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]
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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!