will also attach to the nitrogen, making a mess.

[Dr_Sister]

has anybee actually gone from eugenol to safrole in decent yeild? or any yield? I've read alot of the theory, but it didn't sound as though anybee had actually visited the Eugenol --> safrole Valhalla yet.
7.10.01

[Rhodium]

Oh yes, look at my page under the eugenol section, there are several successful eugenol conversion stories there.

[Aurelius]

why don't you just react with a stong potassium base and isolate the salt (phenol potassium salt) -- yes it will convert the alkyl halide to an alcohol, but this is ok,  now add the salt/alcohol compound to a weak base with CH2I2 as Rhodium suggested.  this way the phenols have already been deprotonated for the swap.  the weak base should be enough to catalyze the rest of the rxn

[Rhodium]

Because then the chloro side chain would react with the potassium phenolate, forming a dimer.

[psychokitty]

A new pet theory of mine is to react oxone with isoeugenol to form the glycol which would then be reacted with 15% H2SO4 to form the final MVK. 

This should work because even under drastic conditions, Oxone does not oxidize phenol so I doubt it will react much with isoeugenol's phenolic group (thus minimizing side reactions). 

The ketone could then be reacted ala Leukart (Leukard?) into the formamide and the cleavage and methyleneation reactions carried out from there.

Oh, well.  It's just an idea.