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Forum Description: Discuss the technical details of the preparation of drugs
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Old 10-26-2005, 10:18 AM   #21
kiss_the_cook
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ml graduated cylinder with the help of a little distilled water. If the
nickel catalyst is allowed to dry out, it may burst into flames. It must be
kept covered with water. Again the chemist pours off as much of the water
as possible. Then he adds a solution of 25 grams of sodium hydroxide in 250
ml of distilled water to the nickel in the graduated cylinder. The cylinder
is stoppered with a cork or glass stopper (not rubber) and shaken for 15
seconds. Then it is allowed to settle again and as much of the sodium
hydroxide solution as possible is poured off.
The catalyst is now ready to have the sodium hydroxide removed from it.
All traces must be removed, or it will not work. The chemist adds as much
distilled water to the cylinder as it will hold, then shakes it to get the
nickel in contact with the clean water. He lets it settle, then shakes it
again. When the nickel has settled, he pours off the water and replaces it
with fresh distilled water. This washing process is repeated 25 times. It
takes that much to remove all the sodium hydroxide from the catalyst.
After the water has been poured off from the last rinse with distilled
water, 100 ml of rectified spirit (95% ethyl alcohol) is added to the
nickel and shaken. After the nickel has settled, the alcohol is poured off
and the washing is repeated two more times with absolute (100%) alcohol.
The result is 75 grams of Raney nickel in alcohol. It is transferred to a
bottle that it will completely fill up. If necessary, more alcohol (100%)
is added to fill up the bottle. Then the bottle is tightly stoppered. When
the chemist is ready to use it, he shakes it to suspend the nickel and
measures out the catalyst. One ml contains about .6 grams of Raney nickel
catalyst.
It has been claimed that a more active catalyst can be made by adding
the sodium hydroxide solution to the nickel-aluminum alloy instead of vice
versa But when this is done, care must be taken that the foam doesn't get
out of control. Also, the alloy must be stirred into the solution so it can
react. Other than that, the catalyst is prepared in exactly the same way.
There are several ways to do the reductive amination reaction. Each
will be described. By far the most convenient and most suited to the needs
of the clandestine chemist is a process using platinum black catalyst
instead of Raney nickel. Platinum has the advantages of working very well
at room temperatures and low pressures of hydrogen. It furthermore does not
have the ferromagnetic properties of Raney nickel. This means a magnetic
stirrer can be used to agitate the reaction mixture inside a suitable glass
container. Besides this, platinum gives nearly quantitative (100%) yields
of product using considerably less catalyst than with Raney nickel. Add to
this the fact the platinum catalyst is reusable many times over, and can be
easily obtained with no suspicion in the form of platinum coins and ingots.
All these considerations clearly point to the use of platinum as the method
of choice for the underground operation.
Reductive alkylation with platinum is done in a very easily constructed
apparatus. The reaction vessel, or "bomb," is a champagne bottle, 1.5
liters or larger. Champagne bottles are built to withstand pressure, and
have no problem standing up to the 30 pounds of pressure used in this
reaction. In the interest of safety, however, the outside of the bottle is
coated with a layer of fiberglass resin about 1/2 inch thick. This guards
against accidental overpressurization and fatigue cracking. Fiberglass
resin is easily obtained at the local auto supply store.
To do the reaction, 300 ml of phenylacetone is put into the bottle,
followed by 300 ml of 40% methylamine in water. The two of them react
immediately to convert a good portion of the mixture into the intermediate
Schiff's base. The mixture gets warm, and some methylamine gas fumes off.
It is even better here to use the anhydrous methylamine gas in a cylinder.
This hard to come by item is used by cooling the cylinder down in a
freezer, then tipping the cylinder upside down and cracking open the valve
to drain out 150 ml of pure methylamine gas into a chilled beaker.
To the mixture in the champagne bottle are then added 500 ml of 190
proof grain alcohol and 5 grams platinum oxide (Adam's catalyst). A
magnetic stirring bar is then slid into the bottle, and it is attached to
an apparatus like the one shown in Figure 17.
The apparatus shown in Figure 17 can be constructed by anyone with
access to machinist's tools. Alternatively, the clandestine operator can
have it made for him with little or no chance of anyone suspecting its real
purpose. The threads are fine, and coated with Form A Gasket immediately
before assembly. The valves are of the swagelock type.
Before beginning production using this device, the joints are checked
for leakage by brushing soapy water on them and looking for the tell-tale
bubbles.
The chief danger in using the hydrogenation apparatus is from fire due
to leaking hydrogen coming into contact with spark or flame. The magnetic
stirrer is a possible source of static-induced sparks. To eliminate this
danger, it is wrapped in a sturdy bread or garbage bag. This prevents
hydrogen from coming into contact with it. Good ventilation in the
production area likewise prevents hydrogen from building up in the room.
To begin production using this device, the champagne bottle is attached
to the rig immediately after filling with the reactants. The air is sucked
out of the bottle by attaching the exit valve, a vacuum line leading to an
aspirator. After sucking out the air for 30 seconds, this valve is closed,
and hydrogen is fed into the bottle from the cylinder until it has
pressurized to a few pounds above normal air pressure (i.e., a few pounds
show on the gauge). Then the input valve is closed, and the bottle is
vacuumed out once more. Now the bottle is practically free of air. The exit
valve is closed once again, and hydrogen is let into the bottle until the
gauge shows 30 pounds of pressure. This is 3 atmospheres of pressure,
counting the 15 pounds needed to equal air pressure. Magnetic stirring is
now started, and set at such a rate that a nice whirlpool forms in the
liquid inside the bottle.
The hydrogen used in this reaction is of the purest grade available.
Cylinders of hydrogen are obtained at welding supply shops, which generally
have or can easily get electrolytically produced hydrogen. This is the
purest grade. The cylinder must have a regulator on it to control the
pressure of hydrogen being delivered to the bomb. The regulator must have
two gauges on it, one showing the pressure in the cylinder, the other
showing the pressure being fed into the line to the bomb.
After beginning stirring the contents of the bomb, an induction period
of about an hour or so usually follows during which nothing happens. No
hydrogen is absorbed by the solution during this period. It is not known
just why this is the case, but nothing can be done about it. Use of
prereduced platinum catalyst does not eliminate this delay. (Prereducing is
a procedure whereby the platinum catalyst is added first, and then
contacted with hydrogen to convert the oxide of platinum to the active
metal.)
In an hour or so, hydrogen begins to be absorbed by the solution,
indicating production of methamphetamine. The pressure goes down on the
gauge. More hydrogen is let in to maintain the pressure in the 30 pound
range. Within 2 to 4 hours after uptake of hydrogen begins, the absorption
stops. This indicates the end of the reaction.
The valve on the cylinder is now closed, and the exit valve slowly
opened to vent the hydrogen gas outside. Now the bottle is removed from the
apparatus, and the platinum is recovered for reuse by filtering the
solution. The platinum is stored in absolute alcohol until the next batch.
Many batches can be run on the same load of platinum catalyst, but it
eventually loses its punch. It is then reworked in the manner described
later.
The filtered reaction mixture is then poured into a 2000 ml round
bottom flask, along with 3 or 4 boiling chips. The glassware is set up as
shown in Figure 3 in Chapter 3. The chemist heats the oil no hotter than
110C, and distills off the alcohol and water. When the volume] of the
mixture gets down to near 500 ml, he turns off the heat and]` transfers the
reaction mixture to a 1000 ml round bottom flask with 4 boiling chips. He
sets up the glassware for fractional distillation as shown in Figure 5 in
Chapter 3, and continues distilling off the alcohol. The temperature shown
on the thermometer should be about 80C. When the volume of the reaction
mixture gets down to about 400 ml, he turns off the heat and lets it cool
off. He attaches a 250 ml round bottom flask as the collecting flask and
begins a vacuum distillation. The last remnants of alcohol are soon gone,
and the temperature shown on the thermometer climbs. If he is using an
aspirator, when the temperature reaches 80C, he changes the collecting
flask to a 500 ml round bottom flask and distills the methamphetamine under
a vacuum. If he is using a vacuum pump, he begins collecting
methamphetamine at 70C. He does not turn the heat setting on the buffet
range above l/3 of the maximum. Virtually all of the material distilled is
methamphetamine. He will get between 300 and 350 ml of clear to pale yellow
methamphetamine, leaving about 20 ml of residue in the flask. A milky color
to the distillate is caused by water being mixed with it. This is ignored,
or removed by gentle heating under a vacuum.
The distilled methamphetamine is made into crystals of methamphetamine
hydrochloride in the same way, as described in Chapter 5. He puts about 75
ml of methamphetamine in each Erlenmeyer flask and adds ether or benzene
until its volume reaches 300 ml. Then he bubbles dry hydrogen chloride gas
through it and filters out the crystals formed. The yield will be close to
380 grams of pure methamphetamine.
It is in the catalyst preparation and recycling that the clear
superiority of the platinum catalyzed reductive alkylation method becomes
obvious. In the succeeding methods using Raney nickel, one is dependent
upon a supply of aluminum-nickel alloy for making Raney nickel. To make
platinum catalyst, one needs only obtain platinum metal and one group of a
series of readily available chemicals. The basic metal itself, platinum, is
easily obtained from coin or other precious metal dealers. The underground
chemist thereby shields himself from suspicion by using the cloud of dust
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Old 10-26-2005, 10:19 AM   #22
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kicked up by avaricious or misguided individuals who purchase platinum
metal thinking this will tide them through society collapse.
The process used to turn platinum metal into active catalyst is
identical to the method used to recycle worn out platinum catalyst into
reborn material. The first step is to dissolve the metal in aqua regia.
Aqua regia is a mixture of three parts hydrochloric acid, and one part
nitric acid. Only laboratory grade acids in in their concentrated forms are
used for this process. Lower grades may well introduce catalytic poisons
into the precious metal. The nitric acid is the 70% material. The
hydrochloric acid is the 37% laboratory material. About a pint of mixed
acid serves well to dissolve the few grams of platinum needed to run
man-sized batches of methamphetamine. The acids are simply mixed, and then
the platinum metal is added. A few fumes of NO2 are given off in the
dissolution process. Occasional swirling and some heating speeds the
process of dissolving the platinum. The dissolution converts the platinum
to chloroplatinic acid H2PtCl6. This substance is the starting point for
both of the alternative pathways to active platinum catalyst.
When all of the platinum metal has disappeared into solution, heat is
applied to boil away the acid mixture. Then some concentrated hydrochloric
acid is added, and this too is evaporated away to dryness.
The addition and evaporation of hydrochloric acid is repeated several
times until the residue is free of nitrites.
With chloroplatinic acid thusly obtained, the manufacturing chemist has
two alternative methods with which to convert it into active material ready
for use. The first method is the classical route involving a fusion of the
chloroplatinic acid, or preferably its ammonium salt, with sodium nitrate
at a temperature of about 450 C. This method entails the obvious
difficulty of accurately measuring and controlling such a high temperature.
One can read all about this method in Organic Syntheses, Collective Volume
I, pages 463 to 470.
The second method uses sodium borohydride to convert the acid directly
into platinum black. This method is simpler and produces a much more active
catalyst. The procedure is based on the method given by Brown and Brown in
the Journal of the American Chemical Society, Volume 84, pages 1493 to 1495
(1962). The yield is about 3 grams of the extra high activity catalyst, and
does the job of 5 grams of the catalyst prepared by the classical method.
To prepare this catalyst, 8 grams of chloroplatinic acid is dissolved
in 80 ml of absolute alcohol. Then, in another beaker, .8 grams of
laboratory grade sodium hydroxide is dissolved in 10 ml of distilled water.
This is diluted to 200 ml of total volume by adding absolute alcohol, and
then 7.71 grams of sodium borohydride is added. The
alcohol-NaOH-water-sodium borohydride solution is stirred until the
borohydride is dissolved. The borohydride solution is now added to the
chloroplatinic acid solution with vigorous stirring. It is added as quickly
as possible without letting the contents foam over. A large amount of
hydrogen gas is given off while the borohydride reduces the chloroplatinic
acid to platinum black. This process is done in a fume hood or outside to
prevent hydrogen explosions.
About one minute after all the borohydride solution has been added, the
excess borohydride is destroyed by adding 160 ml of glacial acetic acid or
concentrated hydrochloric acid. The solution is then filtered to collect
the platinum black. It is rinsed with a little absolute alcohol, with added
filter paper and all (to prevent loss of catalyst sticking to the paper),
directly into the champagne bottle for immediate use. If it must be stored
before use, it is put in a tightly stoppered bottle filled with absolute
alcohol.
The next method uses Raney nickel catalyst instead of platinum. It
works just as well, but requires that the chemist be able to heat the
reactants to about 80C. Also, somewhat higher pressures are used, so a
glass reaction bottle is not adequate; it must be made of stainless steel
at least 1/8 inch thick, for safety's sake.
First, the chemist must find out how high the heat must be set to get
an 80C temperature in the contents of the bomb. He fills the bomb
half-full of isopropyl rubbing alcohol and turns on the heat. He keeps
track of the temperature of the alcohol while stirring it with the
thermometer. He finds the heat setting needed for an 80C temperature and
how long it takes to reach that temperature. Then he removes the isopropyl
alcohol from the bomb and rinses it out with ethyl alcohol.
He is now ready to run the reaction. If he has methylamine gas in a
cylinder, he puts 1 liter of 95% ethyl alcohol (190 proof grain alcohol) in
the bomb. If he has 40% methylamine in water, he uses 1 liter of absolute
ethyl alcohol. Then he adds the same amount of methylamine as used in the
first method described in this chapter. If he used methylamine gas from a
cylinder, he adds 100 ml each of ether and benzene to the bomb. Then he
adds 90 grams of Raney nickel catalyst and 25 grams of sodium acetate.
Finally, he adds 300 ml of phenylacetone to the bomb.
Now the chemist seals up the bomb and pipes in the hydrogen to a
pressure of 300 psi. He turns on the heat and begins shaking the reaction
bottle. The reaction begins to kick in at a little over 40C. He begins
timing the reaction when the temperature reaches 50C. He continues the
reaction for 8 hours, making sure that the pressure stays at 300 psi.
Then he stops the shaking and heating and lets it cool down. After it
has cooled, it is filtered to remove the catalyst. The filtered catalyst
cannot be allowed to dry out, or it will burst into flames. He keeps it
wet. The bomb is rinsed out with 100 ml of alcohol. The alcohol is
filtered, then added to the product. The catalyst is dumped down the drain
and flushed away with a lot of water.
The alcohol, benzene, and ether are distilled off, then the
methamphetamine is distilled under a vacuum, as described earlier in this
chapter. The yield is about the same as from the previous method.
The next method allows the chemist to use nitromethane, dragster fuel,
in place of methylamine. Since everybody, including the narcs, knows that
methylamine is required to make methamphetamine, this gives the underground
chemist a chance to throw the narcs a curve ball. The way this works is
that nitromethane is first put into the bomb along with Raney nickel and
reduced to methylamine.
Phenylacetone is then added, and methamphetamine is produced.
To do the reaction, the chemist puts one liter of absolute ethyl
alcohol and 450 grams (350 ml) of nitromethane inside the bomb. The
nitromethane is either of laboratory grade, or has been fractionally
distilled (boiling temperature 101C) to purify it. He adds 63 grams of
Raney nickel to the bomb and seals it up. He pipes in hydrogen to a
pressure of 300 psi and begins shaking. He heats the mixture up to about
85C, and continues for 3 hours. Then he turns off the heat, and lets it
cool off while shaking for about 45 minutes. Then the shaking is stopped,
and the hydrogen pressure is released. He adds the following to the bomb:
100 ml each of ether and benzene, 25 grams of sodium acetate, 45 more grams
of Raney nickel, and 300 ml of phenylacetone. He seals up the bomb, and
pipes in hydrogen at a pressure of 300 psi. Shaking is begun and the bomb
is heated to 80C. He keeps this up for 8 hours, being sure to keep the
pressure at 300 psi.
After 8 hours are up, he turns off the heat and lets it cool off for an
hour with shaking. Then he stops the shaking and releases the pressure -
slowly. The mixture is then filtered as before, and the bomb is rinsed out.
Then the reaction mixture is distilled as described before. The yield is
about 300 ml of methamphetamine. It is turned into crystalline
methamphetamine hydrochloride as usual.
The bomb can be used to make smaller batches of methamphetamine. But
the bomb and cylinders are not easily packed up and moved, so the bomb is
best suited to industrial-scale production.
The reaction times and pressures I have given are not written in stone.
The time required to complete the hydrogenation can be reduced by using
more Raney nickel or platinum catalyst, increasing the hydrogen pressure,
or using less alcohol.
If the underground chemist has to make his own one-gallon reaction
bottle, he uses stainless steel 1/8 to 3/16 inch thick, such as a section
of stainless steel pipe. For a volume of about one gallon, it should be
about 16 cm in diameter and 20 cm in height. The bottom is Tig welded on,
this process being much easier if it starts out a few millimeters larger in
diameter than the pipe section.
The top of the tank has 2 holes drilled in it. One small one in the
center of the tank is an entrance for the hydrogen gas. This has a section
of stainless steel pipe about 5 inches long welded around it. It is usually
necessary to melt in some stainless steel welding rod while making this Tig
weld, to get it strong enough. This top section is then welded onto the top
to create the reaction vessel shown in Figure 18.
A steel rocking frame is then welded onto the outside of the reaction
vessel as shown in Figures 18 and 19. The area where it is welded should be
reinforced. All welds are done with a Tig welder.
The chemist can now assemble the bomb. He starts out with heavy wooden
planks as the base. This will keep vibration to a minimum. He sets up and
bolts down the frame. He attaches some clamps to this frame, then puts
sheaths and bearings on the arms of the steel rocking frame, and suspends
the reaction vessel about 6 inches off the ground. It should swing back and
forth easily.
Now he attaches a band around the reaction vessel, just below where the
steel rocking frame is attached to the reaction vessel. The band is
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Old 10-26-2005, 10:19 AM   #23
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attached to the rocking arm, which is attached to a spindle on the driving
pulley, as shown in Figures 19 and 20. Both these joints should swivel
easily. The driving pulley is about 10 cm in radius. The pulley on the
motor has a radius of about 2 cm. The spindle, which extends from the
driving pulley to the rocking arm, is about 3 cm from the center of the
driving Pulley.
The motor is the usual 1760 rpm type of motor, with a power of at least
1/30 hp. When the motor is turned on, it spins the driving pulley, which
moves the rocking arm back and forth, which in turn shakes the reaction
vessel.
The chemist is now ready to test the system. He opens up the valve and
puts 2000 ml of distilled water in the reaction vessel. He closes the valve
and turns on the motor to begin shaking. If any water comes out the top of
the stainless steel pipe, he secures the wooden base to minimize vibration.
He shuts it off and opens the valve, then siphons out all the water.
He now runs a line of heavy rubber tubing from the hydrogen cylinder to
the stainless steel pipe. He crimps in the end of the pipe, then pushes the
rubber hose down over the pipe, at least halfway to the tank. He superglues
it to help hold it in place. Then he covers the entire length of the hose
with a series of pipe clamps so that it does not blow out or slip off the
pipe. This hose is slung over a sling in the frame so that it leads
straight down to the reaction vessel. There must be enough slack to allow
for the rocking motion.
If any water came out of the pipe in the test run, the hose must have
catalytic poisons removed from it by boiling it in 20% sodium hydroxide
solution, then rinsing it off in boiling water.
The chemist closes the valve and begins putting pressure in the tank,
starting with a pressure value of 50 psi. He brushes soapy water around the
joints to look for any leaks. If there aren't any, he works the pressure up
to 300 psi. If leaks are found, he tries brazing over the faulty joint. His
welds must be nearly perfect.
To use the bomb, the reactants are added to the bomb with a funnel
through the faucet. If any sodium acetate is left clinging to the valve, it
will prevent a good seal. The Raney nickel is added with a pipette. When
the reaction is over, the products are siphoned out with a bent section of
glass tubing. Vacuum from an aspirator speeds up this process considerably,
as does using large-diameter tubing.
More information on these reactions can be found in Reactions of
Hydrogen by Adkins, published in 1937 by the University of Wisconsin Press.
References
Organic Reactions, Volume 4, page 174.
Journal of the American Chemical Society, Volume 61, pages 3499
and 3566 (1939); Volume 66, page 1516 (1944); Volume 70, pages
1315 and 2811 (1948).
Reductions in Organic Chemistry, by Milos Hudlicky.
--------------------------------------------------------------------------
Reductive Alkylation Without The Bomb
--------------------------------------------------------------------------
The process of reductive alkylation using the hydrogenation bomb, as
you saw in the previous chapter, is not without difficulties or dangers.
Just for starters, consider the danger of hydrogen gas building up in a
poorly ventilated workplace. Add to that the danger of the bomb blowing up
if the welding of the seams is not done well. Also think about the hassle
involved in making enough Raney nickel to produce multi-kilos of
methamphetamine. The last problem can be minimized by reusing the Raney
nickel used in the previous batch. In this way, the underground chemist can
get away with adding only half as much fresh nickel as would otherwise be
added, but he must be doing one batch right after another to keep it fresh.
All of these problems, except for the hydrogen gas danger, can be
eliminated if he is able to get his hands on activated aluminum turnings.
In this method, the aluminum turnings take the place of hydrogen gas as the
catalyst in the reductive alkylation process. The yields are very good, the
process is very simple, and no special equipment is required. The reaction
is also quick enough that it can be used in large-scale production.
Activated aluminum is next to impossible to purchase, but very easy to
make. The raw material is aluminum foil. The foil is amalgamated with
mercury by using mercury chloride. The result is aluminum amalgam.
To make activated aluminum, the chemist takes 100 grams of the aluminum
foil, and cuts it into strips about 2Yz cm wide, and 15 cm long. He folds
them loosely, and puts them into a 3000 ml glass beaker or similar
container. He does not stuff them down the neck of the flask or similar
container from whence they would be hasslesome to retrieve. He packs them
down lightly so that they are evenly arranged, then covers them with a .1%
solution (1 gram in one liter of water) by weight solution of sodium
hydroxide.
He warms the mixture by setting it into a hot water bath until a
vigorous bubbling of hydrogen gas has taken place for a few minutes. He is
careful here that the mixture does not overflow! Then he pours off all the
sodium hydroxide solution as quickly as possible, and rinses the strips
with distilled water, and then with 190 proof vodka. This preliminary
treatment leaves an exceedingly clean surface on the foil for amalgamating
with mercury.
While the surface of the strips is still moist with vodka, he adds
enough of a 2% by weight solution of mercury QI) chloride (aka mercuric
chloride, HgCI2) in distilled water to completely cover the foil. He allows
this to react for about 2 minutes, then pours off the mercury solution. He
rinses off the strips with distilled water, then with 190 proof vodka, and
finally with moist ether. Moist ether is either purchased as is, or made by
adding water to anhydrous ether with stirring until a water layer begins to
appear at the bottom of the ether. The chemist uses this material
immediately after making it.
Method 1
In this method, the activated aluminum turnings react with alcohol to
produce hydrogen gas. This hydrogen then reduces the Schiff's base formed
from methylamine and phenylacetone to give methamphetamine.
The chemist needs a magnetic stirrer-ho/plate to do this reaction. On
top of the stirrer-hotplate, he places a Pyrex bowl or cake dish large
enough to hold a 3000 ml flask. The bowl or dish cannot be made of metal,
because the magnetic stirrer will not work through it.
He places the 3000 ml flask in the dish and fills it with cooking oil
until the oil reaches about halfway up the sides of the flask. He must be
sure to leave enough room for the oil to expand as it heats up. He puts the
magnetic stirring bar in the flask along with 1600 ml of absolute alcohol
or 190 proof grain alcohol. Then he adds 340 ml of phenylacetone and 450 ml
of 40% methylamine in water. Now he turns on the magnetic stirrer and
begins heating the oil in the dish. He keeps track of the temperature of
the oil with a thermometer, and does not allow it to go above 100C. While
the oil is heating up, he adds 180 grams of activated aluminum turnings to
the flask. He makes sure that the stirring is fast enough that the turnings
do not settle to the bottom of the flask. The reaction mixture will quickly
begin to turn grey and foamy. The aluminum is added at such a rate, the
bubbling and foaminess it produces does not overflow the flask. When all of
it has been added, a condenser is fitted to the flask, and water flow is
begun through it.
The chemist now lets them react for 8 hours. He keeps the temperature
of the oil bath at 100C, and the stirring strong. The activated aluminum
slowly dissolves and produces hydrogen gas. The explosive danger from this
gas is eliminated by running a length of tubing from the top of the
condenser out the window.
When the 8 hours are up, he removes the flask from the oil bath and
wipes the oil off the outside of the flask. He filters the solution to
remove the aluminum sludge, then rinses the sludge with some more alcohol
to remove the last traces of product from it. The rinse alcohol is added to
the rest of the filtered product.
The underground chemist can now distill the product. He pours it in a
3000 ml round bottom flask that is clean and reasonably dry, and adds a few
small pieces of pumice. He places the flask on the electric buffet range,
then sets up the glassware for fractional distillation, as shown in Chapter
3. He begins heating it. The first thing that distills is a mixture of
alcohol, water, and methylamine. This occurs when the temperature shown on
the thermometer is about 78-80Q C. He collects about 1600 ml of this
mixture, then removes the flask from the heat. He lets it cool down, then
pours the contents of the 3000 ml flask into a 1000 ml flask, along with a
few fresh boiling chips. He puts about 15 ml of alcohol in the 3000 ml
flask. swirls it around to dissolve the product left clinging to the
insides, then pours it into the 1000 flask.
The chemist again sets up the glassware for fractional distillation,
with a 250 ml flask as his receiver. He applies a vacuum, preferably from
an aspirator, and begins vacuum distillation. When the boiling gets under
control, he begins heating the flask. The last remnants of alcohol and
water will soon be gone, and the temperature shown on the thermometer will
climb. When it reaches about 80C with an aspirator, or about 70C with a
vacuum pump, he quickly changes the receiving flask to a clean, dry 500 ml
flask, and reapplies the vacuum. He will get about 350 ml of clear to pale
yellow methamphetamine free base. A few milliliters of tar will be left in
the distilling flask. The liquid free base is converted to crystals by
dissolving it in ether or benzene and bubbling dry HC1 through it, as
described in Chapter 5.
The underground chemist gets an even purer product by varying this
procedure slightly. Once the 1600 ml of alcohol, water, and methylamine is
distilled off, he pours a mixture of 650 ml of 28% hardware store variety
hydrochloric acid and 650 ml of water into what remains in the 3000 ml
flask, after it has cooled down. A lot of heat is produced in the mixing
because the methamphetamine free base is reacting to make the
hydrochloride. So he adds it slowly, then swirls it. When it has cooled
down, he stoppers the 3000 ml flask with a cork or glass stopper and shakes
it vigorously for 3 to 5 minutes. It should pretty much all dissolve in the
hydrochloric acid solution. Now he adds 200 ml of ether or benzene to the
flask and shakes it up well. The ether or benzene dissolves any unreacted
phenylacetone and tar. He lets it sit for a few minutes. The ether and
benzene layer floats to the top. He pours it slowly into a 1000 ml sep
funnel, so that the top layer all gets into the sep funnel. Now he lets it
set, then drains the lower acid layer back into the 3000 ml flask.
The acid must now be neutralized to give back amphetamine free base, so
it can be distilled. The chemist mixes up a solution of 350 grams of lye in
400 ml of water. When it has cooled down, he pours it slowly into the acid
solution in the 3000 ml flask. A lot of heat is generated from the
reaction. When it has cooled down, he stoppers the flask and shakes it
strongly for about 5 minutes. When standing, the amphetamine forms a layer
on top. He slowly pours it into a 1000 ml sep funnel. He drains the water
layer back into the 3000 ml flask. The methamphetamine layer in the sep
funnel may have some salt crystals floating around in it. He adds 100 ml of
benzene to it plus a couple hundred ml of a dilute lye solution. He
stoppers and shakes the mixture. The salt will now be dissolved in the
water. He drains the water layer into the 3000 ml flask and pours the
methamphetamine-benzene solution into a clean 1000 ml flask. There is still
some methamphetamine left in the 3000 ml flask, so he adds a couple hundred
ml of benzene to it. If there is a lot of undissolved salt in the flask, he
adds some more water to it. Now he shakes the flask to dissolve the meth in
the benzene, then lets it set. The benzene comes up to the top. He pours it
off into the sep funnel, and drains off the water layer. He pours the
benzene layer into the 1000 ml flask with the rest of the product.
He can now begin distilling it. He adds a few boiling chips, sets up
for fractional distillation, and proceeds as described in Chapter 5. The
yield once again is about 350 ml of free base, which makes close to 400
grams of pure crystal.
Method 2
This method is not as good as the first one. It takes longer, it uses
up more chemicals to make a given amount of product, and less can be
produced at a time.
The equipment is set up as in Method 1. Into the 3000 ml flask is
placed 1575 ml of 190 proof alcohol and 150 ml of distilled water. Then the
chemist adds 150 ml of phenylacetone and 220 ml of 40~o methylamine in
water. He begins magnetic stirring and adds 160 grams of activated aluminum
turnings. He heats the oil bath to 100- C or so and attaches a condenser
to the 3000 ml flask. He begins water flow through the condenser and gently
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boils the contents of the flask for 16 hours. At the end of this time, he
removes the flask from the heat and lets the aluminum sludge settle. He
filters the alcohol solution, rinses the sludge with alcohol and adds the
filtered alcohol to the rest of the product. Then he proceeds as described
in Method 1. The yield is about 150 ml of methamphetamine.
Method 3
This method is not as good as Method 1 either. Ether is used as the
reaction solvent, which adds danger and expense. The ether is better used
to produce the crystals. Another problem with this reaction is that it is
done so dilute that large amounts can't be made at one time.
In the same set-up used in Methods 1 and 2, the underground chemist
places 1000 ml of absolute ether in a 3000 ml flask. Then he adds 100 ml of
phenylacetone and 160 ml "f 40% methylamine. He begins stirring and adds 65
grams of activated aluminum turnings. He attaches an efficient condenser,
runs cold water through it, and heats the oil bath to 45-50C. He gently
boils the solution for 6 hours. The activated aluminum reacts with the
water in the methylamine to produce hydrogen.
When the six hours have passed, he distills off the ether and treats
the residue as described in Method 1, i.e., distills it under a vacuum,
etc. The yield is about 90 ml of meth.
For more information on this method, see U.S. Patent Nos. 2,146,474 and
2,344,356.
Method 4
This variation on the activated aluminum method of reductive alkylation
has the advantage of using methylamine hydrochloride directly in the
reaction soup. Since methylamine is now very dangerous or impossible to
obtain commercially, and also since the best method for making methylamine
yields methylamine hydrochloride, the usefulness of this variation is
obvious.
This method involves the addition of an alcohol solution containing the
Schiff's base formed between methylamine and phenylacetone onto the
activated aluminum. In the other methods, the opposite order of addition
was employed. To maximize yields of product, the competing side reactions
are suppressed. In the case of activated aluminum methamphetamine
production, the main side reaction is the reduction of phenylacetone into
an interesting, but quite useless pinacol. It has the structure shown on
the next page:
This side reaction is minimized by keeping the amount of water in the
reaction mixture to a minimum, and also by using a healthy excess of
methylamine. This scheme of things encourages the phenylacetone to tie
itself up with methylamine to form the Schiff's base, rather than float
around freely in solution where it could be reduced by the aluminum.
To do this reaction, two 2000 ml volumetric flasks are obtained.
Volumetric flasks work well for this reaction because the chemist can swirl
around their contents quite forcefully without danger of spillage. They
also pour pretty well. One volumetric flask is for preparing the activated
aluminum, and is also the ultimate reaction vessel. The other volumetric
flask is for the preparation of the Schiff's base. The lab work is
organized so that both products are ready to react at about the same time.
Into the volumetric flask destined to be the ultimate reaction vessel,
the chemist places 108 grams of aluminum foil. It is cut into one inch
squares. The best brand of aluminum foil for this purpose is Heavy Duty
Reynolds Wrap. It is then treated with sodium hydroxide solution as
described in Method 1. After a few good rinses to remove the sodium
hydroxide, it is ready to become activated aluminum. To do this, the
volumetric flask is filled almost to the neck with distilled water,
followed by the addition of 4.51 grams of HgCl2. The flask is swirled to
dissolve the mercuric chloride, and then every few minutes for the next 30
minutes. During this time, the water becomes a cloudy grey color, and the
aluminum loses its shine. The water is then decanted off the aluminum, and
the flask is filled up with fresh distilled water to carry away unreacted
mercury. After a period of swirling, the rinse water is poured off, and the
rinse repeated with a fresh portion of distilled water. On the last rinse,
the chemist makes sure that the water drains off well. This leaves
activated aluminum ready to go.
In the second volumetric flask, Schiff's base is made. To do this,
163.5 grams of sodium hydroxide is dissolved in one liter of 190 proof
vodka. To this is added 270 grams of methylamine hydrochloride. This
methylamine is dry so that the chemist is not weighing water contamination.
If this is home brew methylamine hydrochloride, the first crop of crystals
is acceptable material, but the second and third batches of crystals are
recrystallized as described in Organic Syntheses, Collective Volumes I, II
or III. Look in the table of contents for methylamine hydrochloride. The
mixture is kept cool during the addition to prevent methylamine gas from
escaping. Good stirring is also essential. The result of this operation is
an alcohol solution of methylamine. Some salt and water are formed.
To make the Schiff's base, 200 ml of phenylacetone is then added to
this solution. The addition produces a fair amount of heat, and some
methylamine fumes are driven off as a result. Active swirling of the flask
keeps this to a minimum. The chemist also tips the flask during swirling to
dissolve any phenylacetone which may be stuck up in the neck of the flask.
This is the Schiff's base solution.
To do the reaction, the Schiff's base solution is poured onto the
activated aluminum. Once the pouring is complete, they are swirled together
energetically for a few seconds, then a thermometer is carefully lowered
into the flask. Following this, a section of plastic tubing is stuffed into
or over the top of the volumetric flask, and led outside. This is for fume
control. The reaction mixture is swirled continuously for the first few
minutes. The temperature rises quite rapidly because the reaction is really
vigorous. It is necessary to have a bucket of ice water close by to dunk
the reaction vessel into to keep it under control. The experimenter strives
to keep the reaction mixture in the 50 to 60C range. After the initial
rush, occasional swirling is acceptable, so long as the temperature
guidelines are followed. After 90 minutes, the reaction is complete.
To process the product, the alcohol solution containing the product is
poured off into the distilling flask. The mud-like gunk at the bottom of
the flask contains a fair amount of trapped product. This gunk is
untreatable as is, but with some lightening up, it can be filtered. A lab
product called Celite is added to the gunk until it appears more amenable
to filtration. As an altemative, washed white sand, found in the cement
section of your friendly neighborhood store, is a good substitute. This is
mixed in with the gunk until it lightens up a bit. Then two portions of 200
ml of warm vodka (190 proof) are mixed in and the trapped product is
filtered out of the gunk. These gunk filtrates are added to the main
product, and the whole mother lode readied for processing.
The first step is to place all the liquid into the distilling flask
along with a few boiling chips, and remove the alcohol with a vacuum. A
fractional distillation then gives pure methamphetamine free base ready for
crystallizing into the hydrochloride.
The same method can be used to give MDMA just by substituting MDA
phenylacetone for regular phenylacetone.
--------------------------------------------------------------------------
Methylamine
--------------------------------------------------------------------------
From time to time, an underground chemist's supply of methylamine may
be cut off. If this happens, it is handy to be able to make a supply of his
own methylamine until he is able to get his hands on some of the ready-made
stuff.
The reaction to produce methylamine is cheap, but requires a lot of
labor. Two molecules of formaldehyde react with ammonium chloride to
produce a molecule of methylamine hydrochloride and The glassware is set up
as shown in Figure 3 in Chapter 3. The chemist places 1000 grams of
ammonium chloride and 2000 ml of 3540% formaldehyde in the 3000 ml flask
sitting in the pan of oil. (These chemicals need not be a very high grade;
technical grade is good enough.) He puts a thermometer in the oil next to
the flask and begins slowly heating it. As it warms up, he swirls the flask
to dissolve the ammonium chloride crystals. Over the period of an hour, he
raises the temperature of the oil bath to 106C. He holds the temperature
there for five hours.
Then he turns off the heat and removes the flask from the pan of oil.
Some liquid will have collected in the 2000 ml flask; he throws it out and
rinses the flask with water. The 3000 ml flask is set in a pan of room
temperature water to cool it off. A good amount of ammonium chloride
crystals precipitate from the solution. He does not want these chemicals,
so he filters them out. He returns the filtered reaction mixture to the
3000 ml flask and again sets up the glassware as shown in Figure 3. A 250
ml flask is used as the collecting flask. The reaction mixture should be
clear to pale yellow.
He turns on the vacuum source and attaches it to the vacuum nipple of
the vacuum adapter. He boils off the water and formic acid in the reaction
mixture under a vacuum. Heating the flask in the oil pan speeds up the
process, but the oil is not heated above 100 C When the volume of the
contents of the flask is reduced to about 1200-1300 ml, he turns off the
vacuum and removes the flask from the oil pan. The flask is put in a pan of
room temperature water to cool it off. Some more crystals of ammonium
chloride come out of solution. He filters out these crystals and pours the
filtered reaction mixture into a 2000 ml flask. He sets up the glassware as
before, and again boils off the water and formic acid under a vacuum. He
does
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not heat the oil above 100 C
When the volume of the reaction mixture has been reduced to about 700
ml, crystals of methylamine hydrochloride begin to form on the surface of
the liquid. It looks a lot like a scummy film. When this happens, the
vacuum is disconnected and the flask is removed from the oil bath. The
flask is placed in a pan of room temperature water to cool it off. As the
flask cools down, a lot of methylamine hydrochloride crystals come out of
the solution. When the flask nears room temperature, it is cooled off some
more with some cold water. This will cause even more methylamine
hydrochloride to come out of the solution.
The chemist filters out the crystals and puts them in a 1000 ml
3-necked flask. The crystals look different from the crystals of ammonium
chloride, so he should have no trouble telling the two apart. These
crystals soak up water from the air and melt, so he does not waste time
getting them in the 3-necked flask after they are filtered.
He takes the filtered reaction mixture and pours it in a 1000 ml sep
funnel. The reaction mixture contains dimethylamine hydrochloride and some
other garbage, and he wants to remove some of this unwanted material before
he proceeds to get the rest of the methylamine hydrochloride. He adds 200
ml of chloroform to the sep funnel, and shakes it with the reaction mixture
for 30 seconds. He lets it set for a couple of minutes. The chloroform
layer should be on the bottom. It has a lot of dimethylamine hydrochloride
and other garbage dissolved in it. He drains out the chloroform layer and
throws it out.
He pours the reaction mixture into a 1000 ml round bottom flask and
again sets up the glassware as shown in Figure 3. He reattaches the vacuum
and continues boiling off the water and formic acid under a vacuum. When
the volume of the mixture reaches 500 ml, he removes the flask from the hot
oil and places it in cool water. As it cools off, more crystals of
methylamine hydrochloride appear. He filters the cold reaction mixture to
obtain these crystals. He transfers them to a beaker and adds 200 ml of
cold chloroform to the beaker. He stirs the crystals around in the
chloroform for a few minutes, breaking up any chunks. This dissolves any
dimethylamine hydrochloride in the product. He filters the crystals in the
beaker, then puts them in the 1000 ml, 3-necked flask along with his first
crop of methylamine hydrochloride crystals. He throws away the chloroform
and retums the reaction mixture to the 1000 ml flask.
He boils the reaction mixture under a vacuum again. When its volume
reaches about 150-170 ml, he turns off the vacuum and removes the flask
from the hot oil. He pours the reaction into a beaker and stirs it as it
cools down, to prevent it from turning into a solid block. Once it has
cooled down, he adds 200 ml of cold chloroform to the slush. He stirs it
around with a glass rod for a couple of minutes, being sure to break up any
chunks. The mixture is then filtered. The crystals of crude methylamine
hydrochloride are kind of gooey, so it may not be possible to filter out
all the chloroform. But he does the best he can. He returns the filtered
crystals to the beaker and adds 100 ml of cold chloroform to the crystals.
He stirs it around again, then filters the crystals. He must do a better
job of filtering out the chloro form this time. These crystals also absorb
water from the air and melt. As soon as this last crop of crystals is
filtered, he adds them to the other crystals in the 3-necked flask. He may
have to pack it down to get it all to fit. The yield of methylamine
hydrochloride is about 425 grams. He may wish to stopper the flask and dry
the crystals under a vacuum, although it is not essential.
The compound the underground chemist wants is methylamine, not
methylamine hydrochloride. Methylamine is a gas which turns into a liquid
at -6C (21F). He will now neutralize the hydrochloride with sodium
hydroxide and liquefy the methylamine gas produced.
The glassware is set up as shown in Figure 21. The 3-necked flask is
sitting on the hotplate. It contains methylamine hydrochloride crystals. He
puts the long condenser in the central neck and stoppers the other neck of
the flask. He adds 100 grams of sodium hydroxide to the flask. (Lye is an
acceptable substitute.) It may begin to react to form methylamine and salt,
but it will not get very far without water. He dissolves 220 grams of
sodium hydroxide or lye in 350 ml of water and sets it aside for the time
being. He puts a sep funnel in the third neck of the 3-necked flask. He
connects a stillhead to the top of the condenser and attaches the shorter
condenser to it. The water jacket of the condenser is filled with rubbing
alcohol. The water entrance and exit are plugged to hold in the alcohol.
The outside of this condenser is packed with enough dry ice to keep it good
and cold, in the vicinity of 0F. He insulates this dry ice packing so that
it does not evaporate too quickly. He attaches the vacuum adapter to the
condenser, then connects a section of plastic tubing to the vacuum nipple
to carry fumes of ammonia outside. He attaches a 500 ml round bottom flask
to the vacuum adapter. This flask is cooled by placing it in a styro foam
container. He pours in alcohol until the rubbing alcohol is halfway up the
sides of the flask. He adds dry ice to this alcohol bath until its
temperature is about -10F. (He adds the dry ice slowly at first to keep
the alcohol from foaming over.) He keeps it at this temperature until he
has collected all the methylamine. Ice water is run through the long
condenser, as described in the chapter on N-methylformamide.
He adds the sodium hydroxide solution to the sep funnel and drips it
onto the methylamine hydrochloride and sodium hydroxide in the flask. It
reacts rapidly to form methylamine and salt. The heat that the reaction
produces causes the methylamine to be driven off and condensed in the
collecting flask. He swirls around the flask to get the sodium hydroxide
into contact with the methylamine hydrochloride. When all the sodium
hydroxide has been added, he closes the valve of the sep funnel and allows
it to react for a few minutes. Then he slowly heats the flask to drive off
the methylamine. He may have to add some water through the sep funnel to
get the methylamine hydrochloride on the bottom of the flask in contact
with the sodium hydroxide.
In the meantime, liquid methylamine has been collecting in the 500 ml
flask. It is mixed with some water which made it through the long
condenser, and also some ammonia. He allows the temperature of the alcohol
bath surrounding the 500 ml flask to rise to 0F after all the methylamine
has been boiled out of the 3-necked flask. He holds it at that temperature
for half an hour. The ammonia will evaporate and exit through the plastic
tubing. Since ammonia gas is poisonous, this tubing runs outside.
Then the chemist adds an equal volume of water to the liquid
methylamine, about 220 ml. He has just made about 450 ml of 40% methylamine
in water. The water allows him to keep it at room temperature. He pours it
into a champagne bottle and tightly stoppers it. This methylamine can be
used to make N-methlyformamide, but cannot be used in the hydrogenation
bomb. It may contain traces of chloroform, which would poison the Raney
nickel catalyst. Since methylamine is cheap, he will buy it when possible.
Methylamine can be made by other methods as well. For example, it can
be made in 71% yield by reacting methyl iodide with hexamine, also known as
hexamethylene tetramine. Good directions for making this substance from
ammonia and formaldehyde can be found in Home Workshop Explosives by yours
truly. The production details for methylamine are found in the Journal of
the American Chemical Society, Volume 61, page 3585, (1939). The authors
are Galat and Elion.
It can also be made by degrading acetamide with Clorox. See Journal of
the American Chemical Society, Volume 63, page 1118, (1939). The authors
are Whitmore and Thorpe, and the yield is 78%.
It can also be made via the Curtius reaction in a yield of 60%. See
Helv. Chim. Acta, Volume 12, page 227, (1929). The authors are Naegeli,
Gruntuch and Lendorff.
References
Journal of the American Chemical Society, Volume 40, page 1411 (1918).
--------------------------------------------------------------------------
The Ritter Reaction: Amphetamines Directly From Allylbenzene
--------------------------------------------------------------------------
A most interesting sidelight appears in an article by Ritter and Kalish
found in the Journal of the American Chemical Society, Volume 77, pages
4048 to 4050. This sidelight was a bit of research done by a grad student
as part of his master's thesis. The grad student just happened to work out
the experimental details for converting allylbenzene directly into
amphetamine.
The main thrust of the article was the good Dr. Ritter telling of his
new method for converting double bonds into amines. The method which he
pioneered has since come to be known as the Ritter reaction. This versatile
reaction can well serve the underground operator as an alternative pathway
to the amphetamines.
The Ritter reaction in general is a reaction whereby amides are made by
adding an alkene to a mixture of a nitrile in sulfuric acid. After the
amide is made, it is then boiled in hydrochloric acid solution to give the
corresponding amine.
The particular variation on this theme in which we are interested deals
with the case in which the alkene is the now familiar and highly useful
allylbenzene. When it is added to a solution of acetonitrile in sulfuric
acid, the following reaction takes place:
[SNiP]
The acetyl amide thusly produced is not isolated and purified. Rather,
it is added in the crude state to hydrochloric acid, and boiled for several
hours. A hydrolysis reaction almost identical to the one seen in Chapter 5
takes place producing the prototype amphetamine, benzedrine.
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Old 10-26-2005, 10:22 AM   #26
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The acetyl amide of amphetamine is very similar to the formyl amide of
methamphetamine produced by the Leuckardt-Wallach reaction. Its main
difference is that it is more difficult to hydrolyze to the corresponding
amphetamine by the action of boiling hydrochloric acid. It must therefore
be boiled with the acid for a longer period of time than the formyl amide.
The manufacturer may well find it to his advantage to boil the tar left
over at the end of the process once more with fresh hydrochloric acid. This
will likely yield an additional measure of amphetamine from the stubbornly
unreactive amide.
This small hassle with the hydrolysis process could be avoided if HCN
were used as the nitrile in sulfuric acid solution. However, the extreme
danger of dealing with hydrogen cyanide more than outweighs the additional
work needed when using acetonitrile.
To do the reaction, a solution of 450 grams of concentrated sulfuric
acid in 400 grams acetonitrile is made by slowly adding the acid to the
acetonitrile. Both ingredients are cold when they are mixed together, and
the temperature of the mixture is kept in the 5-10C range during the
mixing by setting the reaction container in ice. An admirable reaction
vessel is a glass beer pitcher.
When the addition of the acid to the nitrile is complete, the pitcher
is taken out of the ice, and 236 grams of allylbenzene is slowly added to
it with stirring. The mixture quickly turns an orange color, and begins to
warm up.
Stirring is continued on an occasional basis, and the temperature of
the mixture followed. It slowly climbs to 50C, and then more rapidly to
80C, as the color of the mixture darkens.
When the temperature of the mixture reaches 80C, the pitcher is cooled
down, first by setting the pitcher in cool water, and then into ice. When
it has cooled down, the mixture is poured into a gallon of cold water
containing 15% by weight of Iye. The Iye solution neutralizes the sulfuric
acid, and dissolves most of the acetonitrile. The neutralization of the
acid by the Iye solution produces a great deal of heat. The Iye solution is
gently stirred during the addition, and then stirred more vigorously during
the following minutes. After a few minutes of stirring, the mixture is
allowed to sit for a few minutes. A yellow oily layer floats on the top of
the solution. This yellow oil is the crude amide. If the oil were to be
allowed to sit for a while longer, it would begin to form crystals of crude
amide. There is no need for this, however, so the processing continues
immediately.
The top yellow layer is poured off into a sep funnel, and any water
carried along is drained off. Then the yellow oil is poured into a 2000 ml
round bottom flask. It is now ready for hydrolysis with hydrochloric acid
solution to make amphetamine. The approximate volume of the crude amide is
determined, and five times that volume of 15% hydrochloric acid solution is
added to it. Fifteen (15) percent hydrochloric acid solution is easily made
by starting with the 28% hardware store hydrochloric acid, and adding just
about an equal volume of water to it. A wise move here is to rinse the
inside of the sep funnel with acid. This rinses off the amide clinging to
the glass insides of the sep funnel.
When the acid has been added to the amide, the mixture is swirled. They
usually mix together well. If they don't, stronger acid is used. Adding
some full strength acid to the mix should do the job. Then a few boiling
chips are added to the flask, a condenser attached to the flask, and heat
applied to boil the mixture at reflux.
The reflux boiling is continued for 10 hours. During this time the
mixture will turn black. At the end of the boiling period, the mixture is
allowed to cool down. When it is cool, 200 ml of benzene or toluene is
added to the flask. The mixture is shaken well for a couple of minutes,
then allowed to sit. The benzene floats up to the top, and has dissolved in
it most of the unreacted amide, and other unwanted garbage.
The benzene layer is then poured off into a sep funnel, and any water
layer carried along drained back into the flask. The benzene layer is
poured off into another container for future processing. It may be
difficult to tell exactly where the benzene layer ends and the water starts
because of their similar color. A sharp eye and good lighting help to spot
the interface of the two fluids.
The acid solution of the amphetamine is now made alkaline to liberate
the free base for distilling. To do this, Iye is added to the acid solution
in the 2000 ml flask. Assuming the use of about 1200 ml of 15% hydrochloric
acid solution, one 12 oz. can of lye does the job. The mixture is first
swirled to release heat, then shaken vigorously for five minutes. I cannot
emphasize enough the importance of vigorous and prolonged shaking here
because the amphetamine base initially formed tends to dissolve
unneutralized amphetamine hydrochloride. The oily droplets protect the
hydrochloride from contact with the lye solution unless the shaking is
strong and prolonged.
When the shaking is completed, the mixture is allowed to cool down.
Then 300 ml of benzene or toluene is added to the flask, and shaking
continued for a minute or two. After sitting for a couple of minutes, a
benzene-amphetamine layer floats above the water layer. This is poured off
into a sep funnel, and the benzene-amphetamine layer poured into a 1000 ml
round bottom flask.
The amphetamine-benzene mixture is distilled in exactly the same manner
as described in Chapter 5. The boiling point of benzedrine is 10 to 20C
lower than meth. The yield of benzedrine is in the range of 100 to 150 ml.
The benzedrine produced by this reaction is either used and removed as
is, or it is converted to methamphetamine. A very good and simple process
for doing this can be found in the Journal of the American Chemical
Society, Volume 62, pages 922-4. The author is Woodruff. The yield for this
process is over 90%, so a greater volume of methamphetamine comes out of
the reaction than the benzedrine input. This is because the gain in
molecular weight achieved by adding the methyl group outweighs the small
shortfall from 100% yield.
For those who have difficulty reading the Woodruff article, meth is
described as B-phenylisopropylmethylamine. The amine is benzedrine.
If the benzedrine product is used as is, the producer makes it as the
hydrochloride salt. This is made the same way as methamphetamine
hydrochloride. An alternative to the hydrochloride salt is the sulfate
salt. This more hasslesome procedure calls for the use of cooled solutions
of amphetamine base in alcohol and cooled solutions of sulfuric acid in
alcohol. Furthermore, a recrystallization from alcohol-ether is required
because trapped excess sulfuric acid in the crystals causes them to turn to
mush or worse. By using HCl gas, the excess acid floats off as gas.
An excellent review of this reaction can be found in Organic Reactions,
Volume 17. Nearly double these yields can be obtained if the underground
chemist is willing to risk using hydrogen cyanide instead of acetonitrile.
The hydrogen cyanide is made inside the reaction flask from sodium cyanide
and sulfuric acid. For complete directions, see Organic Syntheses,
Collective Volume 5, page 471 to 473. The name of the compound is alpha,
alpha, Dimethyl beta phenethylamine.
A good alternative to the Ritter reaction is a two step procedure first
reacting safrole with hydrobromic acid to give 3,4-methylenedioxyphenyl-
2-bromopropane, and then taking this material and reacting it with either
ammonia or methylamine to yield MDA or MDMA respectively. This procedure
has the advantages of not being at all sensitive to batch size, nor is it
likely to "run away" and produce a tarry mess. It shares with the Ritter
reaction the advantage of using cheap, simple, and easily available
chemicals.
The sole disadvantage of this method is the need to do the final
reaction with ammonia or methylamine inside a sealed pipe. This is because
the reaction must be done in the temperature range of 120-140 C, and the
only way to reach this temperature is to seal the reactants up inside of a
bomb. This is not particularly dangerous, and is quite safe if some simple
precautions are taken.
The first stage of the conversion, the reaction with hydrobromic acid,
is quite simple, and produces almost a 100% yield of the brominated
product. See the Journal of Biological Chemistry, Volume 108 page 619. The
author is H.E. Carter. Also see Chemical Abstracts 1961, column 14350. The
following reaction takes place:
To do the reaction, 200 ml of glacial acetic acid is poured into a
champagne bottle nestled in ice. Once the acetic acid has cooled down, 300
grams (200 ml) of 48% hydrobromic acid is slowly added with swirling. Once
this mixture has cooled down, 100 grams of safrole is slowly added with
swirling. Once the safrole is added, the cheap plastic stopper of the
champagne bottle is wired back into place, and the mixture is slowly
allowed to come to room temperature with occasional shaking. After about 12
hours the original two layers will merge into a clear red solution. In 24
hours, the reaction is done. The chemist carefully removes the stopper from
the bottle, wearing eye protection. Some acid mist may escape from around
the stopper.
The reaction mixture is now poured onto about 500 grams of crushed ice
in a 1000 or 2000 ml beaker. Once the ice has melted, the red layer of
product is separated, and the water is extracted with about 100 ml of
petroleum ether or regular ethyl ether. The ether extract is added to the
product, and the combined product is washed first with water, and then with
a solution of sodium carbonate in water. The purpose of these washings is
to remove HBr from the product. One can be sure that all the acid is
removed from the product when some fresh carbonate solution does not fizz
in contact with the product.
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Old 10-26-2005, 10:23 AM   #27
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Once all the acid in the product is removed, the ether must be removed
from it. This is important because if the ether were allowed to remain in
it, too much pressure would be generated in the next stage inside of the
bomb. Also, it would interfere with the formation of a solution between the
product and methylamine or ammonia. It is not necessary to distill the
product because with a yield of over 90%, the crude product is pure enough
to feed into the next stage. To remove the ether from the product, the
crude product is poured into a flask, and a vacuum is applied to it. This
causes the ether to boil off. Some gentle heating with hot water is quite
helpful to this process. The yield of crude product is in the neighborhood
of 200 grams.
With the bromo compound in hand, it is time to move onto the next step
which gives MDA or MDMA. See Chemical Abstracts 1961, column 14350. Also
see Journal of the American Chemical Society, Volume 68, page 1805 and
Journal of the Chemistry Society, part 2 1938, page 2005. The bromo
compound reacts with ammonia or methylamine to give MDA or MDMA:
To do the reaction, 50 grams of the bromo compound is poured into a
beaker, and 200 ml of concentrated ammonium hydroxide (28% NH3) or 40%
methylamine is added. Next, isopropyl alcohol is added with stirring until
a nice smooth solution is formed. It is not good to add too much alcohol
because a more dilute solution reacts slower. Now the mixture is poured
into a pipe "bomb." This pipe should be made of stainless steel, and have
fine threads on both ends. Stainless steel is preferred because the HBr
given off in the reaction will rust regular steel. Both ends of the pipe
are securely tightened down. The bottom may even be welded into place. Then
the pipe is placed into cooking oil heated to around 130C. This
temperature is maintained for about 3 hours or so, then it is allowed to
cool. Once the pipe is merely warm, it is cooled down some more in ice, and
the cap unscrewed.
The reaction mixture is poured into a distilling flask, the glassware
rigged for simple distillation, and the isopropyl alcohol and excess
ammonia or methylamine is distilled off. When this is done, the residue
inside the flask is made acid with hydrochloric acid. If indicating pH
paper is available, a pH of about 3 should be aimed for. This converts the
MDA to the hydrochloride which is water soluble. Good strong shaking of the
mixture ensures that this conversion is complete. The first stage of the
purification is to recover unreacted bromo compound. To do this, 200 to 300
ml of ether is added. After some shaking, the ether layer is separated. It
contains close to 20 grams of bromo compound which may be used again in
later batches.
Now the acid solution containing the MDA is made strongly basic with
lye solution. The mixture is shaken for a few minutes to ensure that the
MDA is converted to the free base. Upon sitting for a few minutes, the MDA
floats on top of the water as a dark colored oily layer. This layer is
separated and placed into a distilling flask. Next, the water layer is
extracted with some toluene to get out the remaining MDA free base. The
toluene is combined with the free base layer, and the toluene is distilled
off. Then a vacuum is applied, and the mixture is fractionally distilled. A
good aspirator with cold water will bring the MDA off at a temperature of
150g to 160 C. The free base should be clear to pale yellow, and give a
yield of about 20 ml. This free base is made into the crystalline
hydrochloride by dissolving it in ether and bubbling dry HCl gas through it
as described previously.
Dr. Shulgin prefers another method of converting the free base to the
hydrochloride. Rather than bubbling dry HCl through an ether solution of
the free base to get the crystalline hydrochloride, he prefers to dissolve
about 25 ml of the free base in about 150 ml of anhydrous isopropyl
alcohol, and neutralize this mixture with around 150 drops of concentrated
hydrochloric acid. Then the product is precipitated out of solution by
adding 300 ml of anhydrous ethyl ether, shaking well and letting the
mixture sit for a while before filtering. I do not feel this procedure is
as suitable for the production of crystals as the one I have given. There
are several reasons for this. First of all, Dr. Shulgin prefers the routes
using LAH reductions of the nitrostyrenes. Underground operators must face
the facts that LAH and large amounts of anhydrous ethyl ether are not
likely to be available. To tout this as the preferred pathway leads to an
easy shutdown pinchpoint for the central chemical scrutinizers. There are
also methods of using sodium borohydride or sodium cyanoborohydride as the
reducing agent for the reductive alkylative (aminative) reaction with
phenylacetone to yield amphetamine or methamphetamine. These substances are
pretty easily made taboo for the general public; aluminum foil is not. This
is the reason for my presentation of the aluminum foil reduction method as
the preferred route. It has nothing to do with the narco swine's accusation
that I was unfamiliar with this other method. I love to hate these
creatures! See the article called "Synthetic Reductions in Clandestine
Amphetamine and Methamphetamine Laboratories - A Review," in the
pseudoscientific journal, Forensic Science International, Vol. 42 (1989),
183-199, by the groveling narco swine, Andrew Allen and Thomas Cantrell. It
would be good for these beings to get into private industry where they
could be productive.
Back to the reasons why I prefer dry HCl precipitation of the free
base. With a less than 100% pure free base, the resulting crystalline
hydrochloride has one hell of a thirst for water. This results in a mush
that is better handled by my method. The first few crops of crystals from
the HCl bubbling can be kept as same, and the later, more polluted product
can be segregated, and this can be given the curative attention it needs
through washing with more ether, or recrystallizing from alcohol and then
ether. If all I have to face as my nemeses are the likes of Allen and
Cantrell, the future is secure for manufacturers everywhere!
--------------------------------------------------------------------------
Methamphetamine From Ephedrine
--------------------------------------------------------------------------
Ephedrine and Pseudoephedrine
Ephedrine and pseudoephedrine are structurally mirror images of each
other. This is possible because they have a chiral center, the isopropyl
carbon to which the nitrogen atom is attached. If the reduction is done in
such a manner that the chiral nature of the substance is not jumbled (i.e.
racemization), then ephedrine and pseudoephedrine give rise to "l" and "d"
methamphetamine, respectively. The "l" form is several times more potent
than the "d" form. Meth produced from phenylacetone is a racemic mixture,
meaning that it is a 50-50 mix of the "l" and "d" forms of meth. Obviously,
a batch of pure "l" form is most desirable, a racemic mixture is OK, and
pure "d" form is bad news.
Many of the direct and indirect reduction methods retain the chiral
nature of the starting material. A good general rule is if the production
method does not use boiling acids, racemization does not occur. One can
then conclude that only the direct reduction with palladium black, and the
hydroiodic acid and red phosphorus methods lead to racemization of the
starting material.
What then if you are starting with pseudoephedrine, and you want as a
result a racemic mixture for a product, but aren't using the palladium
black or hydroiodic acid routes? This problem can be sidestepped by
dissolving the pseudoephedrine (hydrochloride or sulfate) in some
concentrated hydrochloric acid, and boiling it under reflux for a couple
hours. The result is a 50-50 mix of ephedrine and pseudoephedrine which
upon reduction will give a racemic meth mixture.
Procedure For Obtaining Pure Ephedrine From Stimulant Pills
In the present chemical supply environment, the best routes for making
meth start with ephedrine as the raw material. To use these routes, a
serious hurdle must first be overcome. This hurdle is the fact that the
most easily obtained source of ephedrine, the so-called stimulant or
bronchodilator pills available cheaply by mail order, are a far cry from
the pure starting material a quality minded chemist craves. Luckily, there
is a simple and very low profile method for separating the fillers in these
pills from the desired active ingredient they contain.
A superficial paging through many popular magazines reveals them to be
brim full of ads from mail order outfits offering for sale "stimulant" or
"bronchodilator" pills. These are the raw materials today's clandestine
operator requires to manufacture meth without detection. The crank maker
can hide amongst the huge herd of people who order these pills for the
irritating and nauseating high that can be had by eating them as is. I have
heard of a few cases where search warrants were obtained against people who
ordered very large numbers of these pills, but I would think that orders of
up to a few thousand pills would pass unnoticed. If larger numbers are
required, maybe one's friends could join in the effort.
The first thing one notices when scanning these ads is the large
variety of pills offered for sale. When one's purpose is to convert them
into methamphetamine, it is very easy to eliminate most of the pills
offered for sale. Colored pills are automatically rejected because one does
not want the coloring to be carried into the product. Similarly, capsules
are rejected because individually cutting open capsules is just too much
work. Bulky pills are to be avoided because they contain too much filler.
The correct choice is white cross thins, preferably containing ephedrine
HCl instead of sulfate, because the HCl salt can be used in more of the
reduction routes than can the sulfate.
Once the desired supply of pills is in hand, the first thing which
should be done is to weigh them. This will give the manufacturer an idea of
how much of the pills is filler, and how much is active ingredient. Since
each pill contains 25 milligrams of ephedrine HCl, a 1000 lot bottle
contains 25 grams of active ingredient. A good brand of white cross thins
will be around 33% to 40% active ingredient. 25 grams of ephedrine HCl may
not sound like much, but if it is all recovered from these pills, it is
enough to make from 1/2 to ounce of pure meth. This is worth three or four
thousand dollars, not a bad return on the twenty odd dollars a thousand lot
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Old 10-26-2005, 10:25 AM   #28
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of such pills costs.
To extract the ephedrine from the pills, the first thing which must be
done is to grind them into a fine powder. This pulverization must be
thorough in order to ensure complete extraction of the ephedrine from the
filler matrix in which it is bound. A blender does a fine job of this
procedure, as will certain brands of home coffee grinders.
Next, the powder from 1000 pills is put into a glass beaker, or other
similar container having a pouring lip, and about 300 ml of
room-temperature distilled water is added. This is stirred at low speed for
10 minutes. The water is then poured out of the beaker through a filter and
set aside. The sludge from the pills is returned to the beaker, and another
250 ml of room-temperature distilled water is added. Once again, stir for
10 minutes, then pour through a filter.
A little more water can be poured over the sludge to rinse the last of
the ephedrine out of it. At this point, the sludge should be nearly
tasteless and gritty in texture. The water filtrate should be clear and
very bitter. The filtrate contains all the ephedrine.
The filtrate is now collected into one beaker and heated over a burner
until it reaches a gentle boil. One half of the water is boiled off this
way. The liquid is then removed from the heat and poured into a glass
baking dish to more slowly evaporate away the remaining liquid. The
resulting crystals of ephedrine can then be rinsed with some cold acetone.
Certain brands of pills are loaded with gummy binders. These brands are
recognizable because they are very difficult to crush into a powder, and
the hot water extract from them is not easily filtered into a clear
solution. When evaporated down to pure extract, they produce a yellow gummy
residue at the bottom of the evaporation dish. This gummy mess is not
suitable for processing into high grade drugs. The gum is easily removed
from the desired product just by adding a few hundred mls of cold acetone
to the extract of 1000 stimulant pills, and grinding the gummy mess with a
glass rod until the crystals of stimulant are freed from the gum, and a
fine dispersion of them floats freely about. The gum colors of acetone
yellow, and the floating crystals will be white. Then by filtering this
mixture, one obtains the pure crystals of active ingredient free from the
polluting binder in the pills.
Indirect Reduction
A popular alternative method for making methamphetamine uses ephedrine
as the starting material. This method was not covered in the original
edition of this book. It is now presented in all its glory for the
education of the reader.
The reasons for the popularity of this method are twofold. Firstly,
this method does not require the use of methylamine because the methylamino
group is already incorporated in the ephedrine molecule. Secondly,
ephedrine is still easily available. It is much more easily obtained than
phenylacetic acid. This may change in the future, but at present an
underground chemist can buy 1000-lot quantities of stimulant pills
(containing 25 milligrams of ephedrine) by mail at very reasonable prices.
The utility of this method is not limited solely to ephedrine.
Pseudoephedrine and phenylpropanolamine can also be used as starting
materials. This means that Sudafed and Dexatrim, and their generic
equivalents, can be used as raw materials for clandestine amphetamine
manufacture. The active ingredient is easily separated from the diluents in
the pills by the method given in this book.
The bad thing about this method is that foul impurities generated
during the manufacturing process are easily carried into the final product.
Due care must be practiced by the chemist during the purifi- cation to
exclude this filth. Unscrupulous and/or unskilled manufacturers turn out
large volumes of crank containing this abomination. The impurities not only
ruin the finer aspects of the meth high, but they also have a pronounced
deleterious effect on male sexual function.
One can quickly see that all a chemist needs to do to turn ephedrine
into meth is to replace the alcohol OH grouping with a hydrogen atom. This
is not done directly. Instead, a two step process is used whereby the OH is
first replaced by a chlorine atom, and then this chlorine is removed by one
of several reductive processes, to be replaced with a hydrogen atom. To
illustrate:
[SNiP]
There are several general methods for converting an alcohol group into
a chlorine atom. Substances such as thionyl chloride SOCl2 phosphorus
pentachloride (PCl5), phosphorus oxychloride (POCl3), phosphorus bichloride
(PCl3), phosphorus pentabromide (PBr5) and phosphorus tribromide (PBr3) can
all be used to convert the alcohol group to either a chloride or bromide.
Essentially the same reaction conditions are followed when using any of the
above listed substances. The only difference is how much ephedrine or PPA
(phenylpropanolamine) the substance can chlorinate or brominate. See the
table below:
Substance Molecular Reacts with this many
Weight moles of ephedrine
SOCl2 119 1
PCl3 137 2
POCl3 153 2
PBr3 271 2
PCl5 208 3
PBr5 430 3
molecular weight of ephedrine HCl=202, PPA-HCl = 188
Using the above table, a person can quickly calculate how much
ephedrine or PPA will react with a given amount of chlorinating agent. Use
of excess chlorinating agent will result in a higher percentage yield based
on the ephedrine used, but after a point, this is wasteful. The following
example takes this largess to an extreme, but achieves 100% conversion of
ephedrine to chlorephedrine. This procedure can be followed with all the
chlorinating agents. The reaction is fairly easy to do. The main
precautions are to make sure that the glassware is free of water, and
taking one's time to be sure the mixture stays sufficiently cold. It is
also wise to avoid doing this reaction in very humid conditions.
To convert ephedrine to chlorephedrine, a 2000 ml 3-necked flask is
nestled into a bed of ice. A mechanical stirrer is put down the middle neck
of the flask as in the preparation of butyl nitrite. One of the outside
necks is plugged by sticking a cork into it. The other neck is used as a
chemical addition portal. Into this neck, 360 ml of chloroform is added.
Then 360 grams of PCl5 is added. When this mixture has cooled down (about
1/2 hour), 240 grams of ephedrine hydrochloride is added to the brew. It is
added by placing a small plastic funnel into the neck of the flask. This
ensures that it falls into the mix, rather than being scattered along the
walls of the flask. The ephedrine hydrochloride is added in small portions
over a 45 minute period. Stirring is fast enough that the PCI5 remains in
suspension, and the ephedrine hydrochloride quickly mixes into the brew.
Adjusting the angle of the funnel so that it aims the ephedrine HCI toward
the center of the whirlpool is a fine point that gives best results.
The serious experimenter may wish to try replacing the chloroform
solvent with l,l,l-trichloroethylene. This very cheap solvent can be found
in hardware stores, and has solubility characteristics similar to
chloroform. No doubt a greater quantity of trichlorethylene would have to
be used, but it would take another item out of the chemical supply loop.
When all of the ephedrine HCl has been added, an additional 60 ml of
chloroform is added. Then the funnel is replaced with another cork, and the
stirring is turned up a bit. The stirring is continued for two hours. Then
the stirring is turned off, and the flask is allowed to sit for 45 minutes
or so. During this period, the unreacted PCl5 settles to the bottom of the
flask. At the cold temperature inside the flask, some crystals of ephedrine
HCl will appear floating on the surface of the brew.
When all has settled inside the flask, the mixture IS carefully
decanted off into a one gallon glass jug. Great care is taken during this
decanting to make sure that all of the settled PCl5 remains behind. If any
of it were mixed in with the product chlorephedrine it would be reduced in
the succeeding hydrogenation to phosphine, PH3, an exceedingly deadly gas.
If it appears any is being carried along, the mixture is filtered.
Next, the product is precipitated from the chloroform solution in the
gallon jug. This is done by slowly adding ether or, better still, mineral
spirits (cheap and easily available in large amounts) to the gallon jug
until it is nearly full. The mixture in the gallon jug is continuously
stirred during the addition of the ether or mineral spirits for best
results. Chlorephedrine does not dissolve in ether or mineral spirits, so
as the solution changes from chloroform to predominantly ether, the product
is thrown out of solution in the form of crystals. If an oily layer forms
at the bottom of the jug, this means a dirty batch. The oil may eventually
crystallize, but more likely it must be separated, dissolved in an equal
volume of chloroform, and precipitated once again by adding ether or
mineral spirits.
After the addition of the ether or mineral spirits, a large mass of
crystals fills the jug. This is the product. The jug is stoppered, and put
into the freezer for an hour to let the crystals fully grow. The crystals
are then filtered out and rinsed down with a little bit of cold acetone.
Then the crystals are spread out to dry on china plates or glass baking
dishes. The yield of chlorephedrine hydrochloride is in the neighborhood of
250 grams.
Production of Meth
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Old 10-26-2005, 10:25 AM   #29
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To make meth from chlorephedrine, the chlorine atom is replaced with a
hydrogen. This reduction is accomplished by any of several methods. Lithium
aluminum hydride does the best job of completely converting the
chlorephedrine into meth, but it is very expensive, and a watched chemical.
Zinc dust, on the other hand, is cheap and easily available, but it leaves
a large proportion of the chlorephedrine unconverted. The most practical
and effective way to turn out large volumes of meth is by catalytic
hydrogenation. It is possible to use Raney nickel as the catalyst for this
hydrogenation, but it has to be used in quite large amounts to do a good
job. Potassium Hydroxide (KOH) also has to be added to the bomb in an
amount equal to the chlorine given off by the chlorephedrine, i.e., one
mole of chlorephedrine would require one mole of KOH added. Platinum can
also be used to reduce the chlorephedrine, but it too has to be used in
large amounts to get good results. Furthermore, it is rapidly poisoned by
the chlorine and becomes useless.
The best catalyst to use for this reduction is palladium, in the form
of palladium black on charcoal, or palladium on barium sulfate. The
palladium stands up well to the chlorine, and can be used to run many
batches before it needs to be recycled. Palladium works fine at low
pressures of hydrogen, and can be used with the champagne bottle
hydrogenation system pictured in Chapter 11.
To do the reaction, a champagne bottle of at least 1.5 liters volume is
filled with 50 grams sodium acetate (anhydrous) and 700 ml of distilled
water. The pH of this solution is then made neutral (pH 7) by dripping in
diluted acetic acid. This forms an acetic buffer which prevents the
solution from becoming acidic when chlorephedrine hydrochloride is added to
it. It also neutralizes the hydrochloric acid formed when the chlorine atom
is removed from the chlorephedrine molecule. Then 40 grams of 5% palladium
black on charcoal (palladium content 2 grams) is added, and finally 125
grams of chlorephedrine hydrochloride is added.
Sodium acetate is now on California's list of less restricted
chemicals, so it is wise to avoid using sodium acetate as such. This is not
the least bit troublesome, and shows just how stupid the people are who put
it on the restricted list. To avoid the need for sodium acetate purchases,
acetic buffer is made from vinegar and sodium hydroxide. To do this, 700 ml
of vinegar is used instead of distilled water. It should be the cheapest
grade of white distilled vinegar, because this is likely to be made just by
diluting glacial acetic acid with water down to a 5% strength. Then to this
700 ml of vinegar, sodium hydroxide pellets are slowly added until the pH
of the solution is around 7. This takes about 23 grams of NaOH.
The champagne bottle is then attached to the hydrogen line pictured in
Figure 17 in Chapter 11, and the air is sucked out and replaced with
hydrogen as described in that chapter. Then the pressure of hydrogen is
increased to 30 pounds, and magnetic stirring is begun. The solution soaks
up hydrogen for several hours, during which time the pressure is maintained
around 30 pounds by letting more hydrogen into the bottle.
When absorption of hydrogen ceases after several hours, the reaction is
complete. The hydrogen valve is turned off at the cylinder, and hydrogen
inside the bottle released outside through a line of tubing as described in
Chapter 11. Stirring is stopped, and the palladium on charcoal catalyst is
allowed to settle in the bottle. When it has settled, the solution is
carefully poured out of the bottle into a beaker, taking care to try to
leave all the catalyst behind in the bottle. The solution is then filtered
to remove suspended Pd on charcoal catalyst.
The catalyst is returned to the bottle, which is then refilled with a
fresh batch, or filled with hydrogen to protect the catalyst.
Before proceeding further with the processing of the filtered batch, it
is wise to look more closely at the nature of the by-products produced by
this method of making meth. There are twin villains to be dealt with here:
These substances, or closely related ones, will always be formed when
making meth by this method. The chlorephedrine is the result of incomplete
reduction to meth, and the aziridine the result of an intermolecular
reaction between the chlorine atom and the nitrogen atom of the
chlorephedrine. It is likely that the aziridine by-product is more easily
formed when the bromoephedrine variation of this synthetic route is chosen.
There are two things which aid in the formation of the aziridine. They are
exposure to strong bases such as lye and heat. To minimize formation of the
aziridine, one first of all aims for as complete a reduction as possible of
the chlorephedrine to meth. Next, during processing, one backs off on the
heavy duty use of lye, using bicarb instead to neutralize the last of the
acid. Finally, the distillation is done as quickly as feasible under vacuum
to get the least heat exposure to the unreduced chlorephedrine. Obviously,
the first point is the most important.
To proceed, the filtered batch is reacted with lye with strong shaking
until litmus paper says that the pH is around 7. Then bicarb is added to
finally make the solution basic. The fizzing and venting of CO2 gas is a
hassle at this point, but it is worth it to avoid the formation of the
aziridine. A 2000 ml flask is a good vessel in which to do the
neutralization procedure. One must periodically vent off the built up CO2
gas after bicarb has been added.
Upon standing after the shaking, a layer of meth floats on top of the
water layer. Then 200 ml of benzene or toluene is added, and the jug is
shaken again. After standing for a couple of minutes, the benzene-meth
layer floats nicely upon the water. This is carefully poured off into a sep
funnel, and the benzene-meth layer is poured into a 500 ml round bottom
flask. The water layer is discarded.
Next, the product is distilled as described in Chapter 5. Here also is
a point at which lazy or unskilled operators err and thereby leave their
product polluted with chlorephedrine. You see, it is next to impossible to
completely convert the chlorephedrine into meth. The conversion can be
encouraged by using plenty of catalyst, sufficient pressure, and ample
reaction time in the bomb, but there will still be some left unreacted. As
the catalyst wears out from doing repeated batches, the proportion of
chlorephedrine in the product will increase. Only by doing careful
fractional distillation, can the chlorephedrine be removed.
Chlorephedrine's solubility characteristics are so similar to meth's that
it can't be removed by crystallization or rinsing the crystals. When doing
the distillation, the meth distills at the usual temperature range. The
next fraction which distills is chlorephedrine. Since this chlorephedrine
can then be cycled back into the hydrogenation step, it makes both economic
and ethical sense to remove it from the product. By skipping the fractional
distillation, lazy operators costs themselves an added measure of meth
yield from their raw material inputs.
The chlorephedrine free base thusly obtained is too unstable to keep as
such. Its must immediately be reacted with HCI to form the hydrochloride.
Palladium Black on Carbon Catalysts
Since palladium black on carbon catalyst is on the narco swine's watch
list of chemicals, it is wise for the operator to make his own supply.
Luckily, this is not too difficult, and gives a catalyst that is fresher
and more active than off the shelf catalysts.
To make the catalyst, the chemist first obtains Norit or Darco brand
activated charcoal, and washes it with nitric acid. This is done by
measuring out about 100 grams of the charcoal, and then putting it into a
beaker along with 10% nitric acid. They are mixed together into a watery
slurry, and heated on a steam bath or in a boiling water bath for 2 or 3
hours. After the heating, the carbon is filtered and rinsed liberally with
distilled water until the last traces of acid are rinsed from it. This
requires about a gallon of water.
The acid washed carbon is then transferred to a 4000 ml beaker. A few
grams of the carbon sticks to the filter paper and is otherwise lost, but
this is OK since the idea is to get about 93-95 grams of carbon into the
beaker. 1200 ml of distilled water is added to the beaker, and it is heated
with stirring to 80 C. When this temperature is reached, a solution of 8.2
grams of palladium chloride in 20 ml of concentrated hydrochloric acid and
50 ml of water is added. This acid solution of palladium chloride is heated
for a couple of hours before it is added, because PdCl2 dissolves slowly in
the acid solution. It is not added until all the PdCl2 is dissolved. If
PdCl2 dihydrate is used, the amount used is increased to 10 grams.
When the PdCl2 solution has been added and stirred in, 8 ml of 37%
formaldehyde solution is added and mixed in. Next, the solution is made
slightly alkaline to litmus by adding 30% sodium hydroxide solution to the
beaker dropwise with constant stirring. Once the solution has become
slightly alkaline to litmus paper, the stirring is continued for another
five minutes.
Next, the solution is filtered to collect the palladium black on
charcoal catalyst. It is rinsed ten times with 250 ml portions of distilled
water. Then after removing as much water as possible by filtration, the
catalyst is spread out to dry in a glass baking dish. It is not heated
during the drying process since it could burst into flames. When it has
dried, it is stored in a tightly stoppered bottle and used as soon as
possible. This process gives about 95 grams of 5% palladium black on
charcoal catalyst.
Direct Reduction
This section deals with the direct conversion of ephedrine,
pseudoephedrine, or phenylpropanolamine to meth or benzedrine respectively.
This conversion can be accomplished by one of four methods. These four
methods will be covered and explained in the order of best method to worst
method. These conversions are all possible because ephedrine,
pseudoephedrine, and phenylpropanolamine are all benzyl alcohols, and
benzyl alcohols are the easiest of all alcohols to reduce to the
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corresponding hydrocarbon.
These methods all have the advantage of being quick and simple, but
they also have their unique disadvantages, along with the general shared
disadvantage that the starting material must be gathered bits at a time
from bottles of pills.
Method 1: Lithium Metal in Liquid Ammonia Reduction
This is a new method, and is the best one I've seen come down the pike
in ages. This procedure was pioneered by a clandestine operator in
California. Unfortunately, he was busted because he bought a jug of
ephedrine to use as his starting material. Had he been more cautious, and
isolated the ephedrine from legal pills, he may well have gone undetected.
This method is ideally suited for the rapid production of truly massive
amounts of crank. It suffers from the need to use liquid anhydrous ammonia.
This is very smelly stuff, especially in the quantities needed to make
large amounts of meth. The smell problem means that this method can only be
used in countryside locations, preferably in a large shed with a strong
breeze passing through it. In this way, the production masters can position
the reaction so that they are upwind from the fumes.
The countryside location has the further advantage that tanks of
anhydrous ammonia are not at all out of place in such a location. In every
agricultural area, tanks of anhydrous ammonia ply the roads all through the
growing season. Farmers use it for nitrogen fertilizer on their crops,
especially corn. The local co-op hauls out the tank to the farmer, who then
applies it to his crops at his leisure. The implication of this is obvious.
A well thought out large scale meth production scheme would center upon
renting some nondescript piece of land, planting some corn on it, and then
getting a tank of "anhydrous" to fertilize the crop. The resulting product
will pay much better than corn. A less well thought out plan would involve
getting a tank of anhydrous ammonia from a chemical supplier and taking it
to a countryside location for further use. In either case, the ammonia is
of the same grade.
This method of making crank is based on the research of Gary Small and
Arlene Minnella as published in the Journal of Organic Chemistry, Volume
40, pages 3151 to 3152 (1975). The article is titled "Lithium-Ammonia
Reduction of Benzyl Alcohols to Aromatic Hydrocarbons. An Improved
Procedure." It results in the 100% conversion of ephedrine, pseudoephedrine
or PPA in a reaction time of 10 minutes or so.
A disadvantage of this procedure is that it demands the use of the free
bases of ephedrine or PPA. Since the material as isolated from the pills
will be either the hydrochloride or sulfate salt, a free basing and
subsequent distillation is called for to get pure free base, free from salt
and traces of water, which would interfere with this reaction.
A good procedure to follow to get this pure free base is to dissolve
the hydrochloride salt in alcohol, and add NaOH or KOH pellets to the
solution until the hydrochloride is all neutralized, and then distill off
the alcohol, and finally collect the free base by vacuum distillation. The
boiling point of ephedrine is around 225C at normal pressure, and 135C at
12 mmHg vacuum. For PPA, the boiling point is a little bit lower. In doing
this distillation, the condenser should not have water flowing through it
because the free bases melt at 77C and 101C respectively. If cold water
should flow through the condenser, it would plug up with the solid.
Instead, the condenser should be filled with water, and it should be
allowed to stay in there until it nears boiling. Then a bit of fresh water
can be flowed in. The receiving flask should be packed in ice to assure
that all the free base is condensed there.
This method is superior to dissolving the hydrochloride in water and
neutralizing the salt with NaOH in that solvent and then trying to extract
out the free base with ether or toluene, and then proceeding with the
distillation, because the free bases are soluble in water and form
hydrates. They also distill with steam. However, when using the sulfate
salt as raw material, one may have no choice but to use the latter method
because the sulfate salts do not dissolve well in alcohol.
With a supply of free base in hand, it is now time to consider the
lithium metal in ammonia reduction method. A very good review of this
procedure can be found in the book Reduction: Techniques and Applications
in Organic Synthesis by Augustine, pages 98 to 105. At the heart of this
method is the fact that lithium metal, or sodium metal, or even potassium
metal can dissolve in liquid ammonia to form blue colored solutions that
have powerful reducing properties. Such solutions are often referred to as
"dissolved electrons." These solutions are stable unless water gets in
them, or unless they are contaminated with iron from the ammonia tank. When
the free bases of ephedrine or PPA are added to these "dissolved
electrons," they are quickly and easily reduced to meth or benzedrine
respectively. To do the reaction, a 3000 ml round bottom 3 necked flask is
set inside a styrofoam tub. The purpose of the tub is to provide
insulation, because once liquid ammonia gets out of the cylinder it starts
to rapidly boil away until the liquid is lowered to its boiling point of
-33C. This boiling can be kept under control by adding dry ice to the tub.
If a cylinder of ammonia is being used, it is a good idea to cool it down
before use by putting it in a freezer. With a tank from the co-op, this is
not practical. To get the liquid ammonia out of the tank or cylinder,
either clear plastic tubing or rubber tubing is placed over the exit valve
of the tank or cylinder, and run into the 3 necked flask. Use of metal, and
especially copper, is to be avoided. Then the cylinder is tipped upside
down, so that the valve is at the bottom of the cylinder. This assures that
liquid comes out rather than gas. Next the valve is cautiously cracked
open, and liquid ammonia is run into the flask until it is about 1/2 full.
It will quickly boil away until the volume of the ammonia is down to about
1000 ml, and then more slowly because the ammonia has cooled to its boiling
point. Then wearing rubber gloves and eye protection to keep the fumes out
of the eyes, a magnetic stirring bar is placed in the flask, and the tub is
put on a magnetic stirrer, and stirring is begun. Now 14 grams of lithium
metal is put into the flask. Lithium usually comes in the form of turnings
inside a sealed glass ampule under inert atmosphere. It can be used
directly as such. If lithium wire is being used, it should be cut into
short lengths, and rinsed off with petroleum ether prior to use. The
lithium metal quickly dissolves, forming a blue solution. Next, 500 ml of
tetrahydrofuran is added to this solution. The purpose of the THF is to aid
in the dissolution of the ephedrine or PPA which is to be added next. I can
see no reason why anhydrous ether can't be used instead of THF, if this is
easier to obtain. Next 110 grams of ephedrine (or 100 grams of PPA) is
dissolved in 500 ml of THF or ether, and this solution is added to the
lithium in ammonia solution over a period of 10 minutes. After allowing the
reaction to proceed for an additional 10 minutes, the reaction is quenched
by slowly adding water to the ammonia. This is done dropwise at first, and
then more rapidly until the blue color disappears from the ammonia
solution. The flask is then taken out of the styrofoam tub, and the ammonia
is allowed to evaporate overnight. When the ammonia is gone, some more
water is added to the remaining ether (or THF) solution to dissolve the
salts of lithium in the bottom of the flask. After separating the water
layer, the ether layer is dried using anhydrous sodium sulfate, and the
meth or benzedrine is obtained as the hydrochloride salt by bubbling HCl
gas through the ether solution as described back in Chapter 5. Distillation
is unnecessary because of the lack of formation of by products in this
reduction. It would just be a colossal waste of ether.
One may justifiably ask now, "How is this such a great mass production
method, when one is only getting 100 grams of product out of each batch?"
The answer is that the work can easily be organized so that one batch after
another is quickly turned out by this method. Each individual batch only
requires a few minutes of attention. After one flask is filled with
ammonia, another may be set up and filled, resulting in a virtual assembly
line procedure.
Before moving on here, there is a possible complication which must be
addressed. This is the possibility that a tank of ammonia may only be
putting out ammonia gas, rather than spewing liquid. This is no great
hassle. In that case, the 3000 ml 3 necked flask is well packed in dry ice,
and rubbing alcohol poured on the dry ice to create a very cold bath. When
the ammonia gas hits the very cold flask, it will be condensed to a liquid.
This may actually be a better procedure because it will assure that the
ammonia does not have dissolved iron in it from the tank. Iron interferes
with some lithium in ammonia reductions. I am not sure whether that is the
case with this particular reaction. Input from serious experimenters is
welcome.
It is also possible to use sodium metal or potassium metal in this
reaction. Sodium is much cheaper than lithium, but is on the California
list of less restricted chemicals. Use of sodium may also result in partial
reduction of the benzene ring. For details on this modified procedure, see
the aforementioned Journal of Organic Chemistry article. I suspect that the
partial benzene ring reduction could be avoided if sodium metal were used
in the procedure given here rather than the modified procedure using sodium
given in the JOC article. That procedure uses ethanol instead of THF.
Allowance would have to be made in calculating how much sodium metal to use
for the greater atomic weight of sodium (23 versus 7).
Method 2: Wolff-Kishner Reduction
This method of directly reducing ephedrine, pseudoephedrine, or
phenylpropanolamine to meth or benzedrine uses hydrazine hydrate as the
reducing agent. The Wolff-Kishner reduction is generally used to
deoxygenate ketones to the corresponding hydrocarbon, but in this case, it
can be used on these particular substances to reduce them. No doubt, this
is because the benzyl alcohol grouping has a ketone nature due to
tautomerism.
The Wolff-Kishner reduction has the advantage of not producing great
plumes of stink. It could likely be done in an urban setting without
arousing the suspicions of nosey neighbors. Further, the reactants are only
moderately expensive, and not tightly controlled at present. Fair amounts
of product can be turned out at a rate of one batch per day.
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