Alrighty rooty
KERPLUNK KERPLUNK you should all kerplunk, lwr or not.
you know something i now have worked out a new synthetic modality.
the kerplunk... If i were to say, how could one reduce cyclicisation from basification so that it were not able to immediately cyclicise... what is the difference compared to the basification workup and this idea of diluting with alcohol to help hold the stuff in... what would help prevent the aziridine forming, which i can see, although it is a very unstable 3 member ring, it has to be reduced to release it. It doesn't have to be strong mind you.
Would sodium react with aziridine in the desied way? I have to have a close look at the structure's hydrogen counts to see if the hydrogen could be donated directly by the....
D'OH of course, what is a birch reduction?
the use of sodium metal (or other group one metals) to withdraw the extra hydrogen from ammonium and donate it to a hydroxyl group so as to saturate it's bonds and dehydrate it.
The page i linked to, which obviously nobody actually read, showed a diagram which clearly showed that the re-hydroxylation process caused by a hydroxide reacting with the halogen, and this OBVIOUSLY is going to liberate sodium in an active form if it enters a low hydration enviroment, if only for a moment as the substitution occurs that puts the hydroxide on the site of the halogen and the halogen forms an ion with the sodium.
Looking at the chemical dynamics involved in the kerplunk process, i propose an alternative method, which quite possibly could in fact be an alternative reduction method, based on Phase Transfer Catalysis.
This kerplunking thing involves the salt sodium iodide (the result of adding sodium hydroxide to the iodine laden reaction mixture) being present, so there would have to be this salt in the environment. The reaction requires the participation of hydroxides, so there has to be an excess of sodium hydroxide to the reaction. Here is a proposed reaction mechanism, not really taking into account the mechanism, just to illustrate how the presence of water and the nonpolar phase contribute to this:
Na+OH- + H+I- + methamphetamine-OH --PTC reflux--> Methamphetamine + Na+OH- + I- + H2O ---> methamphetamine + Na+OH- + H+I- + OH-
This reaction is driven forward primarily by heat which increases molecular kinetics, and the fact of the phase boundary which permits freebase ephedrine to expose it's water soluble one and only part, it's hydroxyl, to the polar phase.
At the phase boundary, the ephedrine is reduced to iodmeth, which is then immediately cyclicised to the aziridine, which then can go further to be reacted with the sodium ion at the phase boundary to decyclicise, possibly taking the hydrogens from the nonpolar solvent, unsaturating it. A-La birch reduction, except done as PTC.
This is such a simple experiment that I think it would be worth seeing if say, 240mg, a single 240 pill, were subjected to this treatment directly, without even addressing the gaks or anything. If the ingestion of the acid/base extracted product of this experiment gave noticable or more than noticable activity, this is a route of synthesis that should be pursued. proper ratios of the NaI and NaOH will be established, lengths of reaction time etc etc.
This reaction is so beautiful in its elegance and simplicity, that even if with maximum optimisation it only yields 50%, this is an acceptable situation because of the fact that no difficult chemicals are required, just a refluxing setup that can handle strong alkali.