Author Topic: When substituting GAA for Formic acid...  (Read 6801 times)

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unnilhexium

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Re: When substituting GAA for Formic acid...
« Reply #20 on: December 17, 2001, 08:51:00 PM »
Rhodium:  Has there been a post on this?  I would be interested in knowing how it was isolated, how much was isolated, and how it was verified to be acetone peroxide.
As far as the danger factor, I can say that swim has done this almost every week for a while, without any mishaps.
Whether or not acetone peroxide is formed, swim can vouch for the safety of this method.

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unnilhexium

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Re: When substituting GAA for Formic acid...
« Reply #21 on: December 17, 2001, 09:08:00 PM »
Although I will be the first to say that Rhodium knows way more than I do, I don't believe that performic/acetic acid would react with acetone to form acetone peroxide.  In cases where acetone peroxide was formed, what was the water content of the peracid, and the concentration of the h2o2?  Swims OTC reagents are more "watered down" than all of those ACS grade reagents the bees higher up the chain probably are using.  Swims h2o2 is ~25%, are the other cases using higher concentrations, like maybe 50%?  Either way, I am here to learn rather than to teach, I just thought that my post might be useful to some other bees, as so few peracetic experiences have been posted.

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Chromic

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Re: When substituting GAA for Formic acid...
« Reply #22 on: December 17, 2001, 09:37:00 PM »
I know peracids form DMDO from acetone, I'm would not be surprised to hear that they can further oxidize it to acetone peroxide. Rhodium, I doubt that peracetic stock solutions decompose that much within 24hrs! The ref probably refers to how diluted solutions of peracetic acid will slowly decompose into H2O2 and acetic acid.

I still don't get my failures, I suppose I should give acetone a whirl....

Rhodium

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Re: When substituting GAA for Formic acid...
« Reply #23 on: December 18, 2001, 01:38:00 AM »
As far as I remember, the identity of the acetone peroxide was cerified by filtering it off, drying it and striking it with a hammer (it detonated). I do not remember who performed the experiment, or what the exact reaction conditions was. But it is also documented in TSII that these white crystals may form. I guess it has to do with the solvent composition. Acetone peroxide is insoluble in water, but soluble in acetone and other organic solvents. I don't know about formic/acetic acid.

Chromic: The peracetic acid decomoposition figure was in regard to "self-prepared" solutions from HOAc/H2O2. Commercial 32% peracetic acid has stabilizers added, and it is also stored in the cold to last longer.


noj

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Re: When substituting GAA for Formic acid...
« Reply #24 on: December 18, 2001, 03:10:00 AM »

B)SWIMS yields have been lower, and never have been sucessfully aminated when using DCM as a solvent, but acetone has produced yields in excess of 50%, which have aminated beautifully.




I can say that the first half of this statement was exactly what I experienced. Using DCM as the solvent I distilled a yellowish fluid which took the characteristics of ketone; viscuous liquid, familiar smell, and would not freeze. Unfortunately, it would not aminate in any attempt.

So you are suggesting a 12 hr peracid formation and no more, and using acetone as the solvent. I may try this in microscale amounts to see what happens.

Are there any other solvents that would work to replace DCM?


A theory is a tool - not a creed. -J. J. Thomson

Osmium

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Re: When substituting GAA for Formic acid...
« Reply #25 on: December 18, 2001, 03:13:00 AM »
It was me who brought up the subject of acetone peroxide first back in 1997.
During a big scale standard performic using 35% H2O2 and 85% HCOOH according to Shulgin/Fujisava & Deguchi some insolubles were seen in the formic rotovap removal step. Since me and my buddy doing the reaction both had knowledge of common household explosives we already expected something like that to happen earlier or later, so we filtered the shit, washed the filter paper and air-dried it. Then we ignited it, causing it to burn rather violently. There weren't that many crystals (most probably still in solution) and since we didn't dry it completely, just enough so it would burn no detonation took place. For saftety reasons no acetone was used in this reaction anymore, which made the reaction even more volume-efficient although more care was required to add the isosafrole this way.

I want to suggest the following variation:
Many bees can get or make diluted formic acid, like 50-60%. If I had problems getting stronger formic than that I'd try to use a mixture of acetic and formic acids instead of only acetic.
Example: 1mol 30% H2O2, 1.5-2 mol diluted HCOOH, additional glacial acetic acid to make a 3-4:1 organic acids+H2O2:H2O ratio.
This mixture should produce largely performic acid, while the additional acetic acid will take care of the solubility issues. Maybe this mixture will work more consistenly than peracetic acid.

goiterjoe

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Re: When substituting GAA for Formic acid...
« Reply #26 on: December 18, 2001, 03:57:00 PM »
Osmium:  did you add the isosafrole directly to the peracid, or did you solvate it with DCM or something else?

Sed quis custodiet ipsos custodes?

Osmium

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Re: When substituting GAA for Formic acid...
« Reply #27 on: December 18, 2001, 08:36:00 PM »
The isosafrole was added directly and undiluted to the performic.
Since isosafrole solubility in the performic is low you have to take your time, usually it took like 3 hours or so. The formyl glycol is completely soluble in the reaction mixture though. The temp was kept between 28-33°C to ensure a rapid enough reaction. Too much cooling will slow it down too much, and too much unreacted isosafrole, detectable by a thick oily layer on top will accumulate. When this happens, the isosafrole being added too fast, the temp will eventually rise, isosafrole solubility will go up, reaction rate also goes up, more isosafrole will react per given time and this might result in a runaway reaction especially when doing really big scale and unsupervised performics this way. Just take your time, drip it in slowly, stir it continuously, check the temp occasionally during the post-reaction stirring and nothing bad will happen.

Well, I sorta lied. Most of the time the addition funnel was swirled around with a little acetone after the addition to clean it a bit and get all the iso in, but that was a tiny amount compared to the original procedure.

When I did the performic for the first time in a 6L flask without acetone the internal temperature seemed to have stabilized around 28°C about 30 mins after addition with some external cooling and magnetic stirring.
Then suddenly I heard a scream outside, my ex being stung by a bee or wasp. Since she had taken some MDMA an hour before and showed an allergic reaction and was near faining I immediately drove her to the hospital, where she had to spend the night and the following day under surveillance in the intensive care unit due to her 'extreme physiological reaction' aka raised blood pressure, dilated pupils, fast heart beat, sweating, dry mouth etc.  ;)  She didn't really feel that bad (except for having to come down in an intensive care unit...), but the docs wanted to make sure she wouldn't die unexpectedly.  :)  Talk about a botched attempt at tripping  :P .
Anyway, after about 2-3 hours, when I made sure she would live I came back to the lab, and the temp inside the flask had risen to 38°C! The post-addition reaction is definitely delayed when doing it without acetone! But the reason for this temperatre raise was rather the big flask size (meaning low surface area) and insufficient cooling, since the cooling water was piss warm (> 30°C) and all the ice I used had long ago melted. So I changed the cooling water, added some ice and no more surprises happened that day. Of course I went right back to the hospital AFTER I made sure my precious batch would survive this incident. Yes bees, never forget where your priorities are. Sometimes the girlfriend has to step back and make way for more important stuff hehe.
Yield in that run was the usual 60%. Girlfriend survived without any permanent physiological damage. But she was a damn nutcase anyway...

goiterjoe

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Re: When substituting GAA for Formic acid...
« Reply #28 on: December 18, 2001, 09:22:00 PM »
damn Osmium, you used to perform reactions like that with other people there, much less ones that you were involved with and they were under the influence?  I don't know the situation, but that doesn't sound like something that should be promoted.  Neither does leaving a reaction, although it was completely understandable in your scenario.  You must have been sweating bullets at the ER though, knowing what awaited your arrival when you got home.

Sed quis custodiet ipsos custodes?

Rhodium

  • Guest
Re: When substituting GAA for Formic acid...
« Reply #29 on: December 19, 2001, 02:11:00 PM »
MDP2P yield: 60%
GF yield: Quantitative

Osmium

  • Guest
Re: When substituting GAA for Formic acid...
« Reply #30 on: December 19, 2001, 03:22:00 PM »
And now, after many years the whole thing became pretty much meaningless anyway. I spread and shared my capped love among the local rave and hedonist community, and she spread her love among a few dozen other guys since then.
Mainly she spread her legs and shared the juices with whoever was willing to taste her nectar. I don't think she ever knew what love is.
All the MDP2P is long gone, and she is gone too, although not quite as long. All that remains are fading memories. [sniffle]

AND THIS DAMN FUCKING RAGE I FEEL FOR THAT STUPID BITCH! Fuck you, wherever you may be right now. Die you stupid piece of SHIT!
:P

goiterjoe

  • Guest
Re: When substituting GAA for Formic acid...
« Reply #31 on: December 19, 2001, 04:18:00 PM »
sounds like the levee just broke... :o

Don't worry Osmium, I think everyone meets someone in their life that is like that.  I know I have, and it made a better person out of me after that experience.

Sed quis custodiet ipsos custodes?

goiterjoe

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Re: When substituting GAA for Formic acid...
« Reply #32 on: December 19, 2001, 08:35:00 PM »
the peracetic reaction when performed with DCM aminated fine for SWIM.

Sed quis custodiet ipsos custodes?

noj

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Re: When substituting GAA for Formic acid...
« Reply #33 on: December 20, 2001, 02:47:00 AM »
What? No details?

A theory is a tool - not a creed. -J. J. Thomson

PoohBear4Ever

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Re: When substituting GAA for Formic acid...
« Reply #34 on: December 20, 2001, 06:48:00 AM »
Is this the one:

Post 207868 (missing)

(goiterjoe: "Re: Peracid oxidation of isosafrole - a Review", Methods Discourse)
?

PB


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Chromic

  • Guest
Re: When substituting GAA for Formic acid...
« Reply #35 on: December 20, 2001, 09:23:00 AM »
Rhodium, I doubt the rate of decomposition that you suggest is correct. I found a reference on peracetic acid decomposition, and this applies to solutions made from H2O2 and acetic acid with sulfuric acid catalyst (0.1-5%), as you can see peracetic acid is stable at ambient temperatures without stabilizers for months at a time. I'd also like to point out that all solutions usually come to equilibrium within the first 7 days (no matter the concentration). It's from uspto.com patent #5,349,083:

Peracetic acid (wt%)
Weeks  Ex 2      Ex 3   Ex 4
0      12.51     1.10   0.78
1      11.95     1.03   0.76
2      11.48     1.07   0.79
3      11.62     1.26   0.83
4      11.90     1.24   0.89
5      --        0.83   0.92
6      11.87     1.29   0.98
8      11.79     --     --
11     --        0.98   0.81
12     11.38     --     --
13     11.72     --     --



Btw, does anyone know of some easy chemical test which will show the presence of peracetic acid? KI should go to I2 but that would happen with H2O2 with any acid, so are there any other easy tests that use common inorganics?


Chromic is still scratching his head why he has had only failures...

goiterjoe

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Re: When substituting GAA for Formic acid...
« Reply #36 on: December 20, 2001, 10:21:00 AM »
yep, that's the one.  after being buried in the ground for six months, it was dug up and aminated, and it salted out.  Unfortunately, the humidity sucked it right back in during filtering it, so a bioassay is waiting on the evaporation of the water used to reclaim salt.

Sed quis custodiet ipsos custodes?

unnilhexium

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Re: When substituting GAA for Formic acid...
« Reply #37 on: December 20, 2001, 12:49:00 PM »
SWIM always ended up with a very ketone-esque substance using DCM.  Had a similar but more so peppery smell than his high quality ketone, as well as a more opaque color.  Amination ended up in a black tarry mess (xylene extraction of the mixture, aqueous hcl to extract the goodies from the xylene).  The DCM attempts were similar to those used by yellowjacket on this thread. Regardless, SWIM finally figured out how to get formic, so he likely will throw away the rest of his acetic, as the yields suck in comparison.

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noj

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Re: When substituting GAA for Formic acid...
« Reply #38 on: December 20, 2001, 03:44:00 PM »
Oh shit, I just realized why the peracetic failed for me. I forgot to add the 15% H2SO4. So what did I attempt to aminate?

A theory is a tool - not a creed. -J. J. Thomson

Chromic

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Re: When substituting GAA for Formic acid...
« Reply #39 on: December 20, 2001, 04:01:00 PM »
If you didn't do the 15% H2SO4 rearrangement then you were attempting to aminate isosafrole epoxide or isosafrole glycol.