safrole > mdp2p

[darius]

Okay I'm sure at least one of two other people have seen this, as it's in the DEA dox on mdma trafficing.  On page 11, towards the bottom in the grid, "Conversion of Safrole to Mdp2p using sulfuric acid, sodium hydroxide, and solvents;..."

It then lists the proper chemical reagents required for isosafrole conversion, but why and where the hell did they come up with that?  I thought that had been debunked a long time ago... so why would they keep it in their "current" reports?  (

http://www.usdoj.gov/ndic/pubs/642/642p.pdf

)

Or maybe I'm wrong and this is some supasekret backdoor the heavies use? 

lata
D

[Rhodium]

They are just giving an incomplete listing of chemicals so that they don't unnecessarily dish out proper syntheses.

[darius]

so it is possible?  I'm to take it that this is more or less a red herring in terms of getting it to work huh? Or are there any leads?

thanks
D

[Rhodium]

There is nothing more to it than that they are outlining the conversion of safrole to isosafrole, which then is oxidized with a peracid to the glycol(ester) and rearranged to MDP2P:

1)

https://www.thevespiary.org/rhodium/Rhodium/chemistry/isomerizafrole.html

2)

https://www.thevespiary.org/rhodium/Rhodium/chemistry/peracid.html

[darius]

but I'm talking strictly about the bottom box next to MDp2p, they outline two ways of getting the ketone.  One is with isosafrole, the other with safrole (which is what intrigued me).  Why isn't it possible to use mercury II sulfate and sulfuric acid (I know it's done for the hydration of alkynes)? 

I know with alkynes it creates -enol and ketones in equal parts, the reaction can then be shifted towards the direction of ketone by it's removal (la chatliers prin.).

Since alkenes are more reactive than alkynes it seems like it would work logically maybe not or someone else would've figured that out by now.

D

btw - I read that sulfuric acid hydration on alkynes will not yeild any amount of detectible product without the Hg(II)SO4 as a present catalyst in the reaction.  I noticed, when I checked out your page, none of the sulfuric acid hydrolysis/hydration methods mentioned using the mercury2sulfate catalyst...maybee it's an alkyne only rule, that could be crossapplied to alkenes.

[Rhodium]

You can in theory perform an aminomercuration of safrole to MDMA, but it doesn't work well in practice, and it uses a shitload of toxic mercury salts.

Another therory says you can hydrate safrole to MDP2Pol using 70% H2SO4, but this does not work well in practice either (UTFSE for "MDP2Pol")

The whole DEA document is bunk, the same table informs that dichloromethane is flammable, which it is not.

[darius]

yeah, I've read about the trials and mistrials that occured from tBoc's method and know it ain't gonna happen.  Least not how he spells it out. 

Here's what I'm thinking (I'll research first before I try of course!).  Safrole, h2so4, hgso4, and h2o in solution, should produce (relatively quickly) a ketone and the corresponding -enol (r-ch3-coh=ch2) in equilibrium. 

I think, the err of tboc's ways is that he never actually performed his synthesis, nor did any research behind the mechanisms that make it work.  Russian scientists found out (accidentlly, when a thermometer broke dumping mercury inside the flask of H2SO4 and alkyne, that HgSO4 formed in situ was necessary to drive forward the hydration of alkynes).  Albeit tboc no doubt saw H2SO4 as a hydration method(it's ref. all over the place as a common method for attaining ketones) , but generally leaves out the mercury sulfate, which is necessary for the reaction to occur, because it's common knowledge - unless you don't know the reaction mechanism.  This method requires far less mercury salts than aminomercuration, and from what my instincts tell me, will be relatively simple.  Of course any Hg substance is in some way or another toxic and should be handled with care. 

Unlike aminomercuration this wouldn't require the use of NaBH4, and would instead should yeild a 50% ketone and 50% -enol (which using by removal of ketone would disrupt the equilibrium, the reaction striving to maintain such would continue to convert the -enol into ketone to maintain such --application of La Chatliers principle).  Which continually drives up the ketone yeild.

Being that this would skip straight to ketone, an amalgamation could be run, but like I said I need to read up on this more, and maybe ask around.  But the idea is to skip from safrole straight to MDp2p.

thanks for your time
D

also this may be the same reason most people fuck up the sulfuric acid hydration of their safrole, they aren't using the proper catalyst.  Besides who wants a secondary alcohol when you can skip straight to ketone?

[Rhodium]

These are actual articles from the literature on hydration on allyls to 2-propanols. It is not promising:

https://www.thevespiary.org/rhodium/Rhodium/pdf/mdp2pol/

[terbium]

These are actual articles from the literature on hydration on allyls to 2-propanols. It is not promising:
The oxymercuration of safrole and subsequent reduction with NaBH4 works easily and in high yield. The biggest drawback to this procedure is that it requires a stoichiometric amount of mercury. Also you only get alcohol not ketone so you still have to perform some oxidation.

Perfomic acting on isosafrole is an excellent route to MDP2P.