Author Topic: When substituting GAA for Formic acid...  (Read 6802 times)

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OChem

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When substituting GAA for Formic acid...
« on: April 28, 2001, 11:29:00 AM »
What changes need to me made? Would i use them interchangibly, gram for gram? mole for mole?


Idle hands.......

Chromic

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firecracker

  • Guest
Re: When substituting GAA for Formic acid...
« Reply #2 on: April 30, 2001, 12:14:00 AM »
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

  • Guest
Re: When substituting GAA for Formic acid...
« Reply #3 on: April 30, 2001, 04:07:00 AM »
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

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Re: When substituting GAA for Formic acid...
« Reply #4 on: April 30, 2001, 12:02:00 PM »
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 æpizzazzÆ.
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 youÆre
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 ArbyÆs 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
couldnÆt 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 ôketoneö: 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 dpHarmaÆs post in the ôSuccess with
Nitromethaneö 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
didnÆt 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) dpHarmaÆs 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 itÆs pure and say fuck it.
Oh, and the hydrometers in the pet store for measuring
salinity are nice for acetic because theyÆre 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 wonÆt 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 youÆre out there and listening, youÆre 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 donÆt 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, itÆs a
sure bet theyÆve 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 ækickersÆ 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 donÆt want to
wind up with some shotgun amination product. And letÆs
face it...I donÆt want to repeat the purely academic
research of others.
Maybe IÆm 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 (IÆm
delusional) IÆm just trying to get it all in at once.
For every soul that comes out of the woodwork to post,
you can be sure thereÆs ten who are reaping the benefits
in quiet thankfulness. Ok, two quotes and IÆm 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

  • Guest
Re: When substituting GAA for Formic acid...
« Reply #5 on: April 30, 2001, 09:52:00 PM »

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

  • Guest
Re: When substituting GAA for Formic acid...
« Reply #6 on: October 09, 2001, 09:24:00 PM »
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

  • Guest
Re: When substituting GAA for Formic acid...
« Reply #7 on: December 14, 2001, 01:38:00 AM »
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

  • Guest
Re: When substituting GAA for Formic acid...
« Reply #8 on: December 14, 2001, 02:56:00 AM »
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

  • Guest
Re: When substituting GAA for Formic acid...
« Reply #9 on: December 14, 2001, 03:39:00 AM »
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

https://www.thevespiary.org/rhodium/Rhodium/chemistry/peracid.html




noj

  • Guest
Re: When substituting GAA for Formic acid...
« Reply #10 on: December 17, 2001, 02:40:00 PM »
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

  • Guest
Re: When substituting GAA for Formic acid...
« Reply #11 on: December 17, 2001, 03:11:00 PM »
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

  • Guest
Re: When substituting GAA for Formic acid...
« Reply #12 on: December 17, 2001, 03:59:00 PM »
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

  • Guest
Re: When substituting GAA for Formic acid...
« Reply #13 on: December 17, 2001, 07:07:00 PM »
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

  • Guest
Re: When substituting GAA for Formic acid...
« Reply #14 on: December 17, 2001, 07:16:00 PM »
unnilhexium, God bless you  :)  :)  :) !

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


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unnilhexium

  • Guest
Re: When substituting GAA for Formic acid...
« Reply #15 on: December 17, 2001, 07:56:00 PM »
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

  • Guest
Re: When substituting GAA for Formic acid...
« Reply #16 on: December 17, 2001, 08:12:00 PM »
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

  • Guest
Re: When substituting GAA for Formic acid...
« Reply #17 on: December 17, 2001, 08:38:00 PM »
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

  • Guest
Re: When substituting GAA for Formic acid...
« Reply #18 on: December 17, 2001, 08:43:00 PM »
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. ;)

106

Rhodium

  • Guest
Re: When substituting GAA for Formic acid...
« Reply #19 on: December 17, 2001, 08:48:00 PM »
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.