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Reduction of Harmine with sodium metal/ethanol

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Hello.

My reasons for trying this is mostly out of curiosity, sometimes in a harmala extraction you are stuck with lots of harmine, which is irreducible by Zn/AcOH. So I decided to give this a try, its easy and quick enough. Sodium metal isn't hard to obtain, and the reaction is as simple as dropping it in and watching it bubble. Lithium metal might work too, and it is more OTC.

Typically these reactions are done and much better yielding if done with a NaHg amalgam, to control the reactivity of the sodium. But mercury is toxic and lots of it is required, so its not worth it.

So here is 100mg of harmalas purified by A/B precipitation, it is actually mostly harmaline, I used up most of my harmine in previous experiments, but this will have to do for now. In the future I will test this again using pure harmine.

10315_5078fa6e-8901-4cac-92d3-7be36e38acaa_20160824_131600.jpg


So dissolving in warm anhydrous ethanol, and adding 0.5g of sodium metal (large excess is needed, about 10 mol equivalent)

10315_1e255e48-5f9f-4056-ab3b-33833a94163a_20160824_133429.jpg

10315_e7492d8b-3f25-453c-8757-34c11fdbf021_20160824_133507.jpg



And here is the TLC (40:10:1) MeOH:EtOAc:10%aqNH3
10315_82c31828-452d-4706-8aba-0001154fbb44_20160825_180619.jpg



The one on the left is the starting material, the right is post-reaction.

Not a whole lot seemed to happen, the harmine and the harmaline are mostly unchanged. The TLC is streaky so its hard to be definitive, the harmine spot is elongated but looks relatively unchanged, there is some dark streaks leading up to the harmaline, this could be some THH, but its impossible to be definitive.
 
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