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IMPROVEMENT
for AL/Hg REACTIONS.
================================
RollWitMe (Newbee) 02-19-01 09:41 No 174315
High Temp Amalgamation
Not sure if anyone else has done this but SWIM this morning did. Added 0.4g
of HgCl2 to 750mL MeOH.
Stirred and heated until boiling. Let cool to ~55C. Added 27.5g Al. Basically
instant amalgamation. How does SWIM know it's amalgamation and not MeOH
boiling off of the aluminum. Well the aluminum is floating on top and the
solution is starting to turn grey. Immediately started dripping
Ketone/Nitro/MeOH 25g/20mL/50mL at a rate of 3-4 dps. Typical yield of 17-19g
on previous runs for SWIM, this one resulted in 22.5g. Might have been better
ketone, or maybe adding the solution to an already pissed off boiling
amalgamation helps boosts yields. Work up was done in the typical way, 35%
NaOH, extracted w/ Toluene, washed 4X w/ dH2O 1X w/ Sat'd NaCl. Rotovapped
down to 100mL. Dried w/ 30g MgSO4. Gassed, filtered, washed & dried.
Hoo-ray. I like to cook!
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Rhodium (Chief Bee) 02-19-01 13:24 No 174349
22.5g freebase or 22.5g hydrochloride salt?
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RollWitMe (Hive Bee) 02-19-01 13:44 No 174355
That's 22.5 of the salt. SWIM must admit that he wasn't prepared for immediate
amalgamation and had to run inside to go get the ketone out of the freezer
and run back losing valuable time. Next time SWIM will know better and have
everything ready to go before hand when starting it hot.
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Seillean (Newbee) 02-21-01 11:57 No 174709
RollWitMe - How many times did you have to gas to get the almost an ounce of
xxxx.hcl out of the 100ml toluene? I have heard that somebody has seen the
same amount gassed in about 500ml of toluene and that shit was thick, like a
milkshake, twice! Was the stuff fluffy or like flour when it was dried?
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RollWitMe (Hive Bee) 02-21-01 21:10 No 174788
1 gassing, took about 10 minutes of bubbling. the color is really white, but
the texture is like flour, kinda compresses packs easy. taste is definitely
right. measured dose definitely works. ran the same high temp amalgamation
again today w/ same results. im pretty pleased. I did notice one thing. when
doing it this way, all the aluminum does not react. Even using 500mg of hgcl2
for 27.5g Al. I only let it spin for 1.5 hours on top of that. Stinks like
MeAmine when I add the NaOH so on and so forth, workup is easy. gas inbetween
125-175 mL toluene. until it looks like a soda can of white gelatin material.
this seems to save time and boost yields for me, waiting to hear back from
others if they try it.
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sYnThOmAtIc (Hive Bee) 02-21-01 21:48 No 174793
Sure I know someone who could verify this but firtst he needs o know a lil
more. For one he has never done that al/hg with an addition rate that fast.
What were you using for a flask size wise and what kind of cooling setup
condenser wise?
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Antibody2 02-22-01 07:15 No 174866
Synthomatic - a 2l flask is ideal for that size amalgamation. It seems like
alot of flask but with the fast addition rate you NEED the head room. I've
seen it done with a 300ml west condenser w/ addition funnel atop the
condenser.
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RollWitMe (Hive Bee) 02-22-01 14:10 No 174934
Sure, once you get a nice rolling boil, add the aluminum, turn off the
outside heat. Wait about 1 minute and then start dripping your ketone into
it. 2L 3 neck flask w/ a 7 stage reflux condensor. Actually when running this
reaction pace, my condensor has never clogged, gurgled, choked whatever. When
starting the amalgamation at lower temps, you're dripping ketone nitro into
the solution and its not all reacting, so when it does get hot you have this
build up of ketone that reacts and gets the reaction out of hand sometimes.
This doesnt happen when you drip it in when the temp is already boiling. Nice
3 drips per second the entire time. Good yields, Less time. (30 minute
addition, 1.5-2h stir time.) Workup the usual way.
================================================================================
BENZOQUINONE
to KETONE
======================
RollWitMe (Newbee) 02-19-01 00:11 No 174253
SWIM dreamed up some Ketone this evening. I know everyone has seen this
before but SWIM just wanted to add a few things not listed on the normal
write-ups for people new to this ( like myself ).
120g p-Benzo
2g PdCl2
50mL H2O
400mL MeOH
All allowed to stir together for 2 hours in a 2L 3-Neck Flask w/ low heat to
ensure everything is in solution.
An egg-shaped stir bar works best for RB Flasks. ( Of course I dropped one in
and it fell right through the bottom of my Flask the first time I ever did
this. Oops. )
In a 250mL addition funnel was placed 150g Alkene w/ 50mL MeOH.
This was mounted and started dripping while a 9 stage reflux condensor was
placed in another neck.
Addition was made over a period of 45 minutes while a decent reflux was
attained.
Stirring proceeded for 6 hours with heat on, allowed to spin for 2 additional
hours while cooling.
While cooling 1500 mL of 5% NaOH was made up and allowed to stir.
Also 1.7 L of 1N HCl was made.
It says to filter the entire mess, I say skip it, who cares. Wastes time and
product if you ask me.
Dump your solution into the HCl. Using a 4L beaker works best, throw in a
stir bar and let it spin in the HCl for a few minutes and then dump 500mL DCM
and crank the stirring again for 5 minutes ensuring really good mixing. Turn
off the stir bar and let settle for 15 minutes. Decant as much of the top layer
as you can and then dump the rest into a sep funnel to seperate the rest.
Wash your DCM layer 2x w/ Sat'd Sodium BiCarb.
I think we all know about the crap ( looks like frog eggs/gunk/green apple
splatter etc) that forms in the middle. Well it contains a lot of product so
make sure you keep it w/ the DCM washes.
Wash your DCM layer 1x w/ Sat'd NaCl.
Same thing, don't throw away too much, if it has a strong methylene chloride
smell it most likely has some goods still in it. Save your washes to extract
once in the end.
Wash your DCM layer 3x w/ 5% NaOH
We all know the first wash is really dark black, also the middle gunk layer
is becoming smaller w/ each NaOH wash. After your 3rd wash, combine all
washes in the 4L and extract 1x w/ 100mL DCM. Turn the stirring on full tilt
for 5 minutes. Your final DCM wash will be a lot lighter then all the washes
and easy to decant/seperate. After the last wash throw 50g anhydrous MgSO4
and filter. Distill off the DCM w/out Vacuum and save for a later day. SWIM
has 2 vac pumps, one that boils Alkene at room temperature and is more
powerful then SWIM can find a use for until he gets a bleed valve for it. The
other ones boils alkene at 92C and knows to watch for ketone @ ~ 130C. Well
only 2 drops of unreacted alkene came over at ~95C and then a neon green (
very pretty, SWIM first tone runs were darker yellow w/ only slight green
undertones compared to this which was practically glowing flourescent green )
fluid came over @~138-145C and amounted to ~100mL's which is roughly 110
grams. The previous darker tone aminated @ ~ 60 % molar yield so SWIM expects
this to be a little better.
Anyone have any other findings they'd like to share that I missed. I do think
that not filtering and using less washed helps w/ yield a lot. Let me know if
anyone else dreamed up something different. Peace.
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noj (Hive Bee) 02-23-01 11:45 No 175082
I've noticed the problem with filtering too. The first nap I took using a
reflux on the wacker I placed in freezer overnight, and alot of the
hydroquinone became immobilized on the bottom of the flask. Maybe that would
help out.
Also, the color of the ketone. I see posts mentioning that a lighter yellow
color is better than the deeper flourescent color. Having only had a couple
successful dreams, both a dark yellow flourescence and a pale lemonade color,
I noticed the roll was slightly milder with the color being pale. Whereas
when it was deeper, 140mg left me on the floor for about 30 minutes reveling
in the intricate textures of the carpet, unable to stand up.
Anyone know what influences the color of the ketone?
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RollWitMe (Hive Bee) 02-23-01 13:22 No 175096
Yeah could anyone fill in about the ketone color variations? What is the
exact color of 100% pure MD-P2P?
I've also had a palish yellow w/ green tones, a dark yellow w/ green tones
and a fluorescent green w/ no yellow tones in sight. All aminated fine,
texture of product varied but that's just from gassing and recrystallization.
Any input?
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terbium (Hive Addict) 02-23-01 13:28 No 175098
Pure MDP2P should be a pale yellow.
LT/ :
no, it is blank like water, when you discharched the first and last few ml of
your distillate. If you keep it under a N2 atmosphere in a tightly closed
bottle, it will stay that way. Leaving it open to the air for too long will
give it that pale yellow color.
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RollWitMe (Hive Bee) 02-23-01 13:42 No 175099
Pure yellow with no green at all? Weird, cause i swear this stuff is like
neon green. I even distilled it twice which I was real hessistant to do
because of decomposition worry. Well it works so I guess I can't complain.
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LT/
: Vacuumfilter the green oil through very fine active coal a few times, that
should leave you with pale yellow ketone. If not, try after that simply to
wash your green ketone with warm distillated water and separate the water and
dry the clean ketone with NaSO4 or silicagel or MgSO4.
Test a small portion of your green ketone for platinum rests by acidifying
with HCl and adding a few drops of stannous chloride solution : a yellow or
brown colour develops according to the quantity of platinum present. The
yellow colour is soluble in ether, thus rendering the test more sensitive.
The dilute HCl will render the green colour allready to a much paler colour,
so you can see the difference in colours easily.
================================================================================
P2P
KETONE FROM EPHEDRINE(-TABLETS or BULK)
===========================================
(Translated
by LT/)
Bwiti (Hive Bee) 02-16-01 19:27 No 173860
What's up folks?! Last night I was poking around a patent database when I ran
into an interesting P2P synth. Here's why I think this patent would be useful
to evil chemists: Someone can scrounge up a shit-load of pseudoephedrine from
cold pills, or ephedrine from ephedra powder, but the hard part is obtaining
RP. Who wants to scrape RP off of match-books? Fuck that! I did my best to translate
the patent, but it still needs work. Anyone here good with german? (LT/: I
did)
------------------------------------------------------------
------------------------------------------------------------
Procedure
for the Production of Phenylacetone (P2P).
Patent # : DE3200232
(addition for patent application P 30 26 698.9-42)
The invention concerns a new arrangement of a procedure for the production of
phenylacetone.
The subject of the principal patent (patent application P 30 26 698,9-42) is
marked as a procedure for the production of Phenylacetone from Ephedrine by
sulfuric acid (H2SO4), by the fact that one executes the conversion to P2P
with 50-70 % acid at 150 to 155*C and in the presence of 0,02-0.5 %
zinkchloride as a catalyst and that one continuously distillates the formed
Phenylacetone out by means of steam distillation, directly from the beginning
of the reaction.
It was now found that one can execute the conversion also in the presence of
0,05 to 0.3 % of other metalchlorides in place of 0,02 to 0.5 % zinkchlorid.
As other metalchlorides are suitable Iron(III)chloride and in particular
aluminumchloride, borontrifluoride and Titan(III)chloride, which are used as
Lewis acids in organic chemistry.
The concentration of the sulfuric acid is selected in such a way, that it
amounts to a content in the reaction mixture of 50-70 weight %.
The reaction runs particularly well with a weight/weight(w/w) sulfuric acid
content from approximately 60 %.
For the continuous discharge of the Phenylacetone from the reaction mixture,
water vapour is initiated into the mixture, which removes the developing
Phenylacetone immediately from the mixture.
The received distillate is extracted with toluene and the latter is removed
by distillation. Thus one obtains Phenylacetone, whith a purety of
over 99,5 %.
For a source of Ephedrine comes Ephedrine, Pseudoephedrine, Norephedrine and
Norpseudoephedrine as well as Bis-(1phenyl-2-methylaminopropyl1)-ether
in consideration, whereby the reactionmechanism for such Ephedrines is
particularly important, no direct results for so far for (-)-pseudoephedrin
and (-)-norpseudoephedrin. The Ephedrine preferably is used in a
weight/weight ratio of approximately 1:1 to 1:10, preferably 1:2 to 1:5
compared to the acid.
The yields, which can be obtained with the new procedure, are within
the 80 % range. The procedure runs at a relatively high rate/min.
A further advantage of the procedure consists of the fact that it can be
executed continuously . Thus one can let a hot aqueous solution of the
Ephedrine of choice flow into the hot acid, whereby the
Phenylacetone/Water azeotrope continuously gets distillated out. Here it is
only necessary, to remove the developing ammonium salt, e.g.
methylammoniumhydrogensulfat occasionally.
The use of the mentioned metal halides in place of ZnCl2 offers advantages
regarding environmental protection, because these are more harmless and do
not disturb the biological reduction of the waste water.
Example
1
1025 g 75 % sulfuric acid are mixed with 2 g AlCl3. In there one dissolves
426 g (= 2.58 mol) Ephedrine or Pseudo-ephedrine derivate from 50-100*C.
Subsequently, the mixture is heated up to 145-150*C. At 125*C steam in
moderate current is introduced in the fluid for better mixing. At 145*C one increases
the steam introduction and distills in a period of 2 1/2 to 3 hours the
Phenylacetone/Water azeotrope over. From the distillate one isolates by
toluene extraction the raw Phenylacetone, which is free from Propiophenon.
After distillation with a short Vigreux reflux column attached also, one
receives Phenylacetone, yield 270 g (78%)with a purity upto 99.8 %.
One gets similar yields from Nor-ephedrine or Nor-pseudo-ephedrine for
Phenylacetone in a yield of approx. 80 %.
Example
2
In 1000 g 79 % sulfuric acid, an amount of 100 g (-)-Pseudoephedrin-derivate
gets dissolved, whereby the H2SO4-concentration is adjusted to 65 to 66
weight%. This solution is poured into one of the necks of a three-neck
roundbottomflask, mixed with 4 g AlCl3 and heated up to 125-130*C.
By injecting steam, one increases the temperature to 145-150*C and keeps it
going in a steady rate from now on with a flow-rate of approximately 1 to 5
g/min.
The 70-90*C warm solution of the (-)-pseudoephedrin(derivate) mixed with
79 % sulfuric acid solution(weight ratio 1:1) is added by means of a
steam-heated dropping funnel. The Phenylacetone turns thereby into an
azeotrope and is similar to example 1 regenerated.
In both cases, after 4 hrs, the reaction is interrupted for 5 minutes and
during that 5 minutes there is so much sulfuric acid removed that the
original volume is re-created. Then the reaction is continued. The removed
sulfuric acid can be re-used after one removes the
methylammoniumhydrogensulfat developed during the conversion. The yield of
Phenylacetone amounts to 76 %.
Example
3
1350 g 79 % sulfuric acid is added through a reactionflask neck and mixed
with 590 g 95 % (+)-Ephedrine.
10 ml 18 % TiCl3 is added subsequently, the solution mixed and the mixture
heated to 125*C, and then heated to 145-155*C with steam, the distillate
collected, from which by toluene extraction 358 g Phenylacetone were
isolated. From this, 335 g = 73.6 % yield of Phenylacetone, with a purity of
99.5 % was collected by fractionated distillation over a Vigreux column.
Example
4
In 1350 g 79 % sulfuric acid is dissolved under agitating 561 g d-l-Ephedrin
(99-100 %), mixed with 15 g BF3 / glacial acetic acid solution (10 %) and
heated to 125*C.
One injects steam and increases the temperature thereby to 145-155*C whereby
developed Phenylacetone is collected. After approx. 6 L steam distillate is
collected, the conversion is terminated. One isolates 386.4 g Phenylacetone
from the distillate by toluene extraction and distillation. From this, 367 g
(80.6 %) pure Phenylacetone is collected .
Example
5
To 400 kg 60 % sulfuric acid added in a distillation apparatus, 500 kg of 80
% sulfuric acid are being gear-pumped. Added to this mixture is 400 kg
(-)-pseudoephedrine (60 %) under mixing, and 1.5 L aluminum chloride solution
(30 %) introduced. One heats the reaction mixture to 125-130*C and introduces
then steam, while increasing the temperature to 145-150*C ,
whereby a mixture of steam/Phenylacetone distills over. After approx. 2000 1
steamdistillate is collected, one terminates distillation. From the
distillate the lower heavy oil phase, consisting of Phenylacetone, is
separated and the aqueous phase is extracted with approx. 400 1 toluene. The
separated Phenylacetone and the toluene extracts are combined and
concentrated by distillation. The remaining arrears are afterwards
fractionated distilled. One receives pure Phenylacetone to 155 kg (80 %).
------------------------------------------------------------
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terbium (Hive Addict) 02-17-01 07:42 No 173956
Re: P2P via German Patent.
That is a great find now that red Phosphor(rP) is so hard to get. P2P from
OTC reagents! The methamphetamine would be racemic but it sure beats scraping
matchbooks to get rP.
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foxy2 (Hive Addict) 02-21-01 12:35 No 174715
How would one produce anhydrous Lewis Acids?
Can hydrated FeCl3 be dehydrated in any reasonable way?
Would anhydrous HCl gas and dry iron fileings be the way to go?
------------------------------------------------------------
uemura (Hive Bee) 02-21-01 12:53 No 174719
Would anhydrous HCl gas and dry iron fileings be the way to go?
Think so, at least Gattermann-Wieland uses this to get anhydroneous AlCl3
from Al and HCl.
------------------------------------------------------------
PolytheneSam (Hive Bee) 02-21-01 16:34 No 174755
You can get anhydrous FeCl3 from some electronics companies. Its mixed with
water and used to etch printed circuit boards. I have a mail order
catalog around somewhere that has it in.
------------------------------------------------------------
terbium (Hive Addict) 02-22-01 15:49 No 174948
But according to the patent you would not seem to need anhydrous materials.
Steam is injected into the pot as the reaction is proceding in order to steam
distill off the P2P as it is formed. The patent even talks about doing this
as a continuous process where ephedrine is also continously added.
It seems to me that hydrated aluminum chloride should work just fine. Also,
zinc chloride in most any form should work.
------------------------------------------------------------
jim (Chem_Guy) (Newbee) 02-23-01 09:16 No 175060
I found a similar article quite a while ago, but it didn't mention any
yields. I am glad to find out that the yields are respectable.
My suggestion is: Don't steam distill, it will complicate things.
Take the sulfuric acid and ZnCl2, put into flask. Heat and add the
crude ephedrine pills. The ephedrine turns into P2P, the fillers are
chewed up. Extract with nonpolar like toluene after reaction has run
its course and cooled down. Use P2P in any fashion you like to get
racemic amphetamines.
------------------------------------------------------------
COMMENT:
For
those of you who have access to bulk amounts of pure ephedrine, like in asia,
from MaHuang, this is the preferred way of making P2P in continuous big scale
operation there.
Steam distillation is then preferred.
After that, you convert the P2P with the OnePot Meth ICE method to racemic
d,l-methamphetamine, and with the help of d-tartaric acid, convert that to
d-methamphetamine, and l-methamphetamine.
Or use hydrogenation techniques. LT/
WISDOMwillWIN
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High
yielding iso-safrole to 3,4 methylenedioxyphenyl-2-nitropropene procedure.
By
Antibody March
2001.
Having had a few successful dreams while synthing TMA2 from asarone and PMA
from anethole via the pseudonitrosite route, Antibody was delighted to find
that iso-safrole suffers from none of the yield limiting factors suffered by
either asarone, which easily polymerizes during nitration or anethole whose
pseudonitrosite is difficult to hydrolyse in satisfactory yields. In two
consecutive reactions with iso-safrole near quantitative yields of the
pseudonitrosite were obtained. Its pseudonitrosite is also more stable during
hydrolysis. The hydrolysis method outlined below is gentler than that in
common usage and was inspired by a Weiland ref that Uemura came up with and a
re-read of TSII.
1. Nitrosation
of iso-safrole.
A 2l rb flask is charged with 2.5M NaNO2 (173g ) in 250mls dH2O. The flask is
placed in an icebath and the NaNO2 is dissolved with mag stirring. 0.5M
freshly distilled [1] iso-safrole(89g***) was dissolved in 900mls diethyl ether (distilled from
Zerostart starting fluid). This is added to the flask. A pressure equalized
dropping funnel charged with 1.25M H2SO4 in 500mls dH2O is placed in the rb
flask. A hose is attached to the top of the funnel leading outdoors [2].
After the content had been allowed time to cool, the H2SO4 solution was
dripped in over 6 hours time, with slow mag stirring, ice being replaced as
necessary. Flask was then allowed to sit for an additional 9 hours while ice
was allowed to melt. During this step, a 6-7cm layer of white spongy
precipitate will form at the interface of the two layers.
The dropping funnel is removed, and the reaction mixture is stoppered, and
shaken vigourously, with care being taken not to break flask with mag stir
bar [3]. The entire content is gravity filtered using coffee filters and a 2l
gasoline funnel. The etheral layer and the aqueous layers are saved for later
[4]. The filter cake is then scraped into a 2l beaker containing 1l dH2O and
stirred with a spoon for a couple of minutes. What will happen is that all
the NaSO4 will settle at the bottom, while all the pseudonitrosite will float
in suspension. The water is decanted with the suspended pseudonitrosite from
the NaSO4 which can be saved for other uses if desired.
The water layer with pseudonitrosites is vacuum filtered and washed with
additional dH2O. The filter cake can then be washed 2X with EtOH (ethanol)or
more expediently the filtercake is then dropped into a beaker containing
200mls EtOH and stirred thouroughly, and then vacuum filtered.
Yield 0.49M pseudonitrosite (from iso-safrole 98%***) (127g) as white crunchy
granular nuggets. [4]
Hydrolysis
of pseudonitrosite.
A 2l beaker sitting in an ice bath is charged with a mixture of 0.5M KOH (28g***) dissolved in 700mls EtOH. When
mixture has reached 10°C the pseudonitrosite is added portionwise over 10-15
minutes with care being taken not to allow temperature to exceed 20°c. The
solution is mag stirred vigourously until all pseudonitrosite has gone into
solution. While this is stirring prepare 500mls of 2M aqueous HCl (approx
105mls 31% HCl and 395mls dH2O) and refrigerate. When all the nitrosite is in
solution it was vac filtered and the filtrate returned to the ice bath and
one tray of ice-cubes is added and the whole cooled to 5°C. Then as 500mls
cold dH20 is added slowly the solution goes from an umbra to an ochre
color,the chilled dilute HCl solution is added as a tiny stream to the
stirring solution over 5-10 minutes. During the addition the solution
becomes cloudy and most of the ice melts. The entire mixture is poured into a
4l wine jug containing 2l dH2O. And the entire mixture is refrigerated for a
couple hours. During which time the entire jug will transform into a bright
yellow crystal matrix, and probably a brilliant yellow bottom oil
layer, which is also the nitropropene in oil form. The crystals and solution
are decanted from the oil layer and vac filtered, the filtercake is dissolved
in 300-400mls boiling IPA (isopropylalcohol) to which the yellow oil layer is
also added. Agitate until all is in solution, then allow to cool slowly [5]
to room temperature when it may be refrigerated for an additional hour to
complete recrystalization. Then vac filter, wash filter cake with dH2O,
and place in a stoppered filter flask charged with dry silica gel and attach
to low vac (fridge compressor) overnight to desicate.
Yield 0.36M 3,4 methylenedioxyphenyl-2-nitropropene 73% (80g***) as bright yellow needles with
the texture of compressed glass wool insulation.
Overall molar yeild 72%***.
*** ATTENTION!
The assumed molecular weight of safrole (178g/mol) is actually the molecular
weight of MDP2P!!!
Safrole is 162g/mol!
89g safole are (89/162)=0.549 moles, not 0.50 moles! Yield of 127g=0.533mol
pseudonitrosite means (0.533/0.549)=97%. Somebody better recheck those
numbers again. 
Fester Fiend
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