|
|
|
DETAILED METHODS for NON-CHEMISTS
LIST of SYNTHESIS :
I.----- Sassafras rootbark -or- (chemical synthesis)--> SAFROLE.
II.---- SAFROLE--> IsoSAFROLE--> MDP2P ketone--> MDMA , MDA, MDEA.
III.--- Lowpressure Catalitic Reduction--> P2P ketone-->
METHAMPHETAMINE, (METH, ICE).
IVa.-- 2,5-Dimethoxybenzaldehyde + PTC (PhaseTransferCatalist)-->
Nitrostyrene-->
2C-H (2,5-DMPEA , 2,5-dimethoxyphenethylamine)-->
2C-B and many more highly interesting unexplored 2C-(X) analogs,
-or-
IVb.-- PEYOTE-Cactus--> MESCALINE--> MESCALINE Nitrostyrene-->
2C-H--> 2C-B etc.
V.---- 2C-B a la Lycaeum.
VI.--- AMPHETAMINE PRECURSORS CLEANING/WORKUP.( The Cure)
VII.-- EPHEDRINE to METHAMPHETAMINE + RP/I2.
VIII.- SIMPLE HCl GASSING/BUBBLING APPARATUS.
IX.--- NITROMETHANE --> MDMA.
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
INSTRUCTIONS for NON-CHEMISTS - :
METHODS :
I.----- Basic-Extraction -or- Supercritical-Extraction-->
Steam-Destillation.
II.---- Fractional destillation--> Aliquatt336+KOH (a la Osmium)-->
Classic Performic (a la Ritter)--> Al/Hg
(a la Osmium) -or- NaBH4 reductive amination (a la LaBTop) -or- lowpressure
reduction (a la KrZ).
III.--- Lowpressure hydrogenation (a la KrZ)--> Destillation-->
Reductive Amination NaBH4 (a la LaBTop) -or-
low pressure technique (a la KrZ).
IVa.-- Addition + PhaseTransferCatalist (a la Rhodium and Beaker)-->
Lowpressure Catalitic Nitrostyrene
Reduction (a la KrZ) or Beaker's synthesis--> --> Addition (a la
Shulgin).
Or 2C-B synthese a la Lycaeum .
-or-
IVb.---- Supercritical-extraction -or- (chemical synthesis)-->
Nitrostyrene synthesis (a la Rhodium)-->
Electrochemical Reduction (a la Uncle Fester)--> Addition (a la Shulgin).
V.------ 2C-B a la Lycaeum.
VI.----- AMPHETAMINE PRECURSORS CLEANING/WORKUP.( The Cure)
VII.---- EPHEDRINE to METHAMPHETAMINE + RP/I2.
VIII.--- SIMPLE HCl GASSING/BUBBLING APPARATUS.
IX.----- NITROMETHANE --> MDMA.
**And anything else found economical interesting for the creative home
brewer**
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
METHODS merits :
First of all :
Dr. Alexander Shulgin : No need for words, the greatest !
Paul Nels Rylander : for his extensive work on practical hydrogenation
techniques. Hat off !
Strike : For creating this place, and giving a wealth of information in her
books. A big hug ! (Still did not
received your books, how come?).
Eleusis : For starting a really interesting discussion in the early days of
this board, ultimately costing him his
freedom.
The Lycaeum : For sheltering this place for so long allready, against
mainstream US policy, and not interfering
with our freedom of speach.
Second:
Overall methods :
Rhodium, Osmium, Rev drone, Labrat, Cesium, Spiceboy, Ritter, Beagle boy,
KCN, Station, Sunlight, Sumerian,
Gyrogearloose, iudexk, Ymir, Methyl Man, Psychokitty, Chem_Guy, Bankrobber
(and some more, fill them in
later).
Hydrogenation :
KrZ (mainly !), Rylander, pHas3d, Titanium, Equarius (and some more, I fill
them in later).
Electrochemical Reduction :
Uncle Fester (mainly !), Dwarfer, Worlock, WizardX etc.
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
SAFROLE:
Materials :
Same as for IsoSafrole.
Chemicals:
16-18 L non purified safrole oil 70-90% pure.
20 L industrial Silicone oil or Peanut oil for oil-heatingbath.
+++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++
Method :
S1. - First you have to clean your safrole oil by fractional distillation.
S2. - This means that you separate different fractions of your impure reagens
fluid (safrole here), those
fractions will have different boiling points. That way you split the
impurities from your desired oil.
S3. -You start heating up your impure Safrole and let it first come to a
steady constant boil at the first temp
where this will happen, under your vacuum, reached by your vacuum pump; keep
the temp at that point until
no more fluid comes over in the collecting flask, put that aside after
releasing the vacuum, put the
cleaned/dried collecting flask on again, and put vacuum on again, and then
slowly incline the temp until boiling
starts again, repeat as many times that you reach different boiling temps (at
least 5 C apart from eachother).
S4. - You will at a certain temp (here ~ 130-145 C , depends on the strength
of your vacuum), get the
biggest fraction, which is safrole, and the other fractions will be only very
small. These other fractions can
be used ~ 5x again in next batches (see below at S8.).
S5. - If you use a 22 Liter 3-neck flask for it, and you don't have a big
magnetic stirrer, you must use boiling
chips in it, about 1 % oil-volume procent, so for a ~3/4 filling = ~16-18
liter filling (never use more then ~3/4,
or fluid, not vapour, will boil into your condenser) you need 160-180 ml
chips roughly (~).
S6. - Measure them in a measured beaker in ml volumes, don't worry about the
loose spaces between them.
S7. - If you use a magnetic stirrer bar ( MUCH better!) and an aluminium pan
as an oilbath, filled with
peanut- or silicone oil, so you can use the stirrer, because the pan is from
aluminium ( stirring strong and big
enough), then there is no need for boiling chips, they would even damage the
flask in one run. They would
work as a grinding machine on the innerside of the glass flask, together with
the big magnetic stirbar; or if
you use a overhead stirrer, like a variable speed drill, or a non-sparking
induction electro-motor; together with
the stirrer propellor.
S8. - Any for-or after-run(s) at a temp more then 5 degrees C different from
your main safrole body, you must
throw back in the next 16-18 L safrole batch you start up after some day(s).
After 5x doing this, you throw
both away, it's more rubbish then safrole by then. You re-use these fractions
5x because they allways will still
contain some pure safrole oil.
S9. - Pure safrole oil is light yellow and smells a bit sharper sweet then
the ketone, MDP2P
(MethyleneDioxyPhenyl-2-Propanone), which has a much softer sweeter smell and
is a bit more yellow then
the pure safrole; if you work perfect, the pure safrole and the pure ketone
will have no color at all, and the
ketone will be a bit more syruppy (thicker) then the safrole.
S10. - Safrole can be fractionally distilled at ~130-140 C temp using a new
refridgerator pump(as your vac
source, 1/8 horsepower, buy them from a fridge repair shop, $120) or a normal
oil-filled vacuum-pump or much
better: use allways a diafragm-vacuumpump, no oil which can and will be
contaminated every time you use a
oil filled pump, so it looses its vacuum-power; and standard glass
distillation setup with a 40-60 cm icewater
cooled fractionating/reflux-condenser and using a 22 L roundbottom flask
hanging in an oilbath filled with
peanut oil or better silicone oil as an egally heating source, and a big
collecting flask.
S11. - Under the aluminium oilbath you would use a magnetic stirrer/heating
plate with enough electrical
power/watt's. Don't let the 22 L flask touch the bottom of the aluminium pan,
keep it ~1 cm above the
bottom, to prevent extreme hot-spots which could decompose your safrole or
ketone.
S12. - Grounded standard glass-connections/fittings should allways be used on
your distilling glassware.
S13. - Cold circulating water for the condenser comes via 2 tubes (one
hanging loose at the water level in the
icewater bucket) from an aquarium water-pump (expensive ones 70-80 dollars,
cheap ones 10-20 dollars),
submersed in a styrofoam isolated bucket or drum filled with ice cubes in
water, which you re-new from time
to time.
S14. - Distillation generally takes 4-5 hours depending on size, and heat
applied. Always a good idea to
insulate the fractionating column, and 22 L flask-neck with the
condenser/refluxer on it; with heavy duty
aluminum foil. Just wrap it around all the glass parts. Make ~1 cm2 holes, 5
cm apart from each other, in the
aluminium wrapping then, to see what happens inside the glass parts.
S15. - The main safrole oil body (ca. 15.5-17.2 L), which boils (at~ ~130 C)
and comes over at your vacuum
( should be 20 mbar or lower), you collect to proceed to make:
=================================================================================
ISOSAFROLE (Aliquatt336/KOH method) :
Materials :
1--Magnetic stirrer/heating combi plate + minimal 1 big magnetic eggshaped
stirrerbar, to use in roundbottom
flasks, and 1 straight one, for flatbottom flasks.
or:
1--Kg boiling chips. (Pumis-stones, crushed raw flowerpot pieces, crushed raw
porcelaine, cat-litter).
and :
1--22 L round-bottom, 3-neck, glass vacuum-flask with 3 standard grounded
neck- fittings.
1--portion High-vacuum silicone-grease (Merck f.e.), to thinly grease all
grounded glass-fittings, allways both
male and female grounds.
1--Still head, to connect one of the grounded necks of the 22 L flask to the
grounded inlet of the
condenser.
1--40 to 60 cm glass condenser, preferably the one you see with ~ 8-12
glassballs blown inside ( for use as
reflux condenser).
1--big enough (min. 5-10 liter) collecting glass-flask with standard grounded
fitting.
1--Vacuum glass-alonge with male and female standard grounded fittings and
vacuum-tube fitting.
1--Vacuum tubing, 3 meter long, shorten it to the minimal length from alonge
to pump, must fit tight on the
alonge and the vacuum pump. The shorter, the better the vacuum. The remaining
part you use for your
aspirator vacuum, you will use it for volatile solvents removal/recovery.
1--Water driven PTF, Nylon or PVC vacuum aspirator, connected to a water tap
with sufficient pressure and
cold enough water, to use in case of electrical power failure and for
evaporating low boiling vapours, f.e.
methanol, acetone, dichloromethane etc. Never use an oil-filled vacuumpump to
do that. A diafragmpump can
do it, but why should you take the risk of damage to your expensive pump,
when you can use a $40 aspirator
for simple solvents evaporation ?
1--Big thinwalled flatbottomed aluminium pan, to fit the 22 L flask in. Buy
it at a chinese restaurants supplier-
shop.
2--Glass or digital thermometers, -30 to+300 C, one to use in oilbath or
icebath and one in the flask-neck,
long enough to reach the fluid inside. The best would be to have another one
with small grounded glassfitting
in a 2-neck Claisen type still-head setup between the 22 L flask and the condenser,
to measure vapour temps.
This is not directly necessairy, but is handy to see if the vapour temp
suddenly varies, that means you have
to put vacuum off and collect that last fraction, because the next fraction
is coming.
1--10 L jerrycan with peanut oil or better silicone oil (the big oil-company
brands suppliers have it, such as
Exxon, Shell, Mobil).
4--Big lab-stands with 8 lab-clamps to rig up your distillation setup.
1--Big bucket or drum, isolated with styrofoam or insulation blankets used in
building industry, to use as
ice-water circulating tank for the reflux/condenser.
1--Aquarium or fish-pond water-submersable circulation pump in that bucket or
tank..
1--5 meter long water tubing, cut in half to fit the condenser and the
watertap or circulating pump.
1--Multiple (6) electrical connections box with main ON/OFF switch. Panic :
all electricity OFF.
1--Fire-extinguiser, for those unlucky moments. CO2 or special chemical-gas
filled one. Better not a powder
filled one, you will find out why, when you have to clean that stuff.
1--Drying oven, up to 350 C. old household-one sufficient enough, preferable
electric. Gas burning type gives
off water vapour and an open flame is not safe in a lab environment.
1--10 L filter flask, heavy walled, with vacuum side-adapter fitting. With
some creativity you can use a big
thickwalled glass Chianty wine bottle with a 2 hole stopper, one hole for the
Buchnerfilter and one for the
vacuum.
1--5 Liter (~) PTF or PP or PE or PVC or porcelaine or glass Buchner funnel.
1--Set of commercially sold rubber V-shaped rubbers in different sizes, for
Buchner and to fit in mouth of
filterflask.
1--Pack of round filterpapers, to fit nearly exact in the Buchner filter
funnel. Attach the filterflask fitting to
the tapwater-aspirator-vacuum pump for a safe vacuum.
1--~20 L clear plastic carboy used in drinking water utilities : ( to use as
a self constructed separator-funnel :
cut a 5 cm hole in the center of the bottom to use as filling opening, which
you can close later with a 5 cm
rubber stopper, so must be nice round, and push firmly a big rubber stopper
with a center hole, in the
excisting mouth at the top of the carboy. Fix the stopper with iron wire, so
it can never plop out, or safer,
use any clamp which fits the mouth of the carboy and covers the stopper
~half. Push a tight fitting glasspipe,
with a glass-valve attached to it with a small piece of silicone-tubing which
tubing you strap with those nylon
straps used in car-repairshops, into the stopper, not extending above the
other end of the stopper. Voila !)
4--25-30 Liter PTF or PPP or PE plastic jerrycans, cleaned and dried.
1--Box of heavy duty Reynolds wrapping aluminium .
1--Big steady lab table with a vinyl, or the like, coating.
2--Comfortable chairs, to sit in during those long waiting hours.
1--Small TV with antenna. Less entertainment-greedy persons can help
themselfs with a ghettoblaster
radio/tape-recorder/CD-player.
1--Pile of Playboy's, Hustler etc. or a big vibrator, also very handy to
separate layers in your home-made
separator funnel ! Just keep it tight against it. Must be ON then. It
vibrates the oil out of the fluids !
Chemicals:
15.5-17.2 L purified safrole oil >98% pure.
5.611 kg KOH flakes (~98%, industrial grade)
1 kg Aliquatt336 (Methyl-tri-octyl-ammonium-chloride) ~>98% pure, from
Merck or Fisher etc.
3 kg Florisil (=magnesium silicate=CAS 1343-88-0 )~>98% pure.
5 L DiChlorMethane ~>98% pure.
1 kg pack of silicagel beads 2-5 mm from Merck, Fisher etc.; or 1 kg
MgSO4.7H2O industrial grade.
5 L Silicone oil from Shell, Exxon etc.
Tapwater (H2O) from your government, and lots of ice cubes or blocks .
+++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++
Method :
I1. - If you have any doubt that your now pure Safrole oil is not dry, so has
some water in it, first dry it by
shaking or mixing in your 22 L flask (or a suitable 20 L jerrycan) with a
stopper in all necks at least 1 hour
with 5% weight/weight silicagel beads or MgSO4.7H2O which are both first
dried in an oven for 3 hours at
250 C. Then decant(in case of silicagel) or filter the MgSO4 off and proceed
as soon as possible. Your oil
MUST BE DRY !
I2. - If you must filter MgSO4 off, then use the big Buchner filter with a
round filter paper in it, pre-wet the
paper with some oil, push all airbubbles away formed under it, and carefully
decant your oil/MgSO4 mix in the
middle of your filterpaper, better use a big spoon laying in the middle of
your paper to pour slowly in, so you
don't disturb the fixation of the filterpaper, until at least a 2 cm layer is
reached, now put your aspirator
vacuum on, attached to the 10 L vacuumflask, take the spoon out, then you can
proceed somewhat faster
decanting while the vacuum sucks much faster then mother earth's G-force. The
MgSO4 stays behind on the
filterpaper. Don't leave any MgSO4 in the container, swirl from the beginning
to have it good mixed with the
fluid. Otherwise you have a truckload of MgSO4 left in the container, wetted
with Safrole, and how do you
get that out then ?
I3. - Pour 10 kgmoles safrole oil ( ~16.219 kg) in an open 22 L flask, only a
thermometer immersed in the fluid,
add carefully 12 kgmoles KOH flakes (~5.611 kg) via a widemouth plastic
funnel (the solution will immediately
turn black.brown): crush the KOH to not too small particles, ~1-2 cm, first,
f.e. in a thickwalled plastic bag
with a big hammer, ONLY if they are really big. Normally you don't need to do
this! Don't get carried away by
your enthousiasm and slam it, just push, be carefull, KOH in your eyes is not
pleasant at all. Don't crush it
too small, you must be able to decant or filter the oil later easily.
I4. - Stir for 10 minutes with the magnetic stirrbar or overhead stirrer ,
the solution will warm up allready
caused by some exothermic effect, nearly no KOH will dissolve, which is no
problem at all and is normal.
That's why there may be NO water in this stage of the reaction ! Or the KOH
will dilute in the water and can
not be filtered off later, and more washing steps are then needed.
I5. - Keep stirring and add 5 kgmol% pure PTC (PhaseTransferCatalyst)= here
Aliquatt336 (~811 gram), and
everything will 'seem' to slightly change color and take a slight shift in
viscosity.
When adding aliquat, the aliquat will float on top until the temperature
rises,then it mixes all up into one fase.
I6. - Now commence heating/stirring and read your thermometer in the fluid,
after ~ one hour it will reach
80 C , keep the heat at 80 C for only 5 minutes, then the heat must be shut
off totally, then allow the fluid
to stir until roomtemperature is reached again. Don't forcefully cool with
icewater or so. This will take ~2
hours.
I7. -After cooling to room temperature, the mixture is poured out of the
flask into a 25-30 L jerrycan, trying
to keep as much KOH flakes in the flask as you can without loosing too much
oil, wash the flakes with 250 ml
DCM and add that to the IsoSafrole allready poured out, and then you dilute
the decanted IsoSafrole with 5 L
DCM (DiChloroMethane), shake thoroughly, and pour out and filter that mixture
over 1 Kg Florisil (=magnesium
silicate=CAS 1343-88-0 ) in 3x equal portions, the second and third time
renewing the Florisil again (1Kg) in
your Buchnerfilter setup. Just scrape the old, used Florisil away with the
big spoon, a littlebit left on the
filterpaper will do no harm at all. Try to not move the filterpaper, and wet
it a bit with a spoonfull new oilmix
again, before you pour the next 1 Kg portion Florisil in the funnel. So
remember : you need 3 Kg Florisil , filter
in 3 portions of 1 Kg.
I8. -Wash then all Florisil, collected together, with 333 ml DCM 3x, so 1
Liter DCM totall, and add that DCM,
after you let the Florisil precipitate, to the main IsoSafrol/DCM mix. If it
is cloudy with some Florisil , use a
new filterpaper in the Buchner funnel, and pour those 750 ml DCM with the
washed out IsoSafrole in it
through the filter into the main mixture.
I9. -You now have a mix of pure IsoSafrole and DCM in the vacuum flask, which
you have to pour out 3x into
a normal, for chemical storage used, 25 L plastic polyphenyl PTF or
polyethylene PE jerrycan.
I10. -DCM is then removed at ~60 C oilbath-temp under reduced pressure from
your water-aspirator in your
22L destillation setup.
I11. -You now have pure isomerised olefin, IsoSafrole, purity ~>96 %, left
in your destillation flask and
recovered also your again pure DCM from your collector flask (change the
flask several times) to use again.
I12. -[THIS STEP IS ONLY NEEDED WHEN THE pH IS TOO HIGH -or- YOU THINK THERE
IS STILL TOO MUCH
WATER LEFT IN THE ISOSAFROLE] .
Check the pH of the pure IsoSafrole with a pre-waterwetted pH paper, and if
it is extensively higher then
pH 11 , that means there is still too much KOH in the oil, which quickly will
decompose the oil when you have
to store it, so then you wash it 1x with 1 L water to get rid of any KOH,
which will dissolve in the water part.
In a big 20 L carboy separator funnel, fill the IsoSafrole and the 1 Liter
water, shake as hell, and separate the
water on top of the oil then as carefully as you can, so no water will stay
in the oil. Test then if the pH of the
IsoSafrole is not too high, should not exceed 11.5 .
Now you add 5% in weight, dried silicagel to this still littlebitt water
holding IsoSafrole oil, to remove all
traces of water. Shake 10 minutes and then decant the oil or leave it in
until you proceed with the next step
and then decant in your clean 22 L destillation flask or whatever you use in
that step first.
I13. -You proceed with this IsoSafrole to make :
=================================================================================
MDP2P : MethyleneDioxyPhenyl-2-Propanone (Classic Performic acid method) :
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
Isosafrole --> MDP2P via Modified Classic Performic Acid :
Materials :
Same as for ISOSAFROLE, plus :
1--minimum 500 liter stainless steel milk coolingtank, with a big-ass cooling
coil in the double walls, preferable
in the bottom also.
1--Mixer motor, 220 Volt, non-sparking, induction type, for :
1--Mixer propellor + axle (diam. 1.5 to 2 cm), stainless steel, diam. 40 to
60 cm.
1-- 100 liter plastic container to prepare the PerAcid mix.
and/or :
1--big-ass 80 liter dripping funnel, stainless steel, plastic or glass.
Homemade is cheap.
1--1 meter cooled refluxing column, glass or stainless steel, to fix on the
only opening of the milktank which
is left open to the air.
5--meter heating cable, chemicals resistant, to use in milktank for the
hydrolisis step with 15 % H2SO4.
Chemicals :
Reaction :
27 kg IsoSafrole, purity >/= 96 %.
99.7 kg DiChloroEthane, ClCH2CH2Cl, Industrial quality >/= 98 %.
or :
99.7 kg DiChloroMethane, CH2CL2, Industrial quality >/= 98 %.
8.3 kg SodiumBiCarbonate, NaHCO3, pure.
41.5 kg Formic Acid, HCOOH, 86 %.
25.1 kg HydrogenPeroxide, H2O2 30 %.
22.43 kg Sulfuric Acid, H2SO4 Industrial quality ~99 %.
127.07 kg water, H2O, pure.
42.4 kg Methanol, CH3OH, Industrial quality >/= 98 %.
Extraction :
To extract from 218,9 kg hydrolized Glycol/15%H2SO4/CH3OH mix :
60 liter DCM or DCE = 3 x 20 liter, Industrial quality >/= 98 %.
Method :
Here are the figures for a 27 KG batch of Iso-safrole to MDP2P :
---(all figures multiplied with: 27000 grams devided by 16.25 grams = x
1661.54 ) ---
M1. - Combine 16.25 grams [ 27 kg ] of Isosafrole with 50 ml [=60 gram (1
liter DCE or DCM=1,2 kg), so
99.7 kg] DCE (DiChloroEthane) or DCM (Dichloromethane) plus 5 Grams [8.3 kg]
Sodium bicarbonate
(Sodium Hydrogen Carbonate).
M2. - Let it stirr for 2-3 hours, depending on the strength of your mixer [a
total of 135 kg ].
This gives it time to form a pH-buffering complex which facilitates the next
reaction enormously.
M3. - Seperately s.l.o.w.l.y combine (under external cooling) 25 gram [41.5
kg] 86% Formic acid and 15.1
grams [25.1 kg] 30% Hydrogen Peroxide (to create Performic acid) and cool to
0 C.
Note : It is critical to cool when preparing this mixture or else it will,
after sitting for 3 or 4 hrs without
cooling, start boiling and nasty fumes will fill your lab and you will have
to evacuate the place.
M4. - Then drip this cold Performic-acid [66.6 kg] VERY VERY slowly , into
the 135 kg ISO-DCE-Sodium
bicarbonate mix, keeping temp under 40 C with external ice-bath or other
means of cooling until all is in , CO2
bubbles out of the reaction mix while dripping in (and watch the temp for the
following 1-2 hours, after
completing dripping in, closely, so it still can not exceed 40 C).
M5. - Stir !VIGOROUSLY!, preferably with an overhead stirrer, for a total of
6(six) hours.
M6. - Stop stirring and move the whole batch in portions to a big seperatory
funnel, and let it sit for one
hour in there.
M7. - It will be orange-juice color DCE/pre-MDP2P(Glycol) mix at the bottom
and clearish performic acid mix
(H2O2/HCOOH) on top, the orange layer with the pre-MDP2P (Glycol) and DCE is
heavy, so it goes fairly fast
to the bottom of the funnel.
M8. - Important Note: --------------------------------------
Many members have reported a switch of layers when they used DCM. Iso/DCM
layer on top OR at bottom !
There is a perfectly logical explanation for this phenomenon : The one's
who's cooling equipment functioned
o.k. and thus kept the temperature between 36-40 Celsius will see the
Glycol/DCM at the bottom after
separation period, because they still have all their DCM left in the mix. The
one's who were not so lucky and
let the temperature get out of hand will see the orange layer at the top, due
to an extensive loss of DCM
which evaporated into thin air. The densities of the normal Glycol/DCM mix
and the PerAcid mix lay close
together, so if you evaporate too much DCM this balance is switched and
suddenly the PerAcid mix is the
heaviest layer, and falls to the bottom. You will notice then a light
yellowish PerAcid mix at the bottom and a
orange-juice coloured Glycol/DCM mix on top. This is no reason for real
worry, unless you boiled most of the
DCM away (not good for your health if you were in the same room
(carcinogenic) AND not good for the
reaction which did not have enough cooling capacity anymore in the last
stage, depending on how high you
overshoot the temp. Boiling temp of DCE = 83 C, DCM = 40 C , that's the
reason WHY you must keep the
temp under 40 C when you use DCM! And you must also do this when you use DCE
!
Instructions are allways given with a reason, which is in literature expected
to be common knowledge, but
not here at a forum crowded with C(r)ooks (hehe) and a few real chemists.
Thought I owed the Cooks the explanation for this reason.
--------------------------------------------------------------------------------------------------------
M9. - Seperate into a new empty container and evaporate
(low-vacuumdistillation, but KEEP the TEMP under
60 C!! so use more vacuum , so go lower then 700 mbar if the temp rises too
high) the DCE off and stock
that recovered DCE for future use.
M10. - Add 180 grams [only HALF the amount necessairy! so 90 grams = 149,5
kg] of 15% Sulfuric acid
(H2SO4) [so : add 22.43 kg 99% H2SO4 to 127.07 kg water], boil it until it
starts refluxing back with slight
addition of 60ml=51 gram Methanol [only HALF! needed, so 25.5 gram = 42.4 kg
Methanol (1L methanol=0.85
kg)] through the cooling/reflux condenser added on the distillation kettle
for 2 hrs. No longer then 2 hours !!!
Or you will begin to loose product-yield.
You now converted the Glycol to raw MDP2P, mixed with some pollutants.
M11. - Let it cool and extract 3 times with enough DCM (or DCE), (minimum 10
reactionvolume-percent per
extraction). M12. - Combine the DCM or DCE extractions and then boil the
solvent (DCM or DCE) off (in fact
no vacuum needed, but if you are in a hurry:)with one or more aspirators
combined or diafragm vacuumpump
to get brown oil that is peppery and cardamon smell.
M13. - You get around 16 grams [26.6 kg] -dirty- MDP2P.
M14. - To get the real clean MDP2P, you will have to vacuum-distillate this
dirty MDP2P-base again to get a
reasonable yield of about 73-75 % (grammole-percent)= 17.8 kg clean MDP2P
which should be light yellow,
or if you distill exact and have no leaks to let tiny amounts of air in, and
you don't let the temp go over 170 C,
at ~20 mbar vacuum, it would be clear with no color.
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
Note:
In weight/weight procents you get 16 / (16.25 / 100%) = 98.46 w/w % ,
but yield is scientifically allways given in Mole-percents, so:
(16 gram x 178.188=molecularweight MDP2P / (16.25 gram x 162.188=molweight
Iso / 100%) =
2851.008 grammole / (2635.555 grammole / 100%) = 108.17 mole %.
But the effective mole % after distillation (=ultimate clean-up, no washings
then necessary!) is 75%.
20 mbar x 0.01450138 = 0.29 psi, which is good enough for all distillations
we work with !
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
Here are the four threads on the old board I found back again which are
relevant for the classic performic:
1. http://hive.lycaeum.org/ubb_board/Forum4/HTML/000121.html
LaBTOP-Gyro performic results - Sumerian .
2. http://hive.lycaeum.org/ubb_board/Forum4/HTML/000130.html
LaBTop-Gyro's Modified Performic Questions - Synthia.
3. http://hive.lycaeum.org/ubb_board/Forum4/HTML/000120.html
New Performic Scale Up Question - artech.
4. http://hive.lycaeum.org/ubb_board/Forum4/HTML/000092.html
The correct way to mdp2p via performic - gyrogearloose .
And this is the original Classic Performic post in the thread :
http://hive.lycaeum.org/ubb_board/Forum3/HTML/000613-3.html
NaBH4 question : solution: One Pot ! :
Classical Per-acid oxidation of Isosafrole to get Piperonylacetone (MDP2P):
(Iso.) [R]-CH=CH-CH3 ----> [R]-CH2-C(=O)-CH3 (Pip.Ac.)
R=Methylenedioxyphenyl
The PerAcid solution is made from 25 g. HCOOH (formic acid)(86% ,starting
from 99% HCOOH) and
15.1 g. 30% H2O2 (hydrogen peroxide).
This sol. is added to a mixed sol. of 16.25 g. Isosafrole(>/=90%) and 1,5
g. Na2CO3 (!!) in 50 ml
CH2Cl-CH2Cl at 35-40 C.
The temp. is during 6 Hrs. mixing regularaly checked and kept within 35-40 C.
The solvent is evaporated (vacuum, keep TEMP! UNDER! 60 C.!)
Residue is boiled with 180 g. 15% H2SO4 for 2 Hrs.
Extraction with 3 x 100 ml.CHCl3, wash with water,dry over MgSO4 and
evaporation of the solvent gives a
brown oil (purity >/=90%).
Supplemental purifying by Kughelruhr destillation (~70 C, 0,2 Torr) gives
70-75% yield of MDP2P
(>/= 95% pure!)
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
And this is the latest info from Ritter, who by the way posted this method
first, then Beagle_boy , then me,
then Gyrogearloose, so this method needed 3 times posting to get the
attention needed, so lets call it from
now on the Classic Performic, to avoid any misunderstandings:
Ritter
(Stranger)
06-20-00 14:26
Re: LabTop modified performic method?
The reaction runs best as described in my writeup! Adding carbonate to
formic/peroxide first would surely lead
to a nasty volcano and would not help any. Carbon Dioxide is emitted as
performic is slowly added to
alkene/carbonate solution.
As far as advances are concerned a few things have been realized. Extremely
vigourous stirring, such as that
produced by a mechanical stirring rig, seems to increase yields. If a
considerable amount of isoalkene is
recovered during vacuum distillation an easy solution is to add more
performic acid mix to rxn. This is usually
an indicator that the peroxide used has degraded somewhat below 30%.
With this MDP2P you proceed to make :
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
NaBH4 : REDUCTIVE AMINATION of MDP2P and P2P :
---------------------------------------------------------------------------------------------------------
REACTION MECHANISMS :
H
| H H CH3
C6 \ / /
// \ C N
// \ / \ / \
O--C5 C1 C H
H2C/ | || |\
\ | || H3C H
O--C4 C2
\\ / \
\\ / H
C3
|
H
.
.
. C11H15NO2
.
. 3,4-METHYLENEDIOXY-N-METHAMPHETAMINE
.
. EXTASY
.
.
.
.
O
v
O CH2CCH3
/ \ //\ /
H2C | || + H2NCH3 -- Methanol ->
\ / \\/
O
.
.
MDP-2-P + Methylamine gas
.
.
.
.
NCH3
v
O CH2CCH3 __> Extract with Silicagel
/ \ //\ / /
H2C | || + H2O --- NaBH4 --->
\ / \\/
O
.
.
IMINE Water
.
.
.
.
NHCH3
|
O CH2CHCH3
/ \ //\ /
H2C | ||
\ / \\/
O
.
.
3,4-METHYLENEDIOXY-N-METHAMPHETAMINE
.
NOTE :We know now, july 2000 , that it's much better to follow the basic
rules from the P2P to
Methamphetamine synthesis also for the MDMA and MDA synthesis, in fact you
MUST use silicagel (pre-dried
at 300 C for 2 hrs) in all relevant steps, especially, when you make the
imine/amine conversion by adding
NaBH4 to the MDP2P/Methanol/Methylamine-mix, to obtain the perfect results,
for both MDA and MDMA.
So keep this in mind when you read the following texts !!!
The imine is formed when you mix MDP2P with 10% w/w MeNH2 / MeOH,( so then
allready you must have
added the 20% w/w pre-dried silicagel beads, to directly take up the water
formed by the imine reaction
mechanism), not when you crystalize, mixing acetone, that you do with the
pure distillated base. No imine
left there. The imine is hydrolized with the flooding with water (ev. mixed
with 5% NaOH or KOH, as Sunlight
happily found out for the MDA One Pot ammoniumacetate and NH3 gas route ).
I will soon fill in a picture of the total mechanism into the MDA route, with
molecular drawing of the imine,
many seem not to know what the exact mechanism is, I'll help you out.
If you make the acetone/HCl mix in advance for the crystalisation of your
destillated clean amine-base, you
must use it as soon as you can, or it will even become red, depending on how
much HCl you bubble in.
And add the acetone/HCl mix then slowly to the MDA (or MDMA or MDEA or
Meth)-base while medium stirring,
not the other way round, that would lead to decomposition at the start of the
adding of a part of your base,
due to too acidic conditions.
It has been seen that vigorous stirring results in very fine crystals ;
medium and at the end slow stirring
results in more voluminous crystals, which is a logical effect of giving the
crystals time and a more undisturbed
medium to grow together.
The best is to keep your percentage of HCl fairly low, to avoid early
decomposition.
---------------------------------------------------------------------------------------------------------
MDP2P--> MDA :
Materials :
Chemicals :
---------------------------------------------------------------------------------------------------------
Method :
To simplify life for you all, here's the ULTIMATE FOOLPROOF EASIEST WAY to
make:
MDMA, MDA, MDEA (use ethylamine instead of methylamine) if you have the chems
available!
A practical way to make Honey (tinted bases) is as follows:
(Edit 15/07)
Parts | M D A -base || Parts | M D M A -base
0,5 | MDP2P (oil) || 1,0 | MDP2P
3,0 | MeOH (solvent) || 3,0 | MeOH
1,0 | A.Acetate (salt) || 0,3 | MeNH2(gas)
0,1 | NaBH4(reductor) || 0,1 | NaBH4
These quantity-parts are in weight!
So: you can choose if you want to work in gram OR kg.
Following starting quantity is 25 kg MDP2P or ev. gram, but then you must
divide all other quantities by 1000,
so kg's and/or liters ):
Prepare 6x20 L yerrycans in wich you can fill each 12,5 L cooled, (-20 C)
MeOH.
In each yerrycan you dissolve 1,25 kg methylamine in the cooled MeOH
(methanol).
Let the MethylAmine dissolve in the -20 C cooled MeOH wich you already put in
the freezer one night before!
Use a upside down laying gastank with MA (30-45' angle)and fill with a thick
synthetic black rubber hose the
liquid-MA as deep as possible in the MeOH. SLOWLY! It takes ca. 10 min., per
yerrycan.
The yerrycan stands on a digital balance, so you know the weight added.
Surround the hose with a wet towel at the filling opening of the yerrycan for
the unhealthy smell.
When ready fill all the yerrycans with the MeOH/MeNH2 mix in the
reactiontank.
[Add in case of (MDA) now the AAcetate (in the pure methanol) instead of the
MeNH2 gas !].
Cool now the reactiontank to +5 C and start the mixer anticlockwise, so the
fluid circulates from bottom to
top. This way no air is mixed in, so less oxidation. Add at +5 C the 25 L.
MDP2P .(pre-cooled).
Start then directly (because a slow reaction starts already), every ca. 5
min, addition of the NaBH4, ca. 3
soupspoons per time. Use a funnel and wash every time with a little methanol.
Keep all holes closed inbetween
or it stinks!
Because of the excessive cooling the temp. will not rise much, only to +15 C.
Wait again till ca. +7 C to add again. Are you impatient and add to quick,
then the mix will start heating,
evenso boiling! This may never occur,then your product will be lost !
This process takes ca. 7 hours. Ending temp. will be ca. 25 C. Stop after 7
hrs. the cooling and let react
with mixer on for 29 hours.
After this time, you prepare 200 L clean water, which you mix with 10 Kg NaOH
or KOH, until all is dissolved.
This 5% water/NaOH-mix you add to the cooling tank (fast), then you messure
the pH, should be between
11,5 and 12. (If you add coincidently acid instead of NaOH base, greenish fat
form in and on the fluid).
Stop after 10 min. the mixer and let the raw brown base precipitate 30 min to
the bottom and tap off the
base through the valve at the bottom. Stop tapping when you see lighter color
(water) coming.
Add now 3 liter methylenechloride (dichloromethane=CH2Cl2) to the tank, mix
10 min., stop the mixer, wait
again 30 min. and tap off the rest of the base, now diluted in the
CH2Cl2.This gives totally ca. 43 L raw base.
Now we remove the CH2Cl2, Methanol and the water in a simple distillation
setup, with low vacuum circa
500 mbar, with magnetic mixer/heater, mixerpin teflon, glassware with NS29
connections ( 20 L 2-neck
flatbottom flask PYREX!, thermometer, cooler 60 cm, glas-alonge and 10 L
collecting flat-bottom erlenmeyer
flask).
Start at 35->55 C for CH2Cl2, then 55->85 C for methanol and 130 C for
all the water. Re-use the CH2Cl2
and the methanol! Now you are left with ca 28 L half-clean MDA or MDMA
amine-base (depending on the fact
if you used Am.acetate or MeNH2 gas, colour is light brown).
Now we will clean the raw base by 2 times recrystallisation with acetone 98%,
(m)ethanol 98%, and after that
washing min. 3 times with acetone 98%.
Use 20 L P.P. plastic buckets to do this.
Mix 5 L base (cold) and 10 L icecold acetone. Leaf inductionmotor-mixer on.
Bubble HCl-gas 99% through with 1 meter StainlessSteel pipe, (inner diameter
min 5-8 mm) until white
crystals form.
Stop when pH= 7,0 and start with the next 5 L base.
The first one will rise again to ca. pH=8,0.
Later you can bubble again a littlebit HCl-gas through until again pH=7.0 or
even to pH 5.0 .
Let the crystals precipitate and pour the upper acetone off.
Re-dissolve the wet crystals now in the minimum quantity of HOT(nearly
boiling) methanol or ethanol in a
metal bucket (because its hot !) until you see no more crystals, so you now
have a saturated solution in
(m)ethanol!
Pour 5 L of this solution back in the plastic bucket, and add 5 L Acetone,
which is -15 C.
When cooling down, you will see crystals form again,in a dirty solution. Wait
until no more crystals come, pour
off again and dissolve again in hot (m)ethanol. Do this as many times until
you have snowwhite crystals. Dry
on glasplates on the floor with blower.
You now have H(M)ONEY in the Bank.
---------------------------------------------------------------------------------------------------------
MDP2P--> MDMA
Materials :
Chemicals :
---------------------------------------------------------------------------------------------------------
Method :
------------------------------------------------------------------------------------------
Preparation of MDMA by reductive amination with sodium borohydride
by Labtop (written by Quicksilver, editted by LaBTop)
------------------------------------------------------------------------------------------
- Introduction
Until recently reductive amination with NaBH4, for the production of MDMA,
was assumed to be inferior to the
well-known NaCNBH4 route (that has been popularized by Alexander Shulgin for
the production of MDA) and
other synthetic routes, like aluminum amalgam. The following method proves
that the NaBH4 reduction actually
is superior to all other common routes used in clandestine chemistry.
The method is relatively simple, it doesn't require complicated equipment.
The work-up on the reaction mixture
is simple and efficient. The method is very usefull for big scale production
of MDMA and gives high yields
(+90%!).
There is a relatively rapid formation of the imine and the imine is reduced
relatively rapidly.
There's no reduction of the ketone to the secundary alcohol, as one might
expect(2). In similar reactions,
the water!! that is produced during the forming of the imine (Schiff Base) is
removed from the reaction before
the imine is reduced.
As we know now,much better with pre-dried (3 hrs in oven, 300 Celsius)
Silicagel beads, 3-5 mm diameter,
take a quantity of 20% weight compared to your MDP2P weight. Because of the
stability of the imine, this is
not necessary for the production of MDMA, but should in fact allways been
done, to reach maximum yields !
This reaction is an improvement of a known synthesis (1), a similar reduction
in an aqueous sollution of
ethanol was performed, but the yields were only 31%.
- Synthesis :
MDP-2-P + methylamine-> intermediate imine +H2O-> MDMA freebase->
MDMA HCl salt.
- Ingredients
MDP-2-P 1000 g
Methanol 3000 g (>99%)
MeNH2 (gas) 300 g (99,9%)
(Be very carefull with MeNH2-gas: it is toxic and carcinogen, but when
handled with care, no problems.
I advice to not use a gasmask, because when you smell it, you can avoid it,
but with mask you are not
warned and it can be uptaken through your skin! Use wet towels to avoid
problems at ev. leaking points!)
NaBH4 100 g
(NaBH4 is a common reducing agent. Do not spill NaBH4 on hands or face
without noticing it(e.g. whiping
sweat off your face), or you will be punished with red spots there which will
never go away!
It takes minutes before you feel the pain, and then its too late.
So wash face and hands with water, frequently.)
filtered clean H2O
33% HCl
conc.NaOH solution
DCM (DiChloroMethane)
Acetone >98%
- Equipment :
*-- There are several options for the reaction vessel. One could think of a
500 to 1500 L stainless steel milk
cooling tank, that is modified to ones needs. But a fermentation tank
(plastic or stainlees steel, from 20 to
8000L), with small modifications will do just as fine. Or one could buy a 1m3
(=1000 L.) plastic tank
everywhere at second hand tank and cans stores. Have a handy manhole to
clean, are totally airtight and as
a bonus, have a nice tap-valve at the bottom.They ship NaOH ,33% HCl etc. all
over the world with them.
*-- A solid diaphragm vac.pump is recommended for the vac. distillation. For
example a Vacuubrand Type
MD 4C, 3.0 m3/h. It sucks from 1.7 to 11.2 m3/hour, ask for Chemistry
Design(PTFE) series.
*-- MeNH2-gas is made by reacting MeNH2.HCl with conc.NaOH. (An other option
is to react 40% MeNH2 with
dry KOH.) (I will add a lot more on MeNH2 synthesis shortly.)
- Step by step :
1) Preparation :
Dissolve 300 gram, not ml ! methylaminegas in chilled 3000 gram methanol (-20
C).
Cool in the mean time the reaction-mixture to +5 Celsius.
Start the mixer (anticlockwise so no air is mixed in) and add the 1000 gram
MDP-2-P.
NOTES: Make 300 gram MeNH2-gas by reacting MeNH2.HCl with NaOH. Or dissolve
the methylaminegas at
hand from a gas cylinder in methanol, using an upside down laying (45
degree's) gascylinder with (fluid)
methylaminegas in it, no pressure regulator on it. Attach a thick black
synthetic rubber hose to the valve,
open that valve slowly ,while the hose is down at the bottom of your first
jerrycan with icecold Methanol,
which stands on a big flat digital balance. Surround the hose with a wet
towel. Add slowly 300 gram gas in
the jerrycan. Be aware of a popping sound when the gas implodes when it
enters the Methanol. Don't let
suck back, close the valve everytime suddenly.
2) Reaction :
Start adding NaBH4, one teaspoon ca. every 5 minutes, H2-gas bubbling has to
disappear before adding again,
temp. should be between 8-18 deg Celsius. (Wash down with methanol). Adding
of the white NaBH4 powder
will take 7 hours. With mixer on let it sit for 29 hours more.(4 hours will
do for people that are in a hurry,loss
20-30% yield).
NOTES: When the reaction vessel is opened it should be covered by a wet
towel, so the methylamine-gas can
be absorped by the water. (1 L water absorps 1000 L NH3.) An airlock might be
sufficient for that goal too.
Do not airtight the flask, let a thin tubing out the window,wrapped at the
end with a WET towel!
3) Work-up I :
Leave the mixer on. Add 8 L clean H2O with 1%=80 mL 33% HCl. (The 80 mL HCL
is redundant, don't add
it at all!).
(When making MDA as your endproduct, you add 5 weight % NaOH or KOH to the
water, to facilitate a good
separation in the following separation procedure).
Liquid will be greenish brown, pH=10,5 (11,5 is better than 10). !!When green
soap possibly starts to form:
you made a mistake, you added far too much HCl ( To avoid any risk: do not
add it at all Redundant!!)...
Brown freebase will sink to the bottom of the vessel. Tap off, till a bit
clear water is coming out of the valve.
Close then the valve.
Add 200 mL DCM to the reactionvessel and mix for 10 min. Stop the mixer and
wait 30 minutes. The DCM with
the rest of the freebase will sink to the bottom. Tap off. Combine the two.
There will be app. 1750 mL of
base fluid + DCM.
NOTES:
You can again basify the water with conc NaOH sol. to pH =13-14 and tap off
the last oil.
The 8 mL 33% HCL (1%) is added to the water to make sure any unreacted NaBH4
is neutralised.
4) Work-up II :
A vac.distillation setup is prepared. First the methanol, DCM, water and
other lowboiling stuff are removed,
then at 165 C the clean freebase comes over. Approx. 1.0 L. freebase.
NOTES:
Step 1. The water and other lowboiling stuff comes over at 130 C. Remove when
nothing more comes!
Step 2. Set on 165 C. At first around 140-145 C you see the first little
drops of clear oil condensate and at
160-165 C and 20-18 mbar it starts Running!
To distill of the water, methanol and other low boiling stuff from the
reaction mixture, the use of an aspirator
is sufficient! To get the freebase out, the use of a decent vacuum pump is
recommended.
5) Crystallization :
Mix the base 1:4 with clean,cold(-10 to -20 C) acetone and bubble through
with a Stainless steel pipe 8 mm
x 1 meter with HCl-gas 99%. SLOWLY! After ca. 5 min a thick, white crystal
mass will form. Check frequently
with pH-meter ( aquarium shops sell good ones from Hanna Instruments for
circa US$ 60.- ), or pH papers
from Merck, until pH = 7 to 5 . If the mix get too hot, place back in big
freezer to cool and proceed with next
cold batch. Be very carefull not to go under pH=7 to 5, because then your
powder will solute again and you
must add base again until pH comes up again to 7. So keep always at least 20
mL freebase ready in case of
mistakes ! Dry the acetone/powder mix in a Buechner-funnel with aspirator
vacuum. Dry again on glassplates
on the floor under airconditioner or slow blowing fan's in a dry room.
- Epilogue :
There are reasons to believe that the salt form of the amine can be used, ( I
don't think it will be interesting,
without high decrease of yields LT/ 10-07-2000) but the gas method is by far
preferrible.
Ethylamine can be used to produce MDEA.
Ethylamine is a gas above 17 C, but a fluid under 17 Celsius, so very
convenient when first placed in a freezer,
just pour it in the icecold methanol then.
Ammonium acetate or NH3 gas to produce MDA is another possibility, Sunlight
and Cesium have researched
the Ammonium Acetate process further and reached yields of ~ 50-65 %.
The same method was tried with P-2-P, first with unsatisfactory results when
NO !! water was removed,
because the imine that's formed here isn't as stable as the MDMA or MDA
imine. When you remove the water
while forming,with a drying agent, Silicagel, this also works (12-07-2000)
perfectly, even better !!!
- References
1. Noggle, F. T.. Jr., DeRuiter, J., and Long, M. J..
"Spectrophotometric and
Liquid Chromatographic identification of 3,4-Methylenedioxyphenylisopropyl-
amine and its N-Methyl and N-Ethyl Homologs." Journal of the Association
of
Official Analytical Chemists, Vol. 69. No. 4. 1986, pp. 681-686.
2. Shellenberg. K. A.. "The Synthesis of Secondary and Tertiary Amines
by
Borohydride Reduction." Journal of Organic Chemistry, Vol. 28, Nov. 1963
pp. 3259-3261.
3. J. Weichet, J. Hodorova and L. Blaha, "Reductive amination of
phenylacetyl-
carbinols by sodium borohydride." Coll. Czech. Chem. Commun. 26,
2040-2044 -
CA 56, 5864c (1962)
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
MDP2P--> MDEA :
Materials : Same as for MDMA.
Chemicals : Same as for MDMA, except :
1.--- A equimolar amount of Kg Ethylamine, CH3CH2NH2, compared to the amount
of Methylamine in above
One Pot's. A gas at +17 C, a fluid gas under that temperature !
---------------------------------------------------------------------------------------------------------
Method : Same as for MDMA.
Only switch methylamine gas for ethylamine gas or fluid-gas.
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
|
|
|
|
|
P2P--> METHAMPHETAMINE, racemic mix. :
---------------------------------------------------------------------------------------------------------
Materials :
See MDMA, Isosafrole etc.
---------------------------------------------------------------------------------------------------------
Chemicals :
See MDMA, exept :
Change MDP2P to P2P, Phenyl-2-propanone.
Method :
The original link is broken, or the file is deleted, so:
LaBTop .......... posted 06-23-99 01:04 PM
Member
Making of d,l-Meth (Ice) .
Ingredients:
• 138 gram P2P = +/- 1 grammole.
• 1000 ml Methanol (+ 10 % weight Methylaminegas dissolved in it = +/- 100
gram)= +/-3gmol.
• 36 gram MgSO4.7H2O , magnesiumsulfate (dry at 300 C for 2 Hrs in oven to
get MgSO4.1H2O)= to dry
Methanol/M.A. mix .
• 200 ml Silicagel balls +/- 3 to 5 mm (dry at 300 C for 2 Hrs in oven,
changes to dark brown! ),=to attrack
2 gmol H2O, during imine forming.
• 15 gram NaBH4 as a reducing agent for the formed (waterfree !) Imine.
IMPORTANT: THE REACTION IS VERY SENSIBLE FOR ANY WATER
(fluid or vapour in the
air!).
First quickly crunch your pre-dried (oven, 300 C, 3 hrs.)DRY MgSO4 to pop
corn shaped rocks in a mortar,
sieve the powder out, and directly put the rocks under max. mixing in the
Methanol/Methylamine mix and close
the pot to let no water from the air in.
Keep mixing for 10 minutes, then all the water will be taken up to the MgSO4.
Let stand and wait till all the
MgSO4 is on the bottom. Now quickly tap off the now DRY MeOH/MA mix in a 2L
reaction flask and close that
one.
Wash directly your empty pot with lots of water, to remove the smell of
methylamine so you can safely store
it.
Now add the 200 ml (measure in beaker, neglect the free spaces) DRY Silicagel
beads (2-5 mm) and a
magnetic mixer bar also in the 2L flask and close again. Keep 2L flask in
Silicone-oil bath at 20 C.
Silicone-oil only slowly warms up! Do not apply heat now, it's only meant as
a cooling medium in this stage.
Now add SLOWLY via a dropping funnel the 138 gr P2P to the 2L flask under
strong mixing. The temperature
rises to 23 C during the (waterfree) Imine forming. The water from this
reaction is taken up by the dried
Silicagel! This takes 30 minutes. Let then mix for another 1 hour.
The reactionmix color changes from light yellow to coffee+milk color. Temp=
23 C.
Stop mixing after this 1 hour and pour the fluid off into a 2L glas
erlenmeyer with flat bottom and add a
mixbar. The remaining Silicagel is washed 3 times with 50 ml DRIED (use
silicagel) methanol, to catch the
remaining Imine, and those 2 x 50 ml is also poured into the 2L erlenmeyer.
Now put the 2L erlenmeier on
magn.mixer, in a icecubes/methanol bath (-10 C) and start strong mixing. Put
a Funnel on top of 2L
erlenmeier, in rubber ring. Now start adding, every 5 min., a teaspoonfull
(flat off!) of boro and wash in with
minimum methanol. After every spoonfull, stopper the funnel loosely with a
rubber stopper. This takes 2,5 hrs.
DO NOT exceed a temp of more then 20 C !! You can add the next spoon at +/- 8
C. Solution color is light
clear orange/brown.
Let mix in total for 8,5 hrs.(could perhaps be lot less hours, do'nt want to
know: time is NOT money!)
The total volume is +/- 1900 ml.
Add then the mix to 5 L dest. water in a 10 L flask, under magn.mixing. The
pH=12 .
Add then 500 ml DiChloroMethane (DCM) and mix strongly for 30 min. Let oil
precipitate and a dark,
honey-coloured layer of DCM+oil is on the bottom.
Decant the waterpart with an aspirator + siliconetube.
Fill the rest (water+DCM+oil) in a seperator funnel and tap off only the
DCM+oil = 550 ml.
(DCM boiling point=40 C).
The leftover MgSO4 and boro salts stayed nicely in the waterpart.
Then dry the DCM+oil with some DRY MgSO4 and decant in 2L erlenmeier.
Wash this MgSO4 with some fresh, DRY DCM and add the DCM washings to the now
dry DCM+oil. Total
volume DCM+oil =1000 ml, colour is honey/red.
Start now bubbling this 1000 ml with HCl-gas, while 2L erlenmeier stands in
icebath on magn.mixer and mix
strongly.
Check pH frequently, proceed until pH 6.
Pour the now acidified 1000 ml in a 2 L evap.flask and put on Rotavap
machine. Speed= 100 rpm , temp= 80 C,
mode=p/auto, little vacuum=800 mbar, to hold the flask.
After distillating off nearly all the DCM, suddenly the contents of the flask
turns from dark honey colour to
creamy milk color and it dries out to a round cake on the bottom.
Remove the 1 L DCM, now in the collector flask, and hang that empty flask on
again.
Now put full vacuum on to remove the last traces of water.
Cleaning by 3 x recrystalization: Put MINIMUM quantity of hot (40 C) DRY DCM
(or dry 98+% Ethanol) in the
flask until the last remains of the dry stuff dissolves, and add 4 x this
DCM-quantity in the form of DRY
acetone. Close with stopper and put 1 hr in freezer.
A solid dirty-white crystal mass is formed with a layer of dark red fluid on
top of it.
Decant the fluid and repeat this step another 2 x and 2 Hrs. You have, the
last time, snow white crystals.
Dry Weight = 141,5 gram, close to quantitative yield.
You can eventually melt this crystal mass in a alu flatbottom pot on a
heaterplate at 170-175 C. Then let this
melt, VERY SLOWLY, and do not go higher then necessary to melt it, or its
starts smoking ( you have your
first quick-test then: enjoy!). Cool down to 150 C again, really slowly, 1
degree C per 30 min. (regulate with
your temp controller!), and you got d,l-ICE, after you let it very slowly
again cool down to roomtemperature
(with a closed lid on it!, its hygroscopic ! ).
Advantage: you removed ALL the water in this process!!!
You can better make the sulfate salt following Logicals method :
Let 10% H2SO4/Ethanol mix acidifying a 1:4 mix of freebase Meth/Ethanol. This
is not so hygroscopic. Filter
and dry the crystals.
So now you know at last how to make ICE cream....... Ravers LOVE it!!!! LT/
------------------
EMOTIONSwill always beFREE!
--------------------------------------------------------------------------------
LaBTop .......... posted 06-23-99 01:19 PM
Member
Yohoo, forgot to tell:
Use d-Tartraric acid to get d-Meth !!!!!!!!
2 Flies in one hit....
Ask your beloved moderator, the unforgettable Mr. Spit_tartrar_Ball, he knows
how to do that, he recently
posted the method, but needs a little explaining for most of you, I'm afraid.
But thou should NOT be afraid, its
easy!
Then you have d-Meth (the softer part) AND l-Meth (which is speedy only).
Life becomes easier and
easier......? LT/
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
Sunlight's method of preparing 10% Methylamine solution in Methanol, from
aquaous 40% Methylamine .
This is a convenient adaptation of the NaBH4 One Pot procedures using
aqueous Methylamine instead of the
gaseous form.
He liberated the MeNH2 as a gas with dry NaOH pellets :
sunlight
(Hive Researcher)
07-10-00 02:15
If you should try to use directly a 40% aq. MeNH2 solution you will get a 60
% yield based on the pure ketone.
The procedure to dehydrate ( get rid of the water-part) the aq. methylamine
is, for example:
Put in a 2-neck flask 700 grams of commercial dry NaOH, and using a
compensating pressure separatory funel
attached to one of the necks, add slowly over one hour 350 cc of aq.
methylamine to the NaOH. In the other
neck attach a rubber stopper with a teflon tube and to it a glass tube with a
gas diffusor ( a tiny glasfunnel
with a glasfilter glued in it with 6 seconds glue or two component glue or
just melt it tight with a torch ), and
bubble the MA-gas in 1000 cc of methanol in a flask in a methanol- or
water/ice bath.
Reaction is endothermic, finally you can heat a bit the NaOH containing flask
to force the liberation of the
last gas, but it's not really necessary, just shake it to see a homogeneus
paste.
The compensation of pressure can be done using a regular separatory funel if
you attach a 1-hole rubber
stopper with a teflon tube connecting to the NaOH flask, if you use a 3-neck
flask you can use the other
neck, and if you use a two neck flask, you can use in one of the necks a
2-hole rubber stopper, 1 hole
connecting to the stopper in the neck of the separatory funel and one to the
... dripping hole of it (sorry, it's
my english...)
You can refill your sep. funnel with aq. methylamine if it's not enough big
to complete the whole liberation of
all the gas, close the valve and close the other tube, open it and put the
aq. solution in, then stop it and
free the other tube.
The absortion of methylamine in methanol at 0-5 C is perfect, you don't even
need to redirect possible fumes
from the methanol, there aren't, but stop the flask with some papertissue to
prevent the entry of humidity.
The gas diffusor can be done with a regular glass tube, try to enlarge a bit
one of the ends, and then try to
weld inside it a piece of fine filterglass for the gas bubbles feed, it will
act as a diffusor, not very good, but
enough, and it won't heighten the pressure too much (one stopper could jump
and you would have a toxic
ambient atmosphere of methylamine in your viginity).
Probably using a pipette will work, absortion is very good.
You can weight finally the 10% methanolic solution of methylamine to know the
exact weight of gas you have
in it (you weighted it before).
You will have a bit of water, but don't worry, mix it with the ketone (350
grams), add silica gel (160 gr) and
shake and let stand , shake and so on ... during an hour, filter and wash the
silica with 200 - 300 cc of
methanol, add the NaBH4 at +7 C ( an ice/salt bath works fine) to get from 75
- 87 % of the desired product
depending on the purity of your ketone.
You can dehydrate the methylamine gas by passing it through a flask with
NaOH, but it's not necessary due
to the addition of silica gel.
Beaker
(Hive Researcher)
07-10-00 10:11
From http://rhodium.lycaeum.org/chemistry/meam-pdc.txt
:
" KrZ (Hive Researcher) : The mix {MeNH2 + 2H2O (The product of
catalytic hydrogenation of methylamine)
in methanol with Na2SO4} was split in half and each half sat with 1500g of
Na2SO4 for an hour, with
occasional stirring. The Na2SO4 ( sodiumsulfate) was filtered off for a long
time, until it was quite dry in
appearance, the mix halves were combined and washed 2x with 1L of CH3OH
(methanol), which was filtered
off and added back to the solution."
sunlight
(Hive Researcher)
07-11-00 00:39
We did something similar with MgSO4, trying to dry a mixture of 40% MeNH2 and
methanol, and the end
product was titrated and it was about 3 % instead of 10 % w/w
(weight/weight), the MgSO4 had a strong
smell of methylamine, so we thought most of the gas was ended in the water
and in the magnesiumsulfate,
and we tried the above procedure, that works fine. But we are not God or the
Queen of England. They use
"we" as a pluriform all the time.
WISDOMwillWIN
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
IVa.--- 2,5-DIMETHOXYBENZALDEHYDE---> 2CH---> 2CB
Consult for more details this thread :
http://hive.lycaeum.org/wwwthreads/perl/showflat.pl?Cat=&Board=methods&Number=26600&page=0&view=collapsed&sb=5
Posted by :
Beaker
(Hive Researcher)
07-09-00 00:48
2CB for the LAH impaired
The following is a synthesis of 2CB from 2,5-dimethoxybenzaldehyde that does
not require the use of the
slightly hazardous and/or difficult to obtain reagents normally associated
with its synthesis, notably LAH,
pressurized H2, and Br2. No doubt some clandestine chemists have been
discouraged from attempting the
synthesis of what is, IMHO, a pretty cool substance by the nature of these
reagents and the lack of a clearly
written procedure for an alternate route that does not use them. However,
alternate routes do exist, and one
of them is detailed below. Note that this route does require one additional
step to acheive the nitrostrene
reduction than with the use of H2 or LAH, but that the yield is actually
substantially higher than what others
have reported with those reducing systems. Also, the bromination procedure is
somewhat unrefined at present
and does not result in the greatest of yields or the easiest of workups, so
feel free to use the classical
procedure if you want to make or buy your own bromine. As a final note,
although this route will happily
accomodate batch sizes of ~50g in 2L glassware, it does not scale anywhere
near as well as catalytic
hydrogenation, so if you're trying to go huge, it's probably not for you.
Scaleup should not be a problem, but due to the rather low product loading
that you can obtain with the
method as written, it is rather impractical at >50g scale. Bigger than
that and I would suggest that one look
into catalytic hydrogenation a la KrZ's mescaline writeup or finding a way to
cut the amount of solvent back
quite a bit. For most people, ~80g of 2CB out of 100g, or $60 worth of
2,5-dimethoxybenzaldehyde is more
than enough.
Step 1
Condensation of 2,5-dimethoxybenzaldehyde with nitromethane
In a 500mL RBF equipped with a relfux condensor and a stir bar, place 100g
2,5-dimethoxybenzaldehyde, 15g
ammonium acetate, and 250mL of nitromethane. Heat to a gentle reflux while
magnetically stirring. Maintain
reflux for ~45min, by which time the color of the solution should progress
from clear/yellow to a deep
reddish-black. Remove heat and carefully pour the hot rxn mixture into 1L of
ice-cold 70% IPA. Allow the
IPA/rxn mixture to stand for a while. You should now have a flask full of
orange solids floating in red/black
mother liquor. Vacuum-filter the solids and wash them with additional
portions of ice-cold 70% IPA until the
filtrate is no longer reddish(It will become very slightly orange in color
with small amounts of dissolved
nitrostyrene). Thoroughly dry the collected orange solids by pulling air
through the filter for a while and then
dry under vaccum. It is very important that the nitrostyrene be completely
dry before proceding to the next
step.
Yield - 106.1g (84%) of 2,5-dimethoxynitrostyrene
Purity - Single spot by TLC, NMR is clean
Step 2
Sodium borohydride reduction of 2,5-dimethoxynitrostyrene
Into a dry 2L RBF flask equipped with a stir bar was added 400mL of anhydrous
ethanol(If you can't get
anhydrous ethanol, use anhydrous IPA. DO NOT USE METHANOL!!!). The rxn was
cooled to 0C in an ice/water
bath and 36.2g of sodium borohydride was added(slight H2 evolution). A
pressure-equalized addition funnel
was charged with a pre-made saturated solution of 50g
2,5-dimethoxynitrostyrene in THF(about 600mL) and
attached to the flask. A piece of tubing was attached to the top of the
addition funnel and run outside to
vent the hydrogen that will evolve during the course of the reaction. While
maintaining the ice/water bath,
all of the bright yellow nitrostyrene solution(refill the addition funnel if
necessary) was slowly(reaction is
exothermic, so watch it) added to the sodium borohydride solution over the
course of ~90 min (Note: gas will
evolve over the course of the addition. It is H2. Be careful). After the
addition is complete, the rxn was
allowed to stir for an additional 10 min and then poured into a 4L erlenmeyer
containing 1L of H2O and a 3"
stir bar (H2 evolution). While stirring, 250mL GAA (Heavy H2 evolution) was
carefully added (one could use
400 mL 31.45% HCl). The quenched reaction mixture was divided into three
portions. In a 2L sep funnel, each
portion was combined with 500mL Et2O(or toluene) and 500mL brine. The funnel
was shaken and the aqueous
(bottom) layer was discarded. The organics were washed with 3 additional
500mL portions of brine. This was
repeated with the other two portions. The organics were combined, dried over
MgSO4, filtered and the solvent
evaporated to give a clear yellow oil.
Yield - 47.0g of crude 2,5-dimethoxynitroethane
Purity - Two spots by TLC. NMR analysis indicates a 50:1 molar ratio of the desired
product to dimeric
impurity(this is the only impurity present). Adjusted yield of
2,5-dimethoxynitroethane is 45.2g (89.5%).
Step 3
Catalytic Transfer Hydrogenation of Crude 2,5-dimethoxynitroethane
The crude product of the previous step was dissolved in 400mL MeOH and placed
in a 1L RBF equipped with a
stir bar. In a separate beaker away from all combustible materials, 1g of 10%
Pd/C was carefully wetted down
with MeOH and the resulting slurry transferred to the rxn flask. To the rxn
flask was added 62g ammonium
formate. The flask was equipped with a reflux condensor, a piece of tubing
was attached to the top of the
condensor, and the end of the tubing was submenged in a container of water
(this works to exclude O2 from
the rxn while allowing the evolving CO2 to escape). The rxn was gently
refluxed for 24 hr.(CO2 evolution),
cooled, filtered through celite to remove the Pd/C, and the solvent
evaporated. The residue was taken up in
150 mL of Et2O (or toluene) and 300 mL of H2O and the pH adjusted to >12
with 20% NaOH. The mixture was
transfered to a sep funnel, shaken, and separated. The aqueous layer was
extracted with 2 x 100 mL portions
of Et2O (or toluene). The combined organics were dried over MgSO4, filtered,
and gassed with HCl (2CH x HCl
is partially soluble in DCM, so don't gas in that solvent). The resulting
white crystalline solids were filtered,
washed with Et2O, and allowed to air dry to give 2CH Hydrochloride.
Yield - 43.8g (94%) of 2CH Hydrochloride
Purity - Single spot by TLC. NMR is clean.
Step 4
Bromination of 2CH Freebase
The 2CH x HCl was dissolved in a 300 mL H20. The pH was adjusted to >12
with 20% NaOH and the aqueous
layer was extracted with 4 x 100 mL DCM. The DCM was evaporated to give 2CH
freebase, which was
dissolved in 500 mL of 3:1 AcOH/H2O. The rxn was cooled to 0C in an ice/water
bath. 37.3g of 48% aq. HBr
was added, followed immediately by 23.8g of 30% H2O2. The rxn was stirred for
6 hr, allowing the ice bath
to melt. The majority of the AcOH was removed under vacuum and the nasty
reddish-black rxn mixture was
partitioned between 1L H20 and 500 mL EtOAc(EtOAc was found to be much better
for dissolving the
impurities in this rxn than Et2O or toluene. This is messy at first, but
everything should go into solution after
much agitation). The layers were separated and the aqueous extracted with an
additional 500 mL EtOAc.
The aqueous was basified to pH >12 with 20% NaOH and extracted with 3 x
200 mL portions of Et2O.
The combined organics were washed with 400 mL brine, dried over MgSO4,
filtered and gassed with HCl.
The resulting tan crystalline solids were filtered and recrystalized from
boiling 1:1 IPA/Toluene to give pure
2CB x HCl as a white crystaline solid.
Yield - 34.0g (57%) of 2CB Hydrochloride
Purity - Single spot by TLC. NMR is clean.
I have references for the two reduction steps and the bromination, but can't
seem to find them. If someone
asks really nicely I might be persuaded to find and post them.
Also, before some jackass reads this procedure and asks me why 4 eq.of sodium
borohydride is used for the
reduction, here is a interesting little table for your reading pleasure.
(Eq. NaBH4) -> Molar ratio of 2,5-dimethoxynitroethane to dimer
(2.5) -> 6.25 : 1
(3.5) -> 44 : 1
(4.0) -> 50 : 1
Rhodium
(Chief Bee)
07-09-00 05:55
Beaker - this was certainly one of the single best posts to the Hive after
the software change! Great!
http://rhodium.lycaeum.org
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
2C-B Synthesis a la Lycaeum.
4-Bromo-2,5-dimethoxyphenethylamine
____________________________________________________________
List of Chemicals :
100g 2,5-Dimethoxybenzaldehyde
10g Ammonium acetate
200g Nitromethane
Isopropyl Alchohol (IPA)
500ml Tetrahydrofuran (THF)
Anhydrous Calcium Chloride (eg, Drierite)
NaOH
HCl
20 gram Bromine
Glacial acetic acid
Methylene chloride
25 grams of LAH
____________________________________________________________
List of Materials :
500ml boiling flask
200ml boiling flask
condenser
electric heater/heating mantel
oil bath
boiling chips
filter paper
separation funnel
high-temperature distillation flask
250ml filter flask
2 250ml beakers
500ml beaker
vacuum pump and hose
thermometer
____________________________________________________________
DISCLAIMER #1: It should be perfectly clear that 2-CB, also known under a
variety of names such as "venus",
"bromo", "erox", or "nexus", is currently a
Schedule-I substance. In order to protect us from ourselves, our
government has dutifully made it illegal to posses, manufacture, or
distribute any amount of 2-CB for any
purpose. Any persons caught breaking this law are subject to prosecution,
imprisonment, dehumanization,
demonization, humiliation, character defamation, intense personal harrasment,
and to top it all off - drug
diversion. You've been warned.
DISCLAIMER #2: It should be made perfectly clear that laboratory chemistry is
a very unforgiving art form. It
can take years to master even the simplest of reactions and tiny mistakes can
literally blow up in your face.
Although this synthesis in not overly complex, it contains some hazards and
will take a good deal of laboratory
skill, some sophisticated equipment, and a couple of days to complete. Please
use caution when testing the
final product - it is always best to start off with minute amounts and build
dosage slowly so as to minimize
any unforeseen adverse effects.
2CB is not exactly easy to make, but it is pretty straightforward. There
aren't any very tricky reactions or
especially messy procedures and the chemicals are not particularly suspicious
to obtain (anymore than
anybody buying chemicals or lab equipment today is suspicious to the
authorities). But, like any synthesis of
this nature, patience and precision are most imperative. Be sure to make the
measurements exact, keep
temperatures precise and check the colors or consistency of all
intermediates. A general chemistry
background is also very helpful, but not necessary if you lake the time to
learn about what you are doing.
____________________________________________________________
The basic precursor for synthesizing 2C-B is 2,5-Dimethoxybenzaldehyde
(2,5-DMB). Although you can even
make this compound, the procedure is fairly time involved. For our purposes,
it is best to start off purchasing
this material.
The first procedure is to change the 2,5-DMB into 2,5-dimethoxynitrostyrene.
We do this by heating a
mixture of 2,5-DMB and nitromethane in the presence of a catalyst, ammonium
acetate. Set up an apparatus
for refluxing. 'Refluxing' is basically boiling a solvent in such a way that
the solvent continually evaporates,
condenses, and is returned back to the boiling vessel. To do this we set up
the apparatus as shown.
Click for small image (http://www.lycaeum.org/drugs/Phenethylamines/2C-B/synthesis/reflux-thumb.jpg)
Click for larger image (http://www.lycaeum.org/drugs/Phenethylamines/2C-B/synthesis/reflux.jpg)
Place 100 grams of 2,5-DMB into a 500 ml flask and add 200 grams of
nitromethane. Most of the solids should
dissolve but if they don't immediately, don't worry - they will, once you
start heating them. When most of
them are dissolved, add 10 grams of ammonium acetate. Place the flask into an
oil bath on an electric
hotplate, connect the condenser and start a slow water flow through the
condenser. DO NOT use open flame
in any of these procedures. Nitromethane is very flammable! It is, in fact,
rocket fuel. It's dangerous enough
using an electric hot plate because of the sparks produced when the
thermostat clicks on and off, but if you
keep reasonable ventilation and a watchful eye on things, you should be okay.
Turn the stove up to about
100 degrees celsius, the boiling point of nitromethane, and adjust it until
the solution is boiling nicely. In a
short time the color of the solution will turn yellow. Four hours later, when
you are done refluxing, the color
should be a deep red.
Immediately set up for vacuum evaporation. If you let the solution cool off
too much it may spontaneously
crystalize, making it more difficult to purify, so do a little planning ahead
of time. Turn the heat off, detach
the condenser from the flask and add a few boiling chips to mixture. Boiling
chips provide a very large surface
area for lots of small boiling bubbles to form. This will keep the solution
boiling smoothly without any "bumps"
or big erratic bubbles. Connect the vacuum hose and apply a vacuum very
gently at first and build up to a
rolling boil without boiling up into the hose. As the solution evaporates,
the flask will cool down and you will
have to adjust the heat of the hot plate to keep a steady boil going.
Eventually, you will remove enough
solvent and the whole mass will crystalize into bright pumpkin-orange
crystals.
Turn off the heat and remove the vacuum hose from the flask. Always remove
the hose from the flask before
turning off the water. Otherwise, as the pressure drops water may be sucked
into your product. Add 100ml
of boiling isopropyl alcohol (IPA) to the mass and stir it as well as you
can, breaking up all of the clumps. Your
hot plate may still be hot and if you are working near it be sure NOT to splash
any of this nitrostyrene onto
the hot surface. The resulting fumes are a very potent teargas, something you
don't want to experience! Let
the flask cool and then pour off the red-colored alcohol solution. Add
another 100ml of boiling IPA to the
crystals and rinse as before. Rinse at least two more times or until
needle-like crystals form out of the
amorphous orange mush. Filter these crystals off and air dry completely.
There must not be any alcohol left in
the crystals, as this will ruin the lithium aluminium hydride (LAH) in the
next step. This is
2,5- Dimethoxynitrostyrene (2,5-DMNS).
Dissolve 50 grams of 2,5-DMNS in 300ml of anhydrous (dry) THF. If you cannot
find anhydrous THF, then you
will have to dry it the best you can. Do this by adding a drying agent (such
as Drierite, or anhydrous Epson
salts, or Silicagel) to the THF, let it sit overnight or longer, and then
filter it out. This should get most of the
moisture out of the THF that would otherwise ruin your expensive LAH.
Arrange your refluxing setup with a 2-liter, 2-neck flask in the oil bath, a
magnetic stir bar in the flask and a
drying tube attached to the condenser. This can be a spare tube, plugged with
cotton and filled with Drierite,
that is attached to the open end of the condenser to prevent moisture from
the air entering the reaction.
Put 750ml of dry THF into the two neck flask and start to stir at a slow
speed.
SLOWLY add 25 grams of LAH to the stirring THF, NOT the other way round (LAH
is nasty, dangerous stuff.
It ignites in the presence of water, it's poisonous to breathe, to touch etc.
Read up on it...). If you start
adding the LAH too fast it may spark, so take your time. It fuzzes as it hits
the THF, so add it carefully and
let it easily mix into the THF. Now you are going to add your nitrostyrene
solution. This is the reason for the
two neck flask. As you add this to the swirling THF, it fizzes up pretty
vigorously. Heat is generated and the
THF starts to evaporate. Get the water running through the condenser and
carefully add a little of the
nitrostyrene solution (2,5-DMNS) through the extra neck. When the fizzing
starts to catch up with you,
stopper the neck up quickly to keep the fumes from escaping and let the
reaction calm down and cool down
a little. Repeat this many times until you have added all of the
nitrostyrene. When you are done you should
have a dirty gray solution fizzing away nicely. Slowly raise the temperature
until reflux is reached and hold it
there for 24 hours.
Turn off the heat but leave the stirrer on and let the flask cool down. Once
cold, SLOWLY add isopropyl
alcohol (IPA) dropwise to neutralize any excess LAH. This will cause
considerable fizzing. Make sure you are
stirring while you add the IPA; if not, a layer of IPA will form and then any
stirring that is done will result in
the whole solution jumping right out of the flask. Take your time with this
until there is no reaction with the
addition of any more IPA.
This gray aluminium slush is nearby impossible to filter out of the solution,
but with the addition of 5Oml of
15% NaOH it becomes a white solid, and quite filterable. Now filter out the
solids (you will be keeping the THF
solution), and then wash the filter cake with a litth extra THF. Combine the
THF filtrate and the washings
into a boiling flask.
Now you must remove the THF from the mixture. This is done by simple
distillation under vacuum. Set up the
apparatus as shown. Add a few boiling chips to the flask and place it in the
oil bath. Start the vacuum and
increase until full strength is reached. As the THF evaporates, the flask
cools down and needs more pressure
to cause boiling. Finally, use the hot plate to cause steady boiling.
Eventually you will be left with a
dark-brown/goldenish oily residue. This is very crude
2,5-Dimethoxyphenethylamine, also known as 2C-H,
which you need to purify.
Suspend the oily residue in 1 liter of distilled water and make it slightly
acidic (pH of around 4) by adding HCl.
The 2,5-DMPEA will become a water-soluble hydrochloride salt and dissolve
into the water; other reaction
byproducts will remain water-insoluable and can be easily removed. Add the
solution to a suitably sized
separation funnel and add 50ml of methylene chloride. Shake vigorously and
let the phases separate. Drain
out the methylene chloride. Repeat this washing with three more 50ml portions
of methylene chloride. This
should remove much of the solution's color and it will remain only slightly
yellow. We must now freebase the
solution before our final purification by fractional distillation.
Make the solution very basic by slowly adding a strong solution of NaOH. The
mixture will immediately take on
a milky appearance. Shake the mixture vigorously for a few minutes to make
sure the 2,5-DMPEA.HCl is
converted to the freebase. This freebase is a dark oil which will separate
and start to settle out. Extract the
oil by washing, as above, with portions of methylene chloride, but this time
keep the washings. Combine all
the methylene chloride washings and remove the solvent by distillation as
above for removing THF. You will
be left with around 50ml of a dark oil.
Now we will distill the oil under reduced pressure and at a relatively high
temperature. To do this we use a
slightly different setup than the one used to remove the solvents. We won't
need the condenser in this case
and the flask should be much smaller (around 100 to 250ml) to adequately
accommodate the smaller volume
of oil. Setup the apparatus as shown. Make sure you use a water trap. Any
cold water entering the system
will crack the flasks and ruin the procedure. Also make sure to add boiling
chips to the flask. Oils tend to really
spatter and the chips are absolutely necessary. Bring the system up to full
vacuum slowly. There will probably
still be some methylene chloride that will boil off and end up on the
receiving vessel. This is ok. As we heat
the system it will eventually evaporate out of the flask. At full water
pressure on the aspirator, the oil bath
will need to reach 195 Celcius before the 2,5-DMPEA will start to come over
as clear, waterlike oil. Keep the
temperature and pressure constant as the oil slowly drips over. This will
take some time depending on your
exact setup. When you are satisfied that you have distilled out all the
product turn off the heat and
disconnect the vacuum from the flask. You should have around 20 grams of pure
water-white 2,5-DMPEA.
(2C-H).
Click for small image (http://www.lycaeum.org/drugs/Phenethylamines/2C-B/synthesis/distill-thumb.jpg)
Click for larger image (http://www.lycaeum.org/drugs/Phenethylamines/2C-B/synthesis/distill.jpg)
Now we will brominate the 4 position of the benzene ring of our 2,5-DMPEA. We
do so with pure elemental
bromine.,a fluid. Bromine is by far the nastiest stuff you'll ever want to
come across. As soon as you open
the bottle it will start to crawl out. If you noticed how well packed your
bottle of bromine was, you were
probably expecting something like this. Use this only in a fume hood if
possible. Don't even open the bottle in
your house or the whole house will smell like bromine for days and days.
Fortunately, we don't have to deal
with it for very long. If you have no access to a fume hood (which is
probably the case) then at least pick a
well ventilated area, away from any nosey public, and have a large jar with
an airtight seal available. Place
your 2,5-DMPEA in a 250ml beaker and weight it on a digital scale. Add to it,
this same amount of glacial
acetic acid. Place another 250ml beaker on the scale, quickly open the
bromine and weigh out the same
weight as your 2,5-DMPEA. Add to it that same amount of glacial acetic acid
and quickly add the 2,5-DMPEA
solution to it. After a few quick stirs, seal it in the large airtight jar.
The beaker will heat up but it shouldn't
be a problem with these quantities. If you scale this up you may need to rig
up an external cooling water
bath.
Light yellow solids will slowly form and in a few hours the solution will
cool down. The beaker should pretty
much now be solid with light yellow crystals of 2CB-HBr.
This 2CB-HBr has many associated forms involved with it and for a consistent,
predictable drug we will need
to convert it into the hydrochloride salt. Take the whole mass of 2CB-HBr and
filter it. Rinse a few times with
cold glacial acetic acid. Place the still-wet crystals into a 500ml beaker
and slowly add a 40% NaOH solution.
Stir briskly and a dark oil will start to settle out. Separate this oil, as
you did above, by extracting with
methylene chloride. You will also distill this oil, under pressure and at
high temperature, as you did above,
and again collect a clear oil. This is pure 2CB freebase.
The final step is making the hydrochloride salt of 2CB. This is done very
easily. Since 2CB is not soluble in
water, we don't have to worry about completely anhydrous solvents that are
usually the case when
crystallizing the final products. Add the freebase oil to lOO ml of distilled
water and slowly add acetic acid
while stirring until the freebase dissolves. This won't take very much acetic
acid. Get this solution stirring
with the magnetic stirrer and slowly add concentrated HCl. A white
precipitate of 2CB-HCl will immediately
form. Continue to add the HCl until the solution is thick with fine white
crystals. Stop the stirring, and when
the crystals settle out, decant the water into another beaker. Add a little
water to the crystals, stir and let
settle. Add this wash to the beaker with the original decanted solution, put
it back on the stirrer and add
more HCl. More crystals should form. Repeat this process until you are
satisfied that all the crystals have
formed. Now add all the crystals together - add water, stir, let settle and
decant repeatedly until the wash
water has a fairly neutral pH. Now you can filter the crystals and air dry.
This is fairly pure 2CB-HCl. Enjoy.
Dosage: in PIHKAL, Shulgin recommends 12-24mg, which is a good range to work
with when taken orally. An
alternate means of administration is by sniffing. I have found this much more
effective. Cut the dosage in
half and expect to feel results within 10 minutes or less! Note: Sniffing can
be very painful! It's best to do
smaller amounts than the whole dose all at once. As know from above, 2CB is
not water soluable and will sit
in your nose burning for a while - and it does burn. But the pain goes away
in short time and the results are
worth it. Experiment!
Reaction Mechanisms :
Click for small image (http://www.lycaeum.org/drugs/Phenethylamines/2C-B/synthesis/chem-thumb.jpg)
Click for larger image (http://www.lycaeum.org/drugs/Phenethylamines/2C-B/synthesis/chem.jpg)
HTML by: Andrew Edmond (Removed many typo's and added some minor notes
to this well written synthesis)
Made possible by: Lycaeum Drug Archives
ADDENDUM :
See the "New IDEAS from ALL !" thread in the Newbee forum for some
additional info.
And should be pleased to get more info where to
find the good 'recepeaces' LT/
Rhodium, Osmium, Rev drone, Siegfried, Labrat, Bright Star, KrZ, Beaker,
Station, Cesium, Spiceboy,
Psychokitty, Chem Guy, KCN, Ritter, Uncle Fester, Methyl Man, Sunlight,
dwarfer, Sumerian, iudexk, Titanium,
Equarius, tBOC, Lilienthal, WizardX, Worlock, Atomic Pickle, Bankrobber,
Ozbee, Epikur, Gyrogearloose, and
perhaps our former Queen, and anybody else I forgot to mention, I would be
glad if you hop in this thread
( but then the one situated in the Methods forum, so this one will stay
clean, after each update !)from time
to time to assist with rewriting or finding any blatently errors, I'm only
human, you too want good write-ups
so nobody get hurt in exploring their hobby.
I'm glad this edit-addy works, I hope it will not be shut off, at least not
for me, I'm intending to do a lot of
work in this thread the coming time, I intend to make it a sort of fast
introductory booklet for all those people
hanging around without the faintest knowledge of chemistry, so we will be
spared from all these beginners
questions for posted methods, and we have some more time for ourselfs then,
just refer to this thread when
questions come up which are solidly answered in here.
I want to gather ALL working methods in here (mentioning the originators of
course, to give credit to whom it
belongs) , edit them a bit for readability, and after that going to add a
extensive Lab Manual as an Addendum.
Rhodium
(Chief Bee)
07-06-00 03:05
This will be added to my page.
http://rhodium.lycaeum.org
WISDOMwillWIN
|
|
|
|
|
METHAMPHETAMINE PRECURSORS CLEANING/WORKUP
Extractomania........by Ozbee and friends..........edited by Placebo
INDEX:
1: Equipment
2: Ingredients
3: Method
step 1:
step 2:
step 3:
step 4:
step 5:
step 6:
4: Acid/Base
5: HCl-Gassing
6: Notes
1: Equipment
* Various jars, glass vessels, beakers etc
* PH paper, or electronic PH tester
* Filter paper or coffeee filters
* A strainer that will fit your filters nicely,
so that you get better surface area then a funnel
* Hair dryer, or heat lamps
* Hot plate, no open flames, only heat elements
* Seperatory funnel, or similar, or tube to siphon
2: Ingredients
-Pills containing psuedo-ephedrine HCl or ephedrine HCl.
-NaOH/Sodium Hydroxide/caustic soda/strong base/lye.
-Epsom salts that have been baked in oven (200c) for an hour to dry.
-Methanol
-Acetone
-Toluene
-Distillated water
3: Method
***note*** :
If pills have red coating, put in jar, with acetone, shake until red coating
is dissolved and then continue as
below.
Step 1: First, put your pills in a jar.
Add methanol about double the volume of the pills.
Cap the jar and shake till they break apart.
Leave to sit for a few hours shaking every 1/2 hour.
Let settle into 2 nice layers then siphon or decant off top layer.
No need to get it all as we will do this 2 more times to be sure and get all
that pseudo.
step 2: Once you have done it 3 times and have the 3 lots of methanol from
above, put them together and
put in freezer.
You want to get it real cold, near freezing and then filter it thru a very
fine filter, this may take some time if
you don't have a vacuum filtration setup but thats ok, we aint in a hurry.
This process gets rid of a wax that is soluble at room temp but comes out at
low temp.
step 3:***note*** : This step is not necessary and only speeds things
up.
After the chilled filter, we will reduce the volume of methanol/pseudo
solution.
So, with good ventilation and a fan blowing over pot, just reduce the volume
of methanol, but not till you
see crystals or anything. Just reduce it to a manageable amount, we just want
a saturated solution, you'll
notice it thicken a bit. Stop, take it off.
step 4: Now you want to pour a thin film of this methanol/psuedo solution out
on a mirror or glass table for
fast evaporation, or you could just leave it laying around a couple of days
and let nature take its course, and
it does make pretty crystals. Scrape all your crystals up when they are dry
and put into another clean pyrex
vessel.
step 5: Now pour Toluene, about double your psuedo volume
(**dry/anhydrous<<use your epsoms!**) over
your powdered psuedo, and heat till just before boiling with your fan blowing
over it.
Boil for 5 mins and then filter. Repeat this with fresh toluene until when
you boil toluene it stays clear. To be
sure of toluene doing its job, after filtering, add water to toluene before
discarding and you'll see the shit
come out.
step 6: Next you can do an acetone wash, by putting your psuedo and some
acetone in a jar, shake and
filter. Dry pseudo and you should have fuckin clean pseudo HCl......
This procedure, rids the pills of:
MCC
waxes
polymers
lactose
and most shit!
BUT, not povidone! More on that later.
You may choose to react your psuedo now.
Or do an A/B (acid/base) extraction, basicly turn it into a freebase, or oil.
Keep in mind..If you do an A/B now, you may lose some psuedo to the povidone.
So what are the choices? Well, povidone is known to go thru Hi/RP, no
problem, but must be steam distilled
out after. Which is a good thing coz you got no seperations or emulsions and
the cleanest meth around.
Povidone is bad because povidone is known to absorb and hold amines. It
depends on what reaction your
doing!
4: A/B: Ok, get your nice dry white powder and add about equal part water.
Now make up a 20% NaOH solution (or 4 parts DH2O:1 part NaOH).
Add Toluene to water/pseudo solution about equal to water volume.
Yes, toluene first, it gives the pseudo somewhere to go instead of being
burned by the base which can break
it up and turn it into aziradines!(toxic)!
Add NaOH solution to water/pseudo/toluene solution till PH 13, and remember
to test PH of water not toluene!
Now shake the jar up very well and let settle into layers.
Seperate toluene layer. Repeat this process 3 times and combine all your
toluene.
You can wash the toluene/pseudo freebase with water now, if you like, and
seperate again.
Now you can either, evaporate toluene for freebase crystals, or you need to
turn the freebase into a Hcl salt
again.
So you can add fresh DH2O (about 2mL for each gram of pseudo) to your toluene
and drop HCl acid slowly
with shaking each time into the toluene. Check pH all the time and stop just
before neutral. Shake again, and
recheck, this is very tricky and takes patience.
Now seperate the water from the toluene.
Now you can evaporate your water to get your pure pseudo HCl.
You can repeat this another 1 or 2 times and get a little more.
5: Gassing,
Gassing makes things easier coz you just gas it, filter and there'r your
crystals, but it is tricky to get the
hang of it and Hydrogen Chloride is dangerous! It will burn your fuckin lungs
instantly if inhaled too much of it!
You need to pipe HCl gas into your jar full of toluene and pseudo freebase,
but the gas and your toluene must
be dry : no water, or everytime the gas forms crystals it will be reabsorbed
by the miniscule amounts of
water.
If you don't know how to extract, you shouldn't play with gas yet.
If you know how to gas then read on...
So, you need to dry your toluene/pfed solution with pre-baked epsom salts to
absorb the water, and then
filter them out. Then gas your solution and you will see a snow storm before
your very eyes.
Then just filter and dry crystals.
But still may contain povidone.
Post merely for informational purposes. I haven't done anything illegal
and nor should you.
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
METHAMPHETAMINE SYNTHESIS
I.----Placebo's compilation of "the Cure" by Ozbee (clean-up of
sudafed and other ephedrine pills) and
various RP/I2(red phosphorous / elemental iodine, pure, crystals)
methods.
placebo
(Hive Researcher)
07-04-00 11:04
Go to Whoah!
Ok, this is a compilation of many peoples' methods.
I believe this to be the best, simplest, fastest, and cleanest method for
producing meth-amphetamine,
in the highest yields possible for RP/I2/E reaction.
Remember, each and every step gives small losses, and this method has the
least steps!
It is a culmination of efforts by Worlock, CHEMMAN, and maybe a few tiny
touches by me.
I re-iterate, I don't want any congratulations except for the write-up
itself.
You will need these things, and no substitutions allowed.
If you can't get this shit, you ain't ready to make the best Go-Go in town.
This is a refinement of all methods, and the next step up from Push Pull, but
nobody should be discouraged
from attempting this, as you will probably find it easier.
pH paper isn't even necessary.
This post is one method from Go to Whoah.
This post has to be followed from Go to Whoah.
Otherwise you can run into trouble, as povidone is not removed in this
extraction.
It will be removed at the end. Each step was chosen to complement the next.
Understand?
Read on.....
Index:
1: Equipment
2: Reagents
3: Extraction of pfed
4: Reaction
5: Steam distillation
6: Crystallisation
Equipment:
Various jars
2L pyrex vessel
2L 2 neck round flat bottom flask
1 condenser, I recommend a coil condenser but a Liebig will suffice.
1 sloping splashhead or better, a steam distillation sloping splashhead.
A steam pressure cooker, that has a release-valve on top.
Hotplate, electric of course.
Filter paper, Buchner and vacuum would be nice too.
Thermometer.
1 Glass stopper.
Lengths of clear pvc tubing.
Pot with vegetable oil, which can fit your reaction vessel.
Reagents:
Iodine crystals.
Red Phosphorous.
Pseudo-ephedrine, or ephedrine.
Methanol.
Toluene.
Acetone.
NaOH.
All must be clean and anhydrous.
Ice.
Extraction of pfed:
This method will deal with the HCl salt of pfed, and a streamlined version of
"the Cure".
All pills are dumped into a large jar and double of this pills-volume in the
form of methanol poured on top.
This is stirred vigourously and let stand to settle thereafter, in the fridge
seems to speed it up.
After the top methanol layer has cleared it is carefully decanted off.
This procedure is repeated 3 times.
All methanol pulls are put together and the methanol boiled off on a
hotplate.
As methanol gets down to the last little bit, it is taken off the heat.
Then a portion of acetone, twice your remaining liquid is dropped in.
This forces the pfed crystals to crash out.
Then the remaining liquid is carefully evaped off.
Washes:
Now you have your crude/dirty pfed HCl.
Next we will be doing successive toluene washes.
Put your pfed crystals in a pyrex (heat proof glass).
Now add toluene to a safe level that can be lightly boiled on the hotplate.
After about 5 mins boiling with stirring, take off the heat and let it settle
a minute.
Now carefully pour off toluene into a filter to catch any remnants of pfed
that may follow.
Now if you get the toluene that has our contaminants in it and add some
water, you will see the crap, crash
from the toluene into the water.
This is the crap that came thru with the methanol pull.
So as we continue to do multiple toluene washes, we will continue to test the
toluene after pouring it off, to
see how we are progressing with the cleanup.
When we have reached a point where no crap comes out of the toluene, with the
addition of water, then we
are ready to try acetone.
Usually about 3 boils in toluene, but of course it depends how much you'r
using.
So, as before we will add a portion of acetone and boil lightly.
Now when we pour off the acetone, we will add a tiny amount of water and some
NaOH.
This is our final test, when you do this and no crap falls out of acetone you
are ready.
This will be the cleanest pfed you have ever seen, guarenteed!
AND, yields should be >90% if you'r carefull! 95% is good.
Reaction :
Smallest reaction to be attempted, especially by newbees, is 1 oz of pfed, so
that even taking into account
sloppiness, lack of experience and losses along the way, you should get some
product.
Ratios of reagents are: 3:3:1 or 1:1:1/3 , ie.E:I:RP aka, equal amounts of
Iodine and pfed, and a one third
amount of RP.
This is calculated on a weight basis, and can be scaled up or down as
necessary, e.g.60gmE/60gmI2/20gmRP
or 120gmE/120gmI2/40gmRP etc etc.
First prepare yourself an icebath. Yes, icecubes and water in a sink or
bucket.
Now, many will say you should add this first or that first.
Well, after much reading of different peoples methods, I say....
Chuck the whole shebang in together, while your flask is on ice, lift and
swirl ingredients together, while
maintaing on ice.
Put your condenser on top and start water running thru, from bottom to top.
Now, the idea is to get the reaction going in the most controlled way
possible, you want to let the reagents
react in the container vessel fixed in the icebath, if at all.
Then move vessel from icebath to room temp.
If things look like they're going too fast, put back in ice bath, you want to
keep the reaction going but only
at a nice slow, controlled pace.
This is also necessary to control vapour in the condenser!
Thick and or dis-colored smoke is bad, and plumes of smoke will escape from
condenser.
Let things progress at a nice slow pace, as things slow too much, you can
start applying heat.
So prepare an oilbath and bring to about 50 C, if there is no more action in
your vessel.
You can move it to the oilbath, and the same goes for it as before, when
things slow down.
Adjust heat up, to say 100 C then 150 C for one hour, to make sure reaction
has completed.
The whole time you should be watching to keep a nice reflux going, and not
too much vapour is escaping
from condenser.
Now remove from heat and disconnect condenser, add ice water to quench
reaction.
The reason for ice water is to calm the reaction down when NaOH is added.
Its up to you if you want to filter out RP or leave it in untill the end.
I would leave it, it will be washed nicely by next process and be easier to
filter.
Now add lots of NaOH to bring reaction mix to + 14 pH.
You cannot over-basify, as meth won't be destroyed, its a tough MF!
Steam Distillation :
Now you need to set up your glassware for steam distillation.
Attach the steam distillation sloping splashhead to top hole of flask, attach
plastic hose to steam inlet and
the other end on the release valve of the pressure cooker that is full of
water.
Attach condenser on the end of splashhead, and rig the whole up so it stays
up.
Place a jar at the end of condenser to catch our distillate.
You want to heat both the pressure cooker, and the reaction flask.
Sit back and get ready for one of the most beautiful sights and smells.
The meth freebase that is sitting on the top of your aquaeous layer in the
flask will vapourise and be carried
across and be condensed in the condenser and trickle down into your jar. It
will sit atop of a bottom layer of
water.
After the last of the oil has come across, change jars and leave the setup to
run for another hour, just to
make sure you got it all.
Any povidone from the pills will be stick behind in the reaction vessel.
It has been noted that some polymer that may have been left from extraction,
may follow the steam.
Crystallisation :
Now we have a jar of water, with this sweet clear oil sitting on top.
Next options are to add HCl acid slowly with stirring until the oil layer
disappears, and then evap the whole lot
to get crystals.
Or, as I found, you may have some polymer that has come over with the steam,
and is now sitting in the
water layer, and it looks cloudy.
I don't want to evap all that, it will just concentrate the shit in there,
(plus its very time consuming evapping
water, plus you risk losing some meth as the water evaps).
I think you should just throw a little toluene into the jar,
and then seperate.
Now your absolutly pure meth freebase is in your toluene!
Now you can either gas, for instant the now clean meth, or
add minimal distillated H2O and then acidify to pH 7, shake, seperate and
evap water for crystals.
Repeat this step if you do it this way, as some more may come in a second go.
With this process from start to finish, you shouldn't need to re-crystalize,
as your product should be the
cleanest shit anybody has ever seen anyway.
But you may want to, for the purpose of growing nice big crystals.
In which case, add just enough hot methanol to dissolve all your meth and
then place in freezer.
The secret is, the slower the evap, the bigger the crystals.
So a nice slow room temp evap over several days might be fun.
Enjoy, and do not attempt anything above, before you completely understand
what you are doing!
You must have a sound understanding of the basics first!
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
--------------------------------------------------------------------------------------------------
How to produce anhydrous (= dry = waterfree!) HCl gas using no
special equipment for all your
amination steps of freebases - by Psychokitty.
--------------------------------------------------------------------------------------------------
To date I have never used Strike's and Fester's method for producing HCl gas.
Reasons for this are as follows:
1. The necessity of laboratory glassware (no OTC hardware).
2. What seems to be a messy proceedure using table salt (but I wouldn't know
exactly as I've never tried it).
3. Difficult dismantling process (at least it seems to be more difficult than
mine).
I don't remember the exact journal reference that inspired my method, but I
do
know that it is described somewhere in Inorganic Syntheses Vol. I.
Okay. First, here is what you need:
1. Beer bottle (transparant).
2. Plastic baby syringe (15 ml capacity) found at the pharmacy section at any
grocery store.
3. Four or so feet of ice-maker transparant-white polyethylene tubing found
at
the hardware store. (I don't remember the exact diameter size. All I know is
that it IS the smallest size available.)
4. One table-leg stopper (rubber, beige or black). Another item of which I
don't
know the size. Just take your beer bottle into the hardware store and see
which size fits snuggly on its top.
5. One aluminum tube that is the exact diameter size as the polyethylene
tubing.
Found at the hardware store but don't know what they are used for. They are
sometimes made of brass.
6. One bottle of sulfuric acid drain cleaner.
7. One bottle of concentrated hardware store muriatic acid (32%?)
Assembling the HCl generator is easy.
1. Use the aluminum tubing to burrow two holes to the top of the table-leg
stopper. Use a twisting motion while appling pressure for about a minute
and eventually the tube will pop through.
2. Place the table-top stopper over the top of the beer bottle. It'll fit
snugly.
3. Insert the polyethylene tubing into the middle-most hole and push through
until the tubing hits the bottom of the beer bottle. With scissors or a knife
cut off the polyethylene tubing about two inches from the top of the beer
bottle.
4. Take the entire table-top stopper inserted with the polyethylene tubing
off
of the beer bottle. Pour into the beer bottle a volume of sulfuric acid about
an inch high off of the bottom of the beer bottle.
5. Replace the table-top stopper/polyethylene tubing on top of the beer
bottle.
Insert the remaining tubing into the last hole of the stopper until about
two inches into the bottle. Cut tubing down to desired length.
6. Pour about twenty milliliters of concentrated HCl into a cup. Extract into
baby syringe until syringe is full (15 mL). NO, the HCl will not dissolve
any part of the syringe in any way.
NEITHER THE HCl NOR THE SULFURIC ACID WILL REACT WITH ANY PIECE OF HARDWARE
USED
IN THIS SYSTEM. THIS SET-UP HAS BEEN TESTED MANY TIMES WITH SUCCESS.
7. Insert the syringe into the middle tubing (the one that extends to the
bottom
of the beer bottle. End should be submerged in Sulfuric acid.) If insertion
is difficult, use a knife to scrape the inside of the tubing to allow the
syringe to fit more easily.
8. Securing the set-up with a clamp of some sort attached to a stand is
optional
but desirable.
9. Have handy on the side a container full of water.
The use of this set-up to gas ones solvent/amine is just as easy.
1. With right hand, hold the tubing that will expel gas and lower into the
solvent/amine solution.
2. With left hand slowly start to inject the HCl solution in the syringe into
the sulfuric acid. Once it hits the acid, there will be alot of fizzing and
foaming and IMMEDIATELY HCl gas will be pumped into the solvent/amine
solution.
Foaming is sometimes a problem as it starts to reach the top of the beer
bottle. Simple wait a while and let it settle and then continue. Sometimes
certain brands of drain opener can cause excessive foaming. If this occurs,
switch brands.
3. One syringe is usually enough for an amount of about 30-40 g of product,
but
if more is needed after all the HCl has been injected, slowly SLOWLY remove
the syringe from the tubing, first be letting a crack of air into the system.
BEWARE that this is suddenly going to bring a minor rush of HCl from the
gassing
tube so make sure that it is submerged when doing this step. To continue,
refill
the syringe and proceed as described above.
4. Once the gassing is complete, leave the syringe ATTACHED to the injection
tube and submerge the gassing tube in the container full of water (If the
syringe is not attached to the injecting tube, the following sequence will
not occur). Weigh down the gassing tube somehow as it must remain submerged.
In a few minutes (about five) the sulfuric acid will cool a bit causing a
sucking-back of the water into the beer-bottle. This will happen very
suddenly
and very fast, but not to worry as the water will only go in as far as the
top
of the beer bottle. This is actually an advantage as in this way one is able
to dilute the remaining HCl gas AND the remaining sulfuric acid. Of course
the
bottle will get hot but if left aside for a few minutes it will eventually
cool making opening the container and dispensing with the acid solution an
easy
task. If the bottle is opened for whatever reason without the above acid
dilution step, HCl gas will be everywhere.
Hope this method will prove useful to you my fellow bees, it sure has been
for me!
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
|
|
|
|
|
Even when you think you made it as clear as you can, still questions arise
which I would not have thought of,
because I see it as common knowledge.
In that sense your question is helpfull, it let me realize that non-chemists
do not know that there is no 100%
Sassafras oil, it's allways a mixture of the essential oils at present in the
extracted plant material, and differs
from geografic situation to situation. Brazil and Vietnam seem to have the
best and relatively high safrole
contents.
75 to 90 %, which means they are lucky to have the good trees there and use
good extraction techniques,
like steamdistillation and vacuum destillation thereafter.
I will change above text to :
Sassafras-oil, usually etc. xx % safrole oil.
Your second question a joke ? What the hell did I write that all for, it is
thoroughly explained there. LT/
WISDOMwillWIN
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
Methyl_Man (Hive Researcher) 06-05-00 10:40 :
METHYL_MAN's WRITEUPS of MeOH BENZO WACKER and MeNO2-Al-Hg.
Consult these threads to avoid unnecessairy questions :
http://rhodium.lycaeum.org/clandestine/gonzo/index.html
http://hive.lycaeum.org/wwwthreads/perl/showflat.pl?Cat=&Board=methods&Number=13991&page=
&view=&sb=&vc=1 and
http://hive.lycaeum.org/wwwthreads/perl/showflat.pl?Cat=&Board=methods&Number=15667&page=
0&view=collapsed&sb=5 and
http://hive.lycaeum.org/wwwthreads/perl/showflat.pl?Cat=&Board=methods&Number=31473&page=
0&view=collapsed&sb=5
---------------------------------------------------------------------------------------------------
Here they are, with minor changes from older versions for greater accuracy.
=================================================================================
Methyl Man's MeOH version of the benzoquinone wacker
Materials:
400mL MeOH (methanol)
50mL distilled H2O
150g p-Benzoquinone
2g palladium (II) chloride (PdCl2)
178g safrole
DCM (methylene chloride; dichloromethane)
NaCl (non-iodized table salt)
Sodium bicarbonate (baking soda)
5% NaOH
HCl (hydrochloric acid, from muriatic acid)
Magnesium sulfate drying agent (epsom salts baked in 400¢XF oven for 2 hours)
Method:
1. In a 2L flask fitted with a reflux condenser and addition funnel place
400ml MeOH, 50ml dH2O,
150g p-Benzoquinone and 2g PdCl2 and leave to stir for a minimum of 60 minutes.
Note that a recent
improvement has been discussed which involves stirring the PdCl2 in the
solvent (MeOH in this case) for
several hours before adding the water and benzoquinone. It is likely that
this does enhance yields a bit by
ensuring maximum efficiency of the PdCl2¡¦s catalytic action. Either way will
work well, however. If you let
the PdCl2 stir alone for a while, when you then add the water and
benzoquinone, let them stir for an hour as
well before beginning the next step so as to ensure complete dissolution of
the benzoquinone.
2. Place 178g safrole mixed with a bit of MeOH in an addition funnel.
3. Add safrole dropwise from the addition funnel over 60 minutes or more.
However, when the addition is
about 80% finished, apply low heat just sufficient to start a mild reflux
(cold water through the condenser).
4. After the safrole addition is complete, leave mixture stirring and
refluxing for 8 hours. (If you must stop at
this point and resume another day, be sure to put the mixture in the freezer,
sealed well. The raw ketone
decomposes unless stored at freezer temperatures.)
5. Filter out the solids present in the mixture, which are hydroquinone (the
degradation product of the
benzoquinone) and PdCl2. This can be done by vacuum filtration or by simple
gravity filtration with coffee
filters. Many prefer gravity filtration with this synthesis because the
solids produced in this reaction are very
fine and are problematic to filter with vacuum. Don¡¦t try to recycle the
PdCl2, as it is too difficult to
separate from the hydroquinone to be worthwhile.
6. Flood mixture with 1.7L 3N (~10%) HCl. (Here's the quick math: add 500mL
of 31% HCl [muriatic acid] to
1150mL H2O to get 1.65L ~10% HCl¡Xclose enough for this purpose.)
7. Extract flooded mixture with 3 portions of DCM (1 x 500mL, 1 x 250mL, 1 x
100mL) in a large separatory
funnel. The desired raw product, MDP-2-P (¡§ketone¡¨), migrates into the DCM
as an oil. Separate the
DCM/ketone layers and combine them.
(Note: when you first hit it with the DCM you will probably observe a bit of
scum which will float on top of
the water layer, which will work its way down during these three extractions
to appear as a blob of spongy
semi-solid interface. It¡¦s actually very mobile and easy to work around;
simply avoid allowing it into your
DCM separations. The same thing will happen in your washes in steps 10, 11
and 12 below, but by then you
will be quite the pro at working with it.)
8. Extract water layer with a final small amount of DCM.
9. Add this final small DCM extraction to the combined oil/DCM solution from
step 8.
10. Wash the ketone/DCM solution with saturated sodium bicarbonate in water
twice (500mL each wash).
11. Wash the ketone/DCM solution with saturated NaCl 3 times (400-500mL each
wash).
(Note: as you do these bicarb and salt water washes, you should be seeing the
ketone/DCM solution getting
progressively more greenish colored; this is visible in the film of solution
that runs down the inner surface of
the sep funnel).
12. Wash the ketone/DCM solution 3 times with 500mL 5% NaOH (500mL each
wash). If you did step 5, you
will have a very easy separation.
(Note: you should also see a very noticeable color change upon doing the
first of these three washes wherein
the ketone/DCM layer becomes a strange, thick reddish-brown, almost orange
color. This happens as the
NaOH pulls the majority of the solvated hydroquinone into its layer, cleaning
the ketone. The NaOH layer in
the first wash will be very dark brown, almost black in fact. The next two
will be a far lighter, watery, orangy
color.)
13. Dry the ketone/DCM solution with ~50g magnesium sulfate.
14. Distill off the DCM using mild heat on a water bath and ice-cold water
through the condenser. This will
take several hours.
15. Add 50mL of high-oleic safflower oil (no additives!!) to the ketone oil
as a buffer to prevent the ketone
from scorching in the distilling flask.
16. Vacuum distill the ketone/buffer oil mixture. This also will take a few
hours, but not as long as distilling
the DCM off did.
17. At 100 to 140¢XC (wherever your particular vacuum dictates), a minor
amount of safrole might come over.
If your safrole-to-ketone conversion was good, there should only be a very
small amount. If it is only a few
drops to a milliliter or two, you can leave it in, and not change/clean
receiving flasks. If you are a stickler for
purity, discard it. It will not harm anything later if you leave it in. But
if it¡¦s more than a couple of milliliters,
get rid of it.
18. At anywhere from 25 to 40¢XC above the temperature your safrole usually
comes over with the same
vacuum, the ketone should begin coming over. You should get about 100 to 120g
ketone. The color of the
ketone coming over will likely be a pale, fluorescent-looking greenish
yellow. In fact it looks not unlike
anti-freeze¡Xa similar ¡§neon green.¡¨ You can stop distilling when the rate
of ketone coming over has slowed
to an agonizing one drop per 90 seconds or so. At this point there is so
little left that it is probably not worth
your time to wait for a drop per 1.5 minutes (it¡¦s not worth mine anyway).
19. Immediately store your precious fluid in the freezer in an airtight
sealed flask or bottle. Happy cooking!
---------------------------------------------------------------------------------------------------------
The MeNO2-Al-Hg reductive amination according to Methyl Man
Since the appearance of Ritter's writeup of this method in Total Synthesis
II, much discussion has taken place
about it but, it has sometimes seemed, little has been clarified. This is due
in large measure to the sensitivity
of this reaction to even the most minor changes in its many variables. With
this writeup, I hope to provide a
clearer view of the method and to allow others to benefit from the hard-won
experience of someone (not me)
whom we'll call Mr. A. Ritter's original writeup, while inspiring, lacked
details about the many nuances that,
once understood, allow the amateur chemist to really understand this
reaction's dynamics. Thus I have tried
with this writeup to help the neophyte who has only physical observations and
scant written material to guide
him (although I suspect and hope that it may even help a few more seasoned
cooks as well).
The first thing I'd like you to look at is the array of interrelating
variables in this reaction that make it so
delicate. They are as follows:
1) the thickness/type of the aluminum
2) the consistency (i.e. flat, ground, etc.)
3) the amount of HgCl2 used in relation to the amount of aluminum
4) the addition rate of the MeNO2/MDP-2-P
5) the size of the reaction vessel in relation to the scale of the reaction
6) the ability to effectively stir the reaction
7) the coldness of the water through the reflux condenser (yes, even that!)
The above factors are sort of submitted in an order of importance (#1 being
most important), but in reality
they are all inextricably related. I observed firsthand the trials and
tribulations of Mr. A as he struggled to
match up the correct combination of ratios and conditions that would allow a
smooth, consistent reaction
and predictable results every time. Finally, after lots of frustration,
confusion, losses, and---in the end---a
revelation, the perfect set of elements was hit upon and recorded.
The scale Mr. A chooses to perform this reaction on is half-scale to the
scale in the Ritter writeup, which was
55g aluminum and 50g MDP-2-P. Therefore this writeup will illustrate the
reaction on a scale of 27.5g aluminum
and 25g MDP-2-P. The subject found for his own personal reasons that this
smaller scale was much easier to
manage (not the least of which is that even with a huge 4-liter separatory
funnel, at this smaller scale it gets
pretty filled up!). There's no doubt that the original larger scale can be
successfully applied, although it would r
require adjustments in the glassware capacity, stirring method, and probably
other elements.
MATERIALS and APPARATUS:
-- 27.5g Reynolds Wrap Heavy Duty aluminum foil
-- 25g MDP-2-P
-- 20 mL MeNO2 of 99+% purity
--750 mL MeOH + 50 mL more for addition funnel + additional small amounts
that will be needed later to thin
the mixture
--400mg HgCl2
-- 2-liter 2-neck flat bottom flask
-- reflux condenser (400mm preferable)
--250mL or 500mL addition or separatory funnel
-- cooling setup (bucket, water pump, tubing, 1 large bag ice)
METHOD:
1. Weigh 27.5g of Reynolds Wrap Heavy Duty aluminum foil (NOTE: it HAS to be
Reynolds and it MUST be the
heavy duty stuff) and then tear it by hand or cut it with scissors into small
rectangles approximately 1" by
.75". Settle down with this task with a good CD or TV show because it is
tedious and may take about
1.5 to 2 hours.
2. With a coffee grinder, "grind" these pieces of foil for
durations of about 10 seconds. Fill the coffee grinder
only loosely (about two thirds full---don't stuff it! That will adversely
change the consistency of the
ground foil). It will probably take about 4 to 5 "loads" in your
grinder to do the whole amount of foil,
depending on the size of your grinder. (In actuality, the foil does not get
"ground," but rather, each
individual piece just gets compacted and compressed. If it is compressed too
heavily, the inner surfaces
of the foil nuggets may be rendered inaccessible to the Hg/MeOH solution,
changing the timing of the
amalgamation and maybe even causing an incomplete or failed reaction.) When
properly done, the foil
should be in gnarled little nuggets about the size of long-grain rice grains
and should look really tight and
small. The smaller, the better for good stirring.
3. Place a 3" stirbar in your 2L flat bottom flask and onto your
stirplate. Add the foil nuggets to the flask and
then proceed to set up your glass, support and clamps so that the reflux
condenser and addition/sep
funnel are securely affixed and your flask is well-centered on the stirplate
(this will be critical when you
begin to attempt stirring!). Also, prepare your cooling, i.e. attach the
inflow and outflow tubes to the reflux
condenser.
4. Carefully add the 400mg HgCl2 to 750mL MeOH to a tightly sealable bottle
and shake to dissolve all HgCl2.
Set this solution aside.
5. Combine the 25g MDP-2-P, 20mL MeNO2, and 50mL MeOH and pour them into the
addition/sep funnel.
Rinse your beaker (or whatever you used) with a tiny bit of additional MeOH
to get the residual ketone and
add it to this MDP-2-P/MeNO2/MeOH solution.
6. Very slowly and carefully (w/gloves, glasses, long sleeves and a Hail Mary
if you're Catholic), using a large
funnel, pour the HgCl2/MeOH solution from step 4 down the condenser.
7. Turn the stirring on full blast for a 5-second burst to intimately mix the
solution and the foil. If you have
prepared the foil as described above, it will easily stir. Give it a few more
5-second stirs over the next few
minutes. I believe that doing this really helps facilitate the amalgamation
process that is about to occur.
8. After about 5 minutes or so, you will begin to see bubbles popping up on
the surface of the MeOH solution.
At first they will be tiny, like champagne bubbles. Then after a few minutes
you will see them joined by
larger bubbles closer to the size of those seen in boiling water. It is
around this same time that the
appearance of the aluminum will change from its normal shiny silver color and
start to take on a dull gray
look, accompanied by a gray cloudy look that begins forming in the MeOH. This
is the magic moment when
you want to begin dripping in your MDP-2-P/MeNO2/MeOH mixture. Set a drip
rate of approximately 2 drops
per second at this point and no faster. You can speed it up a bit later to
accelerate the reaction if desired.
9. Place about 3 lbs ice into your bucket. When you can feel exothermic
warmth begin by feeling the outside
of the flask, quickly add about 2.5 liters water to the bucket (or an
appropriate amount to make very
ice-heavy ice water) and plug in the pump.
10. While monitoring the growing intensity of the bubbling amalgamation, turn
on/off the stirring intermittently
as you did earlier. This time it is to assure distribution of the added ketone/nitromethane
in the reaction
flask but also because the amalgamation seems to gain its vital momentum more
effectively if given some
significant blocks of time (meaning about 30 seconds at a time) in between
"stirring bursts." When the
reaction is clearly starting to get vigorous and hot, crank the stirring to
10 and leave it on.
NOTE: This is where you can take advantage of Mr. A's trial and error
regarding this reaction's parameters.
If you used the kind of foil specified, prepared it as specified, used no
more than the specified 400mg HgCl2,
and used a 2-liter and NOT a smaller flask, you can breathe easy knowing that
the reaction is going to hum
along nicely but will not get out of control, and will result in perfectly
processed aluminum amalgam sludge.
You may think that a 2-liter flask is oversized for this reaction, but that
is precisely the point. The extra
headroom in the glass provides a nice zone of "breathing room" for
the reaction and facilitates good refluxing.
I've seen this reaction get out of hand in a 1000mL flask, and it isn't
pretty, believe me. Use the 2-liter.
11. As the reaction progresses only a few minutes after the addition was
started, you will observe that the
aluminum is breaking up fairly rapidly. This is good, as long as you have the
ketone/nitro mixture dripping
in at a good rate of about 2 drops per second. But be careful with the
addition rate at this point, as a
rate that is much faster than this could easily send the reaction into
overdrive (not good). Your reflux
should be unnervingly vigorous as the amalgamation really starts to pick up
speed, with the MeOH dripping
really fast down out of the condenser. I know it's hard to believe, but this
is what you want, this is good.
I'm telling you, LOTS of trial and error came before this writeup. Trust me.
You will also see sludge already
starting to settle at the bottom and forming a ring on the glass around the
top surface of the spinning
mess. The consistency will get thicker by the minute. Add more ice to your
bucket as needed.
12. At this point you can sort of control the reaction rate by slowing down
or speeding up the addition rate a
bit. Of course the reaction is already barreling along, so you won't want to
speed it up much. The concept
here is that you want the addition of the ketone/nitromethane to be paced
neck-and-neck, as it were,
with the breakdown of the foil as it amalgamates and gets turned into sludge.
In other words, you have
to watch those two things and sort of adjust the addition so that they
proceed at approximately the same
rate. It's tricky, and imprecise, but with a little experience and intuition
you'll get the hang of it. Sure, you
could be lazy and just leave the addition at a steady 2 drops per second the
whole time, but if the
amalgamation peters out way before your addition is finished, and you find
yourself adding your beautiful
ketone to impotent sludge, don't cry to me. The addition should take about
40-45 minutes in total, and as
it's finishing, the state of the aluminum should be about 95% broken down. In
fact the reaction should by
now (~45 minutes after addition was started) look like a really thick,
steely-gray chowder with only minor
small slivers of undissolved aluminum visible if any at all. You will
probably even need to add an extra
20-30mL of MeOH down the condenser at this point (or before) to help it keep
stirring effectively. This is
no problem.
A note about color at this point is helpful too. Comparing successful
reactions to failed ones, I have observed
that there is a distinctive color to the mixture early on that indicates
healthy amalgamation and foretells a
successful run. At a point maybe 30 minutes or so post-addition, the reaction
takes on a color that I would
describe as being "light steely gray with blue overtones." It is a
hard thing to describe shades of gray, but I
will try. It is a light shade, akin to the color of common gray sweat pants,
but like I say with a very slight
suggestion of a blue hue in there as well. This is in contrast to what I saw
in failures resulting from using too
thick of aluminum and not enough HgCl2, where a dark metallic gray with
definite green overtones (from
unreacted ketone) was noted.
NOTE: Another point I would like to make about the timing of the addition
against the breakdown of the
aluminum is that Mr. A found that there was a definite "spike"
curve to the amalgamation reaction which was
easily observed by watching the reflux rate. That is to say, there is a peak
that it builds up to and then
comes down from. At this scale, and using the exact materials described
herein, that buildup to peak and
subsequent slowdown occurs over approximately 25 minutes or so---very fast.
So at only about 20-25
minutes after you first started feeling the amalgamation heating up, it will
have slowed to a reflux of about 2
drops per second, after having been at a peak with a reflux rate so furious
it is a stream, not drops. At one
hour and 15 minutes after you first started the addition, the reflux will
have slowed to a very calm 1 drop per
2 seconds or so. Finally, when...
A) the reflux has slowed to almost no reflux at all
B) if you stop the stirring you do not see any small bubbles anymore
C) no "uneaten" aluminum is visible and the solution is a thick,
uniform gray soup,
...the reaction has essentially finished. It will reach this state at about
one hour 45 minutes to two hours
after addition was started. Nevertheless, you will leave it stirring happily
for a total of three hours after the
addition was finished to assure that the reaction has run its full course and
the conversions that you desire
have had ample time to take place. In fact you should add a bit of external
heat at the point where the
addition has finished and the reflux slows down dramatically, because I¡¦ve
found that if one doesn¡¦t, there
might be a bit of aluminum that refuses to break down all the way which
results in the later extraction being
messier and much more of a hassle. One reason I bring this all up is that
there has been lots of talk about how
this reaction needs 8 hours or 24 hours or even 36 hours to run! But those
time frames apply only in cases
where much thicker aluminum is used, and/or in variations using methylamine
and not nitromethane. Mr. A was
never successful in using thicker aluminum, and doesn't want to be! Why would
someone want to make a
reaction take any more time than it needs? Beats me! I'm mystified! The
approach illustrated in this writeup
optimizes this reaction to finish in 3 hours 45 minutes from beginning to
end, and it probably doesn't even
need that much time.
13. If you chose to apply external heat, turn it off at about 30 minutes
before the targeted finish time.
Otherwise you will have to wait an extra 30 minutes (at least) for it to cool
for the next steps.
14. When finish time has arrived, dismantle your setup, set aside your
reaction flask, and make 750 mL of a
35% NaOH solution (750 mL H2O + 262.5g NaOH) and let it cool to room temp or
below (safety glasses!).
15. Into a separatory funnel no smaller than 2000mL capacity, pour your
beautiful gray reaction mixture,
being very careful to KEEP THE STIRBAR FROM FALLING IN to the sep funnel and
breaking it (that would
be ugly). If your mixture is really thick, you may need to add small amounts
of MeOH to thin it to a
pourable consistency. This is perfectly fine. Wash the final residue out of
the reaction flask with a few
mLs of MeOH and add it to the funnel also.
16. Slowly pour the NaOH solution into the sep funnel (gloves and glasses! no
excuses!). That's right, don't
dump it in wholesale. Basifying should be a gentle process. If you bully
those molecules they may decide
they're being disrespected and choose not to cooperate. Adding the NaOH will
cause the mixture to warm
up a bit as the very last bits of the aluminum are dissolved, which is fine.
Swirl it a couple times and give
it about 10 minutes to cool down to something closer to ambient temperature.
That yummy stinky
methylamine smell tells you that the reaction was successful.
17. When the mixture in the sep funnel has cooled down, extract it once with
400mL toluene followed by
once with 100mL toluene. These are the critical moments for your yield now,
so you be sure to shake long
and hard (at least 3 minutes) during these extractions (I don't have to tell
you to vent do I?!). The
toluene/product layer will of course be on top since toluene floats on water.
Also, be sure to give the
separations ample time to happen (at least 15 minutes); it is easy to tell
when it's okay to separate
because the interface of small toluene bubbles finally resolves and you have
a nice clean line between the
layers. If you like, do as Mr. A does and finish off with a final small
extraction of 50-60 mL toluene just to
get the last of the stuff.
NOTE: Your extractions will contain a tiny amount of the base/metal/garbage
from the bottom layer; this is
inevitable but easily worked around in this way: when you have collected your
combined toluene/product
extractions in a bottle, chill that bottle in the freezer for 30 minutes or
so. When cold, the garbage gets a lot
less mobile and it is easy to decant the toluene away from it. Just be
vigilant while pouring the last 50 mL or
so and avoid letting that glob of crap rejoin the toluene. Yeah, you will lose
the very last 2 or 3 mL, but
that's life. Alternatively, you could filter it through a paper towel, but
you will still lose the same amount
when the towel absorbs it. Just get over it and move on!
18. If you haven't already, drain the garbage layer out of your sep funnel
into a storage bottle or something,
and wash the garbage residue out your sep funnel with water.
19. Wash the toluene/product 4 times (or more) in your sep funnel with 400 or
500mL H2O and a final time
with 500mL of a saturated NaCl solution to remove any traces of solvated
HgCl2.
20. Dry your toluene/product solution with 30g of your favorite drying agent
(MgSO4 recommended) in an
acetone-cleaned, heat-dried bottle for no less than 45 minutes (Mr. A is
superstitious so he lets it sit for
an hour). Shake it a few times during this period.
21. Filter the solution and gas it with that good ol' HCl bubbler setup. Be
smart and use just enough muriatic
(31% HCl) to wet the salt but not enough to make any puddles, and put a wad
of drying agent wrapped
in tissue paper in line somehow between the reaction flask and the tube
leading to your pipette end. Weep
with joy as a bumper crop of white precipitate crashes out of solution.
Expected yield: approximately 20-21.5g raw odoriferous product that will
purify via careful recrystallization
to 17-18g of beautiful snow-white MDMA! Ain't life grand?
~~~"There's a methyl to my madness"~~~
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
|
|
Mean
People Suck 
