Sulphuric Acid Ketone Liberation via Isosafrol Epo

[Rhodium]

I know there is data about this in the search engine.

[Vibrating_Lights]

Diol is yellow and smells like floral  candy only slight hint of base. if vac distilled it will freeze.  when vac distilled it is a clear light yellow with green tints. Don't have bp data thermo was broke.  thermo was broke and observations were taken from vac distillation of an unbuffered oxone run ph 2-3 after 2.5hrs.
VL_

[cheeseboy]

The Diol's BP is higher than the ketone's BP. Isn't that what psychokitty said?
Cheeseboy- a whiteboy with soul, like a black guy without soul
May De Source Bee Wit Chu...Always

[Rhodium]

Definitely - according to Os, at a vacuum where MDP2P distills at about 85°C, the isosafrole glycol distills at 100°C.

[cheeseboy]

Now that's a killer pull for a vacuum, must be one of those refridgerator vacuum pumps eh?!
Cheeseboy- a whiteboy with soul, like a black guy without soul
May De Source Bee Wit Chu...Always

[Chromic]

Fridge pumps pull a really shitty vacuum my my experience...

[El_Zorro]

I'd like some clarification.  For the diol and the glycol to be hydrolized to the ketone, a strong acid is needed.  Not specifically sulfuric acid, just a strong acid.  Alright, here we go.  The glycolization step, (using performic acid) according to LaBTop, if nearly quantitative.  The only losses in the conversion of isosafrole to ketone is in the hydrolization step, right?  Now, I read in an earlier post(fuck!  I can't find it with TFSE!  I'm using the exact same search words I used before,(eugenol, cleave, methoxy) but now I don't even get 1 match!  Were some posts deleted?), that safrole and it's derivatives are energetically polymerized by sulfuric acid.  Is this the reason behind the yeild losses?  Is there another acid that could be used that didn't polymerize the diol or glycol?  I don't think formic would work, it would only convert it to the glycol.  So what, HCl?  Nitric even?  Any ideas?
I sell crack for the CIA

[cheeseboy]

Hey EZ, cheese was reading up in TS II about other acids being used to salt out. Not sure , but maybe Oxalic acid would be a contendor, just a guess though. Cheese can't wait to actually figure out why all this is... Ya, so hydrolyzing with Oxalic acid yields the monoxalic salt . Cool eh? BTW performic acid isn't easily purchased if at all right? Performic is made by adding Peroxide (H2O2) with formic acid.Per-Formic acid, in other words, a peracid.HCl is used most often due to the fact that it's the most common of acids. Cheese thinks that H2SO4 is the shit for salting. No water, just goods, BigR?
Cheeseboy- a whiteboy with soul, like a black guy without soul
May De Source Bee Wit Chu...Always

[Chromic]

It is possible to use p-tosic acid aka p-toluenesulfonic acid aka tosic acid aka 4-methylbenzenesulfonic acid to hydrolyze the epoxide/glycol/glycol ester (ie whatever comes out of the peracid technique).

Read Scooby_Doo's ref,

Post 264135

(Scooby_Doo: "Ref on Isosafrole to diol via electro", Novel Discourse), conversion from the epoxide was done in ~85% yield.

The problem with making this an OTC method is that p-tosic acid made from toluene and 90% sulfuric acid is hard to get sufficiently dry so you can use it in a solvent like toluene (or heaven forbid, benzene) which is very intolerant of water. Blobs of wet p-TsOH will just float around if it's not dry enough.

[El_Zorro]

Hey cheese, I wasn't talking about salting out, at least I don't think so.  I was talking about the hydrolysis of the diol or glycol to MDP2P.  If you used Oxone, then you would end up with the epoxide.  But I was talking about if you used performic acid(made from formic and H₂)₂) to oxidize the iso, then you would eventually end up with the monoformyl glycol.  I was thinking that using LiI would give better yields, but you could only use with on the Oxone procedure, because it wouldn't convert the glycol to MDP2P, just the epoxide.  Does anyone know of anybody using HCl as in the hydrolysis step?

I guess I'm just chasing a quantitative safrole->MDP2P synth.
I sell crack for the CIA

[cheeseboy]

So Solly! Can't believe it was misinterperated. Cheese wouldn't know the answer to that 'yet'. But H2SO4 is used for a reason. It's usually very high in concentration [%95+], where as HCl doesn't get higher than 38% without vaporizing right? The oxone route is amazing you know. If you don't mind losing a few mls of product, the whole procedure from Isosafrole ---> crude MDP-2-P can be done without the use of any non-polars to digest them. Just collect the oil in sep funnel after each step, however you will be losing some of the oil floating around in the aqueous portion, just let the layers seperate really well. Oxone is the shit. OTC, cheap, close to odorless, strong oxidizer, rxn done w/o extra heating or pressure. Cheers, and thanks for all the replies on this one, it was a blast.
Cheeseboy- a whiteboy with soul, like a black guy without soul
May De Source Bee Wit Chu...Always