How To Manufacture The D Enantiomer Of Phenylaminopropane, And 3,4,Methyl-Ene-Dioxymeth-Phenylaminopropane Essay, Research Paper
Re: DETAILED METHODS for NON-CHEMISTS
METHamphetamine PRECURSS CLEANING/wkUP
Extractomania……..by Ozbee 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, electronic PH tester
* Filter paper coffeee filters
* A strainer that will fit your filters nicely,
so that you get better surface area then a funnel
* Hair dryer, heat lamps
* Hot plate, no open flames, only heat elements
* Seperaty funnel, similar, tube to siphon
2: Ingredients
-Pills containing psuedo-ephedrine HCl ephedrine HCl.
-NaOH/Sodium Hydroxide/caustic soda/strong base/lye.
-Epsom salts that have been baked in oven 200c f an hour to dry.
-Methanol
-Acetone
-Toluene
-Distillated water
3: Method
***e***:
If pills have red coating, put in jar, with acetone, shake until red coating is dissolved 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 shake till they break apart.
Leave to sit f a few hours shaking every 1/2 hour.
Let settle into 2 nice layers then siphon decant off top layer.
No need to get it all as we will do this 2 me times to be sure get all that pseudo.
step 2: Once you have done it 3 times have the 3 lots of methanol from above, put them together
put in freezer.
You want to get it real cold, near freezing 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:***e***: This step is necessary only speeds things up.
After the chilled filter, we will reduce the volume of methanol/pseudo solution.
So, with good ventilation a fan blowing over pot, just reduce the volume of methanol, but till you
see crystals anything. Just reduce it to a manageable amount, we just want a saturated solution, you’ll
ice 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 mirr glass table f
fast evapation, you could just leave it laying around a couple of days let nature take its course,
it does make pretty crystals. Scrape all your crystals up when they are dry put into aher clean pyrex
vessel.
step 5: Now pour Toluene, about double your psuedo volume **dry/anhydrous**use your epsoms!** over
your powdered psuedo, heat till just befe boiling with your fan blowing over it.
Boil f 5 mins 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 befe discarding you’ll see the *censored*
come out.
step 6: Next you can do an acetone wash, by putting your psuedo some acetone in a jar, shake
filter. Dry pseudo you should have *censored*in clean pseudo HCl……
This procedure, rids the pills of:
MCC
waxes
polymers
lactose
most *censored*!
BUT, povidone! Me 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, 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 emulsions the cleanest meth around.
Povidone is bad because povidone is known to absb hold amines. It depends on what reaction your
doing!
4: A/B: Ok, get your nice dry white powder add about equal part water.
Now make up a 20% NaOH solution 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 turn it into aziradines!toxic!
Add NaOH solution to water/pseudo/toluene solution till PH 13, remember to test PH of water toluene!
Now shake the jar up very well let settle into layers.
Seperate toluene layer. Repeat this process 3 times combine all your toluene.
You can wash the toluene/pseudo freebase with water now, if you like, seperate again.
Now you can either, evapate toluene f freebase crystals, you need to turn the freebase into a Hcl salt
again.
So you can add fresh DH2O about 2mL f each gram of pseudo to your toluene drop HCl acid slowly
with shaking each time into the toluene. Check pH all the time stop just befe neutral. Shake again,
recheck, this is very tricky takes patience.
Now seperate the water from the toluene.
Now you can evapate your water to get your pure pseudo HCl.
You can repeat this aher 1 2 times get a little me.
5: Gassing,
Gassing makes things easier coz you just gas it, filter there’r your crystals, but it is tricky to get the
hang of it Hydrogen Chlide is dangerous! It will burn your *censored*in lungs instantly if inhaled too much of it!
You need to pipe HCl gas into your jar full of toluene pseudo freebase, but the gas your toluene must
be dry: no water, everytime the gas fms crystals it will be reabsbed 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 absb the water, then
filter them out. Then gas your solution you will see a snow stm befe your very eyes.
Then just filter dry crystals.
But still may contain povidone.
Post merely f infmational purposes. I haven’t done anything illegal n should you.
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METHamphetamine synthesis
I.—-Placebo’s compilation of “the Cure” by Ozbee clean-up of sudafed other ephedrine pills
various RP/I2red phosphous / 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, cleanest method f producing meth-amphetamine,
in the highest yields possible f RP/I2/E reaction.
Remember, each every step gives small losses, this method has the least steps!
It is a culmination of effts by wlock, CHEMMAN, maybe a few tiny touches by me.
I re-iterate, I don’t want any congratulations except f the write-up itself.
You will need these things, no substitutions allowed.
If you can’t get this *censored*, you ain’t ready to make the best Go-Go in town.
This is a refinement of all methods, 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 removed in this extraction.
It will be removed at the end. Each step was chosen to complement the next.
Underst?
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 better, a steam distillation sloping splashhead.
A steam pressure cooker, that has a release-valve on top.
Hotplate, electric of course.
Filter paper, Buchner 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 Phosphous.
Pseudo-ephedrine, ephedrine.
Methanol.
Toluene.
Acetone.
NaOH.
All must be clean anhydrous.
Ice.
Extraction of pfed:
This method will deal with the HCl salt of pfed, a streamlined version of “the Cure”.
All pills are dumped into a large jar double of this pills-volume in the fm of methanol poured on top.
This is stirred vigourously let st 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 the methanol boiled off on a hotplate.
As methanol gets down to the last little bit, it is taken off the heat.
Then a ption of acetone, twice your remaining liquid is dropped in.
This fces 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 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 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 befe we will add a ption of acetone boil lightly.
Now when we pour off the acetone, we will add a tiny amount of water some NaOH.
This is our final test, when you do this no crap falls out of acetone you are ready.
This will be the cleanest pfed you have ever seen, guarenteed!
, 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 losses along the way, you should get some product.
Ratios of reagents are: 3:3:1 1:1:1/3, ie.E:I:RP aka, equal amounts of Iodine pfed, a one third
amount of RP.
This is calculated on a weight basis, can be scaled up down as necessary, e.g.60gmE/60gmI2/20gmRP
120gmE/120gmI2/40gmRP etc etc.
First prepare yourself an icebath. Yes, icecubes water in a sink bucket.
Now, many will say you should add this first 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 swirl ingredients together, while
maintaing on ice.
Put your condenser on top 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 dis-coled smoke is bad, 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 bring to about 50 C, if there is no me action in your vessel.
You can move it to the oilbath, the same goes f it as befe, when things slow down.
Adjust heat up, to say 100 C then 150 C f one hour, to make sure reaction has completed.
The whole time you should be watching to keep a nice reflux going, too much vapour is escaping
from condenser.
Now remove from heat disconnect condenser, add ice water to quench reaction.
The reason f ice water is to calm the reaction down when NaOH is added.
Its up to you if you want to filter out RP leave it in untill the end.
I would leave it, it will be washed nicely by next process be easier to filter.
Now add lots of NaOH to bring reaction mix to + 14 pH.
You can over-basify, as meth won’t be destroyed, its a tough MF!
Steam Distillation:
Now you need to set up your glassware f steam distillation.
Attach the steam distillation sloping splashhead to top hole of flask, attach plastic hose to steam inlet
the other end on the release valve of the pressure cooker that is full of water.
Attach condenser on the end of splashhead, 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, the reaction flask.
Sit back get ready f one of the most beautiful sights smells.
The meth freebase that is sitting on the top of your aquaeous layer in the flask will vapourise be carried
across be condensed in the condenser 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 leave the setup to run f aher 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 ed 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, then evap the whole lot
to get crystals.
Or, as I found, you may have some polymer that has come over with the steam, is now sitting in the
water layer, it looks cloudy.
I don’t want to evap all that, it will just concentrate the *censored* 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,
then seperate.
Now your absolutly pure meth freebase is in your toluene!
Now you can either gas, f instant the now clean meth,
add minimal distillated H2O then acidify to pH 7, shake, seperate evap water f crystals.
Repeat this step if you do it this way, as some me 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 *censored* anybody has ever seen anyway.
But you may want to, f the purpose of growing nice big crystals.
In which case, add just enough hot methanol to dissolve all your meth 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, do attempt anything above, befe you completely underst what you are doing!
You must have a sound understing of the basics first!
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How to produce anhydrous = dry = waterfree! HCl gas using no special equipment f all your
amination steps of freebases – by Psychokitty.
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To date I have never used Strike’s Fester’s method f producing HCl gas.
Reasons f this are as follows:
1. The necessity of labaty 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 me 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 Inganic 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 ste.
3. Four so feet of ice-maker transparant-white polyethylene tubing found at
the hardware ste. 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 black. Aher item of which I don’t
know the size. Just take your beer bottle into the hardware ste 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 ste but don’t know what they are used f. They are
sometimes made of brass.
6. One bottle of sulfuric acid drain cleaner.
7. One bottle of concentrated hardware ste muriatic acid 32%?
Assembling the HCl generat 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 f about a minute
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 push through
until the tubing hits the bottom of the beer bottle. with scisss 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 dissolve
any part of the syringe in any way.
NEITHER THE HCl N 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 me easily.
8. Securing the set-up with a clamp of some st attached to a st is optional
but desirable.
9. Have hy 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 h, hold the tubing that will expel gas lower into the
solvent/amine solution.
2. with left h 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
foaming 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 let it settle then continue. Sometimes
certain brs of drain opener can cause excessive foaming. If this occurs,
switch brs.
3. One syringe is usually enough f an amount of about 30-40 g of product, but
if me 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 min rush of HCl from the gassing
tube so make sure that it is submerged when doing this step. To continue, refill
the syringe proceed as described above.
4. Once the gassing is complete, leave the syringe ATTACHED to the injection
tube submerge the gassing tube in the container full of water If the
syringe is attached to the injecting tube, the following sequence will
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
very fast, but to wry 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 the remaining sulfuric acid. Of course the
bottle will get hot but if left aside f a few minutes it will eventually
cool making opening the container dispensing with the acid solution an easy
task. If the bottle is opened f 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 f me!
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wISDOMwillwIN
Re: DETAILED METHODS for NON-CHEMISTS
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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:
rhodium.lycaeum.org/clandestine/gonzo/index.html
/perl/showflat.pl?Cat=&Board=methods&Number=13991&page=
&view=&sb=&vc=1″ target=_newhttp://hive.lycaeum.org/wwwthreads/perl/showflat.pl?Cat=&Board=methods&Number=13991&page=
&view=&sb=&vc=1 and
/perl/showflat.pl?Cat=&Board=methods&Number=15667&page=
0&view=collapsed&sb=5″ target=_newhttp://hive.lycaeum.org/wwwthreads/perl/showflat.pl?Cat=&Board=methods&Number=15667&page=
0&view=collapsed&sb=5 and
/perl/showflat.pl?Cat=&Board=methods&Number=31473&page=
0&view=collapsed&sb=5″ target=_newhttp://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!
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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”~~~
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WISDOMwillWIN
Re: DETAILED METHODS for NON-CHEMISTS
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!
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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! (See for a blatent error the Chirality thread in the Serious Chemistry forum).
Then you have d-Meth (the softer part) AND l-Meth (which is speedy only). Life becomes easier and easier……? LT/
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Sunlight’s method of preparing 10% Methylamine solution in Methanol, from aqueous 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.
WISDOMwillWIN
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IVa.— 2,5-DIMETHOXYBENZALDEHYDE—* 2CH—* 2CB
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 reflux 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, 1 g 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*
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