Author Topic: Peracetic in DCM - dreams of success  (Read 9697 times)

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Chromic

  • Guest
Peracetic writeup
« Reply #100 on: August 07, 2002, 05:40:00 AM »
The writeup on the bufferred peracetic oxidation in DCM is now available at

https://www.thevespiary.org/rhodium/Rhodium/chemistry/peracetic.chromic.html



Thanks for your support guys!  :)

hCiLdOdUeDn

  • Guest
WOW Chromic, thanks for all your hard work you ...
« Reply #101 on: August 07, 2002, 06:30:00 AM »
WOW Chromic, thanks for all your hard work you put into the writeup. Swim may try peracetic instead of oxone after since the yields are higher and volume is less.

NICE!

hcildoduedn

weedar

  • Guest
Great work Chromic!
« Reply #102 on: August 07, 2002, 03:16:00 PM »
Yet another great method from our favorite self-mutilator ;)

No more use for the Oxone route then?

Weedar

I'm not sure about you guys,but I'm baking brownies!

Chromic

  • Guest
Confirmation of tma-2
« Reply #103 on: August 29, 2002, 06:21:00 PM »
I received this PM a week ago, responded to the sender if it was OK to post it, but no response, so I post it anonymously:

Just wanted to say "Thank you" for your recent work on the peracetic/DCM oxidation. I've been struggling with calamus oil for 2 years now, pseudonitrosite always gave me low yield (5gr TMP2NP from 20gr asarone). I've never been able to aminate this succesfully using Urushibara or Zn, always resulting in a tarry product or nothing.

So I followed your directions on 20 gr asarone but I didn't distill glycol nor ketone, my oxime percipitated as an oil followed by a sloppy amination with Al/Hg. I was really careless throughout the whole process (not my habit, because of former failures didn't really believe in this) and i still got a gram of off-white TMA-2.HCl, after gassing and an acetone wash.

Thanks for your research, it is greatly appreciated! I'm sure this rxn suites asarone perfectly, when the right conditions are there.

SPISSHAK

  • Guest
Are you sure an oxime internediate yeilds an amine
« Reply #104 on: August 30, 2002, 08:55:00 AM »
With Al/Hg reduction?
I've read chem literature for many years, and I don't claim to be elite (because you can never know everything) in the subject which is why I ask this question.
In the literature they attempt to reduce nitroalkenes with Al/Hg under typical conditions (i.e. no acid added, hence basic conditions) and yeild an oxime (unsaturated).
So from what can be infered, if one were to condense a hydroxylamine, to give the oxime, to a ketone and use the aformentioned procedure, logic would say that the hydroxylamine derivitave is produced, and not the saturated nitrogen amime (this compound has psychoactive properties as well) leading one to believe they have the amine when in truth the hydroxylamine is the product.
In typical nitro alkene reductions, acid conditions are employed (presumably to protonate the hydroxlamine, and make it suseptiple to hydrogenation.) so , under these conditions logically the nitro alkene would be reduced to the amine through this hydroxyamine intermediate.
Any one know different, please prove me wrong.


wacko_reaco

  • Guest
reduced solvent trial
« Reply #105 on: August 30, 2002, 02:21:00 PM »
some mother did
200g isosafrole iwas diluted in 200mL DCm and 80g Becarb was added with overhead stirring, the temperature was reduced to 10C with a cold water bath, 800g peracetic acid (made as mentioned aealier and let sit for 5 days) was slowly added over ten minutes, the temperature steadily rose over ten minutes to 33C(also the colour went from colourless to pale yellow) at which time the cold water bath was drained and replaced, the temperature dropped to 26C and the water bath was removed, the temperature rose very slowly to 28C and stayed there. After 4hours, temerature 21C, 400ml of 55 NaOH was added, the solution momentarily went orange and then back to yellow. The majority of the upper layer was poured off and a further 400ml of 5% NaOH was added, this time the orange colour persisted. The aqueous layer was seperated and added to the previous aqueous layer. This aqueous was extracted with 50mL of DCm 9in retrospect i should have evoporated this to see if there was any point, I don't think there was as it was almost colourless). The DCM was distlled off and the glycol taken to 80C, 320mL of MeOH and 1500mL of 15%h2SO4 were added and the solution was reluxed for 2Hrs, heta turned off, stirredf or 15 minutes, then dumped in 2L of ice water, blah blah blah, distilled under vacuum at 140C-155 120mL of yellow oil came over (don't know pressure my gauge is fucked).

Cool huh, that is a ten fold reduction in the DCM

wacka wacka wacka

Chromic

  • Guest
Yes
« Reply #106 on: August 31, 2002, 12:45:00 AM »
>With Al/Hg reduction?

Via a simplified acetic acid Al/Hg a la Antibody2. The acid is apparently necessary to fully reduce the oxime to the primary amine. I've got no way to tell you if TMOH-2 or TMA-2 is made, but the end product will knock your socks off and turn your world upside down.  :)