News:

Registration doesn't require a real email.
Monero Donation Address: 897ESh4QoJgEytJueBPULziMDfNMToXkGMrvtUCJRo2NQRv2CXACHnmEzeMTkwQhnfcZsAc3ctXp6GsedhMfBv983rn5i84

Main Menu

O2 Wacker using p-cresol

Started by OcoteaCymbarum, July 07, 2003, 07:30:00 AM

Previous topic - Next topic

0 Members and 1 Guest are viewing this topic.

OcoteaCymbarum

As I was getting ready for a MM wacker and reading some more about it I ran into a post to this US patent

Patent US3475461



Exemple 5 seems amazing, easy,fast, and high yielding

Basically, 25ml 1-octene with 25 ml methanol are charged in a glass reactor. 1millimol (0.178g) PdCl2 and 5 millimole Cupric Chloride dihydrate(.853g) are added, the reactor is pressurized to 3 atm with O2 at 50 degrees Celsius and shaken for 120 minutes. The products were analysed by gas chromatography. A similar reaction was run in parallel, except this time 1% v/v p-cresol was added before the oxidation. The difference in yeild is simply amazing:

No cresol: 49.6% conversion, with 96.8% being 2 octanone
With Cresol: 81.4% conversion, 98.5% being the 2-octanone.

A 80% yield in 2 hours!

25 ml of 1-octene(density 0.715g/ml) means about 18 grams, having a MW of 112.22 that means 0.16 mol octene

0.16 mol of octene only using 1 mmol of PdCl2(0.178).

That means that using 1.78g PdCl2 we could process 1.6 mol safrole! In just under two hours.
I think its worth looking at, especially for those having experience with O2 wackers.

Anyone tried yet? I'm sure its worth looking into

Antibody2

every single one (of many) O2 wacker experiments ended in abject misery.

pssssst: performic, the benzo wacker works fine too.


SPISSHAK

reagents, you never really know about chemistry until you begin to practice it.

OcoteaCymbarum

with O2 wacker's, I know people like pupillage do.
I agree with u on this. I would try it on a 100g of safrole scale, with a 2L pop bottle.
A 30% increase in yield with no more work, isnt that a charm?

Now I'm not saying the yield would be the same with saf
I tend to think that maybe steric hindrance would slow things down using saf instead 1-octene. The Palladium has to coordinate over the double bond, maybe the benzene ring has a role in that.
But still 80% in 2 hours, thats a quick reaction, and you probably still can recuperate a big part of the used palladium/cupric chloride. Thats of course in the perfect world