OChem (Newbee)
04-28-01 11:29
No 187637
      When substituting GAA for Formic acid...  Bookmark   

What changes need to me made? Would i use them interchangibly, gram for gram? mole for mole?


Idle hands.......
 
 
 
 
    Chromic
(Hive Addict)
04-29-01 14:48
No 187940
      Re: When substituting GAA for Formic acid...  Bookmark   

http://rhodium.lycaeum.org/chemistry/peracetic.txt
 
 
 
 
    firecracker
(Newbee)
04-30-01 00:14
No 188057
      Re: When substituting GAA for Formic acid...  Bookmark   

Chromic (and anyone else),

How reliable is the peracetic route?  A quick perusal of the search engine reveals a bunch of testimonials from bees using the modified performic, but not very many folks talk about their successes and yields from peracetic. SWIF considered this route when their benzo ran out, but decided instead to chase that accursed O2 wacker.

Thanks,
fc


Snap, Crackle, Pop
 
 
 
 
    Chromic
(Hive Addict)
04-30-01 04:07
No 188080
      Re: When substituting GAA for Formic acid...  Bookmark   

Peroxyacid methods work well and use more uncontrollable precursors. There is a larger volume to deal with, with a more involved workup... but... things are easier to work with.
 
 
 
 
    yellowjacket
(Hive Bee)
04-30-01 12:02
No 188150
      Re: When substituting GAA for Formic acid...  Bookmark   

Here is a nice write-up from yesteryear. looks like a workable synth to YJ.


 
  Penis_Seinfeld
(Stranger)
06-05-00 03:04
No 13855
    Re: peracetic prep   Reply
 
Tao Corning [Image] posted 12-28-1999 04:34 PM
NewBee
[Click Here to See the Profile for Tao Corning]
---------------------------------------------------------
This is written to give hope to the peracetic movement,
for those who are tired of breathing copper sulfate and
vac distilling concentrated formic. Furthermore, I have
dreamed of nothing but disappointingly low yields via
performic. Like DpHarma said, they lacked ŠpizzazzĂ.
Peracetic dreams have not been better, but have been
easier by virtue of reagent preparation, and I feel that
just a couple more dreams will have it nailed down. I
first read the idea from Purplxd (reiterated by Gyro)
and tried it in two separate dreams. My lab technique is
pitiful, and I will relay some fuckups so that if youĂre
better than me you can expect to yield accordingly
higher.
In my dream 28.6g 35.7%H2O2 were added over the course
of 5 minutes to a stirring mixture of 60g Glacial Acetic
Acid and 1.2g H2SO4 in a 500ml ArbyĂs flask. (round
bottom for our non-American associates) This was allowed
to stir for 24 hours, after which was added slowly 32.4g
Isosafrole suspended in 50ml DCM. This addition was self
regulated by means of the following glassware
arrangement: into the flask go two condensors stacked on
top one another to make one super-condensor. On top of
this goes the addition funnel. This addition funnel is
not stoppered. In this dream, it was actually a west
condensor and a jacketed column which both came in a
standard 19/22 organic kit. As the addition funnel is
opened and the reaction begins, the heat begins to boil
the DCM, which condenses and cools the reaction. (A
little of the DCM is added to the flask before addition,
as an insurance policy against initial overheating.) The
reaction soon overcomes the ability of the DCM to cool
it, and when this occurs, the vapor pressure of the DCM
blows a little stream of bubbles up into the addition
funnel, preventing further addition until the reaction
has sufficiently cooled for the pressure to drop.
Anyway, the addition was not supervised, but the
reaction allowed to stir as vigorously as possible for
24 hours from the commencement of addition. From halfway
through addition until the end of stirring, the mix
looked like cherry coffee. Those two words should
suffice for you when you see it. At the end of this time
a shitload of chlorinated solvent (TCE & DCM) was used
to extract the goodies, even though it was very likely
separated - I was too brain dead for it to occur to me
that I should check. The solvents were removed under
vacuum and the residue dissolved in the 60ml Methanol
and hydrolyzed in 360ml 15% H2SO4 for two hours at 75
degrees. Upon vac distillation a beautiful flourescent
yellow oil with just a little green condensed out. Final
yield 19.2g crude MDP2P. The lab technique employed here
couldnĂt have been any sloppier without intentionally
trying to fail. The distillation temp range indicated a
lack of purity, but no horrible pre run of iso. But the
truth would never be known because some asshole put too
big of a nitromethane kicker in during amination and
blew most of the solution onto the basement ceiling. The
amination phase of the dream was continued anyway with a
little more methanol and about three and one half grams
of Hcl salt recovered. Given my usual dreaming prowess,
one may safely believe there were at least 5.25g of
ketone left after the eruption. I believe there was at
least 15g at the start, but who knows?
This dream is a recurring one, and came to me just the
same as the previous but with larger amounts, to wit:
120g Acetic, 64.8g Iso, 150 ml DCM, 2.4g H2SO4 and 85.8g
35.7%H2O2. (Not necessarily in that order.) Another
difference in this dream was the lack of patience, and
peracetic formation was only afforded 12 hours, while
stirring remained 24 hours. Of course it was in a 1L
Girlenmeyer (Earl & Meyer, pick your tripe...) flask.
Final yield of ˘ketone÷: 53.2g BUT, before any little
peckers flip up in premature joy, listen to the rest of
this dismal story. There was an obvious forerun of iso,
and the final mix smelled of it, so I knew I would dream
bisulfite before I wasted my hard earned methylamine on
some fucking root beer oil. (Bisulfite after any
distillation is SOOO easy...) Bisulfite crystals still
slightly damp with everclear were over 9 grams and
recovery yielded 6.05g of quality R2D23PO. A subsequent
aminative dream with said ketone yielded 3.8g of
artificial joy that will spread Christmas cheer well
into the new overbilled millenium. (BTW, all my amines
are Y2K compliant.) That amination was subconsciously
modeled after dpHarmaĂs post in the ˘Success with
Nitromethane÷ thread and was 6g Al, 7.1g MeAmHCl, 4.5g
NaOH, apprx 200ml MeOH, apprx 3ml Nitromethane, and
apprx 20cc H2O.
Dream #2 went bad primarily because of incomplete
peracetic formation, I believe.
Someone (?) hypothesized, and I believe this
wholeheartedly, that the peracetic is less brutal to the
methylenedioxy ring than performic. I believe that
because this is true, it affords a longer period of time
in which the proper amount of oxidation has taken place-
and I need the biggest window of opportunity I can find.
Personally, I do not at all mind prepping my peracid the
night before, or the day before. I also believe the
other side of this to be the lack of oxidizing power the
peracetic has and my future plans include more H2O2,
maybe a slightly elevated temperature (35C?), less
solvent and/or strictly acetone (single phase mixture).
On that second dream, I stirred as fast as I could, but
didnĂt see the smooth solution I did with the smaller
batch in the round flask.
Finally I should mention that in my dreams the acetic
acid was homemade with (God bless) dpHarmaĂs recipe
post: neutralizing 5 gallons of grocery store vinegar
with about two cans of lye and baking to dryness in the
oven over several days. (smells like baking bread,
mmm.....) I found that boiling leaves your stove top
covered with the acetate. The dried acetate is mixed
with H2SO4 and distilled, but I believe more than a
trace amount of sulfate remains in the distillate. I
redistilled and got out the sulfate smell, but it
appears that there was a water(?) azeotrope which came
over at about 107 degrees. That was about 400ml and then
it kicked up to the 118 degrees I was expecting for
about the last 120ml, which I collected separately as
pure. This may have influenced my dreams. I really
loathe the copper sulfate treatments, so if someone
knows of a friendly, suitable drying agent for acetic
like MgSO4 or something, please post here. I just treat
the 107C boiling acid like itĂs pure and say fuck it.
Oh, and the hydrometers in the pet store for measuring
salinity are nice for acetic because theyĂre smaller and
look more accurate in the range from 1-1.049rd. (I just
bought it today.)
The H2O2 was pool store shock which was labelled at
about 27%. But my handy dandy wine making hydrometer
(God bless dpHarma) told me that some settling of
contents must have occurred during shipping and
handling. So I put it into a distillation setup and
started boiling the water out of it. When I stopped, the
hydrometer told me it was 35.7% Use the highest
concentration you feel like you wonĂt explode while
making. No guts, no glory. BTW, if you go to a local
glass shop or preferrably a plastics supply house
(yellow pages!), you can get some 1/2 inch thick acrylic
scrap for cheap and then rig it up to hang in front of
your beaker - instant peace of mind.
DpHarma, if youĂre out there and listening, youĂre name
appears more than once already in this post and I would
like to thank you publicly for your contribution to the
Hive. You have been the one I listen to unequivocally,
as I respect the fact that you donĂt pedantically spew
out conjecture but only relay your EXPERIENCE. Your tips
on formic acid concentration were invaluable. Your pet
ether extraction of cann. was a beauty. When I read
someone who disagrees with something you posted, itĂs a
sure bet theyĂve never tried it.
I would like to switch to dreams with aqueous MeAm, but
would like to know the specific gravity (density) of 40%
solution. I would be eternally grateful if some bee in a
less anal country would measure their commercial
solution and tell me a target density. I would also love
the same data for bubbling into chilled methanol, which
I would then dream about as the solvent in a standard
Al/Hg. I love the concept, but I just need a route for
quantitative analysis. In my dreams I usually add little
nitromethane ŠkickersĂ after a while. But be careful of
that dreaded boil-over. So much work can wind up on your
ceiling, and then you start beating yourself up...
When I cleaned up the products from degradation of
hexamine with annhydrous ipa and then chloroform, it
yielded a nice crop of ammonium chloride and yellow
shit. Does the nitromethane reduction run clean? Has
anyone bubbled for the hydrochloride salt and then
cleaned it with chloro to prove its purity? I would go
with the in situ reduction dream, but I donĂt want to
wind up with some shotgun amination product. And letĂs
face it...I donĂt want to repeat the purely academic
research of others.
Maybe IĂm missing the big picture and just using MeOH
saturated with MeAM as best I can manage (without
stinking up the entire neighborhood) will work at the
800ml/mole level. (God bless Osmium)
Sorry to carry on so, but I have so much to say to the
hive and since every post aggravates my paranoia (IĂm
delusional) IĂm just trying to get it all in at once.
For every soul that comes out of the woodwork to post,
you can be sure thereĂs ten who are reaping the benefits
in quiet thankfulness. Ok, two quotes and IĂm done.
Prohibition will work great injury to the cause of
temperance. It is a species
of intemperance within itself, for it goes beyond the
bounds of reason in
that it attempts to control a man's appetite by
legislation, and makes a crime
out of things that are not crimes. A Prohibition law
strikes a blow at the
very principles upon which our government was founded.
Abraham Lincoln
(1809-65)

Government is not reason, it is not eloquence, it is
force; like fire, a troublesome servant and a fearful
master. Never for a moment should it be left to
irresponsible
action.

Thanks, Penis.


marijuana is the flame, heroin is the fuse, LSD is the bomb!
 
 
 
 
    terbium
(Hive Addict)
04-30-01 21:52
No 188275
      Re: When substituting GAA for Formic acid...  Bookmark   


SWIF considered this route when their benzo ran out, but decided instead to chase that accursed O2 wacker.


To answer you PM, I have never done a peracid oxidation but it certainly does look attractive. There are lots of published refs for the use of peracids to produce epoxides and glycols. Use the link to the online volumes of Organic Syntheses that was given in the Serious Chemistry forum.

I did half-heartedly try an O2 Wacker on safrole many years ago and got no results. 'Course I didn't try very hard and I used PdCl2 sans CuCl2.

If the peracetic coversion of isosafrole to glycol works it will be really nice since 35% H2O2 is much easier to get than benzoquinone.

I want to reread the old note that was just posted in this thread. Seems to have a lot of good info. I would think an important point as was mentioned in that post is to mix the glacial acetic acid and 35% H2O2 overnight in the presence of 1% of concentrated sulfuric acid then buffer the sulfuric acid with sodium acetate prior to adding the isosafrole.

 
 
 
 
    PoohBear4Ever
(Junior Service Representative)
10-09-01 21:24
No 222589
      Re: When substituting GAA for Formic acid...  Bookmark   

So, according to Penis, the peracid whould mix for more that 12hr?  Perhaps 18hr would improve chances of peracetic formation without giving too much time to decompose?  Would reduction in temp. inhibit formation, or decomposition, or both? 

Thanks if anyone has any past experiences/knowledge they would like to share,

PB
 
 
 
 
    cheeseboy
(Hive Bee)
12-14-01 01:38
No 247442
      Re: When substituting GAA for Formic acid...  Bookmark   

Swic was lead to believe that Formic acid was a better acid to use that GAA. A friend of Swic is having no luck with the GAA route. So what IS the better acid to use??? if one can get 88%Formic acid no problem , should it be used? cheese think's so!

May The Source Bee With Yous
 
 
 
 
    Chromic
(Hive Addict)
12-14-01 02:56
No 247455
      Re: When substituting GAA for Formic acid...  Bookmark   

Formic is the best choice. A lot of people have had failures with GAA--it is HIGHLY important to wait a considerable amount of time to allow the GAA and H2O2 to react.
 
 
 
 
    Rhodium
(Chief Bee)
12-14-01 03:39
No 247465
      Re: When substituting GAA for Formic acid...  Bookmark   

The performic reaction is easier to get to work, but the acid is more expensive and for some people harder to aquire. But if you do not have any problems getting the formic acid, then use it, preferably in the so-called "Buffered Performic acid Oxidation" found at ../rhodium/chemistry /peracid.html

 
 
 
 
    noj
(Hive Bee)
12-17-01 14:40
No 248526
      Re: When substituting GAA for Formic acid...  Bookmark   

Rhodium, since it was your writeup that prompted my interest in the peracetic route, could you tell me what the maximum time to allow acetic acid and 35-50% peroxide to sit before decomposition occurs, if any? And while sitting, should the solution be stirred?

Are there any methods to test for peracetic acid formation?



A theory is a tool - not a creed. -J. J. Thomson
 
 
 
 
    Chromic
(Hive Addict)
12-17-01 15:11
No 248535
      Re: When substituting GAA for Formic acid...  Bookmark   

It will not noticeably decompose over any reasonable amount of time (just like H2O2), it is relatively stable. If it is diluted, then that's another story.
 
 
 
 
    Rhodium
(Chief Bee)
12-17-01 15:59
No 248547
      Re: When substituting GAA for Formic acid...  Bookmark   

I believe I have a reference that says that peracetic acid decomposes with 10-15% per 24h at RT. As long as you mix the H2O2 and GAA thoroughly in the beginning, you don't need to stir it during peracid formation.
 
 
 
 
    unnilhexium
(Stranger)
12-17-01 19:07
No 248589
      Re: When substituting GAA for Formic acid...  Bookmark   

Having taken the peracetic route more than a few times, it has been SWIMS experience that:
A) Yields decrease when peracetic is allowed to stand any longer than 12 hours or so (as to say yields have consistently been lower with 16, 20, and 24 hour standing time.)  The peracetic acid smells different the longer it stands, which SWIM originally thought was peracetic formation, but now believes to be the decomposition of the peracetic.
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.  Also, external cooling during the addition (ice water bath) has increased yields by as much as 20%.

All isosafrole used was created via osmiums KOH/vacuum reflux, and known to be of high quality, while SWIMS acetic acid is only 90%, and H2O2 is 25%, with a few carefully calculated and measured milliliters of battery acid.  All of SWIMS reagents are OTC.

106
 
 
 
 
    PoohBear4Ever
(Junior Service Representative)
12-17-01 19:16
No 248593
      Re: When substituting GAA for Formic acid...  Bookmark   

unnilhexium, God bless you smilesmilesmile!

You just answered so many of my ponderings in a single post.  I remember reading in a patent that colder temperatures allow for faster peracid formation, thus likely the reason you saw better yields (edit: we tawking about peracid formation or isosass addition?).

Did you notice any acetone peroxide build up? Is this advoided through the post-rxn, pre-distillation washes?

Please give as much info. as possible with your past successe(s), for it would bee most helpful for SWIP,

PB


123456789101112131415161718192021222324252627282930313233343536373839404142434445464748
 
 
 
 
    unnilhexium
(Stranger)
12-17-01 19:56
No 248601
      Re: When substituting GAA for Formic acid...  Bookmark   

While SWIM is TOO FUCKING PARANOID to make any records of past synths, from memory, SWIM can say that:
A)I was refering to the iso addition, using the ice bath.  The product quickly takes a red color (indicating the decomposition of iso) when left to it's own devices, and yields have been terrible.  When an ice bath is used, the mix maintains a pretty orange color.  The monoacetyl(???????)glycol was extracted by flooding the mix with water, and extracting with DCM.  Swims latest, greatest, and untested idea is using a carefully controlled vac reflux during the addition of the iso/acetone into the peracetic, which will be attempted whenever SWIM gets around to buying a 24/40 pressure equalized vacuum proof addition funnel.  Also, peracetic formation always took place at approximately 20-30 degrees celcius.
B)Swim has never noticed any acetone peroxide  at any point in the process.  SWIM believes that to be an urban legend, like ecstasy containing heroin, etc...

Hydrolysis was always done with battery acid (check the specific gravity to determine %) diluted about 45/55 to produce 15% sulfuric, and GENTLY heated for 2 hours, and ketone distilled at ~29"hg with swims BEAST of an aspirator station.  As soon as I get a digital camera, I'll post a picture.

All aminations were of the al/hg variety, using methanol as a solvent (isopropanol was never used successfully), with ~.5 gram blobs of hg dropped into I2 tincture, allowed to react for a few days, and then used to amalgamate.

Anyone can feel free to ask swim any questions, as swim has tried this(both sucessfully and unsuccessfully) many times.

106
 
 
 
 
    terbium
(Old P2P Cook)
12-17-01 20:12
No 248604
      Re: When substituting GAA for Formic acid...  Bookmark   

Swim has never noticed any acetone peroxide  at any point in the process.  SWIM believes that to be an urban legend,
In what way do you believe acetone peroxide to be a legend. It is easy to produce, all you need is to stir the ketone with hydrogen peroxide and a catalytic amount of strong acid. This is a commercial process for producing methyl ethyl ketone (hydro)peroxide, after stirring for a while with the H2O2 and acid the MEK peroxide is salted out and extracted into organic solvent.
 
 
 
 
    Rhodium
(Chief Bee)
12-17-01 20:38
No 248610
      Re: When substituting GAA for Formic acid...  Bookmark   

The acetone peroxide is no urban legend. A bee here isolated the solid crystals from a peracid run, and physically verified it being acetone peroxide.
 
 
 
 
    unnilhexium
(Stranger)
12-17-01 20:43
No 248613
      Re: When substituting GAA for Formic acid...  Bookmark   

As SWIM understands it, which may or may not be correct, acetone peroxide would form as a crystalline precipitate, which SWIM has never seen.  Also, SWIM has been at it for a while, with no explosions to date.  Your mentioning of the catalytic amount of a strong acid has answered a question of swims, which was why wouldn't the acetone peroxide formation threat be the same with performic ala Shulgin (actually credit goes to those two japanese guys, whose names swim cannot remember, after a weekend of indulging in honey).  I have not seen a post yet documenting an actual case of acetone peroxide being formed in this process.  Also, I believe that the h2o2 reacts nearly quantitatively with a large excess of acetic acid over a 12 hour period, with only a nominal amount left over.  Please forgive me if I post any information that is downright ignorant, as I haven't really slept at all since Thursday.wink

106
 
 
 
 
    Rhodium
(Chief Bee)
12-17-01 20:48
No 248614
      Re: When substituting GAA for Formic acid...  Bookmark   

It has been documented several times that a white precipitate MAY form, this thas been even most often reported with Shulgins adaption of the Fujisawa/Deguchi performic acid oxidation, but that is of course because that is the most widely used method. However it does not need to form in a particular batch, and I believe free H2O2 is not necessary, and that peracids very well can form peroxides with acetone on their own.
 
 
 
 
    unnilhexium
(Stranger)
12-17-01 20:51
No 248615
      Re: When substituting GAA for Formic acid...  Bookmark   

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.

106
 
 
 
 
    unnilhexium
(Stranger)
12-17-01 21:08
No 248618
      Re: When substituting GAA for Formic acid...  Bookmark   

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.

106
 
 
 
 
    Chromic
(Hive Addict)
12-17-01 21:37
No 248622
      Re: When substituting GAA for Formic acid...  Bookmark   

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
(Chief Bee)
12-18-01 01:38
No 248663
      Re: When substituting GAA for Formic acid...  Bookmark   

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
(Hive Bee)
12-18-01 03:10
No 248679
      Re: When substituting GAA for Formic acid...  Bookmark   


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
(Stoni's sexual toy)
12-18-01 03:13
No 248680
      Re: When substituting GAA for Formic acid...  Bookmark   

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
(Hive Addict)
12-18-01 15:57
No 248779
      Re: When substituting GAA for Formic acid...  Bookmark   

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
(Stoni's sexual toy)
12-18-01 20:36
No 248852
      Re: When substituting GAA for Formic acid...  Bookmark   

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. wink 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. smile Talk about a botched attempt at tripping tongue.
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
(Hive Addict)
12-18-01 21:22
No 248861
      Re: When substituting GAA for Formic acid...  Bookmark   

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
(Chief Bee)
12-19-01 14:11
No 249028
      Re: When substituting GAA for Formic acid...  Bookmark   

MDP2P yield: 60%
GF yield: Quantitative
 
 
 
 
    Osmium
(Stoni's sexual toy)
12-19-01 15:22
No 249039
      Re: When substituting GAA for Formic acid...  Bookmark   

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!
tongue
 
 
 
 
    goiterjoe
(Hive Addict)
12-19-01 16:18
No 249056
      Re: When substituting GAA for Formic acid...  Bookmark   

sounds like the levee just broke...shocked

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
(Hive Addict)
12-19-01 20:35
No 249168
      Re: When substituting GAA for Formic acid...  Bookmark   

the peracetic reaction when performed with DCM aminated fine for SWIM.

Sed quis custodiet ipsos custodes?
 
 
 
 
    noj
(Hive Bee)
12-20-01 02:47
No 249245
      Re: When substituting GAA for Formic acid...  Bookmark   

What? No details?

A theory is a tool - not a creed. -J. J. Thomson
 
 
 
 
    PoohBear4Ever
(Junior Service Representative)
12-20-01 06:48
No 249274
      Re: When substituting GAA for Formic acid...  Bookmark   

Is this the one: Post 207868 (goiterjoe: "Re: Peracid oxidation of isosafrole - a Review", Methods Discourse) ?

PB


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    Chromic
(Hive Addict)
12-20-01 09:23
No 249290
      Re: When substituting GAA for Formic acid...  Bookmark   

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
(Hive Addict)
12-20-01 10:21
No 249296
      Re: When substituting GAA for Formic acid...  Bookmark   

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
(Stranger)
12-20-01 12:49
No 249334
      Re: When substituting GAA for Formic acid...  Bookmark   

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.

106
 
 
 
 
    noj
(Hive Bee)
12-20-01 15:44
No 249385
      Re: When substituting GAA for Formic acid...  Bookmark   

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
(Hive Addict)
12-20-01 16:01
No 249387
      Re: When substituting GAA for Formic acid...  Bookmark   

If you didn't do the 15% H2SO4 rearrangement then you were attempting to aminate isosafrole epoxide or isosafrole glycol.
 
 
 
 
    unnilhexium
(Stranger)
12-20-01 16:21
No 249392
      Re: When substituting GAA for Formic acid...  Bookmark   

WTF, Are you serious noj??????????  Anyway, for the benefit of those who can't get formic or wacker chems, I will post the results of the last peracetic SWIM ever intends to do.  325ml of 90% acetic, is added to 70ml of 25% h2o2.  Then comes 4ml of 32% sulfuric acid.  The flask is stoppered, thoroughly shaken, and allowed to stand for 12 hours.  At the 11 hour point, it is put in the fridge to chill.  At the same time, 70 grams of high quality isostuffrole is dissolved in 110ml acetone, and put in the freezer.  At the 12 hour point, the peracetic is dumped in a large erlenmeyer flask, sitting in an icebath, on SWIMS magnetic stirrer.  Stirring is commenced, and the iso is dripped in over the course of about 35 minutes.  At about the 1 hour point, the temp has stabilized, and the ice bath is removed,
and stirring is continued for a total of 16 hours.  The mix is divided into 3 ~200ml portions, and each flooded with 600ml cold h2o, glycol/epoxide sepped off, and each portion extracted with 3 x 35ml dcm.  Nasty emulsions formed on the first two portions, which were broken up with salt.  The extracts are combined, washed with h2o, and the solvent evaporated.  Next, 100ml of "methanol flavored heet" is added, and the solution is gently heated.  It is then added to 550ml preheated 15% sulfuric (250ml 32% sulfuric(battery acid)and 300ml dh2o).  It is gently heated and stirred for 2 hours, then flooded with 250 ml h2o, and set in a cold water bath for 20 minutes.  It is then at room temp, and dumped in a sep funnel, where the raw mdp2p is tapped off, the acid extracted with 3 x 90ml dcm.  The combined extracts are washed once with 250ml h2o, and once with 250ml 5% NaOH.  A blacklight is used on the second wash to determine the layers(the ketone layer glows green, the crap layer is black).  The mix is then evaporated of solvent and vac distilled to yield 43.7g of high quality ketone(yield ~57%).  All of SWIMS reagents were shitty OTC reagents, and swim believes that better reagents would give higher yields.
BTW, wanting to impress the hive, swim practiced VERY good lab technique on this run, as this was one of his best yields (usually got more around 45-50% yield).

Good luck

106
 
 
 
 
    noj
(Hive Bee)
12-20-01 17:06
No 249413
      Re: When substituting GAA for Formic acid...  Bookmark   

yea, well, I'm running around on eggshells here, and looking at so many various references, and watching 7 Federal agents lurking around a common locale.. I get forgetful at times. Selectively usually. Found some wood bleach at the hardware store so will attempt again over the next few days.

Anyone happen to know the concentration of the sodium hydroxide included in this a/b kit?

A theory is a tool - not a creed. -J. J. Thomson
 
 
 
 
    PoohBear4Ever
(Junior Service Representative)
12-20-01 17:24
No 249419
      Re: When substituting GAA for Formic acid...  Bookmark   

Got the MSDS report on a common brand found in several hardware store chains, but have since deleted such info. from both memory inside head and inside computer.  Funny thing is that I actually ordered the report first for H2O2, but they only had NaOH listed in the report...

Those bastards,

PB

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    unnilhexium
(Stranger)
12-21-01 04:20
No 249533
      Re: When substituting GAA for Formic acid...  Bookmark   

That's the same h2o2 swim uses.

106
 
 
 
 
    noj
(Hive Bee)
12-23-01 20:02
No 250159
      Re: When substituting GAA for Formic acid...  Bookmark   

The product quickly takes a red color (indicating the decomposition of iso) when left to it's own devices, and yields have been terrible.  When an ice bath is used, the mix maintains a pretty orange color

unnilhexium, are you sure about this? About half way through the iso addition with acetone the solution turned almost black (red). This is the same color as is experienced when performing a wacker. The solution was maintained at 35-38░C. Are you sure the red color isn't simply a successful oxidation? According to the synth at Rhodium's we are looking to extract a dark red liquid, so it seems that this is a sign of success, and that orange would indicate a low yield.

A theory is a tool - not a creed. -J. J. Thomson
 
 
 
 
    unnilhexium
(Stranger)
12-23-01 23:26
No 250199
      Re: When substituting GAA for Formic acid...  Bookmark   

When you flood the mixture with water, the epoxide/glycol that separates out is red, if that is what you are refering to.  But I'm actually pretty sure about this one.  Also, swim maintains a temp well below 35C (with the help of an icebath, and chilling the isosass and peracetic).  I don't remember the post#, but I remember rhodium(I think it was rhodium) stating that the red color from the reaction is caused by the decomposition of isosafrole.  Or then again, maybe I've finally managed to fry my brain.  Either way, all swim can say is that he has not seen a higher peracetic yield(57%), than the one he posted, and that swims brand of rolls are the most sought after in all the land.

106
 
 
 
 
    unnilhexium
(Stranger)
12-24-01 11:04
No 250281
      Re: When substituting GAA for Formic acid...  Bookmark   

BTW, all of the high yielding buffered performic write ups that swim has read(and will be dreaming soon), have said that the extracts are an orange color.  However, that brings swim to a question:  If the classic performic and buffered performic both give quantitative yield of the intermediate, then is the higher yield from the buffered reaction the result of:  A)residual sodium bicarbonate buffering the hydrolisis, or B)the epoxide, which is more prevalent in the buffered performic, has a higher yield in the hydrolisis than the glycol?  Any thoughts?

106
 
 
 
 
    Chromic
(Hive Addict)
12-24-01 11:28
No 250285
      Re: When substituting GAA for Formic acid...  Bookmark   

I bet it's that the bicarbonate encourages the peracid to breakdown, increasing it's activity... uping the yields of the performic. Judging by the mechanism, the glycol and the epoxide would give exactly the same yield (assuming hydrolysis of the epoxide is done in quantative yield) The H2SO4 hydrolysis has about an 80% yield, I'm unsure of the performic, but I'd imagine it to be around 80% as well... giving an overall yield of about 65%.
 
 
 
 
    noj
(Hive Bee)
12-27-01 17:40
No 250849
      Re: When substituting GAA for Formic acid...  Bookmark   

Ok, I guess I did do the 15% rearrangement. I believe the fault was with the peroxide.

Speaking of peroxide, while vacuum distilling the ketone, I noticed a crystalline formation inside the condenser. Fearing what is called acetone peroxide, I tried to wash it out with water. No luck. So I tried using the chem finder to see the nature of this substance. Also no luck. Reading this thread I see that it is soluable in acetone, and that worked. Under vacuum it appeared sometime between 40░ to 140░C. Is there another name for this acetone peroxide? And would continued distillation be okay? Don't have a blast shield and insurance doesn't cover explosions from drug synthesis. Under what conditions does it explode?


A theory is a tool - not a creed. -J. J. Thomson
 
 
 
 
    Ritter
(Master Whacker)
12-27-01 20:14
No 250865
      buffered performic -> monoformyl glycol  Bookmark   

I have verifiable proof that the buffered performic rxn can provide practically quantitative yields of monoformyl glycol.  Back in the day when I used to dream of this rxn, SWIM used to check the mass of the orange syrup resulting when DCM was stripped (using high-vacuum) from oxidation product to make sure the rxn went to completion to provide maximum yields.  I don't remember exactly what the atomic mass of isosaf monoformyl glycol is, but 210 comes to mind.  Therefore if the oxidation of 1mol of isosaf(162g) produced 210g of product, the intermediate was ready for acid hydrolysis.  Sometimes yields were less if the peroxide was bad or whatever, and in these cases the formylglycol was re-dissolved in DCE and subjected to additional performic acid and sodium carbonate (yes I am anal smile ).  This always brought the mass up to the expected 210g/mol.  Acid pinnacol-rearrangement can yield up to 85% ketone.  Much ketone is usually destroyed during standard vacuum distillation, however there are techniques to minimize thermal decomposition providing those ultra-high yields.  They are for me to know and you to find out!tongue
 
 
 
 
    terbium
(Old P2P Cook)
12-27-01 21:42
No 250880
      Re: When substituting GAA for Formic acid...  Bookmark   

Is there another name for this acetone peroxide?
I am more familar with Methyl Ethyl Ketone peroxides. I figure that acetone peroxides are about the same.

The thing is that (with MEK) there is more than one. There is methyl ethyl ketone hydroperoxide which (in a diluted form) is an article of commerce. I have never seen pure MEK hydroperoxide, I had always assumed that it is a liquid. Then there are also other organic peroxides that can be formed from the reaction of methyl ethyl ketone and hydrogen peroxide with acid catalyst; these other peroxides are probably some polymeric form, perhaps a dimer or trimer. These polymeric forms are extremely shock sensitive.

It would be a very good idea to test for any remaining active oxygen (peroxide) in your reaction product to be certain that it has all been destroyed before attempting a distillation. Perhaps shaking with a freshly prepared aqueous solution of ferrous sulfate would be a good way to destroy an remaining peroxide in the ketone prior to distillation.
 
 
 
 
    Chromic
(Hive Addict)
12-27-01 22:24
No 250887
      Re: When substituting GAA for Formic acid...  Bookmark   

Yeah, I imagine the yields of isosafrole monoacetyl glycol are similar to isosafrole monoformyl glycol. Too bad there isn't a better (easy) way to affect rearrangement than a 15% H2SO4 rearrangement.
 
 
 
 
    Rhodium
(Chief Bee)
12-28-01 00:01
No 250907
      Re: When substituting GAA for Formic acid...  Bookmark   

It would surely work to use p-toluenesulfonic acid in a small amount, as it is organic soluble? Has this been tried?
 
 
 
 
    Chromic
(Hive Addict)
12-29-01 05:36
No 251099
      Re: When substituting GAA for Formic acid...  Bookmark   

Hmm, I wish I could experiment with some, but I've got no access to even common organic reagents.

I just reread Tao Corning's post on the peracetic... I guess my trials with uping the H2O2 and AcOH would likely have solved (or at the minimum, helped) his problems. I also wonder what Semtex's ketone->amine yields were on his peracetic? He never posted them. frown