-------------------------------------------------------------------------------
                   MDP2P from safrole using H2SO4 and NH4NO3
-------------------------------------------------------------------------------

NOTE:

Many people doubt the validity of this synthesis. It is possible that it does
not work as advertised. Any success stories with this method is welcome in my 
mailbox: <rhodium@privacyx.com>

-------------------------------------------------------------------------------

This method seems to be a breakthrough in the clandestine synthesis of MDMA. 
For about two years, many people at the Hive have discussed back and forth the 
possibility of using sulfuric acid to add a water molecule across the double 
bond of safrole (so called acid-catalyzed hydration of alkenes) to form MDP2Pol
(3,4-methylenedioxyphenyl-2-propanol). This compound is only a small oxidation 
step away from MDP2P (3,4-methylenedioxyphenyl-2-propanone), which is a direct 
precursor to MDMA and other related compounds. The problem with this approach 
was that the end product most people got was MDP1P, not MDP2. Investigations, 
mostly by the chemist Bright Star showed that this was due to the intermediate 
alcohol MDP2Pol (which itself was formed in quantitative yield) spontaneously 
rearranged itself at room temperature to the isomeric MDP1Pol, which on 
oxidation gave MDP1P instead of MDP2P. The rearrangement takes place in just 
a few hours, or even faster at elevated temperatures or vigorous oxidation 
conditions. What is needed is a gentle, high-yielding oxidation procedure, 
which is to be performed immediately after the formation of the MDP2Pol, so 
that it's converted to MDP2P before it has a possibility to decompose.

Such a reaction is a Cu(II) catalyzed dehydrogenation in the presence of 
ammonium nitrate and acetic acid. 

A ref for that reaction is M. Weiss & M. Appel, JACS 70, 3666-3667 (1948)

According to that ref, the reaction proceeds as follows:

R-C(OH)-R' + 2 Cu(OAc)2 ==> R-CO-R' + 2 CuOAc + 2 AcOH

2 CuOAc + NH4NO3 + 2 AcOH ==> 2 Cu(OAc)2 + NH4NO2 + H2O

NH4NO2 == H+ ==> N2 + 2 H2O

And abbreviated to one line:

R-C(OH)-R' + NH4NO3 == Cu(OAc)2/AcOH ==> R-CO-R' + 3 H2O + N2

In their experimental procedure, they mix 0.0005 mole cupric acetate, 0.0625
mole ammonium nitrate and 0.05 mole of the alcohol in 35 ml 80% acetic acid
in a 100ml RB flak with a reflux condenser, and the mixture is heated with 
shaking. When everything had dissolved, there was a vigorous evolution of N2.
The solution was refluxed for 90 minutes, cooled to room temperature, some 
cold water added and the product was isolated in quantitative yield. 

-------------------------------------------------------------------------------
                    Original idea and experimental procedure
                                by Chem_Wannabe
-------------------------------------------------------------------------------

Overview:

Take your safrole, cool it to 0C. Take an equal weight amount of H2SO4 and
dilute it to 90% and chill to 0C as well. Mix together and swirl until it's
all one color. Add enough water to make the concentration of the acid less
than 20%. Heat a couple minutes if you feel like it, then separate the top
layer and wash with a saturated NaHCO3 (baking soda) solution.

Take this greenish-white alcohol, put in 1/10 weight of NH4NO3 and a pinch of
cupric acetate. Heat until it starts to bubble vigourously, then remove from
heat and wait until the reaction subsides. Dilute with a little ether and pass
through about an inch or two of silica gel. Remove the traces of ether to
obtain a nice pure ketone in good yields.

A Few Notes:

The original 'recipe' used ammonium nitrate (1.2 molar eq.), cupric acetate
catalyst, and acetic acid (80%) as the solvent.

Adding an amount of silica gel equal to the weight of the ammonium nitrate
to the reaction mixture helps boost yields and make workup easier. Filter
off the solvent you are using, wash the silica gel with a little solvent,
then wash your combined extracts with a sat'd NaHCO3 soln, dry solvent with
MgSO4 and remove under vacuum to leave MDP2P.

The original recipe came from a contact I met on the net, who emailed me this
recipe along with some others. The info from my friend is that copper plays a
role. She reports that the rxn mixture starts blue-green, turns brown, goes
back blue-green when rxn done. However that's with a colorless compound. There
are no refs I know of, I think that it might have been her prof's brain-child.

Using 1/10 ammonium nitrate/MDP2Pol (w/w) was the reason for failure with the
first few attempts using no acetic acid in the rxn mixture. My friend suggested
that maybe the stoichiometry of the rxn was off, as one mole of ammonium nitrate
can theoretically make 3 moles of water, which equals 3 moles of alcohol
oxidized to ketone. This is not enough oxidizing agent. One obtains the best
results with a slight molar excess of ammonium nitrate to alcohol.

Further evidence gleaned from various fuck-ups and failures seem to indicate
that cupric acetate AND acetic acid play an important role in the mechanism of
this reaction. The reaction will work without either the cupric acetate or the
acetic acid, since ammonium nitrate is a rather powerful oxidizing agent, but
it goes a LOT faster and a LOT cleaner with the addition of acetic acid and
cupric acetate.

Next time i post on this, i will include a solvent, and see if that can help
facilitate the reaction. The last mixture had two distinct phases, and no PTC to
facilitate the rxn. Perhaps this had an undesirable effect on the results. I
think that the solvent of choice would be acetone. everything will dissolve in
it, it won't be oxidized, and it can be removed quite easily at the water pump.
EtOH or MeOH as solvent choices might pose a little bit of a problem, as they
are alcohols and _might_ want to be oxidized to aldehydes. In the case of MeOH
this would not be good, since oxidation of this would lead to the production of
formaldehyde, a reagant that _can_ act as a reducing agent under higher
temperatures.

Practical Procedure:

Sassafras oil was washed with NaOH soln, then NaCl solution, and MDP2Pol made. 
Strike's MDP2Pol recipe was followed (quite sloppily) safrole chilled, slight 
weight excess H2SO4 with a little water chilled. Mixed at 0C then water added. 
Salt added to water to help get alcohol out on top. alcohol separated with sep 
funnel then passed thru Na2SO4 to dry. 21g MDP2Pol was obtained to be exact, 
undoubtedly containing some impurities since vac distillation was out of the 
question due to time constraints.

This 21g was then combined with 9.4g NH4NO3, 4mL glacial acetic acid, 1 mL H2O
and a dash of cupric acetate. Reflux was then started and maintained for a 
scant 30 min before cooling. The crap at the bottom was filtered off, and the 
liquid thrown onto 50mL of saturated NaHCO3 solution. After the CO2 generation 
had stopped, the water phase was extracted with 3X15 mL of ether, and the 
combined extracts washed with saturated NaHCO3 then saturated NaCl. 
The combined washes were back-extracted with 15mL Et2O and the ether phases 
were combined, dried with Na2SO4 then the solvent removed under reduced 
pressure, yielding approx 20g of a red liquid, smelling of a strange mix of 
ether and cardamon.

Chem_wannabe quickly had his host load a hirsch funnel with about 2g of silica 
sand, carefully poured his red oil through the sand with a little help from the 
aspirator, and washed the sand with a little ether, covering the top of the 
funnel with his hand to let the reduced pressure that was pulling the ether 
through the sand pull off as much ether as possible from the now not-as-red 
liquid in the filter flask.

Chem_wannabe had his host repeat this twice more, then took a TLC analysis of 
the now almost-but-not-quite pure-looking-yellow-with-a-tinge-of-red liquid 
and found to his great pleasure that the red color came from a very small trace
impurity. 'Distillation might not be necessary' he thought.

Weighing his now almost purified yellow oil he found that it smelled just like 
cardamon, not at all like ether and weighed 18.6g.
  

-------------------------------------------------------------------------------
            Experiments with and discussions of the above procedure
                                  by tBOC

Note by Rhodium: 

This document is a collection of several postings from the Hive by tBOC, 
but I have cut out unnecessary text from most of them. Thus I have inserted 
five dashes (- - - - -) between the different posts to make reading easier.

-------------------------------------------------------------------------------

tBOC reads chem_wannabe's ammonium nitrate oxidation procedure, and thinks that
it is rather incredible... almost unbelievable. It just so happens that tBOC
loves to grow flowers, and uses NH4NO3 as fertilizer, and tBOC is also into
photography and just happens to have glacial acetic acid around. Also tBOC was
trying to use glacial acetic acid to get his pennies their brightest and fucked
up, accidentally turning his beautiful penny collection into a nice blue powder.

Well, tBOC happens to be a freak of nature (but we love him so/he's a freak of
nature but we let him go) who likes to take alkenes, make ketones and then
reductively aminate them (with legal ones, of course) so he decides to try this.

tBOC takes all of his safr... er... alkene, and distills it off and puts it into
his refrigerator. He then takes some H2SO4, 97%, and makes it into a 90%
solution and puts that in the 'fridge as well. Now tBOC likes to do things right
the first time so he doesn't have to do them again, so tBOC reads, asks
questions, reads again, and comes to the conclusion that one should hydrate
alkenes AS COLD AS POSSIBLE to ensure that the reaction occurs through an SN2
pathway, and not an SN1 pathway (i.e. cold, so one obtains the kinetic product,
no carbocation rearrangements.)

So tBOC takes his (not)safrole, puts 20g in a RBF with a magnetic stirrer and
puts the whole thing in an ice/salt/H2O bath. He then loads up a dropping flask
with 20mL of his chilled 90% H2SO4 solution and begins to add it to the alkene
at the rate of 1 drop per second. Once all the acid is added, he lets it stir
for another five minutes or so, then he loads up that dropping flask with 80 mL
cold water (about 3C) and adds this to the H2SO4/alkene at the rate of 1 drop
per second.

When all the water was added, tBOC throws the whole thing in a separatory funnel
and waits until it's separated. tBOC then pours out the water into a beaker, and
pours the top layer into a RBF with a magnetic stirrer, then weighs it. Minus
the tare weight, tBOC has _22g_ of his alcohol. Now, theoretical yield on this
process should have been 22.222g. Goddamn it, tBOC is pissed that he didn't get
that last 0.222g out of the reaction.

Oh well. To 20 grams of this alcohol tBOC adds 1.2 molar equivalents of ammonium
nitrate fertilizer, 4 mL glacial acetic acid, 1 mL H2O and a dash of cupric
acetate for flavoring. tBOC then heats gently on his heating mantle (about 25
out of 120) with a reflux apparatus in place, and takes 60mL water and adds 60mL
NaOH to it. Once this solution is made and cooled to room temperature, tBOC
removes the heat from the now yellow reaction mixture and cools this by first
running cold water over the outside of the flask and then by setting it in an
ice bath for about five minutes.

At this point tBOC notices A LOT of white solid at the bottom. tBOC wonders
about this, wondering if perhaps he had added too much NH4NO3 to the reaction.
Oh well, he thinks, and filters it off, takes the remaining reddish-yellow
liquid, and puts it into a sep funnel and adds a total of 9.3mL of his NaOH
solution to the yellow stuff dropwise. Two layers are clearly evident: a bottom
black yucky layer and a top yellow layer with just the slightest tinge of red.
tBOC pours off the bottom layer, then pours the top layer onto some silica sand
in a Hirsch funnel (carefully) and pulls it through with his aspirator. The shit
that comes out is nice yellow beautiful and smells like cardamon. tBOC hates vac
distillation, so he checks the solution with a TLC analysis using an 80/20
Et2O/hexanes mixture with 3 spots made on the same plate, a product spot, a rxn
mixture spot, and a product/rxn mixture co-spot. The rxn mixture spot is
homogenous, and the co-spot reveals that it is definitely not the starting
material. tBOC is happy now that he knows he can make a ketone from a terminal
alkene in a little less than an hour.

But the final score isn't in. tBOC weighs his product and sees that he has 19g.
Goddamn it. tBOC didn't get 100% theoretical yield-- again. tBOC is pissed. tBOC
consoles himself with the knowledge that he doesn't have to vac distill and that
20g of his alkene becomes 19g of his ketone in about an hour. tBOC guesses it
isn't all THAT bad.

Oh yeah, tBOC took that white crystalline stuff, smelled it, tasted it (smelled
like vinegar and ammonia and burned like a motherfucker) and threw some in some
NaOH solution. Ammonia gas boiled out of the solution... tBOC thinks that maybe
this impurity is ammonium acetate. tBOC finds this quite interesting since he
has some sodium cyanoborohydride lying around and just might want to make a
primary amine from a ketone someday. tBOC need to take melting point next time
and analyze to make sure white crap is ammonium acetate.

- - - - -

The reaction mixture was heated for at most 15 minutes. It ran very clean and
you could watch your alcohol turning color to that of the ketone. The color
change was complete within 5 minutes, so at most 10 minutes seem to be needed.
The only reason I kept heating was that there was a lot of white solid on the
bottom of the flask that wasn't dissolving. I thought that this might be
unreacted ammonium nitrate so I kept heating to see if anymore dissolved, or any
color change occurred.

- - - - -

As soon as the alcohol was made and weighed, it was kept cold (very near to 0C)
while adding the rest of the reactants. Reaction appeared to begin almost
immediately (i.e. evolution of a gas.) Gentle heat, not even really to reflux.
If you want to be picky you can monitor the progress with TLC, but I have had no
problems with this reaction going too far and getting too much bad shit.

Last rxn went so clean that after the 50% w/w NaOH soln wash spot was homogenous
to TLC, and it was NOT the same as the alcohol used, as evidenced by co-spot of
starting materials.

- - - - -

tBOC knows that ammonium nitrate can be used to make many secondary alcohols
into ketones (tBOC has oxidized many alcohols in this way in good yields, but of
course never MDP2Pol.) What tBOC (and maybe a couple other bees out there) wants
to know is if this can be used with the Al/Hg in situ MeNH2 production method of
recutive amination. Well tBOC found out, and maybe found out something else
interesting.

tBOC made 5g of a ketone. tBOC used the same procedure he's used before,
not-safrole to not-MDP2Pol and then 1.2mol NH4NO3, 1mol not-MDP2Pol, a couple
milliliters of acetic acid (80%) and a spatula tip of cupric acetate. Gentle
heating for about 15 minutes, followed by cooling under cold running water then
in ice bath followed by filtration of the solid and a single wash with 5mL 50%
NaOH solution yielded a yellow oil smelling sweeeeet like a ketone should.

tBOC starts amalgamating aluminum, puts his 5g of ketone in a sep funnel with
21g 35%nitromethane content racing fuel (as is, straight from package, no
purification of any kind) and shakes the two.

Once the aluminum had amalgamated well, tBOC pours off water, rinses the
sizzzling aluminum with some distilled water, and reaches for some ethanol to
put it in. Unfortunately tBOC doesn't have any. The only alcohol tBOC has is
n-BuOH (n-butyl alcohol, 1-butanol) so tBOC pour 75mL of this over the aluminum
in a 1L beaker and adds the racing fuel/ketone mix over the course of about 35
seconds. The reaction starts going crazy, so tBOC throws a wet rag over the top
of it and sets it in a spare bedroom an takes off to work.

tBOC comes back, finds the aluminum all dissolved, and throws in 300mL 50%NaOH
and dumps the whole thing in a sep funnel. Next morning tBOC pours out the
bottom layer and pours in another 300mL 50%NaOH solution and goes off to work.

tBOC comes back, pours out the bottom again, and filters the top layer (about
70mL of liquid) on a buchner funnel. tBOC then figures he'll do an acid base
extraction on it then crystallize so he checks pH (slightly alkaline: ~9-10) and
starts to add 30% HCl. A white solid started to crash out of solution almost
immediately, but tBOC keeps adding HCl until the pH is about 4, then filters off
the white crap and puts it in the oven to dry while tBOC separates off the
bottom layer of water from the n-BuOH and then smokes a cigarette.

tBOC comes back to find one solid chunk of white crystal in the oven, so he
weighs it. 4.1g. "Damn, that sucks. Should've been a whole hell of a lot more,
especially since I was soooo careful with monitoring this process," thinks tBOC.

Now tBOC has no way of taking a melting point, so he figures he'll just see what
a dab tastes like. tBOC puts a little on his finger and tastes it. Hmmmmm....
salty. BUT tBOC's fingers ALWAYS taste salty to him for some odd reason (don't
ask...please...) so he tastes it again. Yup, definitely salty. But it's not all
that salty tasting and it doesn't look like any salt he's ever seen. So tBOC
takes a decent chunk (about 50mg, maybe 70-80... not sure) and pops it on his
tongue. Yup, definitely tastes rather salty.

tBOC sets it aside, looks up properties of his amine-HCl salt and finds that it
is supposedly soluble in alcohol. Ahhhhhhh, maybe it's in the n-BuOH still,
thinks tBOC. Or it could be in the aqueous phase he just separated. tBOC pours
the water phase on a plate and sets it on top of his oven, which is cooking up
some po... er... brownies and tBOC smokes another cigarette while pondering what
to do and decides to distill off some nitromethane for next time while he tests
a small aliquot of the alcohol for the presence of amine by adding some CH2Cl2
and seeing if anything falls out.

So tBOC sets up his distillation apparatus, which for some reason is a lot more
difficult than he remembers it to be. He puts the distillation head on
backwards, plugs his mantle directly into the wall socket (without a variable
transformer in place) and wonders how that little elf on his coffee table got
into his house.

By the time tBOC gets the distillation apparatus set up he realizes he is
actually quite intoxicated and decides that playing with nitromethane wouldn't
be a good idea, so tBOC closes up shop and takes off for a very wonderful stroll
in the middle of the night, making it back to his place just in time to crawl
onto his roof and watch the most beautiful sunrise of his life.

tBOC goes inside and sees the plate has been sitting on his warm oven for a long
time, and has completely dried out, leaving behind a bunch of crap that looks
like table salt, laced with some kind of white powder. tBOC smiles to himself,
thinking that as soon as tBOC gets some more absolute EtOH he can dissolve the
white stuff in it, leaving behind the (supposed) table salt then add some Et2O
or CH2Cl2 or maybe even some n-hexanes to the alcohol to get out some more of
that wonderful little elf dust.

Success, thinks tBOC. And it's all OTC.

- - - - -

Alright. Since I FINALLY got a useable end product out of the whole
not-safrole-->not-MDP2Pol-->NOT-MDP2P-->MOST-DEFINITELY-NOT-MDMA thing, my
faith in the mechanism of Strike's whole H2SO4 hydration recipe is restored.
But a whole hell of a lot of things DID NOT WORK in the alcohol-->ketone stage.
Here's my thoughts on the matter, FWIW.

1) Cold is the key thing to keep in mind here. The colder the better. Remember
   that little bit about kinetic vs. thermodynamic product? It's fucking true.
   Keep your shit cold with salt/ice/water bath, add your concentrated H2SO4
   (I prefer 90%) COLD and SLOWLY and then add your water COLD and DROPWISE with
   GOOD STIRRING. Since I started using this procedure, I've noticed that my
   yields went way up from about 80% with just dumping hot water in to almost
   100% when adding water fresh from the fridge dropwise followed by a couple
   grams of salt to break up the emulsion. Which brings me to my second point:

2) Any oxidation done on the alcohol, in order to have half a chance of success
   must happen fast and cold. Numerous attempts with refluxing sodium dichromate
   in aqueous H2SO4 resulted in only 20-30% yield, and longer reaction times
   resulted in lower yields. In fact, everything that I tried at over 0C that
   had a reaction time longer than 10-15 minutes had horrible yields. So right
   now I'm scouring through references to cold oxidation methods to find
   something that will work on this lovely compound, preferably with a minimal
   investment.

3) The ammonium nitrate oxidation works, and works well. But it took SEVERAL
   tries to find the right proportions and work-up conditions. Also I personally
   have no intention whatsoever of scaling up the reaction to anything above 20g
   of ketone at a time. So something better has to be found. BTW: I found the
   original reference to this procedure: JACS Vol 70, page 3666 (1948).

4) A common problem is over-oxidation, i.e. the oxidizer used is too reactive
   and tears apart the O-CH2-O ring. Milder reagants need to be found. This
   actually makes research into new methods easier, as one can reasonably focus
   on only methods that are used to convert primary alcohols to aldehydes in
   good yields (MILD OXIDIZING CONDITIONS!!!)

5) Finally, a note on reactivity. The alcohol in question has a horrible
   tendency to migrate to carbon 1 due to electronic factors introduced by the
   substituents on the benzene ring. This thorn in my proverbial side actually
   turns out to be to my advantage when doing oxidations at cold temperatures
   because that same electronic influence makes the oxidation of this alcohol
   go a lot faster than it otherwise would.


- - - - -

First of all, let me congratulate piglet on his astute observation that one can
just use an excess of AcOH and not worry about the exact amount. You da man,
Piglet. When done this way, the ketone is just sitting pretty at the top of the
acid, and the whole reaction mixture is ready for a quick toss in the ol' sep
funnel. Then you just pour out the bottom and save the top. Pure to TLC analysis
and definitely suitable for most any further reaction you choose.

Now on to the fuckups:

tBOC was using 90% H2SO4 to hydrate the olefin to make his alcohol, and kept
ending up with a purple gunk that just sat there when he tried to hydrolyze it.
At most 10% of the olefin converted to the alcohol. After a couple failures,
tBOC thought it just might have been caused by the fact that his acid was old
and impure since it was slightly discolored, but decided to dilute down to 80%
and try once more. Even though his now 80% acid had a slight pink tinge to it,
when he added it to his olefin cold, he got a quantitative yield. Actually 100%
(+/- 1%) conversion to the alcohol. So from the several 90% acid attempts that
failed, and the two 80% attempts that got 100% yields, tBOC concludes that 80%
H2SO4 is the ideal concentration of the acid. 90% seems to be too harsh too our
precious MD-ring.

So, quick review: 90%- bad  80%- good .

Now on to the oxidation. tBOC, once he FINALLY got some alcohol made, weighs out
10g (not bothering to wash or purify in any way) and weighs out 10g of NH4NO3 (a
rather large molar excess, about 2 mol NH4NO3/mol alcohol) and combines these
two in a RBF in an ice bath. tBOC adds a pinch of Cu(AcO)2 and 30ml glacial
acetic acid (aldrich, guaranteed 99+%) and 5mL water straight from the sink. The
alcohol is now sitting on top of the acid and not much is happening, so tBOC
starts with the gentle heating. After about 10 minutes there is a definite
yellow tint to the top layer and acid phase which had initially turned slightly
brown is now entirely bluish-green. tBOC decides to let it run for an hour or so
and see what happens while he goes off to get laid.

When he comes back 1.5h later, tBOC cuts the power, cools down the mixture and
throws it into a sep funnel. After the layers have been sitting for a while (two
bong bowls and a cigarette) tBOC separates the two and does TLC analysis on the
top layer. THE SHIT COMES OUT AS ONE SPOT ON THE TLC. tBOC weighs it (10g,
qualitative... nice!!!) chucks it into the freezer (set to -10C, and it DID NOT
FREEZE, btw) and takes the acid layer, which is now the color of dirty pennies,
and tries to use it on a second batch of alcohol.

10g of alcohol and 10g NH4NO3 are added to the old acid solution, and the flask
is heated again. After 0.5h the whole thing is one dirty black color. FUCK!!
tBOC thinks this shit is screwed and tBOC is right. No pretty yellow layer on
top and tBOC has to resort to extractions with CCl4 to get out his yellow
ketone. Stripping off the solvent tBOC is left with that yellow solid everyone
almost had tBOC convinced he made the LAST time he tried this.

So, once with the acid in excess, and excess NH4O3: good . Second time: bad .
Got it? Good.

- -  - Reductive amination with Al/Hg + MeOH/BuOH + MDP2P + Nitromethane -  - -

Now on to the fuckups with reductive aminations. tBOC sets up two simultaneous
reactions, both with n-BuOH as the solvent using nitromethane reduced as the
in-situ amine source. Same scales with both, 0.25mol ketone with 0.40mol
nitromethane added to 40gAl/Hg in 650mL n-BuOH, only one is with 5g ketone,
the other with 15g. (tBOC forgets the actual weight amounts but knows he
calculated and weighed out these same proportions in each batch.)

The 5g batch runs smooth and clean, no problems. Adding 300ml 50%NaOH and
washing with water results in a nice clear top layer that spits out 4.6g white
crystals when acidified to pH 4 with 30% HCl. The 15g batch, however, instead of
having the yellow color of the ketone disappearing as the reaction proceeds,
starts to turn red and when the 50%NaOH is added after it cools, turns into a
black mess. No amount of washing, A/B extractions, etc, yields any product at
all. tBOC thinks for a minute, reads Shulgin's add-the-amine-in-yourself method
and notices one little phrase: Keep the reaction below 60C....

Well, goddamn. Maybe the 15g batch got a tad too toasty, thinks tBOC. So tBOC
takes another 10g ketone and instead of using straight nBuOH, he mixes it 50/50
with MeOH (with a much lower boiling point, should keep it cool enough, thinks
tBOC....)

And he was right. 10g ketone, same proportions of other reagants (with the
alcohol called for being 50/50 MeOH/nBuOH), dumped in shitloads 50% NaOH after
the reaction was done and it had returned to room temperature, washed with
water, titrated to pH 4 with 30%HCl and out drops 8.2g product.

So, tBOC has learned that once he has his safrole pure, he can put in about 3h
of work and get out up at least 8.2g (likely more) sweet honey crystals as long
as he keeps the following in mind:

At least 1.2 mol NH4NO3/mol alcohol and as much as an equal w/w amount. This
oxidation is actually a catalytic dehydrogenation with CuO as the active reagant
being generated in situ on demand by the NH4NO3.

Excess of AcOH: about 35mL of around 80% AcOH works great for 10g not-MDP2Pol.
Ya just gotta love the generosity of this reaction towards lazy people who hate
measuring shit out .

Keep final reaction cool. Use 50/50 mix MeOH/nBuOH and you should be fine. tBOC
SHOULD have known this, it's been repeated over and over again on this board.
But tBOC has a tendency to make the same stupid mistakes over and over again
without learning from them.

- - - - -        

I separate the not-MDP2P directly from the 80% AcOH. If I dilute with water,
I find that it tends to diminish the top layer, making separation a bitch,
requiring extraction, filtration, distillation, etc.

- - - - -          

In the not-safrole--> not-MDP2Pol stage, the H2SO4 is added at 80% concentration
direct from the freezer at the rate of about 3 drops/sec to the not-safrole
which is being magnetically stirred in a ice-water/salt bath chilled to -5C or
less. Then chilled dH2O is added dropwise at the same or a slightly faster rate
to the sulfate as soon as the H2SO4 is all in. Normally I just use a sep funnel
and as soon as the H2SO4 is all added just pour my water in the top then go
smoke a cigarette or two. Once all the dH2O is added, some salt is then stirred
in to help break up the emulsion. Yields are consistently 100%.


-------------------------------------------------------------------------------

