Author Topic: Peracetic Acid Oxidation  (Read 2465 times)

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aleph

  • Guest
Peracetic Acid Oxidation
« on: August 28, 2003, 04:00:00 PM »
The Peracetic Acid Oxidation on Rhodium's site calls for an NaOH wash before drying and distilling the MDP2P.  It is mentioned that the separation of layers in this wash will be difficult to see.  However, I keep dreaming of 3 layers: a dark (oil, I assume) bottom layer, an apparently identical top layer with a middle layer of seemingly water and flocculant material.  It appears the top and bottom layers grow until the entire solution is uniformly dark and appears to be a single homogeneous mixture.  The solution is too dark to shine a flashlight through.  There must be a way to perform this separation.  Anybody have a clue what's going on, and how to do the separation under these conditions?

methyl_ethyl

  • Guest
Preperation of Peracetic Acid
« Reply #1 on: August 29, 2003, 01:09:00 AM »
Unfortunatley I have never run the peracetic as per Rhodi's site, however I have made peracetic acid.  Could you tell us a little more about your preperation of peracetic acid?  It may have nothing to do with your problem, however I have always questioned this method.  I believe on Rhodi's site it says to wait 12 hours, however most preperations I have read and followed call for waiting ~90hours after the initial preperation to achieve the highest concentrations of the peracid.  Also this is not a stable concoction, if you made your peracid up like 2 years ago, do not expect the reaction to work at all.  There are ways to stabilize it, along with refridgeration, however I do not know if the stabilizing coumpound would negatively effect your reaction.  I can not remember the name of the stabilizer, Sodium pyro something....  :(   Oh well I usually do not reply to these types of questions as I am not a chem bee, however this route has always made me wonder, I am sure one day I will not be able to procure formic acid, so maybe I should probably familiarize myself with this reaction.......

good luck,

m_e


aleph

  • Guest
Peracetic Acid prep
« Reply #2 on: August 29, 2003, 01:38:00 AM »
Peracetic acid prep was scaled down (due to glassware volume constraints) to 375 ml Glacial Acetic Acid, ~81.25 ml H2O2, and ~1.25 ml H2SO4 as catalyst.  Mixed and let stand at room temp for 16 hours.  Used absolutely fresh, at 16 hours.

The synth seemed to go well, just having trouble with the separation of product from basic wash solution.

Chromic

  • Guest
Please post any failures!
« Reply #3 on: August 29, 2003, 07:22:00 AM »
I really doubt this oxidation works as advertised? I never saw any references that the method was based on... it makes me really doubt if it works. Try the peracetic in DCM if you find that you just get black crap from this oxidation (as I did)... perhaps I gave up too soon (the point you're at).

Good luck! :)

aleph

  • Guest
Chromic, the synth went as txt.
« Reply #4 on: August 29, 2003, 06:00:00 PM »
Chromic, the synth went as txt.  Product was very dark red, brown looking, but definately red where the light shone though.  In this method, a syrup is produced, which is collected from a 15% H2SO4 solution, the remaining syrup is extracted from the aqueous acid solution with DCM.  The ketone/solvent is washed with dHOH (no problem), then with 5% NaOH (big problem for me).  Are you suggesting adding more DCM to try to get a separation?  I'm skeptical.  The DCM in the solution may be layering, but the coloration is the same as the aqueous layer; I can't determine layers at all.  If it's the base that's causing the problem, perhaps addition of H2SO4 (enough but to reduce the basicity of the solution) may remedy my problem.  What do you think?  I appreciate your input.

Argon

  • Guest
Peracetic Acid Oxidation
« Reply #5 on: August 29, 2003, 06:30:00 PM »
I would try to distill the red residue straight after the 15% H2SO4 reflux. See what you come up with. Then take a little of that stuff and do the bisulfite adduct test. If it makes crisp hard crystals, you are good. If it makes chicken greese, wash the distillate, and redistill. Then you should have clean double distilled ketone.

Are you sure that you have SAS?

SWINA had a problem like that with another procedure, and wasted a lot of time, thinking he was fucking up somewhere. Then it turned out he had synthetic, artificial, adulterated "sassafrole". As Locrian said, nonfuckwithable.

I would seriously look into that if I was you.

aleph

  • Guest
At this point I'm interested in recovery
« Reply #6 on: August 29, 2003, 08:20:00 PM »
Argon, at this point I'm interested in recovering what will otherwise be lost material.  The label says sassafras oil, Ocotea cymbarum - China.  I think I'll try Rhodium's Congealing Point Determination for safrole, just to verify.  I really think the sassy is good, as the synth went well until the base wash.  In the meantime, I bee still interested in recovering my honey from the foul pooh bear/thief mixture.  Thanks for the input.

Chromic

  • Guest
Poor method
« Reply #7 on: August 30, 2003, 11:04:00 PM »
No, what I'm thinking is that this method tears apart the sassafras molecule... my guess (a complete hypothesis) is that it destroys the methylenedioxy bridge or *something*. When you go to the base wash, you get crap... kinda light brown chunks of insoluble stuff suspended in a black liquid between the two phases (maybe there is a lot of ketone in there, but I had no idea how to recover it). This is why I gave up with trying to get this method to work.

I don't believe the method does work for a lot of bees. I've heard other stories of failure. If you want a good, verified, peracetic method... use:

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



Enjoy! I'm sure your sassafras is good, but check it with all the standard tests. (search under my username)

aleph

  • Guest
thanks, Chromic
« Reply #8 on: August 31, 2003, 03:44:00 AM »
Thanks, Chromic.  Ah, wasted precursors.  The price of education is never cheap.  Back to the sass.  :)

Chewbacca

  • Guest
If SWIC
« Reply #9 on: August 31, 2003, 01:22:00 PM »
If SWIC was ever to try and synth MDMA, then he would most definately follow this peracetic acid route. Very OTC!
Also, does 1LT sass for $15 US sound dodgy or what??!? found another deal, 225 mls for $6.50 US.... do they sound like a sting to you?


aleph

  • Guest
Can't say, Chewy. I dreamt of about $60/kg.
« Reply #10 on: August 31, 2003, 03:10:00 PM »
Can't say, Chewy.  I dreamt of about $60/kg.  Maybe I had a rip off nightmare...

aleph

  • Guest
Chromic, I haven't dreamt about checking my...
« Reply #11 on: September 01, 2003, 05:24:00 PM »
I haven't dreamt about validating my sassy yet: the more I think about it, the less I think it's a problem.  However, I did dream of purifying safrole by  glacial acetic acid extraction, followed by 2 dHOH extractions, then a ethanol/methanol (+dHOH) extraction.  During boiling off residual alcohol and HOH, solution came to a boil at 80C, and MAINTAINED boiling as the temp slowly climbed to 234C.  Is this not a sign of impurities in the safrole?  Methinks there may bee WAY too much misinformation out there.  Thought this was easier than quicker than double distillation for sassy.

Argon

  • Guest
The label says sassafras oil, Ocotea cymbarum...
« Reply #12 on: September 02, 2003, 05:22:00 PM »
The label says sassafras oil, Ocotea cymbarum - China.  I think I'll try Rhodium's Congealing Point Determination for safrole, just to verify.

You are shitting me, right?

Well, see to it yourself.


rudebwoy

  • Guest
Chromic: u shittin me?
« Reply #13 on: September 03, 2003, 01:09:00 AM »

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


^--- nice 

Is 5 hours in the ice bath really necessary after adding in the peracetic acid in to your isosafrole?

G'job.
I totally looked over the peracetic method and was using formic acid like the black plague for few months.  Halleluia.


methyl_ethyl

  • Guest
HMMMM
« Reply #14 on: September 03, 2003, 03:02:00 AM »
Is 5 hours in the ice bath really necessary after adding in the peracetic acid in to your isosafrole?

      Are you being sarcastic?  The literature states not to use an ice bath.  And if you have been running performics, do you not let the slow exothermic reaction take place for five hours after the addition of iso?  My experience with ice baths and performics yield an "it never really took off at all" reaction, I assume this may be worse with peracetics.  Although yields were not bad for a presumed failure.

       What is so bad about formic acid?  Presuming you do not run hundreds of them without changing your pump oil....  

     I also wonder if anyone has run peracetics with stabilized commercially available 35% peracetic acid?


     I hope this is not all mindless drivel, I think I am temporarily brain dead.....   :(


rudebwoy

  • Guest
uhh
« Reply #15 on: September 03, 2003, 04:56:00 AM »
I can't remember if it was sarcastic or not. 
Oh i remember.  I read the url, and it says to put it in a cold water bath and let it go for 5 hours.  So i'm presuming it says to go for 5 hours in the cold water bath. ?
I dunno.  wahtever.  I just can't follow it anymore tonite.  my mind is mushed.

as for formic acid. it burnt the shed down on a farm.  The bottle blew up after like 7 or 8 months.  oh no wait. more like 6.  wait. .. err. 10 months
I forgot about it.


aleph

  • Guest
The label says sassafras oil, Ocotea cymbarum...
« Reply #16 on: September 03, 2003, 03:20:00 PM »
The label says sassafras oil, Ocotea cymbarum - China.  I think I'll try Rhodium's Congealing Point Determination for safrole, just to verify.

You are shitting me, right?

Well, see to it yourself.

I'm not sure what you are referring to.  Yes, the can of oil had a label, don't yours?  But, as it turns out, I haven't yet tested the product, and am inclined not to do so at this point.


methyl_ethyl

  • Guest
Formic Container
« Reply #17 on: September 04, 2003, 03:14:00 AM »
The bottle blew up after like 7 or 8 months

     That sucks rudeboy, was it in the original packaging?  Or did you transfer it to a glass bottle or something.  Formic is usually stored in HDPE with vented caps.  It is never a good idea to transfer formic to a tightly capped glass container.  At least it was in the shed and not in your house.  ::)  

m_e


spectralmagic

  • Guest
Has SWIY tried again?
« Reply #18 on: September 07, 2003, 12:57:00 AM »
Has SWIY tried again?  SWISM screwed up his first attempt somehow (actually, he often doesn't get it right the first time).  He usually doesn't give up until he's tried something at least 3 times...  :)

FYI, all of SWISM's safrole comes from ocotea cymbarum as well, it's what the store had and he wasn't picky.  He gets about 85g of safrole out of 100mL of oil via slow crystallization in the fridge (needs a seed crystal though if not in the freezer).  Distillation of the residual oil yields even more safrole.  The details on this he found somewhere in TFSE...

Safrole's identity was confirmed via odour, visible properties, density, mp, bp, and the fact that after treatment with KOH the mp and bp change to correspond with those of isosafrole, so he's fairly sure.

And about the peracetic...  I think something was wrong with the peracid for SWISM's first attempt, he noticed some O2 bubbling in the flask he prepared it in along with a little white precipitate (where'd *that* come from?), he decided to ignore that and used it anyway after 9 days of aging, the isosafrole went through practically unchanged.  Btw, I was hanging out with SWISM and happened to notice some more peracetic acid aging, on day 2 it had a little bit of that white precipitate again (no noticable bubbling though).

Edit: FYI, it's Chromic's peracetic method that SWISM's been following.


aleph

  • Guest
Try, try again.
« Reply #19 on: September 08, 2003, 04:13:00 AM »
SWIM has been using Rhodium's Peracid Oxidation Review for guidance.  She thinks (after reading this thread) that perhaps the peracetic acid WASN'T yet peracetic when used (after 16 hours of standing).  Nevertheless, performic acid is next attempt.  SWIM will try peracetic again, I think, but later.