epoxidised with 1.5lbs of oxone in a 5 gallon bucket.
What did you use to stir this concoction, and at what speed (1800?)? Will a decent magnetic stirrer suffice?
PB
Fully Informed Jury! (http://www.fija.org/)
(http://www.fija.org/)Post 227831 (https://www.thevespiary.org/talk/index.php?topic=11411.msg22783100#msg22783100)
(uemura: "Ketones from Propenylbenzenes via the di-bromides", Novel Discourse) 62 posts, Ketones from Propenylbenzenes via the di-bromides, Uemura's Höring refs etc. Novel forum. After RhodiumsPost 232994 (https://www.thevespiary.org/talk/index.php?topic=11411.msg23299400#msg23299400)
(Rhodium: "Re: Ketones from Propenylbenzenes via the di-bromides", Novel Discourse) it gets again really interesting. ""I don't understand why noone has tested the hypochlorite or hypobromite route to the halohydrin, and then made the epoxide from that with a base. It is OTC, and very simple." I also don't understand, that's layed out in Uemura's starting post up there in this thread.Post 218193 (missing)
(Ritter: "LiI catalyzed pinacol rearrangement possible?", Chemistry Discourse) Li catalysed pinacol rearrangement possible? Chemistry forum.Post 235999 (https://www.thevespiary.org/talk/index.php?topic=7724.msg23599900#msg23599900)
(Chromic: "Asarone epoxidation by Oxone", Chemistry Discourse) Chromic's Asarone epoxidation by Oxone.Post 241293 (https://www.thevespiary.org/talk/index.php?topic=11347.msg24129300#msg24129300)
(uemura: "Properties of some epoxides", Novel Discourse) Properties of some epoxides, Epoxide Synthesis (described for anethole) and Asarone Epoxide Rearrangement both exellent write ups, wished everybody confirm to this kind of perfectionism and clarity!!!Post 241585 (https://www.thevespiary.org/talk/index.php?topic=6439.msg24158500#msg24158500)
(uemura: "Boiling Point Measurement", Chemistry Discourse) Uemura's Boiling Point Measurement, epoxide thermal rearrangment.Post 265056 (https://www.thevespiary.org/talk/index.php?topic=8999.msg26505600#msg26505600)
(Osmium: "Re: Thermal isosafrole epoxide rearrangement trial", Methods Discourse) Osmium's way of isomerization of an epoxide to the ketone under vacuum.Post 264485 (https://www.thevespiary.org/talk/index.php?topic=8999.msg26448500#msg26448500)
(Vibrating_Lights: "Thermal isosafrole epoxide rearrangement trials", Methods Discourse) Same thread, Thermal isosafrole epoxide rearrangement trials of Vibrating_Lights (=Flip?):Post 243262 (https://www.thevespiary.org/talk/index.php?topic=8989.msg24326200#msg24326200)
(uemura: "Epoxide Rearrangement Example", Methods Discourse) Epoxide Rearrangement Example.Post 280823 (https://www.thevespiary.org/talk/index.php?topic=9123.msg28082300#msg28082300)
(cheeseboy: "Re: mdp2p from oxone", Methods Discourse) mdp2p from oxone thread, Cheeseboy claims success, but has not aminated yet, keeps us sitting on the tip of the chair untill he does!Well, 1-alkene (safrole) to 2-alkene (isosafrole) is obtained by heat and KOH. Then we go onto the oxidation with oxone:
If it's buffered (pH near 7): the 2-alkene becomes the epoxide
If it's unbuffered (pH acidic): the 2-alkene becomes the glycol
(The buffer when used is sodiumcarbonate or -bicarbonate, 85% oxone + 15% -carbonate.)
Then when that's extracted (better stripped of solvents by distillation) and put into the H2SO4 mixture, if it's the epoxide, then it's hydrolysized to the glycol (addition of water, which opens that little epoxide ring). Then the glycol is dehydrated and rearranged by H2SO4 to the ketone by H2SO4. 2hrs of reflux (with stirring) seems to be enough time, yields have always been pretty good.
Then I include your above post, again for clarity reasons, people could get mixed up:
A mix of undistilled (starting from isosafrole) epoxide/diol(=glycol) from an unbuffered oxone rxn subjected to thermal rearrangement resulted in polymerization and no ketone was produced although the mess of polymerized crap did smell of ketone.
Vac distilled (Isosafrole) epoxide from a buffered oxone run yeilded ketone. Which in turn yeilded amine.
Apparently in cheese's last unbuffered oxone run it (. the 2 hr H2SO4 reflux???) was only enough to convert the diol=glycol to the epoxide. how ever after distilling his epoxide he said he submitted it to thermal rearrangement and yeilded what he believed to be ketone. Lets hope he up dates us on his amination.
To clarify more, there seems to be a consensus between various testers at the moment, that there are 3 fractions observed when distilling crude oxonization product: a small forerun of glycol, a big run of ketone, and then a small afterrun of epoxide. Or the other way round.
Now here I can't follow you anymore, how do you know the experienced details of this :
""Apparently in cheese's last unbuffered oxone run it (. the 2 hr H2SO4 reflux???) was only enough to convert the diol=glycol to the epoxide.""
Are you a clairvoyant like Mrs Cleo? Or do you also use HIS computer? :P ;D
Don't take that too serious, you have earned it by multiple promisses of schocking writeups, up till now we have to seethe first one yet.
However, I appreciate your posts and work, don't get upset now suddenly, laddie, you'r prolly to busy to write anything more then short posts, go on pls. LT/
Post 280991 (https://www.thevespiary.org/talk/index.php?topic=8999.msg28099100#msg28099100)
(LaBTop: "Isosafrole Epoxide Thermal Rearrangement Review", Methods Discourse)
Thank you Daddy!