Secrets of Methamphetamine Manufacture

Warning: In some areas of the United States, manufacturing methamphetamine is punishable by a mandatory ten-year prison sentence. The Hip Forums does not advocate any illegal activities. Know the law in your area.

Secrets of Methamphetamine Manufacture (3rd ed.)
by Uncle Fester
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INTRODUCTION
This book is the result of six years experience in the field of
manufacturing methamphetamine. It contains virtually everything I know
about the subject. There are a lot of secrets in this area, hence the title
Secrets of Methamphetamine Manufacture.
A thorough review of the scientific literature on this subject will
show that the descriptions of this process are, at best, vague and
imprecise, at worst, downright wrong. The Russian journals are especially
unreliable.
There are two reasons for this. First of all, the companies holding
patents on the processes want to keep their trade secrets secure, so they
disclose no more than is absolutely necessary to obtain their patents.
Secondly, the articles written by university scientists cover the making of
large numbers of compounds and so do not delve deeply into the details of
making any particular one.
This book fills the glaring gap in published scientific literature. The
reader receives the benefit of my lengthy scientific education at expensive
and prestigious universities and detailed knowledge of these processes that
would otherwise be available only through tedious and expensive
experiments. There is no magic involved, only good chemistry, and I show
how underground chemists manufacture illegal drugs and get away with it.
Skilled and successful underground chemists have usually taken a
college level Organic Chemistry course, with lab, for at least one
semester. In this lab, they get practice in distillation, extraction, and
other skills involved in making methamphetamine. At the very least, they
will go to a college bookstore and purchase the lab manual for the Organic
Chemistry class. That book goes into some detail on how to distill, reflux,
etc.
While this book is not meant to encourage anyone to break the law, it
does point out the ultimate futility of government prohibition of
"controlled substances" by showing just how easily these substances can be
manufactured.
Underground drug manufacturers sometimes enjoy chipping into their own
product. If there is one product which underground chemists can make, and
also enjoy themselves, it is methamphetamine, the fuel that powered the
Third Reich. They need have no fear of messing up their batches while under
the influence of methamphetamine, unlike chemical garbage such as PCP.
Legal methamphetamine is sold under such trade names as Desoxyn,
Methedrine, etc. It is closely related both in structure and effects to
regular amphetamine, called benzedrine and dexedrine.
The difference between methedrine and benzedrine is that meth is more
potent and its effect lasts a longer time. Meth is a potent stimulant
similar in effect to cocaine, but much longer lasting. Where I come from,
if people have a choice between coke and meth, they will choose meth,
unless it's 2 AM. This is because meth is a much better bargain and can
keep a man rolling through a hard day's work or a long night of play, or
both. It sharpens the mind, allowing great amounts of mental work to be
done quickly and error-free. It also sharpens one's reflexes to previously
unknown levels, perfect for football. If you are planning to get into a
fight, there is nothing better. It's not banned from boxing for nothing.
The effects of meth on sexual function is a crap shoot. One day you
will be a sexual athlete, the likes of which has never been seen this side
of the porno flicks, the next you will be a complete failure. The odds in
favor of athleticism are about 3 to 1, but can be improved by moderate
alcohol consumption, and worsened by heavy drinking or immoderate use of
meth. Poorly purified meth also has this drawback. The product should be
distilled carefully.
On the street, methamphetamine is known by such names as meth, crystal
meth, crystal, speed, crank or wire. Most of the stuff on the street shows
the telltale signs of sloppy lab work: yellow crystals, sticky crystals, or
a tendency to soak up water from the air and melt.
Back in the 60s, meth got a bad name because fools were shooting the
stuff up constantly, starving themselves to death or getting hepatitis.
This is how the slogan "speed kills" got started. If you do not have
suicidal tendencies, accept the fact that your sinus cavities are close
enough to your brain. You must also control your intake of meth. I would
recommend no more than 50 milligrams (1/20 gram), no more than three times a
week. Any more than this, and bad effects begin to appear, such as
difficulty in thinking clearly, paranoid behavior and excessive weight loss
leading finally to amphetamine psychosis, which quickly fades upon stopping
consumption of amphetamine. Meth is not physically addicting, but since
good effective stimulation is so enjoyable, it is habit-forming. People
have been known to take extremely large doses, over a gram, and survive
with no after effects, so overdoses are not a problem unless you have some
underlying problem like a bad heart or hard arteries.
I have some recommendations for underground chemists who consume their
own product. First of all, they must eat well whether they feel like eating
or not. Most people can stand to lose 10 pounds or so, but beyond that,
forget it. It has been my experience that a few beers is usually all it
takes to get a speed demon in the mood to eat. They'll probably need a few
beers to get to sleep anyway, so they might as well take care of both
things at once. I also recommend a 1/2 gram of phenylalanine per day. This
is because meth works by releasing stores of norepinephrine from the brain,
charging it up to new levels of activity. The amino acid phenylalanine is
the starting material for making more norepinephrine, and a good supply of
it will help refill spent stocks. They should also take a good
mega-multi-vitamin with the minerals, selenium and zinc. They must not take
methamphetamine closer than 6-8 hours before bedtime, or they will have to
drink the bar dry to get to sleep.
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CHEMICALS AND EQUIPMENT
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The heart of the chemical laboratory is the set of glassware
collectively called "the kit." It consists of several round bottom flasks,
a claisen adapter, a still head with thermometer holder, a thermometer, a
condenser, a vacuum adapter and a separatory funnel (sep funnel, for
short). These pieces each have ground glass joints of the same size, so
that the set can be put together in a variety of ways, depending on the
process being done. For the production of quarter to third of a pound
batches, 24/40 size ground glass joints are used. Also necessary are one
each of the following sizes of round bottom flasks: 3000 ml, 2000 ml and
500 ml; and two each of 1000 ml and 250 ml. Two condensers are also
required, both of the straight central tube variety, one about 35 cm in
length, the other about 50 cm in length.
Other glassware used are several 500 ml Erlenmeyer flasks, about 5
pieces of plain (not Pyrex) glass tubing about three feet long, and a
Buchner filtering funnel with the filtering flask it fits into.
All this glassware costs in the range of $600-$700, and is available at
many scientific supply houses on a cash-and-carry basis. The best equipment
supply house in the Midwest is Sargent-Welch in Skokie. Illinois.
Another necessary piece of equipment is a source of vacuum for vacuum
distillation and filtering the crystal product. Here there are two choices.
each with its advantages and disadvantages.
One choice is the aspirator, also called a water pump. It works by
running tap water through it under good pressure, producing a vacuum in the
side arm theoretically equal to the vapor pressure of the water being run
through it (see Figure 1). For this reason, the best vacuum is obtained
with cold water, since it has a lower vapor pressure. The vacuum is brought
from the side arm to the glassware by an automotive type vacuum hose such
as can be purchased at an auto parts store. The vacuum adapter and
filtering flask each have nipples to which the other end of the hose is
attached, making it possible to produce a vacuum inside the glassware. The
top end of the aspirator is threaded so it can be threaded into the water
source. Alternatively, the threaded head can be pushed inside a section of
garden house and secured by a pipe clamp. The hose can then be attached to
a cold water faucet. The bottom end of the aspirator, where the water comes
out, is rippled and can also be pushed and clamped inside a section of
garden hose leading to the drain. The aspirator is kept in an upright
position and at a lower level than the glassware it serves. This is because
water has a habit of finding its wav into the vacuum hose and running into
the batch. Keeping the aspirator lower forces the water to run uphill to
get into the glassware. The aspirator has the disadvantage that it requires
constant water pressure flowing through it, or the vacuum inside the
glassware draws water from it inside to make a mess of the batch. For this
reason, only city water is used. And, unless the vacuum line is
disconnected from the glassware before the water flow through the aspirator
is turned off, the same thing will happen. The aspirator has these
advantages: it flushes fumes from the chemicals down with the water flow,
costs only about $10, and produces no sparks. A well-working aspirator
produces a vacuum of 10 to 20 torr (2 to 3% of normal air pressure)(The
unit "torr" means one milliliter of Mercury pressure. Normal air pressure
is 760 torr.).
The other choice for a source of vacuum is an electric vacuum pump,
which costs about $200, not including the electric motor, purchased
separately. To avoid the danger of sparks, the motor must be properly
grounded. The pump has the advantage that it can be used in the country,
where steady water pressure is not available. It also produces a better
vacuum than the aspirator, about 5 torr, for faster and lower temperature
distillation. It has the disadvantage of exhausting the chemical fumes it
pumps into the room air, unless provision is made to pump them outside. The
oil inside the pump also tends to absorb the vapors of ether or benzene it
is pumping, thereby ruining the vacuum it can produce and making it
necessary to change the oil.
Another necessary piece of equipment is a single-burner-element buffet
range with infinite temperature control. It is perfect for every heating
operation and only costs about $20 at a department store. Finally, a couple
of ringstands with a few Fisher clamps are used to hold the glassware in
position.
A number of troublesome yet futile laws have been enacted since the
publication of the first edition of this book. On the federal level,
phenylacetic acid and phenylacetronitrile are now restricted chemicals. See
Federal Register, Section 1310.02 Section A, "listed precursor chemicals."
This means that clandestine operators wishing to use these materials will
either have to smuggle them in from abroad, or make them from simpler,
noncontrolled materials. For this last option, see Organic Syntheses,
Collective Volumes I, II, and III. Check the table of contents to find
directions for making the desired substance.
An even more noxious, yet similarly futile law has been enacted in
California. Since this is bound to be the model for similar laws enacted
throughout the country, let's examine it more closely.
The most easily defeated part of the law concems the sale of chem lab
equipment and chemicals. The law states that purchasers of equipment and/or
chemicals in excess of $100 must present proper ID, and that the seller
must save the bill of sale for inspection by officers of the law. Since
most individual pieces of chem lab equipment go for less than $100, this
law is gotten around by keeping one's equipment purchases under $100, and
splitting up one's business between various suppliers. The five finger
discount method while attending college chem lab courses is another option.
Similarly, transfers between friends, and the old fashioned heist from
well-stocked labs are other ways around this law.
The most stringent section of the law is aimed primarily at production
of meth, LSD, MDA and MDMA, PCP, and the barbiturates. Of those chemicals
relevant to this book, it lists: phenylacetone, methylamine, phenylacetic
acid, ephedrine, pseudoephedrine, norpseudoephedrine, phenylpropanolamine,
isosafrole, safrole, piperonal, benzyl cyanide, chlorephedrine, thionyl
chloride, and N-methyl derivatives of ephedrine.
This section of the law states that anyone wishing to purchase these
chemicals must obtain a permit. Anyone wishing to obtain such a permit must
submit two sets of his ten fingerprints to the authorities. It is
interesting to note here that the over-the-counter stimulants which contain
ephedrine sulfate or phenylpropanolamine hydrochloride are exempt from
these restrictions. Dexatrim, and those mail order white crosses, have not
been made illegal. The determined experimenter can easily extract the
needed starting material out of the legal "stimulant" pills.
A third, and less restricted, class of chemicals deals mainly with
meth, and PCP. The chemicals of interest here are: sodium and potassium
cyanide, bromobenzene, magnesium turnings (the last two also have PCP
implications), mercuric chloride, sodium metal, palladium black, and acetic
anhydride. For this class of chemicals, the law requires presentation of
proper ID (i.e., state-issued photo ID) and calls for the seller to record
said ID. The obvious ways around this section of the law are to do business
in less nosy states, or to obtain false identification.
Clandestine operators also need to know that the law allows the central
scrutinizers to add chemicals to the lists without waming or approval. So
the new precursors mentioned in this book could go on the lists of
restricted chemicals at any time.
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THE LEUCKARDT-WALLACH REACTION: AN OVERVIEW
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The best way to produce batches of up to one-half pound in size is by
the Leuckardt-Wallach reaction. It is one of the touchiest reactions there
is, right up there with the Grignard reaction.
The Leuckardt-Wallach reaction involves reacting a ketone with two
molecules of a formamide to produce the formyl derivative of an amine,
which is then hydrolyzed with hydrochloric acid to produce the desired
amine. In this case, the reaction is shown on page 14.
There are several reviews of this reaction in the scientific
literature, the best of them Crossley and More in the Journal of Chemistry
(1949).
The conditions which favor the production of high yields of fine
quality products are as follows. There should be a small amount of formic
acid in the reaction mixture, because it acts as a catalyst. It should be
buffered by the presence of some free methylamine, to prevent the pH of the
reaction mixture from falling too low (becoming too acidic). The presence
of water in the reaction mixture is to be avoided at all costs, because
this really messes up the reaction. It prevents the phenylacetone from
dissolving in the N-methylformamide, leading to low yields of
purple-colored crystal. The directions I give in a later chapter for making
N-methylformamide give a product which is perfect for this reaction.
It is also important that the reaction be done at the lowest
temperature at which it will proceed smoothly, and that the heating be
continued for as long as the reaction is still going. In this way nearly
all the phenylacetone is converted to methamphetamine.
There is one stumbling block in the path of underground chemists: in
1979, the DEA made phenylacetone illegal to purchase or possess.
N-methylformamide is also risky to obtain, although it is not illegal and
is used in industry as a solvent.
However, they are both easy to make. And, because of these
restrictions, the price of methamphetamine has gone above $100 per gram,
while it costs only $1 or $2 per gram to make.

 

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PREPARATION OF PHENYLACETONE
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Phenylacetone, also known as methyl benzyl ketone, or
1-phenyl2-propanone, is easy but tedious to make. In this reaction,
phenylacetic acid reacts with acetic anhydride with pyridine catalysts to
produce phenylacetone plus carbon dioxide and water. In chemical writing:
[Deleted]
A Russian journal tells of using sodium acetate instead of pyridine,
which would be great if it worked, because sodium acetate is much cheaper
than pyridine. However, I have tried it and the results are unsatisfactory.
Typical of those lying Commies.
The reaction is done as follows: Into a clean, dry 3000 ml round bottom
flask is placed 200 grams of phenylacetic acid, 740 ml of acetic anhydride
and 740 nil of pyridine. This is done on a table covered with a sheet of
newspaper, because phenylacetic acid, once it is exposed to the air, smells
like cat urine, and the smell is next to impossible to get rid of. Pyridine
also smells awful. The pyridine and acetic anhydride are measured out in a
large glass measuring cup.
The flask is then gently swirled until the phenylacetic acid is
dissolved. The flask is then assembled with the 50 cm condensa and the
vacuum adapter, as shown in Figure 2a. Before assembly, the joints are
lightly greased with silicone based stop cock grease. This prevents the
pieces from getting stuck together. All pieces should be clean and dry. The
vacuum nipple of the vacuum adapter is plugged with a piece of tape. In the
rounded section of the vacuum adapter is a plug of cotton, then about two
teaspoons of Drierite (anhydrous calcium sulfate), then another plug of
cotton. This makes a bed of Drierite which is prevented from falling into
the flask by a ball of cotton. The purpose of this is to keep moisture from
the air away from the reaction.
Now the underground chemist is ready to begin heating the flask. Notice
that in Figure 2b, the flask is in a large pan which sits on the buffet
range. The pan is filled about half-full of cooking oil (Wesson works
fine). This is so that the flask is heated evenly. The heat is turned about
half-way to maximum, and the flow of cold water through the condenser is
begun. A length of plastic or rubber tubing runs from the cold water faucet
to the lower water inlet of the condenser. The cold water runs through the
condenser and out of the top water exit, through another length of tubing
to the drain. In this way, the rising vapors from the boiling pyridine are
condensed and returned to the flask. A rate of water flow of about one
gallon per minute is good.
Within a half hour, the flask is hot enough to begin boiling. The heat
is then turned down to stabilize the flask at a gentle rate of boiling.
This is called a reflux. The boiling is allowed to continue for 7 hours.
During this time, the reaction mixture turns from clear to brownish-red in
color. Periodically, the rate of water flow coming out of the condenser is
checked, because faucet washers tend to swell after a while and slow down
the rate of water flow.
After 7 hours, the heat is turned off. Twenty minutes after the boiling
stops, the glassware is set up as shown in Figure 3. The cotton and
Drierite are removed from the vacuum adapter. Then 4 pea-sized pieces are
broken off a pumice foot stone (purchased at the local pharmacy). These are
called boiling chips, because they cause liquids to boil faster and more
evenly. They are added to the flask with the reaction mixture in it. But
they are not added until 20 minutes after the boiling stops; otherwise they
could produce a geyser of hot chemicals.
Now the heat is turned back on, a little hotter than when refluxing the
reaction mixture. Water flow to the condenser is resumed. The mixture soon
begins boiling again and the vapors condense in the condenser and flow to
the collecting round bottom flask. What is being boiled off is a mixture of
pyridine and acetic anhydride. The phenylacetone remains behind in the
distilling round bottom flask, because its boiling point is about 100
degrees Celsius higher than the pyridine and acetic anhydride. This process
is called simple distillation. Distillation continues until 1300 ml has
been collected in the collecting round bottom flask, then the heat is
turned off. The 1300 ml is poured into a clean dry glass jug about one
gallon in size which is then stoppered with a cork. At the end of this
chapter, I will describe a process by which this pyridine is recycled for
future use. Since pyridine is so expensive, this cuts production costs
considerably.
What is left in the distilling round bottom flask is a mixture of
phenylacetone, some acetic anhydride and pyridine, and a
high-molecular-weight, tarry polymer which is reddish-brown in color. The
next step is to isolate and purify the phenylacetone.
The flask is taken out of the hot oil and allowed to cool down.
Three-quarters of a gallon of 10% sodium hydroxide solution (NaOH) is
needed. So a gallon-size glass jug is filled three-quarters full of cold
water and about 10 ounces of sodium hydroxide pellets are added to it. A
good quality lye, such as Red Devil or Hi-Test, is a substitute that saves
a good deal of money and works fine. Eye protection is always worn when
mixing this up. It is mixed thoroughly by swirling, or by stirring with a
clean, wooden stick. The dissolution of NaOH in water produces a great deal
of heat. It is allowed to cool off before the chemist proceeds.
About 500 ml of the 10% NaOH is put in a 1000 ml sep funnel, then the
crude phenylacetone mixture from the round bottom flask is poured in the
sep funnel also. The top of the sep funnel is stoppered and mixed by
swirling. When the funnel gets hot, it is allowed to set for a while. Then
the mixing is continued, with the underground chemist working his way up to
shaking the sep funnel, with his finger holding in the stopper. What he is
doing is removing and destroying the acetic anhydride. Acetic anhydride
reacts with the sodium hydroxide solution to prodbce sodium acetate, which
stays dissolved in the water, never to be seen again. Some of the pyridine
and red-colored tar also go into the water. The destruction of the acetic
anhydride is what produces the heat.
After it has cooled down, about 100 ml of benzene is added to the sep
funnel and shaken vigorously for about 15 seconds. The sep funnel is
unstoppered and allowed to sit in an upright position for about one minute.
The liquid in the funnel will now have separated into two layers. On top is
a mixture of benzene, phenylacetone, and red tar. On the bottom is the
water layer, which has some phenylacetone in it. Pyridine is in both
layers.
Two 500 ml Erlenmeyer flasks are placed on the table, one marked "A,"
the other marked "B." The stop cock on the sep funnel is opened, and the
water layer is drained into B. The top layer is poured into A. B is poured
back into the sep funnel, and 50 ml of benzene is added. The funnel is
shaken for lS seconds, then the water layer is drained back into B. The top
layer is poured into A. The purpose of this is to get the phenylacetone out
of the water. Once again the water in B is put in the sep funnel. 50 ml of
benzene is added, and shaken. The water is drained into B and the benzene
layer poured into A. The water in B is poured down the drain and the
contents of A put into the sep funnel along with 400 ml of 10% NaOH
solution from the jug. After shaking, the water layer is drained into B and
the benzene layer poured into A. The contents of B are put back in the sep
funnel and 50 ml of benzene added. After shaking, the chemist drains the
water layer into B and pours it down the drain. The contents of A are added
to the funnel again, along with 400 ml of 10% NaOH solution; the funnel is
shaken again. The water layer is drained into B and the benzene layer
poured into A. The contents of B are returned to the sep funnel, along with
50 ml benzene, and shaken again. The water layer is poured into B and
poured down the drain. The benzene layer is poured into A. The sep funnel
is washed out with hot water.
Now the last traces of pyridine are removed from the phenylacetone. For
this purpose, some hydrochloric acid is needed. Hardware stores usually
have the 28% strength sometimes called muriatic acid. A bottle in which the
acid seems clear-colored is used; the ones with a green tint have been
sifflng around too long.
The contents of A are returned to the clean sep funnel. Then 10 ml of
hydrochloric acid, mixed with 10 ml of water, is added to the sep funnel
and shaken for 30 seconds. The stopper is pulled out to check whether or
not the odor of pyridine has disappeared. If not, another 20 ml of the
acid-water mix is added and shaken. The odor should now be gone, but if it
is not, some more of the mix is added and shaken. Now 200 rnl of water is
added and shaken. Flask A is rinsed out with hot water; the water layer is
drained into B and poured down the drain. The benzene layer is poured into
A. What has just been done is to convert the pyridine into pyridine
hydrochloride, which dissolves in water, but not in benzene. It is now down
the drain.

 

Finally, for one last time, the contents of A are returned to the sep
funnel, along with 200 ml of the 10% NaOH solution. This is shaken and the
water layer drained into B. The benzene layer is allowed to stay in the sep
funnel for the time being; more water will slowly fall out to the area of
the stop cock, where it can be drained out. It is now ready to be
distilled, and stray water must be removed beforehand.
The glassware is set up as shown in Figure 4. Figure 4 shows a
glass-packed fractionating column which an underground chemist can make
himself. The claisen adapter is checked to make sure it is clean and dry. A
clear glass beer bottle is washed out with hot water, then smashed on the
cement floor. A few pieces are picked out that are small enough to fit in
the lower opening of the claisen, yet big enough that they will not fall
out of the bottom opening of the claisen adapter. Pieces of the broken
bottle are dropped in the lower opening until that section of the claisen
adapter is filled to about the level shown in the drawing. The chemist
tries to get it to land in a jumbled pattern, as shown in the drawing. Then
more similarly-sized pieces of glass are dropped in the upper opening of
the claisen adapter until it is filled to the level shown. Again a jumbled
pattern is striven for. The lower opening is then stoppered with the proper
size of glass or rubber stopper. Finally, the outside is wrapped with a
layer or two of aluminum foil, except for the ground glass joint.
The underground chemist is now ready to distill the phenylacetone.
First, here is some information on the process to be performed. The crude
phenylacetone the underground chemist has is a mixture of benzene,
phenylacetone, red tarry polymer, some water and maybe some dibenzyl
ketone. These substances all have very different boiling temperatures. By
distilling this mixture through a fractionating column, the chemist can
separate them very effectively and get a highpurity product. The way it
works is easy to understand. The vapors from the boiling mixture in the
distilling flask rise up into the fractionating column and come into
contact with the pieces of glass inside. Here the vapors are separated
according to boiling point. The substance in the mixture with the lowest
boiling point is able to pass on through, while the other substances are
condensed and flow back into the distilling flask. This is why the pieces
of glass in the column can't be tightly packed, as that would interfere
with the return flow, leading to a condition called flooding. Once all of
the lowest-boiling substance has been distilled, the substance with the
next higher boiling point can come through the fractionating column. In the
distillation process to be described, the order is as follows: benzenewater
azeotrope, 68øC; benzene, 80-ø C; phenylacetone, 120-130-ø C (under a
vacuum of about 20 torr).
Why must the phenylacetone be distilled under a vacuum? Because its
boiling point at normal pressure is 216ø C, which is much too hot.
Distilling it at that temperature would ruin the product. By distilling it
under a vacuum, it boils at a much lower temperature. The exact temperature
depends on how strong the vacuum is; the stronger the vacuum, the lower the
temperature. For example, at a vacuum of 13 torr, the boiling point goes
down to about 105ø C.
The glassware is set up as shown in Figure 5. The distilling flask is
no more than 2/3 full. If the underground chemist has more crude
phenylacetone than that, he has to wait until some of the benzene has
distilled off, then turns off the heat, waits until the boiling stops and
adds the rest of it to the distilling flask.
The glassware should be clean and dry. A faster way of drying glassware
after washing is to put it in the oven at 400øF for 20 minutes. Rubber
stoppers do not go in the oven. Water tends to stay inside round bottom
flasks dried in this way. SO, while they are still hot, the chemist takes a
piece of glass tubing and puts it inside the flask. He sucks the moist air
out of the flask with the glass tubing before it has a chance to cool down
and condense. For the distillation, two 250 ml round bottom flasks are
needed, one to collect the benzene in, the other to collect the
phenylacetone in. Five boiling chips are put in the distilling flask.
The heat source is turned on, to the low range, about 1/4 maximum.
Water must be flowing through the shorter condenser at about one gallon per
minute. When the mixture has begun boiling, the heat is adjusted so that
about one or two drops per second drip into the collecting flask. The
temperature on the thermometer should say about 68øC. For accurate
temperature readings, the tip of the thermometer extends into the stillhead
to the depth shown in Figure 6.
The material distilling at 68øC is the benzene-water azeotrope. It is
about 95% benzene and 5% water. It is milky white from suspended droplets
of water. Once the water is all gone, pure benzene is distilled at about
80øC. It is clear in color. If the liquid in the collecting flask is not
clear or white in color, then undistilled material is being carried over
from the distilling flask. This is caused either by having the distilling
flask too full or by having the heat turned too high. In either case, the
chemist must correct accordingly and redistill it. Once the temperature
reaches 85øC on the thermometer, or the rate of benzene appearing in the
collecting flask slows to a crawl, the heat is turned off because the
chemist is ready to vacuum distill the phenylacetone.
There is a problem that is sometimes encountered while distilling off
the benzene. Sometimes the benzene in the distilling flask will foam up in
the distilling flask instead of boiling nicely. These bubbles refuse to
break and they carry undistilled material along with them to the collecting
flask, leaving a red liquid over there. This cannot be allowed to happen.
One effective method of dealing with this is to turn on the water supply to
the aspirator at a slow rate so that a weak vacuum is produced. Then the
vacuum hose is attached to the vacuum adapter and a weak vacuum produced
inside the glassware. This causes the bubbles to break. Every few seconds,
the vacuum hose is removed, then reattached. In a while, the benzene begins
to boil normally and the vacuum can be left off.
After it has cooled off, the collected distilled benzene is poured into
a labeled glass bottle. It can be used again in later batches of
phenylacetone. The same 250 ml round bottom flask is reattached to the
collecting side, and the vacuum hose attached to the vacuum adapter. The
vacuum source is turned on. If an aspirator is being used, the water is
turned all the way on. All the pieces of glassware must be fitted snugly
together. A strong vacuum quickly develops inside the glassware. The heat
is turned on to about i/3 maximum. The boiling begins again. At first, what
distills over are the last remnants of benzene and water left in the
distilling flask. Then the temperature shown on the thermometer begins to
climb. The phenylacetone begins to distill. When the thermometer reaches
1009 C, the vacuum hose is removed and the collecting 250 ml flask is
replaced with the clean, dry 250 ml flask, then the vacuum hose is
reattached. If a good vacuum pump is being used, the flasks are changed at
about 809 C. This flask changing is done as fast as possible to prevent the
material in the distilling flask from getting too hot during the change
over. If it gets too hot, it distills too rapidly when the vacuum is
reapplied, resulting in some red tar being carried over along with it.
So the vacuum is reapplied, and the phenylacetone is collected. With a
properly working aspirator, the phenylacetone will all be collected once
the temperature on the thermometer reaches 140-1SOQ C. With a good vacuum
pump, it will all come over by the time the temperature reaches 110-llSQ C.
Once it is all collected, the heat is turned off, the vacuum hose is
removed from the vacuum adapter and the vacuum source is turned off.
The yield is about 100 ml of phenylacetone. It should be clear to pale
yellow in color. It has a unique but not unpleasant smell. The flask
holding this product is stoppered and stored upright in a safe place.
Although phenylacetone can be stored in a freezer, to keep it fresh, the
chemist now proceeds to making N-methylformamide.
Once the distilling flask has cooled down, the glassware is taken apart
and cleaned. The red tar left in the distilling flask and the fractionating
column is rinsed out with rubbing alcohol. Then hot soapy water is used on
all pieces. A long, narrow brush comes in handy for this.
One last word about vacuum distillation. To keep the vacuum strong, the
vacuum hose is no more than three feet long. This forces the chemist to do
the distilling close to the source of the vacuum.
Now for that pyridine recycling process I mentioned earlier in this
chapter. After the underground chemist has made a few batches of
phenylacetone, he will have accumulated a fair amount of pyridineacetic
anhydride mixture in the gallon-sized glass jug. He will now fractionally
distill it to recover the pyridine from it. The clean dry glassware is set
up as shown in Figure 7. It has a long-column fractionating column instead
of the short type just used. This is because pyridine and acetic anhydride
are harder to separate, so a longer column is needed to do the job.
The distilling flask is a 3000 ml round bottom flask with 5 boiling
chips in it. The chemist pours 2000 ml of the acetic anhydride-pyridine
mixture into it. The heat is turned on to about 1/3 maximum and the cold
water is started flowing slowly through the condenser. Within a half hour,
the mixture will begin to boil. A couple of minutes later, the vapors will
have worked their way through the fractionating column and hegin appearing
in the 2000 ml collecting flask. The heat source is adjusted so that it is
collecting at the rate of one or two drops per second. Distilling is
continued until 1000 ml have accumulated in the collecting flask. If the
temperature reading on the thermometer goes above 135øC, the heat is turned
down a little to slow the rate of distillation.
Once 1000 ml has been collected, the heat is turned off and it is
allowed to cool down. After it is cool, the distilling flask is removed and
its contents (mainly acetic anhydride) poured down the drain. The contents
of the collecting flask (mainly pyridine) are poured into a clean, dry 2000
ml round bottom flask with 5 boiling chips, or 5 boiling chips are simply
added to the 2000 ml round bottom flask that the pyridine collected in and
that flask is put on the distilling side in place of the 3000 ml flask. A
clean, dry 1000 ml round bottom flask is put on the collecting side. The
heat is turned back on and in a while the distilling begins again. As
before, the rate of distillation is adjusted to one or two drops per
second. The distillation is continued until 750 ml of pyridine has been
collected. Sometimes it does not keep well, but so long as it is used to
make another batch of phenylacetone within a few hours after it is made,
this pyridine works just as well as new pyridine.

 

--------------------------------------------------------------------------
PREPARATION OF N-METHYLFORMAMIDE
--------------------------------------------------------------------------
N-methylformamide is best made by the reaction of methylamine with
formic acid. The reaction proceeds like this:
[SNiP]
The methylamine (a base) reacts with formic acid to form the
methylamine salt of formic acid. The heat that this reaction builds up then
causes this intermediate salt to lose a molecule of water and form
N-methylformamide. Since water is a product of this reaction, the
underground chemist warts to keep water out of his starting materials as
far as is possible. That is because having less water in them will shift
the equilibrium of the reaction in favor of producing more
N-methylformamide.
Both of the starting materials have water in them. The usual grade of
formic acid is 88% pure and 12% water. It cannot be made any purer by
distilling. The chemist can put up with the 12% water, but if a higher
purity formic acid is available, it is worth the extra cost. The usual
grade of methylamine is 40% by weight in water. The majority of this water
can be removed by using the apparatus shown in Figure 8. Methylamine may
also be obtained as a gas in a cylinder. In that case, the methylamine can
be piped directly into the formic acid.
The glassware is set up as shown in Figure 8. The 40% methylamine is in
a 1000 ml round bottom flask attached to a long condenser. In the top of
this condenser is a one-hole stopper. A bent piece of glass tubing is
pushed all the way through this stopper so that the end of the piece of
tubing extends about one or two millimeters below the bottom of the
stopper. This bent piece of tubing then extends down through the center of
the other condenser into the flask containing the formic acid. It should
extend below the surface of the formic acid and end about one centimeter
above the bottom of the flask containing the formic acid. The idea here is
simple. The 40% methylamine is heated, causing methylamine gas to be boiled
out along with some water vapor. These gases then travel up the condenser,
where the water is condensed out, allowing nearly pure methylamine gas to
be forced by pressure through the glass tubing into the formic acid.
The bent tubing has to be bent by the chemist himself from a
3-foot-long piece of glass tubing. Its outer diameter should be about 1/4
inch. The glassware is set up as shown in Figure 8 and he decides about
where the tubing should be bent. If necessary, he will consult the chapter
on bending glass in an Organic Chemistry lab manual. With a little
practice, it is easy. A good source of flame to soften up the glass is a
propane torch with the flame spreader attachment. After it is bent, he will
blow through the tubing to make sure he did not melt it shut.
He is now ready to proceed. All pieces of glassware are clean and dry.
Into the round bottom 1000 ml flask sitting on the heat source is placed
500 grams (about 500 ml) of 40% methylamine in water, along with 3 or 4
boiling chips. Into the other 1000 ml round bottom flask is placed 250 ml
of 88% formic acid. Water flow is begun through the longer condenser. It is
advantageous to use ice cold water in this condenser, because it will then
do a better job of removing water vapor from the methylamine. A good way to
get ice cold water for the condenser is to get a couple of 5-gallon pails.
One of them is filled with ice cubes no bigger than a fist and topped off
with water. Then the section of plastic tubing that runs to the lower water
inlet of the condenser is placed in the pail. Its end is weighted to keep
it on the bottom of the pail. This pail is placed on the table along with
the glassware. The other pail is placed on the floor and the plastic tubing
from the upper water exit of the condenser is run to this pail. By sucking
on the end of the water exit tubing, the ice cold water can be siphoned
from the pail on the table, through the condenser, to the pail on the
floor. The rate of water flow can be regulated to about one gallon per
minute by putting a clamp on the tubing to slow its flow. When the pail on
the table is about empty, the water that has flowed to the pail on the
floor is returned to the table.
The heat on the methylamine is turned on to about i/4 maximum. Soon the
methylamine begins boiling out and moving through the tubing into the
formic acid. The underground chemist checks for gas leaks in the system by
sniffing for the smell of escaping methylamine. If such a leak is detected,
the joint it is escaping from is tightened up.
The methylamine bubbling into the formic acid produces a cloud of white
gas inside the flask containing the formic acid. It makes its way up to the
condenser, then returns to the flask as a liquid. For this condenser, tap
water flow is fine. The rate of methylamine boiling is adjusted so that the
white gas does not escape out the top of the condenser. As more methylamine
is boiled out, a higher heat setting is required to maintain the same rate
of methylamine flow.
In this process, the formic acid gets very hot. It must get hot to
produce good yields of N-methylformamide. It sometimes gets hot enough to
boil a little bit (105øC), but this is no problem. As the chemist continues
bubbling methylamine into the formic acid, its volume increases until it is
double its starting volume, about 500 ml. At about this time, the cloud of
white gas thins and then disappears. This white gas is formed by the fumes
of formic acid reacting with methylamine above the surface of the liquid
formic acid. It disappears because there is no longer much formic acid
left. The chemist now begins checking to see if the reaction is complete.
He pulls out one of the stoppers from the 3-necked flask that contains the
N-methylformamide and sniffs the escaping fumes for the odor of
methylamine. He does this periodically until he smells methylamine. Once he
smells it, he turns off the heat on the methylamine. When the methylamine
stops bubbling into the N-methylformamide, he immediately lowers the level
of the 3-necked flask so that the bent glass tubing is above the surface of
the N-methylformamide. This is done because, as the methylamine cools, it
will contract and create a vacuum which would suck the N-methylformamide
over into the other flask in a flash, ruining his work.
Both flasks are allowed to cool down. The methylamine is almost gone,
so it can be poured down the drain. The next step is to fractionally
distill the N-methylformamide. The glass-packed claisen adapter is used as
the fractionating column. The glassware is set up as shown in Figure 5,
back in Chapter 3. The distilling flask is a 1000 ml round bottom flask
with 5 boiling chips in it. The collecting flask is a 250 ml round bottom
flask. Unlike the distillation of phenylacetone, in this case the
distillation is done under a vacuum from the beginning. The ice water
siphoning system is used for the condenser, because N-methylformamide has a
very high latent heat of vaporization, and, without this precaution, it may
collect very hot in the collecting flask.
The underground chemist is now ready to distill the N-methylformamide.
All of the crude product is put in the 1000 ml round bottom flask. It will
fill it about half full. The vacuum is applied at full strength, and the
heat source is turned on to 1/3 to 1/2 maximum. The water in the mixture
begins distilling. The temperature shown on the thermometer will show a
steady climb during the process.
In a while, the temperature rises high enough that the chemist can
begin collecting the distilled liquid as suspected N-methylformamide. If he
is using an aspirator, he begins collecting in a clean, dry 250 ml round

 

bottom flask when the temperature reaches 95-100øC. If he is using a good
vacuum pump, he begins saving the distilled material at about gSQ C As the
N-methylformamide distills, the temperature rises a little bit above the
temperature at which he first began collecting the N-methylformamide, then
holds steady. This temperature is noted. Distilling is continued until he
has collected 100 ml. Then the heat is turned off. When the boiling stops,
the vacuum hose is disconnected from the glassware.
During the distillation process, a fair amount of methylamine was lost,
leaving the N-methylformamide with too much formic acid. The next step is
to correct this problem.
The 100 ml of N-methylformamide that has been distilled is poured back
in the distilling flask with the undistilled material. The distilled
material is clear, while the undistilled material has turned yellow from
the heat of distilling. The glassware is set up again as shown in Figure 8.
This time, the round bottom flask holding the methylamine is a 500 ml
flask. It has 100 ml of fresh 40% methylamine in water in it. The bent
glass tubing leads into the flask containing the N-methylformamide. This
flask does not need to have a condenser on it.
The heat is turned on the methylamine and the flow of ice water through
its condenser is begun. Soon the methylamine gas is bubbling into the
N-methylformamide, reacting with the excess formic acid in it. Within about
10 seconds, the odor of methylamine can be detected above the
N-methylformamide. The heat is turned off, and when the bubbling stops, the
level of the N-methylformamide is lowered so that it is not sucked into the
other flask. Once the methylamine has cooled off, it can be poured back in
with the good me~ylamine, because it is not exhausted. Once a bottle of
methylamine has been opened, it should be reclosed tightly and the cap
sealed with vinyl electrical tape in order to hold in the methylamine gas.
Now the N-methylformamide is to be distilled again. The glassware is
set up again for fractional distillation as shown in Figure 5. The
distilling flask is a 500 ml round bottom flask, while the collecting flask
is 250 ml. All pieces are clean and dry.
The N-methylformamide is placed inside the distilling flask with 5
boiling chips. (Fresh chips are used every time.) The vacuum is reapplied
and the heat is turned on again to 1/3 to 1/2 maximum. A little bit of
water is again distilled. The temperature shown on the thermometer climbs
as before. When it reaches a temperature 7øC below the temperature at which
it leveled off the first time around, the chemist begins collecting in a
clean dry 250 ml flask. The distilling continues until it has almost all
distilled over. About 10 or 1S ml is left in the distilling flask. If he is
using an aspirator, the chemist makes sure that no water is backing into
the product from the vacuum line. The yield is about 250 ml
N-methylformamide. If he gets a little more, it won't all fit in the 250 ml
collecting flask. If that happens, he pours what has collected into a clean
dry Erlenmeyer flask and continues distilling. N-methylformamide is a clear
liquid with no odor.
The N-methylformamide the underground chemist has just made is perfect
for the Leuckardt-Wallach reaction. Because he began collecting it 7
degrees below the leveling off temperature, it contains a mixture of
N-methylformamide, formic acid and methylamine. To get good results, he
uses it within a few hours after distilling it.
References
Journal of the American Chemical Society, Volume 53, page 1879 (1931).
--------------------------------------------------------------------------
MAKING METHAMPHETAMINE
--------------------------------------------------------------------------
I explained the general theory behind this reaction in Chapter 2. Now,
after doing the reactions described in the previous two chapters, the
underground chemist has phenylacetone and N-methylformamide suitable for
making methamphetamine. He will want to get going before the chemicals get
stale.
The first thing he does is test the chemicals. He puts 5 ml of
phenylacetone and 10 ml of N-methylformamide in a clean dry test tube or
similar small glass container. Within a few seconds they should mix
together entirely. At this point, he may offer a prayer to the chemical
god, praising his limitless chemical power and asking that some of this
power be allowed to flow through him, the god's High Priest. He may also
ask to be delivered from the red tar that can be the result of this
reaction. If they do not mix, there is water in the Nmethylformamide. In
this case, he must distill it again, being more careful this time.
Having tested the chemicals, he is ready to proceed with the batch.
(However, if the underground chemist was reckless enough to obtain
N-methylformamide ready made, he will have to distill it under a vacuum
before it can be used in this reaction.) The phenylacetone he made (about
100 ml) is mixed with the N-methylformamide. The best amount of
N-methylformamide to use is about 250 ml, but any amount from 200 to 300 ml
will work fine. With 200 ml of N-methylformamide, there are about four
molecules of N-methylformamide to one of phenylacetone. This is the bare
minimum. With 300 ml, the ratio is nearly six to one. Any more than this is
a waste of N-methylformamide. The best flask for mixing them is a 500 ml
round bottom flask. After they are mixed, this flask is set up as shown in
Figure 9. The flask is sitting in an oil bath, to supply even heating to
the flask. The oil (once again, Wesson is a good choice) should extend
about 2/3 of the way up the side of the flask. A metal bowl makes a good
container for this oil bath. This is better than a pan, because it will be
important to see into the flask. The fact that the oil will expand when
heated is kept in mind when filling the bowl with oil. A thermometer is
also needed in the oil bath to follow its temperature.
The test material is added to the flask. The heat source to the flask
is turned on. A low heat setting is used so that the rise in temperature
can be closely controlled. The thermometer used in the distillations is
placed (clean and dry) inside the flask.
The rise in temperature of both the oil bath and the flask is
monitored. The contents of the flask are stirred regularly with the
thermometer. The temperature of the oil bath is brought to lOOQ C over the
course of about 45 minutes. Once it reaches this level, the heat is turned
back down a little bit to stabilize it in this area. The chemist must
closely control every degree of temperature increase from here on. The
temperature of the contents of the flask is worked up to 105g C. The

 

contents of the flask are stirred every 15 minutes. At about lOSQ C, the
reaction kicks in, although sometimes the heat must go as high as 110g C
before it starts. When the reaction starts, the contents of the flask begin
to bubble, sort of like beer, except that a head does not develop. A trick
to get this reaction going at a nice low temperature is to gently scrape
the thermometer along the bottom of the flask. Although I have never had
the sophisticated equipment to prove it, it is a pet theory of mine that
this is because ultrasonic waves are generated, producing a condition of
resonance with the reactants that causes the reaction to start.
The chemist wants to keep the temperature down at the same level at
which the reaction first kicked in for as long as the reaction will
continue at that level. Generally, it can go for a couple of hours at this
level before the reaction dies down and an increase in temperature is
necessary. The reaction mixture has the same color as beer and gently
bubbles. The bubbles rise up from the bottom of the flask, come to the
surface, and then head for where the thermometer breaks the surface. Here
they collect to form bubbles about 1 centimeter in size before they break.
This may look like boiling, but it is not. Everything inside the flask has
a much higher boiling point than the temperatures being used. These are
actually bubbles of carbon dioxide gas being formed as by-products of the
reaction. The chemist can tell how well the reaction is going by the amount
of bubbling going on.
When the rate of bubbling slows down to almost stopping, it is time to
raise the temperature. It should only be raised about 3g C. This requires
turning up the heat only slightly. The highest yield of product is obtained
when the lowest possible temperature is used. For the duration of the
reaction, the contents of the flask are stirred with the thermometer every
half hour.
And so the reaction is continued. As the reaction dies down at one
temperature setting, the temperature is raised a few degrees to get it
going again. It will be able to stay in the 1209 to 130Q C range for a long
time. The reaction has a lot of staying power in this range. Finally, after
24 to 36 hours, 140Q or 145Q C is reached. The reaction stops. The chemist
takes his time working up to this temperature because the amount and
quality of the product depends on it.
Once 140ø to 145ø C is reached and the reaction stops, the heat is
turned off and the contents allowed to cool down. It should still look like
beer. A reddish tint means that his prayer failed and he was not delivered
from the tar. Even so, there's still lots of good product in it.
While it is cooling down, the underground chemist gets ready for the
next step in the process. He is going to recover the unused methylamine for
use in the next batch. This cuts his consumption of methylamine to about
half of what it would be without this technique. What he is going to do is
react the unused N-methylformamide with a strong solution of sodium
hydroxide. The N-methylformamide is hydrolyzed to form methylamine gas and
the sodium salt of formic acid (sodium formate). In chemical writing, this
reaction is as follows:
[SNiP]
The methylamine gas produced is piped into formic acid to make
N-methylformamide for use in the next batch.
First, 6 ounces (about 180 grams) of sodium hydroxide pellets are added
to 450 ml of water. A good quality lye is an acceptable substitute. Eye
protection is worn. Once the solution has cooled down, it is poured in a
2000 ml round bottom flask with 5 boiling chips. Then all of the
methamphetamine reaction mixture is poured into the flask along with it. It
is swirled around a little bit to try to get some of the N-methylformamide
dissolved into the water. This does not accomplish much, however, as the
reaction mixture floats on the sodium hydroxide solution. The glassware is
set up as shown in Figure 8 in Chapter 4. The 2000 ml flask containing the
NaOH solution and the methamphetamine reaction mixture sits on the heat
source. The bent piece of glass tubing once again leads to a 1000 ml round
bottom flask equipped with a condenser. The 1000 ml flask once again
contains 250 ml of 88% formic acid.
The heat source is turned on to about 1/3 maximum. The flow of ice
water through the long condenser is begun. In a while, the boiling chips
float up to the interface of the sodium hydroxide solution and the reaction
mixture, and some bubbling and frothing of the reaction mixture begins. The
heat is turned down some, since the temperature of the mixture should rise
slowly from now on. That is because the hydrolysis reaction forming
methylamine tends to kick in all at once, if this precaution is not taken,
leaving the chemist in a dangerous situation with a runaway reaction.
After the first rush of the reaction has subsided and the bubbling of
the methylamine into the formic acid has slowed down, the heat applied to
the 2000 ml flask is increased to maintain a good rate of methylamine flow
to the formic acid. Eventually, all the methylamine will be boiled out.
This will be when methylamine no longer flows evenly into the formic acid.
The flask must not be heated so strongly that water is forced through the
bent glass tubing.
The heat is turned off and the level of the flask containing formic
acid is lowered so that the acid is not sucked back into the other flask.
This formic acid is about half reacted with methylamine. When it has cooled
down, it is poured in a tall glass bottle and kept in the freezer until the
next batch is made, when it is used for the production of Nmethylformamide.
Since it is already half reacted, the amount of methylamine used is reduced
accordingly.
Meanwhile, back in the 2000 ml flask, the methamphetamine reaction
mixture is about 100 ml in volume and has a red color. It floats above the
sodium hydroxide solution. Once it has cooled down, the contents of this
flask are poured into a 1000 ml sep funnel. The sodium hydroxide solution
is drained out and thrown away. The red methamphetamine formyl amide is
poured into a 500 ml round bottom flask with 3 boiling chips. 200 ml of
hydrochloric acid is measured out. (The 28% hardware store variety is fine
for this purpose.) It is poured into the sep funnel and swirled around to
dissolve any product left behind in the sep funnel. Then it is poured into
the 500 ml flask with the product. When swirled around, they mix easily.
The glassware is set up as shown in Figure 2b in Chapter 3. Tap water
flow is proper for use in the condenser. The heat is turned on to the 500
ml flask, and a gentle rate of boiling is maintained for 2 hours. The
mixture quickly turns black. The reaction going on here is metharnphetamine
formyl amide reacting w~th hydrochloric acid to produce methamphetamine
hydrochloride and formic acid. This is a hydrolysis reaction.

 

After the two hours have passed, the heat to the flask is turned off.
While the flask is cooling down, 80 grams of sodium hydroxide and 250 ml of
water are mixed in a 1000 ml round bottom flask. Once again, a good quality
lye is acceptable. If the 35% laboratory grade of hydrochloric acid was
used in the last step, then 100 grams of sodium hydroxide is mixed with 300
ml of water.
When both flasks have cooled down, the black reaction mixture is
cautiously added to the sodium hydroxide solution. It is added in small
portions, then swirled around to mix it. They react together quite
violently. The reaction here is sodium hydroxide reacting with hydrochloric
acid to produce table salt, with formic acid to produce sodium formate, and
with methamphetamine hydrochloride to produce methamphetamine free base.
When the sodium hydroxide solution gets very hot, the chemist stops adding
the reaction mixture to it until it cools down again.
After all the black reaction mixture has been added to the sodium
hydroxide solution, there is a brown liquid layer floating above the sodium
hydroxide solution. This brown layer is methamphetamine free base. It also
has a good deal of unreacted methamphetamine hydrochloride dissolved in it.
This latter has to be neutralized because it will not distill in its
present form. The 1000 ml flask is stoppered and shaken vigorously for 5
minutes. This gets the methamphetamine hydrochloride into contact with the
sodium hydroxide so it can react.
The bottom of the flask is full of salt crystals that cannot dissolve
in the water because the water is already holding all the salt it can.
The chemist adds 100 ml of water to the flask and swirls it around for
a few minutes. If that does not dissolve it all, he adds another 100 ml of
water.
After the flask has cooled down, it is poured into a 1000 ml sep
funnel, and 100 ml of benzene is added. The sep funnel is stoppered and
shaken for 15 seconds. It is allowed to stand for a couple of minutes, then
the lower water layer is drained into a glass container. The brown
methamphetamine-benzene layer is poured into a clean, dry 500 ml round
bottom flask. The water layer is extracted once more with 100 ml benzene,
then thrown away. The benzene layer is poured into the 500 ml flask along
with the rest of the methamphetamine.
The chemist is now ready to distill the methamphetamine. He adds three
boiling chips to the 500 ml round bottom flask and sets up the glassware
for fractional distillation as shown in Figure 5. The 500 ml flask sits
directly on the heat source. The glass-packed claisen adapter is the proper
fractionating column. The collecting flask is a 250 ml round bottom flask.
Tap water is used in the condenser.
The heat source is turned on to 1/4 to 1/3 maximum. Soon the mixture
begins boiling. The first thing that distills is benzene water azeotrope at
68ø C. Then pure benzene comes over at 80øC. Once again, as in the
distillation of phenylacetone, foaming can sometimes be a problem. In that
case, it is dealt with in the same way as described in Chapter 3.
When the temperature reaches 85øC, or the rate of benzene collecting
slows to a crawl, the heat is turned off and the flask allowed to cool
down. The collected benzene is poured into a bottle. It can be used again
the next time this process is done. The same 250 ml flask is put on the
collecting side.
The distilling flask is now cool, so vacuum is applied to the glassware
at full strength. The last remnants of benzene begin to boil, and the heat
is turned back on to 1/3 maximum. The temperature begins to climb. If an
aspirator is being used, when the temperature reaches 80-ø C, the chemist
quickly removes the vacuum hose and replaces the 250 ml flask with a clean
dry one. If he is using a good vacuum pump, he makes this change at about
70øC. The flask change is done quickly to avoid overheating in the
distilling flask.
The methamphetamine distills over. With an aspirator, the chemist
collects from 80øC to about 140ø or 150ø C, depending on how strong the
vacuum is. With a vacuum pump, he collects to about 120ø or 130øC. Once it
has distilled, the heat is turned off and the vacuum hose disconnected.
The product is about 90 ml of clear to pale yellow methamphetamine. If
the chemist is feeling tired now, he may take out a drop on a glass rod and
lick it off. It tastes truly awful and has a distinctive odor, somewhat
biting to the nostrils.
He is now ready to make his liquid methamphetamine free base into
crystalline methamphetamine hydrochloride. Half of the product is put into
each of two clean dry 500 ml Erlenmeyer flasks.
The chemist now has a choice to make. He can use either benzene or
ethyl ether as the solvent to make the crystals in. Benzene is cheaper, and
less of it is needed because it evaporates more slowly during the filtering
process. Ether is more expensive, and flammable. But since it evaporates
more quickly, the crystals are easier to dry off. If ether is used, it is
anhydrous (contains no water).
A third choice is also possible for use as a crystallization solvent.
This is mineral spirits available from hardware stores in the paint
department. Mineral spirits are roughly equivalent to the petroleum ether
or ligroin commonly seen in chem labs. Those brands which boast of low odor
are the best choice. Before using this material it is best to fractionally
distill it, and collect the lowest boiling point half of the product. This
speeds crystal drying. Since the choice of mineral spirits eliminates ether
from the supply loop, the clandestine operator may well go this route.
Toluene is also an acceptable solvent.
With the solvent of his choice, the chemist rinses the insides of the
condenser, vacuum adapter and 250 ml flask to get out the methamphetamine
clinging to the glass. This rinse is poured in with the product. Solvent is
added to each of the Erlenmeyer flasks until the volume of liquid is 300
ml. They are mixed by swirling.
A source of anhydrous hydrogen chloride gas is now needed. The chemist
will generate his own. The glassware is set up as in Figure 10. He will
have to bend another piece of glass tubing to the shape shown. It should
start out about 18 inches long. One end of it should be pushed through a
one-hole stopper. A 125 ml sep funnel is the best size. The stoppers and
joints must be tight, since pressure must develop inside this flask to
force the hydrogen chloride gas out through the tubing as it is generated.

 

Into the 1000 ml, three-necked flask is placed 200 grams of table salt.
Then 35% concentrated hydrochloric acid is added to this flask until it
reaches the level shown in the figure. The hydrochloric acid must be of
laboratory grade.
Some concentrated sulfuric acid (99-98%) is put into the sep funnel and
the spigot turned so that 1 ml of concentrated sulfuric acid flows into the
flask. It dehydrates the hydrochloric acid and produces hydrogen chloride
gas. This gas is then forced by pressure through the glass tubing.
One of the Erlenmeyer flasks containing methamphetamine in solvent is
placed so that the glass tubing extends into the methamphetamine, almost
reaching the bottom of the flask. Dripping in more sulfuric acid as needed
keeps the flow of gas going to the methamphetamine. If the flow of gas is
not maintained, the methamphetamine may solidify inside the glass tubing,
plugging it up.
Within a minute of bubbling, white crystals begin to appear in the
solution. More and more of them appear as the process continues. It is an
awe-inspiring sight. In a few minutes, the solution becomes as thick as
watery oatmeal.
It is now time to filter out the crystals, which is a two-man job. The
flask with the crystals in it is removed from the HC1 source and
temporarily set aside. The three-necked flask is swirled a little to spread
around the sulfuric acid and then the other Erlenmeyer flask is subjected
to a bubbling with HC1. While this flask is being buWled, the crystals
already in the other flask are filtered out.
The filtering flask and Buchner funnel are set up as shown in Figure
11. The drain stem of the Buchner funnel extends all the way through the
rubber stopper, because methamphetamine has a nasty tendency to dissolve
rubber stoppers. This would color the product black. A piece of filter
paper covers the flat bottom of the Buchner funnel. The vacuum is turned on
and the hose attached to the vacuum nipple. Then the crystals are poured
into the Buchner funnel. The solvent and the uncrystallized methamphetamine
pass through the filter paper and the crystals stay in the Buchner funnel
as a solid cake. About 15 ml of solvent is poured into the Erlenmeyer
flask. The top of the flask is covered with a palm and it is shaken to
suspend the crystals left clinging to the sides. This is also poured into
the Buchner funnel. Finally, another 15 ml of solvent is poured over the
top of the filter cake.
Now the vacuum hose is disconnected and the Buchner funnel, stopper and
all, is pulled from the filtering flask. All of the filtered solvent is
poured back into the Erlenmeyer flask it came from. It is returned to the
HC1 source for more bubbling. The Buchner funnel is put back into the top
of the filtering flask. It still contains the filter cake of
methamphetamine crystals. It will now be dried out a little bit. The vacuum
is turned back on, the vacuum hose is attached to the filtering flask, and
the top of the Buchner funnel is covered with the palm or a section of
latex rubber glove. The vacuum builds and removes most of the solvent from
the filter cake. This takes about 60 seconds. The filter cake can now be
dumped out onto a glass or China plate (not plastic) by tipping the Buchner
funnel upside-down and tapping it gently on the plate.
And so, the filtering process continues, one flask being filtered while
the other one is being bubbled with HC1. Solvent is added to the Erlenmeyer
flask to keep their volumes at 300 ml. Eventually, after each flask has
been bubbled for about seven times, no more crystal will come out and the
underground chemist is finished.
If ether was used as the solvent, the filter cakes on the plates will
be nearly dry now. With a knife from the silverware drawer, the cakes are
cut into eighths. They are allowed to dry out some more then chopped up
into powder. If benzene was used, this process takes longer. Heat lamps may
be used to speed up this drying, but no stronger heat source.
The yield of product is about 100 grams of nearly pure product. It
should be white and should not get wet, except in the most humid weather.
It is suitable for any purpose. It can be cut in half and the underground
chemists will still have a better product than their competition. But they
will not cut it until a few days have passed, so that their options are not
limited should one of the problems described in the next few paragraphs
arise.
Here are some of the common problems that arise with the crystals, and
how they are dealt with. To spot these possible problems, the crystals are
first left on the plate to dry out, and then transferred to glass jars or
plastic baggies.
Yellow Crystals. This is caused by not properly rinsing off the
crystals while in the Buchner funnel, or not using enough solvent to
dissolve the methamphetamine in the Erlenmeyer flasks. To whiten them up,
they are allowed to soak in some ether in a glass jar, then filtered again.
Yellow Stinky Crystals. The smell takes a few days to develop fully.
They are left alone for 5 days, then soaked in ether and filtered again.
The smell should not return. (The problem is caused by heating the reaction
mixture above the 145øC upper limit.)
Crystals Refuse To Dry. This can especially be a problem using benzene
as a solvent. It can also be a problem on very humid days. The crystals are
placed in the clean, dry filtering flask, the top is stoppered and vacuum
applied at full strength for 15 minutes. Warming the outside of the
filtering flask with hot water while it is under vacuum speeds the process.
Crystals Melt. Here the crystals soak up water from the air and melt.
This is usually caused by raising the temperature of the reaction too
rapidly, or by collecting too much high boiling material during the
distillation. First, they are put into the filtering flask and a vacuum
applied to dry them out. They are soaked in ether and filtered. If this
doesn't cure the problem, cutting the material to 50% purity should take
care of it.
Crystals Are Sticky. Here the crystals seem covered by a thin layer of
oily material, causing them to stick to razor blades, etc. The problem is
dealt with in the same way as melting crystals.
Crystals Fail to Form. This problem occurs during the process of
bubbling HCl into the methamphetamine. Instead of forming crystals, an oil
settles to the bottom of the flask. This is generally caused by incomplete
hydrolysis of the formyl amide. Perhaps it didn't mix with the hydrochloric

 

acid. It is put in a flask and the solvent boiled off under a vacuum. Then
200 ml of hydrochloric acid is added and the process is repeated, starting
from the hydrolysis of the formyl amide of methamphetamine. The 35%
laboratory grade of hydrochloric acid is used.
In the event of melting or sticky crystals, cutting is first tried on a
small sample of the crystals to see if that will solve the problem. If it
does not, then a recrystallization must be resorted to. This is done by
dissolving the crystals in the smallest amount of warm alcohol that will
dissolve them. 190-proof grain alcohol, 95% denatured alcohol, or absolute
alcohol may be used. Then 20 times that volume of ether is added. After
vigorous shaking for three minutes, the crystals reappear. If not, more
ether is added, followed by more shaking. After being filtered, the
crystals should be in good shape.
A technique which may be used in especially stubborn cases is to
dissolve the crystals in dilute hydrochloric acid solution, extract out the
oily impurities with benzene, and then isolate the methamphetamine. This is
done as follows:
For every 100 grams of crystal, 200 ml of 10% hydrochloric acid is
prepared by mixing 60 ml of 35% hydrochloric acid with 140 ml of water. The
crystals are dissolved in the acid solution by stirring or shaking in the
sep funnel. 100 ml of benzene is added to the solution in the sep funnel,
which is then shaken vigorously for about 2 minutes. The lower layer is
drained out into a clean beaker. It contains the methamphetamine. The
benzene layer is thrown out. It contains the oil grunge which was polluting
the crystals.
The acid solution is returned to the sep funnel and the acid
neutralized by pouring in a solution of 70 grams of sodium hydroxide in 250
ml of water. After it has cooled down, the mixture is shaken for 3 minutes
to make sure that all the methamphetamine hydrochloride has been converted
to free base. Then 100 ml of benzene is added and the mixture shaken again.
The lower water layer is drained out and thrown away. The
benzene-methamphetamine solution is distilled as described earlier in this
chapter. Then, as described earlier in this chapter, dry hydrogen chloride
gas is bubbled through it to obtain clean crystals. (Hydrogen chloride gas
must be made in a well-ventilated area; otherwise, it will get into the
chemist's lungs and do real damage.)
There is an alternative method for converting amphetamine free base
into the crystalline hydrochloride. It is based on the method that South
American cocaine manufacturers use to turn coca paste into cocaine
hydrochloride. This method does not give the really high quality crystals
that the bubble through method gives, but its use is justified when really
big batches are being handled.
In this alternative procedure, the free base is dissolved in two or
three volumes of acetone. Concentrated hydrochloric acid (37%) is then
added to the acetone while stirring until the mixture becomes acid to
litmus paper. Indicating pH paper should show a pH of 4 or lower. The
hydrochloride is then precipitated from solution by slowly adding ether
with stirring. It will take the addition of 10 to 20 volumes of ether to
fully precipitate the hydrochloride. Toluene or mineral spirits may be
substituted for the ether. Then the crystals are filtered out using a
Buchner funnel as described before, and set aside to dry. The filtrate
should be tested for completeness of precipitation by adding some more
ether to it.
References
Journal of Organic Chemistry, Volume 14, page 559 (1949).
Journal of the American Chemical Society, Volume 58, page 1808
(1936); Volume 61, page 520 (1939); Volume 63, page 3132 (1941).
Organic Syntheses, Collective Volume II, page 503.
--------------------------------------------------------------------------
INDUSTRIAL-SCALE PRODUCTION
--------------------------------------------------------------------------
In the previous five chapters, I described a process by which
underground chemists make smaller amounts of methamphetamine, up to about
one-half pound of pure methamphetamine. The process takes about three days
with two people working in shifts around the clock. Thus, the maximum
production level is stuck at one pound per week.
There is a way to break through this production limit, which is to
produce phenylacetone and turn it into methamphetamine by different
methods. These methods produce more in less time, and they are cheaper. Two
of them, the tube fumace and the hydrogenation bomb, are major engineering
projects. But they are no problem for those with a Mr. Handyman streak.
However, underground chemists will not move up to industrialscale
production until they are sure that they are going to be able to sell it
without having to deal with strangersðunless, of course, they want to get
busted.
One major difference in the logistics of a large-scale operation versus
a smaller one is that a different source of chemicals is required. An
outlet that specializes in pints and quarts of chemicals is not going to be
much help when multi-gallons are needed. Here a factor comes into play
which cannot be taken advantage of at lower levels of production. Most
chemical suppliers will not deal with individuals, only with corporations
and companies.
Now the underground chemist can turn this situation to his advantage by
means of subterfuge. First he develops a false identity. He gets some of
the books on false ID andðAbracadabra!ðhe's Joe Schmoe. He uses this
identity to form several companies. If he wants to be official, he consults
the book, How to Forrn Your Own Corporation For Under 50 Dollars, available
in most libraries. Otherwise, he just has some invoice-order forms printed
up for his company. He may also open a checking account for his company to
pay for chemicals. He uses checks with high numbers on them so that they
don't think that he just appeared out of thin air. As an alternative, he
may pay with certified checks from the bank.
The next step is to rent some space as his company headquarters and
chemical depot. Indeed, he'll probably rent a couple such depots to house
hisvarious companies. Now he starts contacting chemical dealers, ordering
enough of one or two chemicals to last for a couple of years. Then he
contacts another dealer and orders a similar quantity of one or two other
chemicals under a different company name. He continues this process until
he has everything he needs. He offers to pick them up so that they do not

 

see the dump he's rented as his headquarters. As a precaution, he equips
these dumps with a phone and answering machine so that they can call him
back. If he doesn't live in a large city, he does business out of town.
That way they won't be surprised that they never heard of him. But he does
not do business too far away from home base, so they won't wonder why he
came so far.
There is a better strategy to follow in getting the equipment and
chemicals needed for clandestine meth production. The best method to use is
to first order the equipment and a couple of the most suspicion arousing
chemicals. Then the underground operator lays low for a while. The narco
swine have a habit of going off half-cocked on their search warrants. If
the initial purchases caught their eyes, they will likely swoop right in,
planning on finding an operating lab, or at least enough to make a
conspiracy charge stick. If they move now, the meth meister will not be
prosecutable, so long as he does not admit guilt. An alternative narco
swine strategy would be for them to initiate intense surveillance upon Joe
Schmoe. So long as Joe is not brain dead, this will be pretty obvious after
awhile. If surveillance is noticed, it is time to put the plan into a deep
freeze, and consider the initial purchases a long term investment rather
than a quick payoff. If Joe is able to get the most sensitive materials
unnoticed, it is then time to quickly get the more mundane items needed and
immediately turn to the production end of the operation.
When it is time for the underground chemist to pick up the chemicals,
he uses a pick-up or van registered in Joe Schmoe's name. As a precaution,
he equips his vehicle with a radio scanner. He buys the book, U.S.
Government Radio Frequencies, and tunes the scanner to pick up the FBI, the
DEA, the state and local police. He picks up the chemicals and returns with
them to his headquarters and depot. He takes a roundabout route to make
sure he isn't being followed. Two tricks he may use to detect a tail are to
turn into a dead-end street and to drive either too fast or too slow. He
leaves Joe's vehicle at the depot and takes a roundabout route home. He
stops at a few bars and leaves by the back exit.
A very common, and quite stale trick is for the narco swine to place a
radio tracing device in the packing materials surrounding jugs of chemicals
purchased by suspected drug manufacturers. All items purchased should be
carefully inspected during the drive away from the point of purchase. If
such a device is found, it is cause for clear thinking action, rather than
panic. While using such a device, the heat will usually lay quite far back
on their pursuit to avoid being noticed. They will rely on the transmitter
to tell them where you are going. It is best not to smash such a
transmitter, but rather keep it in hand, and toss it into the back of
another pickup truck at a stoplight. This is then followed by putting the
plan into a deep freeze until the heat grows bored with you.
The next thing the underground chemist needs is a laboratory location.
A country location makes any surveillance very obvious and keeps chemical
smells out of the way of nosy neighbors. Electricity and running water are
absolutely necessary. Now he loads the chemicals onto Joe's wheels and
heads for the laboratory in a very roundabout manner, keeping an eye open
for any tail and paying close attention to the scanner. He leaves the
scanner at the lab for entertainment in the long hours ahead.
A nice addition to any underground laboratory is a self-destruct
device. This consists of a few sticks of dynamite armed with a blasting
cap, held inside an easily opened metal can. The purpose of the metal can
is to prevent small accidental fires from initiating the self-destruct
sequence. If Johnny Law pays an uninvited visit to his lab, the underground
chemist lights the fuse and dives out the window. The resulting blast will
shatter all the glass chemical containers and set the chemicals on fire.
This fire will destroy all the evidence. He keeps his mouth shut and lets
his lying lawyer explain why the blast happened to come at the same time as
the raid. He has no reason to fear the state crime lab putting the pieces
of his lab back together. These guys learned their chemistry in school and
are truly ignorant when it comes to the particulars of a well-designed lab.
The feds, on the other hand, have a higher grade of chemist working for
them, but they are tiny individuals who are haunted by nagging self doubt,
wondering why after obtaining a Ph.D., they are just faceless cogs in a
machine. To compensate for this, they will claim to make great discoveries
of the obvious. Case in point is an article published in the Journal of
Forensic Sciences. This is a petty journal published by Johnny Law where
the aforementioned tiny individuals can stroke their egos by getting
published. In an article covering the lithium in ammonia reduction of
ephedrine to meth production method featured in this third edition of my
book, the unnamed tiny, frustrated chemists trumpeted "we found that a
nitrogen atmosphere to protect the reaction was unnecessary, contrary to
the claims of the authors who said it was essential."
The authors to which they refer here are Gary Small and Arlene
Minnella, legitimate scientists who were published in a legitimate
scientific journal, the Journal of Organic Chemistry. In their article
covering the lithium in ammonia reduction of benzyl alcohols, they used
really tiny batches that might actually need a nitrogen atmosphere to
protect them, and in no place claimed that it was essential. See the
Journal of Organic Chemistry article cited in Chapter 15 of this book. It
was obvious that the steady boiling away of liquid am monia would form its
own protective gas blanket when done on a scale corresponding to real meth
production.
They further went on to nitpick the purification procedure used by the
real scientists, claiming it was unnecessary. Everyone who reads the
journals knows that it is unnecessary. This is just the protocol that has
been followed by research scientists for the past god-knows-howmany ages.
They just do this so that if they get unexpected results in their research,
they will know that it is not due to impurities in the reaction mix. To
make a great discovery out of finding that these rigorous purification
schemes are not needed for practical production methods just shows how
shallow these people are.
--------------------------------------------------------------------------
PHENYLACETONE FROM B-KETO ESTERS
--------------------------------------------------------------------------
In this chapter, I will cover two separate but similar methods of
making phenylacetone. Neither of them is actually suitable for
industrial-scale production, but they have the advantage of not using
phenylacetic acid. This allows an underground chemist to diversify the
chemicals used, and enables him to defeat a blockade on his phenylacetic
acid supply. Neither of these reactions is foolproof; both require a
certain amount of laboratory skill. The chemicals must be weighed and

 

measured fairly exactly. This is unlike the method described in Chapter 3,
where anything within a ballpark range will work. These methods require a
reliable scale.
Both of these reactions use sodium metal, which is some nasty stuff. It
reacts violently with water to produce sodium hydroxide and hydrogen. It
will also react with air. The chemist never touches it intentionally; if he
does touch it, he washes it off with warm water. Sodium metal comes in a
can, covered with a bath of petroleum distillate. This is to protect it
from water and air. As long as it stays covered, it causes the chemist no
problems.
In this reaction, sodium metal is reacted with absolute alcohol to make
sodium ethoxide (NaOCH2CH3). Ethyl acetoacetate and bromobenzene are then
added to this to produce a beta keto ester. Reaction with acid then
produces phenylacetone.
A side reaction which sometimes becomes a problem is bromobenzene
reacting with beta keto ester to produce di-phenylacetone. This can be
controlled by not using too much bromobenzene, adding it slowly and
stirring it well.
Figure 12 shows the glassware used. The glassware must be very dry, so
it is dried out in the oven for an hour or so. If the sep funnel has a
plastic valve, the valve is taken out before the sep funnel is put in the
oven. The magnetic stirring bar does not go in the oven either. It is
coated with Teflon, so it does not have any water on it. A magnetic stirrer
is necessary to do this reaction, because good stirring is very important.
An extra claisen adapter is needed for this reaction; one is filled with
broken pieces of glass for use as a fractionating column, the other is kept
as is for use in the Figure 12 apparatus.
To begin, the underground chemist puts a bed of Drierite in the vacuum
adapter as shown in Figure 2a, being sure to plug up the vacuum nipple. The
water lines are attached to the condenser and cold water started flowing
through it. But if it is humid, the water flow is not started until the
glassware is assembled.
The can of sodium is opened. A chunk about the size of a medium egg is
needed. The chemist selects a convenient corner of the block of sodium to
work on. With a clean, sharp knife, he scrapes off any discolored skin
there might be in the area he plans to use. Good clean sodium has a bright
metallic look. He keeps the block under the petroleum as he scrapes the
discolored skin.
Now he must weigh the sodium. A 100 ml beaker is filled halffull of the
petroleum distillate from the can of sodium, or with xylene. He puts it on
the scale and weighs it. He needs 34.5 grams of sodium metal, so with a
clean sharp knife. he cuts off a chunk of sodium, transfers it to the
beaker and weighs it. If it is not quite 34.5 grams, he cuts a little more
sodium and adds it to the beaker. This is done quickly, so that evaporation
of the petroleum does not throw the measurement off. Then another 100 ml
beaker is filled half-full of anhydrous ethyl ether. The sodium metal is
transferred to it with a spoon. The petroleum is poured back in with the
block of sodium and the can sealed up so that it does not evaporate. With a
clean sharp knife, the sodium is cut up into little pieces about 1/2 the
size of a pea.
The sodium is kept under the ether while this is being done. Eye
protection is always worn when working with sodium.
After the sodium is cut up, the magnetic stirring bar is put in the
2000 ml flask. Then the sodium metal pieces are scooped out with a spoon
and put in the 2000 ml flask. The glassware is immediately assembled as
shown in Figure 12. One liter (1000 ml) of absolute ethyl alcohol is
measured out. Absolute alcohol absorbs water out of air, so this is done
rapidly. Here's how. The chemist gets a quart beer bottle, marks on the
outside how full one liter is, and bakes the bottle in the oven to dry it
out. When he takes it out of the oven, he sucks the hot, moist air out of
it with a section of glass tubing. Once it has cooled down, he fills it
with one liter of absolute alcohol and stoppers it to keep it dry. He wants
to get the alcohol in with the sodium before the ether on it evaporates,
and this saves him the time of measuring it out.
About 200 ml of the absolute alcohol is put in the sep funnel and the
valve opened to allow the alcohol to flow down onto the sodium metal. Cold
water should be flowing through the condenser. Magnetic stirring is not
necessary at this time, but the 2000 ml flask is sitting in a large pan. A
pail of cold water and a towel are kept handy. Sodium and alcohol react
together vigorously, and the alcohol boils like crazy. The condenser is
checked to see how far up the alcohol vapors are reaching. The chemist does
not want the alcohol vapors to escape out the top of the condenser. If the
vapors are making it more than halfway up the condenser, cold water is
poured from the pail into the pan the flask is sitting in. That cools it
off and slows down the boiling. But if that does not do enough, the wet
towel is put on top of the flask. When the boiling slows down, the towel
and the pan of water are removed, then more alcohol is added to the sep
funnel. A fresh ball of cotton is put in the top of the sep funnel to
protect the alcohol from water in the air. The alcohol is added to the
flask at such a Mte that the boiling of the alcohol continues at a nice
Mte. When all of the original one liter of absolute alcohol has been added
to the flask, the flask is gently heated on the hot plate to keep the
alcohol boiling until the little pieces of sodium are dissolved. If the
chemist has done a very good job, the result is a clear solution. If not,
it will be milkycolored.
The magnetic stirring is now begun, and 195 grams (190 ml) of
ethylacetoacetate is put in the sep funnel over the next 15 minutes. The
solution is heated to a gentle boiling. As it is boiling and stirring, 236
grams of bromobenzene is put in the sep funnel and dripped into it over a
period of an hour. The boiling and stirring is continued for 8 hours.
Then the stirring is stopped and the solution allowed to cool down. A
good amount of sodium bromide crystals settle to the bottom of the flask.
When they have settled to the bottom, the glassware is taken apart and as
much of the alcohol solution as possible is poured into a 3000 ml flask.
The last of the product is rinsed off the sodium bromide crystals by adding
about 50 ml of absolute alcohol to them, swirling around the mixture, then
filtering it. This alcohol is added to the alcohol in the 3000 ml flask.
The glassware is set up as shown in Figure 3 in Chapter 3. A 1000 ml
flask is used as the collecting flask. The alcohol in the 3000 ml flask is
heated. The oil in the pan is not heated above 115ø C. The distillation is
continued until the chemist has collected over 900 ml of alcohol in the

 

collecting flask.
When the alcohol has been boiled out, the heat is turned off and the
flask removed from the pan of oil. As it is cooling off, 1500 ml of 5%
sodium hydroxide solution is mixed. To do this, 75 grams of sodium
hydroxide is put in a flask and 1400 ml of water added. (Lye may be used as
a sodium hydroxide substitute.) When both the sodium hydroxide solution and
the reaction mixture near room temperature, the sodium hydroxide solution
is poured into the 3000 ml flask with the reaction mixture. The magnetic
stirring bar is put into the flask and magnetic stirring is begun. It is
stirred fast enough that a whirlpool develops in the mixture and the~beta
keto ester gets into contact with the sodium hydroxide solution. The
stirring is continued for 4 hours without heating the solution. The beta
keto ester reacts with the sodium hydroxide to produce the compound shown
above, plus ethyl alcohol. This is a hydrolysis reaction.
After 4 hours of stirring, the stirring is stopped and the solution
allowed to sit for a few minutes. A small amount of unreacted material will
float up to the top. If there is a large amount of unreacted material, the
stirring is begun again and 40 grams of sodium hydroxide and 300 ml of
isopropyl rubbing alcohol are added. It is stirred for 4 more hours. But
generally this is not necessary.
The unreacted layer is poured into a 1000 ml sep funnel. A good deal of
the sodium hydroxide solution will be poured off with it. The chemist lets
it sit for a few minutes, then drains the sodium hydroxide solution back
into the 3000 ml flask. The oily unreacted material is poured into a small
glass bottle and kept in the freezer. When a good amount of it has
accumulated, the chemist tries reacting it again with 5% sodium hydroxide
solution. However, this will not yield very much more product, because most
of this oily material is the diphenylacetone byproduct.
The underground chemist is now ready to produce phenylacetone. The
compound shown above will react with sulffiuric acid to produce
phenylacetone and carbon dioxide gas. He mixes up 150 ml of 50% sulffiuric
acid. To do this, he adds slightly more than 55 ml of sulfuric acid to
slightly less than 105 ml of water; if he added more sodium hydroxide and
alcohol to his reaction mixture, he mixes up twice as much 50% sulfuric
acid.
The stirrer in the 3000 ml flask containing the sodium hydroxide is
started up again. Then the 50% sulffiuric acid is slowly added to it. It
will bubble out carbon dioxide like crazy and crystals of sodium sulfate
will be formed. Phenylacetone will also be formed, some of it floating on
the surface of the solution, some of it trapped among the crystals formed.
When all of the sulffiuric acid has been added, and the bubbling of carbon
dioxide has slowed down to just about stopping, the stirring is stopped.
The glassware is set up as shown in Figure 3. The collecting flask is
2000 ml. The 3000 ml flask is slowly heated to boiling. The steam carries
the phenylacetone along with it to the other flask. This process is called
a steam distillation. The distilling is continued until a little more than
1000 ml is in the collecting flask. By then, almost all the phenylacetone
will be carried over into the collecting flask. There will be two layers in
the collecting flask, a yellow layer of phenylacetone on top, and a clear
water layer. There will be some acid dissolved in the water. Forty grams of
sodium hydroxide is dissolved in 150 ml of water, then added to the 2000 ml
flask. The flask is stoppered and shaken for one minute to destroy the
acid. Then 100 ml of benzene is added to the flask and it is shaken some
more. The phenylacetonebenzene layer is poured into a 1000 ml sep ffiunnel
and allowed to sit for a couple of minutes. Then the water layer is drained
off back into the 2000 ml flask. The phenylacetone layer is poured into a
500 ml flask along with a few boiling chips. Then 100 ml of benzene is
added to the 2000 ml flask, which is shaken again for about 30 seconds
before it is allowed to sit for a few minutes. The benzene layer is poured
into the 1000 ml sep funnel and allowed to sit for a couple of minutes. The
water layer is drained out, and the benzene layer is poured into the 500 ml
flask with the rest of the phenylacetone. The glassware is set up as shown
in Figure 5 and the phenylacetone distilled as described in Chapter 3. The
yield is about 125 ml of phenylacetone. (For more information on this
reaction, see Organic Reactions, Volume 1, published in 1942, page 266.)
There is another way to make phenylacetone which is better than the
method just described. It does not take as long to do, and it is somewhat
simpler. As in the first method, the reactants must be measured out
carefully.
In this case, the main reactant is benzyl cyanide, also called
phenylacetonitrile or alpha-tolunitrile. Benzyl cyanide is now a controlled
substance precursor, and so must be made.
Benzyl cyanide is not outrageously poisonous like sodium cyanide. It is
an organic cyanide, called a nitrile. As long as the chemist doesn't drink
the stuff, he's OK. It is a somewhat smelly liquid, clear in color.
This reaction is done similarly to the first method described in this
chapter. First a solution of sodium ethoxide is made, then ethyl acetate is
added, mixed in with benzyl cyanide. This produces a solid called
phenylacetacetonitrile. This solid is then added to sulfuric acid, and
phenylacetone is produced.
The same glassware as shown in Figure 12 is used, except that a 3000 ml
round bottom flask is used. It is dried out in the oven. Now a sodium
ethoxide solution is produced in the same way as described earlier in this
chapter. The chemist starts with a chunk of clean sodium metal that weighs
128 grams. It is weighed out in a 300 ml beaker half-filled with petroleum
distillate or xylene, as described earlier. Then the sodium metal is
transferred to another beaker halffilled with anhydrous ether and chopped
into small pieces with a clean knife. Then it is scooped out with a spoon
and put in the 3000 rnl flask. The glassware is quickly assembled as shown
in Figure 12, with the 3000 ml flask sitting in a pan. Water flow through
the condenser is begun, and 300 ml of absolute ethyl alcohol is put in the
sep funnel. The same precautions as described earlier are used to keep the
alcohol free of water. As the alcohol is allowed to flow in onto the
sodium, the reaction is kept under control by putting cold water in the pan
and wrapping the flask in a wet towel.
When the reaction is under control, more alcohol is added until a total
of 1500 ml has been added. The alcohol is gently boiled until the sodium
metal is dissolved.
Now the chemist mixes 500 grams of benzyl cyanide with 575 grams of
ethyl acetate and stops the heating of the ethanol solution. Just as it
stops boiling, the mixture of ethyl acetate and benzyl cyanide is added

 

with good magnetic stirring. This addition takes about 15 minutes. The
stirring is continued for about 10 minutes after the addition is complete,
then the mixture is heated in a steam bath or in a pan of boiling water for
about 2 hours. Then it is taken out of the heat and allowed to sit
overnight, or at least for a few hours.
The underground chemist has just made the sodium salt of
phenylacetacetonitrile. To collect it, he cools the flask in a mixture of
salt and ice. With a clean wooden stick, he breaks up the chunks of
crystals that have formed, as the flask is cooling down. When it reaches
-10øC, he keeps it at this temperature for a couple of hours, then filters
out the crystals. They are rinsed a couple of times with ether, then, while
still wet with ether, added to a large flask or beaker containing 2000 ml
of water. They are dissolved by stirring, then the flask or beaker is
cooled down to 0øC by packing it in ice mixed with salt. When it reaches
this temperature, 200 ml of glacial acetic acid is added to it with
vigorous stirring. The chemist must make sure that the temperature does not
go up more than a few degrees while he is adding it.
He has now made phenylacetacetonitrile. He filters the crystals off it
and rinses them a few times with water. The crystals must now be kept moist
in order for them to be turned into phenylacetone.
All is now ready for producing phenylacetone from these crystals. In a
2000 ml flask, he puts 700 ml of concentrated sulfuric acid. It is cooled
down to -10ø C by packing the flask in a mixture of salt and ice, then
magnetic stirring is begun. The crystals are slowly added to the sulfuric
acid. They must be moist, or he will get a mess. It takes about an hour to
add the crystals to the sulfuric acid. Once they are added, the flask is
heated in a pan of boiling water and swirled around to dissolve the
crystals. After they have dissolved, the flask is heated for a couple more
minutes, then removed from the pan of boiling water. It is cooled down
slowly to 0ø C by first letting it cool down, then packing it in ice.
The underground chemist puts 1700 ml of water in a 3000 ml flask. Half
of the sulfuric acid solution is added to it. It is heated in a pan of
boiling water for a couple of hours. It is given a couple of good shakes
every 15 minutes. A layer of phenylacetone forms in the mixture.
After 2 hours of heating, the mixture is poured into a gallon-size
glass jug to cool off. Another 1700 ml of water is put in the flask and the
rest of the chilled sulfuric acid solution is poured into it. It is also
heated for 2 hours in a pan of boiling water, then poured into another
glass jug.
The chemist is ready to separate the phenylacetone from the water and
distill it. The liquid in the first jug is slowly poured into a 1000 ml sep
funnel until the sep funnel is full. Most of the phenylacetone layer will
be in the sep funnel, because it is floating on top of the water. The water
layer is drained back into the jug, and the phenylacetone layer is poured
into a large beaker. He adds 300 ml of benzene to the jug, stoppers it and
shakes it for 15 seconds. Then he stops and lets the layer of benzene
containing phenylacetone float up to the surface. It is slowly poured into
the sep funnel, and the water layer is drained back into the jug. The water
is thrown away. This process is repeated with the other jug.
This phenylacetone has some sulfuric acid in it. The chemist puts 150
ml of water in the 1000 ml sep funnel. He also pours half of the
phenylacetone and benzene mixture he got from the two jugs into the sep
funnel. He shakes it with the water to remove the sulfuric acid. The water
is drained out, and the phenylacetone-benzene layer is poured into a 1000
ml round bottom flask. Another 150 ml of water is put into the sep funnel.
It is shaken also, then the water layer is drained off. He pours as much of
this benzene-phenylacetone mixture into the 1000 ml round bottom flask as
he can until it reaches 2/3 full.
The glassware is set up as shown in Figure 5 in Chapter 3, with a few
boiling chips in the 1000 ml flask. The collecting flask is 250 ml. He
distills off a couple of hundred ml of benzene to make room for the rest of
the product. When there is some room, he turns off the heat and waits for
the boiling to stop. Then the rest of the benzenephenylacetone mixture in
the sep funnel is added to the 1000 ml flask. The distillation is continued
until the benzene stops coming over. About 500 to 600 ml of benzene will be
collected.
When the rate of benzene distillation slows down to just about
stopping, the heat is turned off and it is allowed to cool down. Then the
last of the benzene is removed under a vacuum. When the benzene is gone,
the collecting flask is changed to a 500 ml flask and the phenylacetone is
distilled under a vacuum at the usual temperature range. The yield is about
300 ml of phenylacetone. Once the benzene is gone, virtually all of the
material left in the flask is phenylacetone. If there is a high boiling
residue, it is unchanged phenylacetacetonitrile.
References
Journal of the American Chemical Society, Volume 60, page 914 (1938).
--------------------------------------------------------------------------
PHENYLACETONE VIA THE TUBE FURNACE
--------------------------------------------------------------------------
The best way to produce phenylacetone on a large scale and continuous
basis is by a catalyst bed inside a tube furnace. This has several
advantages over the other methods described in this book. Cheap and very
common acetic acid is used to react with phenylacetic acid instead of the
expensive and more exotic acetic anhydride and pyridine. Use of the tube
furnace frees up the glassware for use in other operations. The furnace
requires very little attention while it is in operation, which allows the
underground chemist to spend his time turning the phenylacetone into
methamphetamine. There is no reason why this process cannot be used in
small-scale production. It is just that its advantages really come out when
large amounts of phenylacetone must be produced.
In this process, a mixture of phenylacetic acid and glacial acetic acid
is slowly dripped into a Pyrex combustion tube which is filled with
pea-sized pumice stones covered with a coating of either thorium oxide or
manganous oxide catalyst. This bed of catalyst is heated to a high
temperature with a tube furnace and the vapors of phenylacetic acid and
acetic acid react on the surface of the catalyst to produce ketones. Three
reactions result.
The acid mixture is prepared so that there are three molecules of
acetic acid for every molecule of phenylacetic acid. This makes it much
more likely that the valuable phenylacetic acid will react with acetic acid
to produce phenylacetone rather than with another molecule of phenylacetic
to produce the useless dibenzyl ketone.
The vapors are kept moving in the catalyst tube by a slow stream of
nitrogen and eventually the product comes out the far end of the catalyst
tube. The vapors are then condensed and collected in a flask.
The complete apparatus for doing this reaction is shown in Figure 13.
The combustion tube is made of Pyrex and is about one meter long. It is
about 2 centimeters in internal diameter, with a male 24/40 ground glass
joint on one end and a female 24/40 ground glass joint on the other end. If
the underground chemist cannot buy the tube with the glass joints already
on it, there are many places which will weld these glass joints onto the
tube. He can find such a place by asking around and checking the Yellow
Pages.
The tube furnace must be 70 centimeters in length. The only
commercially available tube furnace that I know of is the Hoskins tube
furnace. It is a fine furnace, but only 35 cm in length. Two of these would
have to be run end-to-end to get the required 70 cm length. The cost,
including a transformer for each of the furnaces, would be over $700. It is
better and cheaper for the chemist to build his own tube furnace.
The tube furnace starts with a section of thinwall iron tubing about 75
cm long and 3 to 3.2 cm in internal diameter. Thinwall iron tubing has a
metal thickness of .024 inch. The outside of the tubing is wrapped with
asbestos cloth or asbestos paper to a thickness of about 2 millimeters.
Asbestos cloth or paper is available at hardware stores.
Fifty feet of 28 gauge AWG nichrome wire is wrapped around the central
70 cm of the tube. The windings are made fairly taut so that the wire sinks
slightly into the asbestos paper. Each winding is evenly spaced from the
previous one, about 1/2 cm apart. One winding must not be allowed to come
into contact with another, or there will be a short circuit.
The outside of the tubing is insulated with 6 or 7 layers of asbestos
paper or cloth. This insulation is held in place by using copper wire
ligatures about 6 inches long, wrapped around the outside of the
insulation, and tied at the ends to make it tight.
The two ends of the nichrome wire are attached to insulated connectors
(two of them) and then to a transformer. The Variac autotransformer is
perfect for this job. It can adjust 115-volt house current anywhere from
140 volts down to zero. The transformer can handle 5 amps of current.
The chemist picks up a couple of pumice foot stones (Dr. Scholl's are
suitable) at the pharmacy. With a hammer and screw driver, he breaks them
into round pieces somewhat smaller than a pea. Any sharp or protruding
edges are knocked off. He makes enough of these pumice pebbles to fill the
combustion tube for a length of 70 cm.
The pumice must now be purified to remove traces of metals and other
garbage. This prevents the catalyst from being poisoned. The pumice pebbles
are put into a 1000 ml beaker along with a wad of glass wool (Angel Hair)
somewhat larger than a fist. The glass wool will be going into the

 

combustion tube, so it must be cleaned off along with the pebbles. The
glass wool is packed down. Then nitric acid is added until both the pumice
and glass wool are covered. The beaker is put on an electric hot plate and
the nitric acid boiled for half an hour. This converts metal impurities
into soluble nitrates, and oxidizes other garbage. The nitric acid is all
poured off and down the drain. The pumice and glass wool are then covered
with distilled water and soaked for 5 minutes. This water is then drained
off and replaced with more water. The water is boiled for 10 minutes, then
drained off. This boiling water rinse is repeated two more times using
distilled water. Finally, the water is drained out and the beaker laid on
its side to drip out the last drops of water.
The pumice pebbles are now ready to be coated with catalyst. About 450
ml of distilled water is put into a clean 1000 ml beaker. The chemist
dissolves 276 grams of thorium nitrate into this water. In another clean
beaker, he dissolves 106 grams of anhydrous sodium carbonate into 400 ml of
distilled water. (He uses A.R. grade chemicals.)
Slowly, and with constant stirring, the sodium carbonate solution is
added to the thorium nitrate solution. Using a mechanical stirrer to stir
the thorium nitrate solution is best, but a glass rod also works.
Thorium nitrate reacts with sodium carbonate to make thorium carbonate
and sodium nitrate. Thorium carbonate does not dissolve in water, so it
forms a white precipitate. Sodium nitrate stays dissolved in water. The
stirring is continued for a couple of minutes after all the sodium
carbonate has been added, then it is allowed to settle. The thorium
carbonate settles into a gooey gunk at the bottom of the beaker. As much of
the water as possible is poured off. Then 600 ml of distilled water is
added to the thorium carbonate and stirred around with a clean glass rod.
The chemist makes sure that all the thorium carbonate gets into contact
with the clean water, and that any lumps are broken up. This dissolves any
remaining sodium nitrate.
The thorium carbonate is allowed to settle again, then as much of the
water as possible is poured off. Small amounts of distilled water are added
and stirred in until a fairly thick paste is formed. Now the purified
pumice pebbles are added and stirred around until they are all evenly
coated with thorium carbonate.
A Pyrex glass cake pan is placed on the electric hot plate. The heat is
turned on to 1/4 maximum and about 1/8 of the coated pumice pebbles are
added to the glass pan. They are heated there with constant stirring with a
thick glass rod, so that the pieces dry out evenly. When the coated pumice
pebbles no longer stick together, they are dry enough. They are transferred
to a clean sheet and an equal amount of wet pumice pebbles are put in the
cake pan. They are dried out like the first group of pebbles. This process
is repeated until all the coated pumice pebbles are dry. Any white powder
that failed to stick to the pumice is collected and saved in a glass jar.
If it is later necessary to change the catalyst bed, this material is
wetted and used to coat new pumice pebbles.
A plug of the purified glass wool about 3 cm long is put into the
combustion tube about 15 cm from the male end. This will hold the catalyst
bed in place. The tube is filled up with the coated pumice pebbles for a
length of 70 cm or so. A small plug of purified glass wool about 1 cm in
length is put every 15 cm. This reduces the danger that tar building up on
the pumice pebbles will block the tube.
The tube is put inside the furnace. If two Hoskins tube furnaces are
used end-to-end, the tube is insulated in the space between the two
furnaces with several layers of asbestos paper or cloth. In this space, the
tube is filled with loose glass wool. This space is not counted as part of
the necessary 70 cm of catalyst bed.
The apparatus is set up as shown in Figure 13. It is tilted at an angle
of about 20 degrees, the end with the sep funnel being higher than the end
with the collecting flask. The sep funnel has a one-hole stopper with a
piece of glass tubing running through it almost all the way to the valve of
the sep funnel. This is a constant pressure device that causes the contents
of the sep funnel to drip into the tube at a constant rate, no matter what
the level of the acids in the sep funnel at a particular instant.
The sep funnel is connected to the female end of the vacuum adapter.
The male end of the vacuum adapter is inserted into the female end of the
combustion tube. The male end of the combustion tube is connected to a
condenser. The condenser is connected to a vacuum adapter, and the vacuum
adapter leads to a 500 ml round bottom flask. The glass joints are lightly
greased and wired together where possible. The furnace must be supported to
prevent its weight from bending the soon-to-become-soft hot glass tube.
Clamps connected to ringstands are used to hold the other pieces in place.
The vacuum adapter connected to the sep funnel is the nitrogen gas
inlet. The underground chemist gets a tank of nitrogen at a welding supply
shop. He has to make sure that he knows how to use the regulators. He runs
a line of tubing from the tank to the "bubbler." The bubbler is shown in
Figure 14. It is a bottle with a 2-hole stopper in the top. One hole has a
section of glass tubing reaching nearly to the bottom of the bottle. The
bottle has about an inch and a half of concentrated sulfuric acid in it.
The purpose of the sulfuric acid is to dry the nitrogen gas and to show how
fast it is bubbling into the apparatus. The other hole has a short section
of glass tubing. Plastic tubing is attached to this tubing and leads to the
vacuum nipple of the vacuum adapter.
And now the time has come for the underground chemist to fire up the
furnace. He places a thermometer capable of reading up to 450øC, or, better
yet, a thermocouple, in the furnace against the outside of the glass
tubing. (If his thermocouple did not come with wiring instructions, he can
find the wiring diagram in the Encyclopedia Britannica and in many
college-level physics textbooks.) The thermometer or thermocouple extends
into the central regions of the furnace. The space at the end of the
furnace between the outside of the glass tubing and the inside of the
furnace's iron tubing is plugged up with pieces of asbestos paper or cloth
to hold in the heat.
He turns on the electricity to the furnace, and begins a slow stream of
nitrogen (about one bubble per second) through the tube. He keeps a sheet
listing the temperatures his furnace gets at various voltage settings on
the transformer. Of course, it takes a while for the furnace to heat up to
its true temperature at a given setting.
Now the tube furnace is heated to 425-450øC, while the slow stream of
nitrogen continues through the tube. The heat turns the thorium carbonate
into thorium oxide. The heating continues for 12 hours, after which the
catalyst is ready to produce phenylacetone.
The chemist mixes 200 grams of phenylacetic acid with 250 ml of glacial
acetic acid. He mixes them thoroughly, the phenylacetic acid dissolving
easily in the glacial acetic acid. (Glacial acetic acid is the name for
pure acetic acid; it is so called because it freezes at a little below room
temperature.)
This acid mixture is poured into the sep funnel and the funnel is
stoppered with the one-hole stopper with the glass tubing constant pressure
device. The temperature of the furnace is 425- 450ø C, and a
one-bubble-per-second stream of nitrogen has been flowing through the tube
for at least 2 hours. The valve on the sep funnel is opened so that about
20 drops of the acid mixture drip into the tube from the sep funnel every
30 seconds.
A slow flow of water is put through the condenser to condense the
ketones as they leave the furnace. The product collects in the 500 ml flask
and the nitrogen gas exits through the vacuum nipple of the vacuum adapter
connected to the condenser. If there is trouble condensing all the acetone,
the 500 ml flask is packed in ice.
It takes about 5 hours for all the acid to drip into the tube. When all
the acid mixture has dripped in, 25 ml of acetic acid is added to the sep
funnel and dripped in. This flushes the last of the product out of the
catalyst bed.
The product in the 500 ml flask consists of a lower water layer and a
brown-colored organic layer on top. It is poured into a 1000 ml sep funnel;
the water layer is then drained off into a clean beaker, and the organic
layer is poured into another beaker. The water layer is put back into the
sep funnel along with 50 ml of benzene, and the funnel is shaken. It is
allowed to sit for a few minutes, then the lower water layer is drained off
and thrown away. The benzene layer is poured in with the organic layer in
the other beaker.
The chemist is now ready to clean up the phenylacetone so that it can
be distilled. He mixes up a supply of 10% sodium hydroxide solution by
adding 10 ounces of lye to 3/4 gallon of water in a glass jug. He pours the
organic layer into the sep funnel, adds 400 ml of the sodium hydroxide
solution and shakes. The water layer is drained off into a clean beaker and
the organic layer is poured into another beaker. The water layer is
returned to the sep funnel and 75 ml of benzene added. The funnel is
shaken, then the water layer is drained off and thrown away. The benzene
layer is poured in with the organic layer. This is repeated three more
times, then the phenylacetone is distilled as described in Chapter 3. The
yield of phenylacetone is about 100 ml.
The temperature of the furnace is raised to about 525øC, and a slow
stream of air is drawn through the tube for two hours. The air is drawn
through by turning off the nitrogen flow, opening up the valve of the sep
funnel and attaching a vacuum hose to the vacuum nipple of the vacuum
adapter on the 500 ml flask side of the apparatus. This air flow burns off
built up crud on the catalyst and charges it up for another run. It is done
after the first run, and then after every few batches.
The furnace temperature is set at 425-450-ø C again and the flow of

 

nitrogen through the tube is resumed. It is flushed out for a couple of
hours, then the sep funnel is filled with acid mix for another run. It is
dripped in as before to get another batch of phenylacetone. In this way,
phenylacetone can be produced on a continuous basis.
If the homemade furnace has trouble reaching the necessary temperature,
the chemist wraps it with more insulation. If that does not do enough, a
lower temperature process can be used by replacing the thorium-oxide-coated
pumice pebbles with manganous-oxidecoated pumice pebbles. The process goes
as follows:
The pumice pebbles are made and purified with nitric acid as described
earlier. In a 1000 ml beaker, 70 grams of manganous chloride (MnCl2) is
dissolved in 300 ml of distilled water. In another beaker, 38 grams of
anhydrous sodium carbonate is dissolved in 500 rnl of distilled water. The
sodium carbonate solution is slowly added to the manganous chloride
solution with constant stirring. Manganous chloride reacts to form
manganous carbonate, which does not dissolve in water and precipitates out.
The manganous carbonate is filtered out in a Buchner funnel as described in
Chapter 5. The crystals are rinsed with distilled water.
The manganous carbonate is returned to a clean beaker and enough
distilled water is added to make it into a fairly thick paste. If too much
water is added, it does not stick well to the pumice. The pumice pebbles
are stirred in until they are evenly coated. The beaker is heated on a hot
plate while the pumice stones are vigorously stirred.
Local overheating must be avoided or the catalyst will be ruined] When
most of the water is evaporated, the catalyst is transferred to a Pyrex
cake pan and gently heated on a hot plate. The pumice chips are stirred
constantly to get even drying. When they no longer stick together, they are
transferred to a clean sheet of paper.
The chemist fills the combustion tube with the catalyst as before and
sets up the apparatus. He heats the furnace to 360-400øC while passing a
stream of nitrogen through the tube. This converts the manganous carbonate
to manganous oxide (MnO). This heating is continued for 8 hours. Then the
heat is reduced to 350øC, while the stream of nitrogen is continued at a
rate of one bubble per second. When 350øC is reached, he drips in the same
phenylacetic acid-acetic acid mixture used earlier in this chapter. The
correct rate is 20 drops every 30 seconds. When it has all dripped in, he
adds 25 ml of acetic acid to the sep funnel and drips it in. He then either
adds more acid mix to the sep funnel for another run, or shuts down the
furnace. If he shuts down the furnace, he must continue the flow of
nitrogen through the tube until it has cooled off. This prevents the MnO
catalyst from being oxidized to MnO2, etc. When he turns it back on, he
must immediately start the nitrogen flow for the same reason. The product
is purified in the same way as described earlier in this chapter.
Since no air is sucked through the tube at high temperature, gunk
builds up on the catalyst and eventually puts it out of commission. When
this happens, the catalyst bed is changed. The yield using the manganous
oxide catalyst bed is not as good as that using the thorium oxide catalyst
bed. Thorium oxide is used, unless the chemist has no choice.
A somewhat more complicated way to do this reaction is to use what is
called a thorium oxide "aerogel" catalyst. A lower temperature and a higher
rate of production are possible. For more information about it, see
Industrial and Engineering Chemistry, published in 1934, Volume 20, pages
388 and 1014.
References
Journal of the Chemistry Society, page 612 (1948); page 171 (1940).
--------------------------------------------------------------------------
MAKING PHENYLACETONE
--------------------------------------------------------------------------
There are many other methods of making phenylacetone described in the
scientific literature. Most of them are dogs, not worth the time and
effort. But there are some good methods of making phenylacetone that I have
not yet described.
An acceptable method is to oxidize methyl benzyl carbinol
(1-phenyl-2-propanol) to phenylacetone (methyl benzyl ketone) with chrome
oxide (CrO3) in pyridine solvent. The problem with this is that methyl
benzyl carbinol is not commercially available, and so must be made from
benzyl chloride grignard reagent and acetaldehyde. This grignard works
well, although there can be a problem getting unreacted benzyl chloride out
of the product. Their boiling points are very close, so distillation does
not separate them completely. But the real question is: Why make the
synthesis of phenylacetone a two-step process when it can be done with one
reaction?
Another two-step method of making phenylacetone is to make benzyl
cyanide from benzyl chloride and sodium cyanide, and then make the benzyl
cyanide into phenylacetone by the method described in Chapter 7. The way to
make benzyl cyanide can be found in Organic Syntheses, Collection Volumes
I, II and III. Benzyl cyanide is listed in the table of contents.
A good way to make phenylacetone is to react methyl zinc reagent with
phenylacetyl chloride. Methyl zinc reagent is made by reacting methyl
iodide with zinc metal, or by adding zinc chloride to methyl grignard
reagent. It is not an especially difficult reaction to do, and the yields
are very good. The problem is that phenylacetyl chloride is expensive and
hard to find, although it can be made from phenylacetic acid and thionyl
chloride SOCl2.
In what is actually the best method of making phenylacetone, two
molecules of methyllithium react with phenylacetic acid to produce
phenylacetone, or one molecule of methyllithium reacts with one molecule of
the lithium salt of phenylacetic acid to produce phenylacetone. This
reaction is done in anhydrous ethyl ether under an atmosphere of nitrogen.
However, organolithium reagents burst into flame upon contact with air.
Although methyllithium is not so bad in this respect as t-butyllithium,
organolithium reagents are dangerous to handle. But, apart from the element
of danger, this is the best way to make phenylacetone. The high cost of
lithium is offset by the high yields of product. This reaction comes in
especially handy in building up the substituted phenylacetones used to make
the psychedelic amphetamine derivatives, such as STP or
trimethoxyamphetamine (TMA).
Another good way to make phenylacetone is to react phenylacetyl
chloride with the ethoxymagnesium derivative of dimethyl malonate.
Hydrolysis with acid then produces phenylacetone. This reaction is
described in the Journal of the American Chemical Society, Volume 70, page
4214, (1948). This can be found in any good college library.
Another good method of making phenylacetone is to use a method called
the Knoevenagel reaction. In this method, the starting material is
benzaldehyde. The advantages to being able to use a wide variety of
starting materials to produce phenylacetone are obvious. A temporary
shortage of one chemical is not sufficient to cripple an underground
chemist's operation. He can also vary his chemical purchases so that there
is not a big run on one particular set of ingredients, which could lead to
suspiciousness and snooping.
This reaction is fairly easy to do, and is pretty hard to mess up, so
long as some basic precautions are taken. The underground chemist does his
best to make sure that his glassware is dry, and the alcohol used is
absolute (100% with no water). He must also do the processing of this
material quickly, because the nitroalkene which is formed in the first
phase of this reaction will not keep. The reaction goes like this:
Benzaldehyde reacts with nitroethane in an alcohol solution with
n-butylamine catalyst to produce a crystalline substance called a
nitroalkene. This nitroalkene can then be reduced by means of iron and HCl
to produce phenylacetone. The reduction is similar to the use of activated
aluminum in the reaction to produce methamphetamine without the bomb, in
that the metal, in this case iron, dissolves and produces hydrogen which
reduces the nitroalkene. It is not as complicated as it sounds, and is
pretty easy to do. The nitroalkene is first reduced to phenylacetone oxime,
which is then hydrolyzed to phenylacetone.
You may wonder, looking at the structure of the nitroalkene molecule,
if it is not possible to reduce it directly to the prototype amphetamine,
benzedrine. The answer is yes. In fact, one method of making the
psychedelic amphetamines such as MDA is to get the properly substituted
benzaldehyde (in the case of MDA the proper benzaldehyde is called
piperonal) and reduce it using a hydrogenation bomb and Raney nickel, or by
use of lithium aluminum hydride. Another good method for reducing the
nitroalkene directly to amphetamine is to use zinc amalgam and hydrochloric
acid in alcohol solvent. A still better method for direct reduction of the
nitroalkene to amphetamine is to use palladium black on charcoal in the
champagne bottle hydrogenation bomb seen in Figure 17 in Chapter 11.
Directions for making palladium black on charcoal are found in the Meth
from Ephedrine chapter. A few grams of catalyst per hundred grams of
nitroalkene works nicely. Reaction conditions are room temp at a hydrogen
pressure of 30 pounds. Hydrogenation is complete in 5 to 10 hours, and the
solvent is 190 proof vodka. Best results are obtained if the nitroalkene is
purified by recrystallizing the crude product from alcohol prior to
reduction.
This reaction is done as follows: Into a clean, dry 3000 ml round
bottom flask is placed 400 ml of absolute alcohol, 20 ml of nbutylamine,
428 grams of benzaldehyde, and 300 grams of nitroethene. The underground
chemist sets up the glassware for refluxing as shown in Figure 2b in
Chapter 3. He includes the drying tube with Drierite as shown in Figure 2a.
He swirls around the flask to mix the contents, then sets the flask on a
hot plate and begins heating it. The water flowing through the condenser

 

should be fairly cool, to be sure of condensing the alcohol vapors. A good,
gentle rate of boiling is what he aims for. He continues the boiling for 8
hours. The solution will turn yellow.
He makes sure that his chemicals, especially the nitroethane, are of a
good grade. Nitroethane is widely used in the paint and varnish industry as
a solvent for cellulose acetate lacquers, vinyl resins, nitrocellulose,
waxes and dyes. If he has the industrial grade, he first distills it before
use. Benzaldehyde smells like bitter oil of almonds and should be clear.
Benzaldehyde is used in flavorings and perfumes.
When the 8 hours of boiling is done, he turns off the heat and lets the
flask cool down. Once crystals begin to appear, he takes off the condenser
and begins stirring the solution with a glass rod. He continues the
stirring, and transfers the flask to a sink of cool water to help speed the
cooling. He continues the stirring until the mass of crystals becomes too
thick to stir, or the flask is cooled off. The idea of the stirring is to
prevent the batch from setting into one solid mass of crystals. The
crystals should be yellow in color.
He now proceeds to purify this 1-phenyl-2-nitropropene. The simplest
way to do this is to add ethyl ether to the crystals until a slurry is
formed (about 500 ml) and then break up any lumps of crystals with a glass
rod. He then filters the slurry through a large coffee filter and squeezes
the mass to force out as much of the ether as possible. Along with the
ether, he will be removing most of the unreacted benzaldehyde and
nitroethene. The crystals will still be yellow, but they will no longer be
sticky and gooey. If he still smells n-butyl amine on them, he may rinse
them with ether again.
A better way to clean up these crystals is to recrystallize them. In
large batches like this one, it is a lot of work and he must make
provisions for exhausting the fumes to the outside to prevent the danger of
explosion, but he will get a cleaner product.
It is done as follows: To the crystals which have been rinsed off with
ether and returned to a cleaned, dry 2000 ml round bottom flask, he adds
just enough hot petroleum ether to dissolve the crystals. This takes in the
neighborhood of 700 ml of petroleum ether. Any type of petroleum ether will
do. If he has access to hexane from some industrial source, that will do
fine. Petroleum ether is flammable, so the way he makes the ether hot is to
place the flask with the crystals into a pan of hot water, and to begin
adding the petroleum ether to it. He swirls it around while adding the
petroleum ether and keeps adding ether until the crystals are dissolved.
The result will be a clear yellow solution. Now he records how much
petroleum ether he added and places the flask on the hot plate and sets up
the glassware for simple distillation as shown in Figure 3 in Chapter 3. A
500 ml flask is fine for the receiving flask. He turns on the heat to the
solution, begins water flow through the condenser and distills off about
1/3 of the ether he added to the crystals to dissolve them. When 1/3 of the
ether is distilled off, he removes the flask from the heat, and cools it
off in cool water, followed by ice water. He doesn't want to place the
flask immediately into ice water, because it might crack.
Now, as the petroleum ether cools off, it will no longer be able to
dissolve the crystals, and they will re-form in much cleaner shape because
the garbage which is polluting them will stay dissolved in the petroleum
ether. Once the petroleum ether is cold, he filters the crystals through a
filtering funnel the same way it was described in Chapter 5. He places the
crystals out to dry on a glass or china plate, and returns the yellow
petroleum ether solution which filtered through to the distilling flask.
This solution still contains a good deal of crystals dissolved in it.
He sets up the glassware as before and distills off another i/3 of the
petroleum ether, then cools off the flask as before. Once again, crystals
will form, although they will not be of as high quality as the first crop.
He filters them as before, and returns the ether to the distilling flask.
Now he distills off about % as much petroleum ether as before, then cools
off the flask and waits for the crystals to form. This will be his last
crop of crystals. He filters them and sets them out to dry. The total
amount of crystals he will get will be about 420 grams.
The underground chemist must now proceed to reduce these crystals of
1-phenyl-2-nitropropene to phenylacetone. If he lets them sit around, they
will begin to poIymerize into a black, gooey mess (though he can delay them
going bad by putting them in the freezer).
Into a clean 3000 ml flask, he places 164 grams of the nitroalkene
crystals he just made. To that he adds 750 ml of distilled water, 400 grams
of cast iron turnings about '/40 inch in size, and four grams of iron
chloride (FeCl3). The flask is placed in a glass dish large enough to hold
it, and cooking oil is added to the dish so that it reaches about half way
up the sides of the flask. He places the flask with the dish of oil onto a
hot plate, and heats the oil to about 105ø C. He puts a mechanical stirrer
into the flask with a glass rod and Teflon stirring paddle, and begins
stirring the mixture in the flask. Once the temperature of the contents of
the flask nears 80ø C, he measures out 750 ml concentrated hydrochloric
acid. He adds it slowly to the flask over a period of 5 hours. The iron
will slowly react with the acid and dissolve, producing hydrogen which will
reduce the nitroalkene to phenylacetone oxime. The oxime then reacts with
more water and HCl to give phenylacetone.
When the acid has all been added, he removes the flask from the heat
and lets it cool down. Then he mixes up 350 grams of sodium hydroxide or I
ye in 1000 ml of water. Once they have both cooled down, he adds the sodium
hydroxide solution to the 3000 ml flask and swirls it around.
He will now distill out the phenylacetone with steam. He adds a few
pumice boiling chips to the 3000 ml flask, and places it on the hot plate.
He sets up the glassware for simple distillation (not fractional
distillation) as shown in Chapter 3. A 1000 ml flask will do fine for the
receiving flask. He heats the 3000 ml flask until it boils. The steam from
the water in the flask will carry the phenylacetone along with it and
deposit them both in the 1000 ml flask. A reasonable flow of about 1 gallon
per minute is enough water flowing through the condenser.
The liquid collecting in the receiving flask has 2 layers, a lower
layer of water, and floating on top of that a yellowish layer of
phenylacetone. He continues boiling the 3000 ml flask until no more
phenylacetone is coming over with the steam. The 1000 ml flask will be
nearly full of water and phenylacetone when the process is finished. Now he
pours both layers into a 1000 ml sep funnel. He drains off the lower layer
of water into a beaker. He pours the top layer of phenylacetone into a 500
ml flask. Now he takes the water layer and returns it to the sep funnel. He
adds 200 ml of benzene and shakes it up. He lets it sit for a while, then
drains off the lower layer of water and throws it out. He pours the benzene
layer into the 500 ml flask along with the phenylacetone.
He can now either distill the phenylacetone as described in Chapter 3,
or reduce more of the nitroalkene. If he chooses to distill each run
separately, he will get about 130 ml of phenylacetone from each run.
The steam distillation can be omitted if a lower grade of phenylacetone
is acceptable. To do this, the chemist simply filters the reaction mixture,
after it has been treated with sodium hydroxide, through a one inch thick
plug of angel's hair. Then he extracts out the phenylacetone by adding a
couple hundred mls of toluene (available at the hardware store in the paint
section), and separating off the phenylacetone-toluene layer floating on
top with a sep funnel. A more careful fractional distillation of the
resulting mixture gives phenylacetone that is almost as pure as with the
steam distillation.
One of the best articles written on the Knoevenagel reaction in the
English language is in the Journal of Organic Chemistry, Volume 15, pages 8
to 14. Another reference is Organic Reactions, Volume 15.
Method 2
This variation of the Knoevenagel reaction will give somewhat higher
yields of product than the preceding method. The reason for the higher
yield is the use in this method of toluene as solvent, and the placement of
a Dean Stark trap above the flask to remove water from the mixture as it is
formed. Removal of water favors the formation of greater quantities of
nitroalkene.
To do the reaction, a 1000 ml round bottom flask is filled, in this
order, with 200 ml of toluene, 100 ml of benzaldehyde, 90 grams (86 ml) of
nitroethane, and 20 ml of butylamine. It is a good idea to swirl the flask
after adding each ingredient to prevent layers from forming. Next the flask
is placed on a one burner electric buffet range with infinite control, and
the glassware is set up as shown in Figure 15.
The Dean Stark trap is attached to the flask, and a condenser is
attached to the Dean Stark trap. Then the buffet range is turned on at a
heat setting high enough to produce a rapid boiling of the toluene, and
cold water is flowed through the condenser. As the reaction is progressing,
the vapors of toluene carry water along with them, and when they turn back
to liquids in the condenser, the water will settle in the trap portion of
the Dean Stark trap because water is heavier than toluene. You will also
note a milky appearance to the toluene due to suspended water in it. The
trap portion of the Dean Stark trap is graduated in milliliters. This
allows you to keep track of how much water has been collected. Half of the
water is collected in the first hour, and the full amount (18 ml) is
collected after five hours of boiling. When this is done, the heat is
removed, and the flask allowed to cool. This phase of the reaction has just
made the nitroalkene.
One should wish to collect the nitroalkene for direct reduction to
amphetamine, one just needs to remove the Dean Stark trap, rig the flask
for simple distillation as shown in Figure 3, and remove the toluene under
a vacuum from an aspirator, using gentle heating from a hot water bath. it

 

should be noted that the nitroalkene has a slight tear gassing effect upon
the eyes, and also irritates the skin. Do not use the stuff as a body balm.
If phenylacetone is desired from the nitroalkene, the toluene solution
produced in the reaction is used directly in the next step. Once it has
cooled down, it is poured into a 2000 ml 3 necked flask. Then into the 3
necked flask is added 500 ml of water, 200 grams of iron powder (40 to 100
meth), and 4 grams of ferric chloride (FeCl3). Then into the center neck of
the flask is put a mechanical stirrer reaching almost to the bottom of the
flask. There should be a tight seal so that the ensuing vapors of toluene
when the flask is heated do not escape by this route. A good condenser is
attached to one of the other necks, and a sep funnel, or dropping funnel
with matching ground glass joint is put into the remaining neck. With
vigorous stirring, the contents of the flask are heated to about 75øC, and
360ml of concentrated hydrochloric acid is added to the flask by means of
dripping it into the mix through the sep funnel over a 2 hour period. The
reaction mixture will boil vigorously. The heating and stirring are
continued for an additional half hour after the last of the hydrochloric
acid has been added.
Next it is time to get the phenylacetone out of the reaction mixture.
Once the flask has cooled down, the iron is filtered out by pouring it
through the plug of angel hair described earlier in this chapter. It is a
good idea to rinse down the trapped iron powder with a dash of toluene to
get any clinging phenylacetone off of it. Then the toluene layer is
separated using a sep funnel. It is poured into a round bottom flask. The
water layer has about 100 ml of toluene added to it, and this is shaken to
draw suspended phenylacetone into the toluene. The toluene layer is then
separated and added to the aforementioned round bottom flask. It is then
rigged for fractional distillation as shown in Figure 5. The toluene
distills off first as the toluene-water azeotrope at 85øC, and then as pure
toluene at 110øC. Once the toluene is mostly gone, vacuum is applied, and
phenylacetone is collected at the usual temperature range. The yield is
about 120 ml of phenylacetone.
--------------------------------------------------------------------------
A New Breakthrough: Phenylacetone From Allylbenzene
--------------------------------------------------------------------------
In 1987, an exciting breakthrough in the field of methamphetamine
manufacture occurred. This new development was so important because it
promised to completely turn the tables on the DEA-led chemical blockaders
and controllers. The new discovery was a patent issued in that year
covering a simple and quick method for converting allylbenzene into
phenylacetone. This method is exquisitely suited for clandestine
operations, and is easily scaled up to industrial proportions.
The extreme importance of this discovery can be appreciated by a quick
review of the chemical supply situation. Phenylacetic acid is now next to
impossible to obtain, with the exception of purchasing it from narco swine
front operations. It is reliably made fiom benzyl chloride by the
directions given in Organic Syntheses, but this is a hasslesome and very
stinky operation. A large scale phenylacetic acid production operation will
not go unnoticed by meddlesome neighbors. Furthermore, the cooks will carry
the evidence on their bodies and clothing for weeks after they have done
their dirty deeds. Turned up noses will follow them wherever they go!
An alternative and very popular route to methamphetamine featuring the
conversion of ephedrine into methamphetamine via chlorephedrine has been
similarly, but less successfully, crimped upon. Here the chemical pinch
points have been phosphorus and palladium black on charcoal. This method of
making methamphetamine was left out of the original edition because of the
noxious nature of the impurities caused by this reaction. They can be
easily carried into the final product if proper care is not taken in
purification. Much of the garbage crank now seen on the streets is made by
this method and contains unreacted chlorephedrine along with related filth.
This chlorinated filth causes a vague "poisoned" feeling as a result of
taking it. Dull aches in the liver and kidney areas can be felt. This slop
also ruins the more subtle and finer qualities of methamphetamine. This
edition will describe how ephedrine is converted into methamphetamine, with
special emphasis given to the key steps in removing the noxious byproducts
from the final product.
The new method of producing phenylacetone from allylbenzene completely
bypasses the roadblock put up by the narco swine. Allylbenzene is in itself
rather overpriced and possibly the subject of central scrutinizer
suspicion. However, for the resourceful manufacturer it is easily made
either in quantitative (100%) yields and pristine purity by the reaction of
arylcopper and allyl bromide, or at bargain basement prices in carload
amounts by the direct Freidel-Crafts reaction between benzene and allyl
bromide. Add to this the possibility of producing amphetamine directly from
allylbenzene by the Ritter reaction, and the position of the chemical
controllers becomes hopelessly complicated. The sure result is the prospect
of floodgates opened wide to massive amphetamine production.
This new reaction can be done in any one of several closely related
ways, each with excellent results. In each of its variations, the overall
path of the reaction is to turn allylbenzene into phenylacetone:
The reaction appears to work in the following manner: Allylbenzene
reacts with two molecules of methyl or ethyl nitrite in alcohol solvent to
produce an intermediate product:
This intermediate product then reacts with water to give phenylacetone.
A key feature of this reaction is its use of palladium chloride as a
catalyst. Because of the high cost of palladium salts, the inventors of the
patent went to great lengths to find ways to make less of it go further.
They discovered that by adding some copper chloride or trimethylamine into
the reaction mixture, the amount of palladium used could be greatly cut.
The drawback to this is that the yield of phenylacetone goes down a little
bit. Both variations will be described here.
A potentially serious problem looms in the path of those who would like
to give this reaction a try. The problem is that alkyl nitrites such as
methyl or ethyl nitrite are not easily purchased. The reason for this is
their use in products which were formerly on sale under such names as
"Rush," "Locker Room," or "Jock Aroma." Inhaling this class of substances
produces an intense head rush, and disorientation. In many states, these
substances are now classified as controlled substances. In all cases, this
properly necessitates great care on the part of the chemist in handling
this material, lest he be overcome. These nitrites are easily made in large
alcohol and the nitrite exists. For example, if butyl nitrite is used with
ethyl alcohol, one could end up with a mixture containing some butyl
alcohol and ethyl nitrite.
The reason for the use of methyl or ethyl nitrite in this reaction is
two-fold. First of all, the matching alcohols are very easily picked up at
the hardware or liquor stores. The second reason is that the methyl and
ethyl nitrites give a little higher yields at lower temperatures. For
example, methyl nitrite gives 90% yield of phenylacetone at a reaction
temperature of room temperature. Butyl nitrite, on the other hand, gives a
87% yield at a temperature of 55øC. The possibility of running a batch at
room temperature makes bathtub size production easy to envision.
The drawback to use of methyl or ethyl nitrites comes from their low
boiling points. Methyl nitrite is a gas with a boiling point of -12øC.
Ethyl nitrite boils at 16.5øC, which is below usual room temperature. Even
cooled well below that point, one could count on it giving off a powerful
aroma. The solution to this problem is to dissolve the nitrite into several
volumes of its corresponding anhydrous alcohol, and then store the solution
in a tightly stoppered bottle in a freezer. This stock alcohol solution is
then added to the reaction mixture when its time comes. This still leaves
the difficult problem of "catching" these nitrites with a condenser when
one makes them in the first place. For these reasons, the most practical
nitrite to use in this reaction may well be butyl nitrite. Its boiling
point of 78øC makes handling it an easy matter. The lucky experimenter may
also be able to purchase it directly off the shelf in the form of "Rush"
type inhalers. If the underground chemists forego a simple recycling
procedure at the end of the rreaction, then the butyl nitrite can be used
with the easily available methyl or ethyl alcohols. All things considered,
this may be the best choice for the clandestine operation. Besides, butyl alcohol smells awful, and is expensive.
The setup needed to run this reaction is simplicity itself. The primary
requirement is a glass container to hold the reactants. For the size of
batch we will be discussing, a 5000 ml round bottom flask or a one gallon
wine jug perform admirably. For scaled up production, a 5 gallon office
water cooler carboy fits the bill nicely.
The second requirement is a stirring device. For the size of batch
amounts, however, so any serious manufacture operation can quickly
stockpile enough in the freezer to supply a massive output. Later in the
chapter, I will describe how nitrites are made.
The alcohols which are best used in this reaction are either methyl
alcohol or ethyl alcohol. Methyl alcohol, also known as wood alcohol or
methanol, is easily and cheaply purchased in the paint section of the
hardware store. Ethyl alcohol, or ethanol, is best purchased as 190 proof
vodka. As such it contains 5% water, but since water is needed for the
hydrolysis stage of the reaction, this presents no problem. In all cases,
it is best to use the alcohol which has the same number of carbon atoms in
it as the nitrite uses. For example, methyl alcohol is used with methyl
nitrite, and ethyl alcohol with ethyl nitrite.
If the number of carbons match between the nitrite and the alcohol,
this makes recycling the alcohol and unreacted nitrite at the end of the
reaction a much simpler matter. The patent does not specify why this is the
case, but I am led to suspect that the possibility of exchange between the

 

discussed here, a magnetic stirrer is perfect. For the larger production
levels, at mechanical stirring rig is advisable. The need for good stirring
is brought about by the fact that the palladium catalysts are not readily
soluble in alcohol. They do dissolve well in water, but since water is a
small fraction of the total solution, the underground chemist can't count
on it all dissolving as the reaction is run. Good agitation brings any
undissolved palladium up into contact with the solution. It does little
good sitting on the bottom of the flask.
To turn out a two mole batch (i.e., a little over 200 ml of
phenylacetone product) by the first, palladium-wasteful method, the
following method is used:
Into the glass reaction vessel is placed three liters of either methyl
or ethyl alcohol. To this is added 236 grams (262 ml) of allylbenzene. If
methyl alcohol is used, 750 ml of water is then added. If 190 proof spirit
is used, then only 630 ml of water is added because it already contains 5%
water. Then 28 grams of palladium chloride is added. The adventuresome
experimenter may dissolve the palladium chloride into the water added to
the reaction instead of putting them in separately. This converts the PdCl2
into the hydrate, which is much more soluble in the water portion of the
solution.
Next, the temperature of the mixture is brought up to the correct
level. For butyl nitrite, the temperature of 55øC is reached by using hot
water, steam, or heating tape. If a wine jug is the reaction vessel, care
is used in rapid and uneven heating, as this could crack the glass. This is
the reason why chemical glassware is made of Pyrex.
When the correct temperature is reached, 5 moles of nitrite is added
with the stirring going full blast. For butyl nitrite, this amounts to 515
grams, or 570 ml.
Almost immediately, the mixture begins bubbling. This buWling is NO gas
being given off as a byproduct of the reaction. It combines quickly with
air to form NO2, the reddish poisonous gas so familiar to those who have
botched batches of explosives. Tubing, or similar gas venting devices, are
attached to the flask to carry this gas outside, or down the drain with the
vacuum of an aspirator.
After the bubbling subsides in a couple of hours, the reaction is
finished. Underground chemists now turn their efforts to getting the
palladium back for reuse, and isolating the phenylacetone product. The
first step in this phase is to filter the solution to get back the
undissolved palladium chloride for reuse in the next batches.
The alcohol-water-nitrite components of the reaction mixture are then
distilled off under a vacuum. The best way to do this is with a
fractionating set-up similar to the one shown in Figure 5 in Chapter 3.
With the large amount of solution to be processed, it is wise to use a 3000
or 2000 ml round bottom flask on the distilling side. When about half the
original load of mixture has been distilled off, the vacuum is
disconnected, and the distilling flask refilled with more of the reaction
mixture. Then the vacuum is reapplied and the distillation continued. This
process is repeated until all the original reaction mixture fits into the
distilling flask. Distillation is continued until the volume of the
solution is reduced to between 300 and 400 ml.
Next the solution is filtered again to get the rest of the palladium
chloride back. The palladium is rinsed with a little alcohol, and the
rinsing added to the rest of the filtered crude product. The crude product
is poured into a 500 ml round bottom flask, and distilled under vacuum as
described in Chapta 3. The yield is nearly 250 ml of phenylacetone.
To use the palladium-conserving method of production, the method
described above is used. The only difference is that the PdC12 is replaced
by a mixture of 1.8 grams of PdCl2, and 5 grams of CuCl. Yield in this case
is more like 80%, or a little over 200 ml of phenylacetone.
Preparation of Nitrites
Butyl Nitrite
Since butyl nitrite is the nitrous acid ester of n-butanol, it is not
surprising that it is easily made by bringing nitrous acid into contact
with n-butanol in the presence of sulfuric acid catalyst. Nitrous acid is
not used directly because it is unstable. Instead it is generated in the
reaction flask by allowing excess sulfuric acid to react with sodium
nitrite in the mixture. The main precaution taken while running this
reaction is to ensure that the temperature of the mixture does not rise
above the prescribed limits.
To make butyl nitrite, a 1000 ml 3 necked flask is equipped with a
mechanical stirrer, a sep funnel with a stem that leads as close to the
danger zone caused by the whirling stirrer blades as possible, and a
thermometer. (See Figure 16.) The thermometer is also placed close to the
stirring blade danger zone so that it measures the temperature of the
solution in the critical initial mixing area. The stirring blades are made
of Teflon so that they can stand up to the sulfuric acid used here. The
metal rod to which it attaches is similarly coated with Teflon. An electric
drill rigged up above the flask is OK for spinning the stirring blades.
Magnetic stirring is not strong enough here because of the heavy
precipitate of sodium sulfate crystals which forms as the result of this
reaction.
The thermometer is secured into place by boring a suitable sized hole
into a cork for the thermometer, and stuffing the cork into one of the
necks of the flask. This prevents the reactants from splashing out while
being stirred.
To do the reaction, the chemist nestles the reaction flask into a
mixture of ice and salt. About two parts ice to one part salt gives good
results. The ice is crushed so that the individual cubes are no larger than
a grape. The ice-salt mixture produces a cooling effect well below the 0ø C
usually obtained from ice. Then the chemist puts 95 grams of sodium nitrite
in the flask along with 375 ml of water. He stirs the mixture while
following the temperature on the thermometer. Meanwhile in another beaker,
he mixes up 25 ml of water, 34 ml of concentrated sulfuric acid, and 114 ml
of n-butanol (butan-1-ol). He puts this mixture into the freezer, and cools
it to 0øC.
When the temperature reading on the nitrite solution in the reaction
vessel falls to 0øC or a little lower, the butanol-sulfuric acid mixture is
introduced a little bit at a time through the sep funnel while the chemist
maintains good mixing. It is added slowly enough that the temperature
reading in the reaction vessel does not stray from the range of -1øC to
+1øC. The beaker is stored in the freezer in between fill-ups of the sep
funnel, so that this solution does not get warm. The entire addition takes
about 45 minutes.
After the addition has finished, the chemist continues stirring for a
few minutes, then lets the mixture stand for an hour and a half. Next, he
filters the solution using the Buchner funnel-vacuum flask set up shown in
Figure 11 in Chapter 5. This filters out the sodium sulfate crystals formed
in the reaction. He pours the filtrate into a 500 ml sep funnel, and waits
for the upper yellow layer of crude butyl nitrite to fully form. This takes
a few minutes.
The lower acid water layer is then drained out of the sep funnel,
leaving only the butyl nitrite layer in the funnel. The chemist mixes up a
solution of I gram Arm & Hammer bicarb, and 12.5 grams of table salt in 50
ml water. He pours this solution into the sep funnel, and swirls well to
get the two layers into contact. A fair amount of fizzing ensues as the
bicarb destroys excess acid in the crude product. Then he stoppers the sep
funnel with a cork, and shakes it vigorously.
Periodically, he allows built up gas to escape. After shaking for a
couple of minutes, he allows the sep funnel to sit. The layers form again.
He drains off the wata layer, and pours the nitrite into a 250 ml beaker.
He adds about 5 grams of anhydrous magnesium sulfate crystals to the beaker
and stirs. This soaks up whatever water is dissolved in the nitrite.
Anhydrous magnesium sulfate is made by baking epsom salts in a thin laya in
a glass baking pan in an electric oven at 4 W F for a couple hours before
use. It is used immediately, or allowed to cool down in a dessicator to
prevent it from soaking up water from the air.
The crude butyl nitrite can be used immediately as is. If there is
going to be a delay before usage, it is decanted off the magnesium sulfate
and distilled. Using a fractionating column, almost all of the product
distills at about 77øC. The yield is about 110 grams (85% yield) of butyl
nitrite. This product can be stored in a freeza for a couple of weeks
before it goes bad. The colder the temperature, the better. Decomposition
products include water, NO2, NO, butanol, and polymerization products of
butyl aldehyde. This cheap and easy process is readily scaled up to fit any
raw material demand the underground chemist may have.
This substance is made in the same way as butyl nitrite, with a few
variations. The nitrite-water solution in the flask has 76 grams sodium
nitrite in 240 ml water. The alcohol-sulfuric acid solution is made by
diluting 60 ml of absolute alcohol (65 ml of 190 proof vodka) with an equal
volume of water. Then the chemist carefully adds 28 ml of concentrated
sulfuric acid to it. He swirls while adding. Then he dilutes this solution
to 240 ml total volume by adding water. He cools both solutions to about
10øC, and adds the alcohol-acid solution to the nitrite solution slowly
with constant stirring over a period of about half an hour.
He pours the reaction mixture into a chilled sep funnel, drains off the
lower water-acid layer, and then quickly adds an ice cold mixture of I gram
bicarb in 50 ml water to the nitrite layer. He quickly swirls and shakes,
and drains off the water layer before the fumes become too intense. He
dries the crude ethyl nitrite over about 5 grams of sodium sulfate, then

 

decants it into at least an equal volume of ethyl alcohol. The alcohol is
absolute alcohol, and deep freezing is required for storage. It is used as
soon as possible. Longer storage is possible if the crude material is
distilled (b.p. 17øC). The difficulties attendant to this operation make
this inadvisable for the underground lab, however.
There is a way around the hasslesome purification procedure that will
allow the underground chemist to use the ethyl nitrite he has made quickly
and easily. The way to do this is to bubble the vapors of the ethyl nitrite
into the reaction mixture. This method avoids the unpleasant and possibly
dangerous procedure with the sep funnel and subsequent distillation. See
Figure 8 back in Chapter 4 on N-methyl formamide. If in that figure, the
methylamine containing flask instead contained the ethyl nitrite reaction
mixture, and the formic acid containing flask instead had the allylbenzene
and palladium chloride in alcohol needed for phenylacetone production, then
one could easily picture how to get the ethyl nitrite vapors to directly
bubble into the phenylacetone production mix without any need to manipulate
the nitrite directly.
To use this variation, the ethyl nitrite is first prepared as described
above. The cold temperature is important to get best yields of the nitrite.
Then the nitrite reaction mixture is poured into a suitable size round
bottom flask, the glassware is set up as shown in Figure 8, and heat is
applied to the nitrite mixture to bubble its vapors into the phenylacetone
production reaction flask. Cold water should not be run through the
condenser, as this may hold back the nitrite. Instead, the water should be
room temperature. The nitrite solution will have to be heated to almost
boiling to get the last of the nitrite to boil out of it. A yield of about
60 grams of ethyl nitrite can be expected from the directions given above.
One could also use methyl nitrite in this variation by substituting
methyl alcohol for ethyl alcohol. This would have the advantage of being
easier to bubble out of the nitrite reaction mixture because the boiling
point of methyl nitrite is -12Q C. This advantage is outweighed by the
poisonous nature of methyl alcohol, and also by the difficulty one would
have trying to keep it in solution while it is being made. It would be hard
to estimate just how much of the methyl nitrite is actually getting into
and staying in the phenylacetone reaction mixture.
Allylbenzene
Allylbenzene is best prepared by one of two routes. The method which
gives nearly quantitative (100%) yields uses phenyllithium. This expensive
and very reactive substance is made by reaction of bromobenzene with
lithium metal in ether solution in a manner similar to producing a Grignard
reagent. The underground chemist needs to be familiar with the use and
production of lithium reagents before attempting this method. The great
reactivity of lithium reagents presents many pitfalls.
This method proceeds as follows: A suspension of 100 grams of cuprous
bromide (CuBr) in anhydrous ether is treated with 670 ml of 1 molar
phenyllithium. The CuBr becomes yellow and dissolves to give a brownish-red
solution which then turns green. Phenylcopper precipitates as a white
powder in 90% yield. The phenylcopper is then separated and reacted with a
molar equivalent of allylbromide to give allylbenzene in 99% yield after
water quenching and usual Grignard workup.
A cheaper and more direct method uses bromobenzene Grignard reagent.
Some precautions are important here. Firstly, bromobenzene is about the
most difficult Grignard reagent to get started reacting. It is very
sensitive to the presence of traces of water. Great care is taken in drying
the glassware and the magnesium turnings. Nitrogen atmosphere is a must.
With these precautions, a beautiful red bromobenzene Grignard reagent is
prepared.
Another important point is that bromobenzene finds use in making PCP.
For this reason, it is on the watched list. Good directions for making
bromobenzene are contained in Vogel 's Textbook of Practical Organic
Chemistry. This fine book is must reading for everyone interested in
underground chemistry.
This bromobenzene Grignard reagent is then reacted with a solution of
allyl bromide to give 82% yield of allylbenzene after quenching and workup.
Complete details can be found in Helv. Chim. Acta, Vol. 17, page 352
(1934). The author is Hershberg.
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The Way Of The Bomb
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"Blessed be the bomb... and all its work."
ð the mutants of Beneath the Planet of the Apes
When underground chemists move up to industrial-scale manufacture of
methamphetamine, it soon becomes obvious that the Leuckardt-Wallach
reaction is not suitable for making large amounts. There are two reasons
for this. N-methylformamide distills slowly, because of its high latent
heat of vaporization. This makes the pro auction of large amounts of
N-methylformamide a very time-consuming process. Secondly, the
Leuckardt-Wallach reaction can take up to 48 hours to complete.
To increase production, a faster method of turning phenylacetone into
methamphetamine is necessary. Reacting phenylacetone with methylamine and
hydrogen in an apparatus called a "bomb" is such a method. A bomb is a
chemical pressure cooker where hydrogen gas is piped under pressure to
react with the phenylacetone and methylamine. It is caed a bomb because
sometimes reactions like this are done under thousands of pounds of
pressure, and occasionally the bomb will blow up. This reaction is done
under a pressure of only 3 atmospheres, 30 pounds per square inch greater
than normal air pressure. so there's no danger of the hydrogenation bomb
going off.
This reaction is called reductive amination. It is not especially
difficult to do, but it is necessary to have the hardware in proper working
condition and to keep out materials that would poison the catalyst.
Reductive amination is a quick, very clean and high-yield process.
Phenylacetone reacts with methylamine to produce a Schiff's base and a
molecule of water. This Schiff's base then reacts with hydrogen and Raney
nickel catalyst and gets reduced to methamphetamine. To encourage the
formation of this Schiff's base, the amount of water in the reaction
mixture is held to less than 10%; 5% is even better. If the underground
chemist is able to get methylamine gas in a cylinder, it is easy to control
the amount of water in the reaction mixture, but 40% methylamine in water
can be made to work with a little effort.
Two main side reactions interfere with the production of
methamphetamine in the hydrogenation bomb. They are both controlled by
properly adjusting the conditions inside the bomb. The first side reaction
is the reduction of the phenylacetone.
The phenylacetone can react with hydrogen and Raney nickel instead of
with methylamine. This side reaction is held to a minimum by not letting
the hydrogen gas pressure get much above 30 psi. It is also controlled by
encouraging the phenylacetone to react with methylamine instead. This is
done by keeping the amount of water in the reaction mixture small, having
enough methylamine around for it to react with, and running the reaction at
the right temperature.
The other side reaction that can be a problem is phenylacetone reacting
with methamphetamine to produce a tertiary amine.
This reaction is held to a minimum by having enough methylamine in the
reaction mixture to tie up the phenylacetone, and by keeping the solution
fairly diluted, so that they are less likely to bump into one another.
If the chemist uses ready-made Raney nickel, which is sold as a
suspension in absolute alcohol, then, if any problems arise, he knows that
the catalyst is not at fault. But those who are old pros at this reaction
can save money by making their own Raney nickel catalyst.
A special alloy of approximately equal parts of aluminum and nickel is
available for making Raney nickel catalyst. Here's how it's done. In a 2000
ml beaker, the chemist dissolves 190 grams of sodium hydroxide pellets in
750 ml distilled water. The solution is cooled down to 10ø C by packing the
beaker in ice. He adds 150 grams of the nickel aluminum alloy to the sodium
hydroxide solution. It is added slowly and with vigorous stirring. The
temperature of the solution must not get above 25øC. The sodium hydroxide
reacts with the aluminum in the alloy and dissolves it, producing aluminum
hydroxide and hydrogen gas. The nickel is left as tiny black crystals. The
hydrogen which bubbles out of the solution causes foaming, so the alloy is
added slowly enough that the foaming doesn't get out of control. If that
fails, 1 ml of n-octyl alcohol helps to break up the foam. It takes about 2
hours to add all the alloy to the sodium hydroxide. When all of the alloy
has been added, the stirring is stopped and the beaker is removed from the
ice bath. The bubbling of hydrogen gas from the solution continues as the
beaker warms up to room temperature. Hydrogen gas is not poisonous, but it
is very flammable. Smoking around it can cause an explosion.
When the bubbling of hydrogen from the solution slows down, the beaker
is set in a large pan of hot water. Then the water in the pan is slowly
heated to boiling. This will get the hydrogen bubbling again, so it is
heated on an electric heater in a well-ventilated area. This heating is
continued for 12 hours. Distilled water is added to the beaker to maintain
its original volume.
After the 12 hours are up, the chemist removes the beaker from the
boiling water bath and stirs it up. Then he allows the black Raney nickel
catalyst to settle to the bottom of the beaker. He pours off as much of the
sodium hydroxide solution as possible. The nickel is transferred to a 1000