Great reading
I found this at one of my favorite places on line and thougt I would share I have the whole shabang but didn't think 200+ pages would be good to copy and paste as I could n't figure out how to upload or link on this site.
Brewing Your Own Ephedrine
I love to guzzle beer. Not that mass-produced
swill, but real beer turned out in small batches by
microbrewers and homebrewers. Beer that has
some body, flavor, and a real kick! Homebrewing
is just a joy, as lots of people have found out.
Stores selling supplies to the homebrewer have
sprung up in every backwater town. They are just
all over the place, and newspapers catering to the
homebrewer or fans of microbrews can be picked
up for free at the local liquor store. The ads in
these newspapers are predominately for mailorder
brewing supplies at discount prices.
What a fortunate coincidence that the industrial
process for making ephedrine is just a fermentation
process using brewer's yeast. This process is
much cheaper than extracting ephedrine from Ma
Huang, and yields 1-ephedrine as the product.
Other chemical processes give product mixtures
that consist of d and 1 ephedrine and pseudoephedrine.
If one wishes to scale up production
beyond that which can be sustained by scrounging
pills and extracting them, this fermentation is
a very viable alternative.
This process uses benzaldehyde as the starting
material, so essentially one could consider this
method as an alternative to the Knoevenagel reaction
back in Chapter Nine. The fermentation action
of the brewer's yeast takes the place of that
List I chemical nitroethane.
Benzaldehyde is easily available, in spite of the
fact that it too is a List I chemical. Oil of bitter
almonds can be used as is, once the HCN it contains
is removed by applying a vacuum to the oil.
On a larger scale, the electric oxidation of the
toluene procedure given in Chapter 9 would give
all the benzaldehyde that could ever be desired.
The fermentation action of brewer's or baker's
yeast converts benzaldehyde to 1-1-phenylpropanol-
l-one-2 in a yield corresponding to about
70% by weight of the benzaldehyde added to the
fermentation mixture. This phenylacetone derivative
is then reductively alkylated with methylamine
by any one of several procedures to give 1-
ephedrine.
One would think that the reductive alkylation
of that phenylacetone derivative would yield d,lephedrine,
and then that reduction of that d,lephedrine
would then give d,l-meth, that same racemic
meth that results from reductive alkylation
of phenylacetone. (Your Uncle prefers the buzz
produced by the racemate over the harsher, more
nerve jangling buzz produced by d-meth.) Apparently,
this isn't the case. The references for this
process claim that solely 1-ephedrine is produced,
and then reduction of this 1-ephedrine, which is
Secrets of Methamphetamine Manufacture
Seventh Edition
174
identical to natural ephedrine, yields that potent
but harsh d-meth.
To start with this project, one would first want
to read a home beer brewing book, such as Better
Beer and How to Brew It, since the processes are
so similar and much of the same equipment and
materials will be used. I have this book, and it is
good. This is all you need to sound like a real
brewer when you head down to the Brew Shop in
your town to pick up supplies.
As with regular beer brewing, one starts with a
brew vat, five-gallon plastic pails work just fine
for this purpose. They should be cleaned, then
rinsed with bleach diluted with several volumes
of water to disinfect the surfaces, then rinsed
some more with clean water to remove the bleach
residue.
Next fill the pails with tap water until they are
half to 2/3 full. We are now ready to brew. See
Drug Trade News, Volume 16, Number 16, page
27 (1941), (I love that reference) and Waller stein
Labs. Commun., Volume 4, Number 13, page 213
(1941). Also see Chemical Abstracts, Volume 17,
page 1484, and Biochemische Zeitschrift, Volume
115, page 282 (1921), and Volume 128, page 610
(1922). These articles will give you some historical
perspective on the process. Then go to Biotechnology
and Bioengineering, Volume 34,
pages 933-41 (1989) and World Journal of Microbiology
and Biotechnology, Volume 16, pages
499-506 (2000) for more contemporary techniques.
Into the pail the brew mixture is made up by
adding molasses to clean warm water. Add
roughly 31 grams of molasses for each quart of
water in the pail, and fill the pail no more than 3/4
full of water because there will be frothing and
foaming when the yeast starts to grow. Then live
baker's yeast is added. The best yeast to use are
the cakes of refrigerated yeast found in the grocery
store rather than the freeze dried packets, although
both would work. It takes a lot of yeast to
do the chemical transformation, so stir in the
package of yeast, and let the yeast grow at about
80° F, like one would when making bread.
When the brew mixture in the pail has been
fermenting for about eight hours at warm room
temperature, it's time to add the benzaldehyde.
Start with about 4 ml of benzaldehyde for each
quart of water in the pail. Once the benzaldehyde
has been added, bubble some air through the culture
using an aquarium pump. Then add about 1/2
ml of acetone per quart of water. Acetone is
found in the hardware store's paint section, and a
bit of it in the mixture increases the yield of
product. Also add about % gram of Epsom salts
for each quart of water. The magnesium in Epsom
salts aids the conversion of the benzaldehyde. Allow
the yeast to work for about four hours, then
add an additional 4 ml of benzaldehyde for each
quart of water in the pail. Adding all the benzaldehyde
at once would tend to poison the growing
yeast and ruin the yield. Then continue the aeration
with the aquarium pump for at least another
eight hours as the yeast completes the conversion
of the benzaldehyde.
During the course of the fermentation, an enzyme
called carboligase (pyruvate decarboxylase)
produced by the yeast converts the benzaldehyde
to phenylpropanol-l-one-2. It is believed that the
enzyme links acetaldehyde or acetic acid made by
the fermenting yeast with the benzaldehyde to
give the product. In any case, in less than a day,
one gets a yield of product amounting to 70% of
the amount of benzaldehyde used.
When the fermentation is completed after about
12 hours or so, it's time to recover the phenylpropanol-
l-one-2 from the brew mixture. The yeast
in the mixture is a problem. With regular beer
brewing, the yeast just settles to the bottom of the
fermenter when the fermentation is complete. Siphoning
is then done to remove the clear beer
from the settled yeast. If you have days to let the
yeast settle, that may be an option. The industrial
process uses centrifugation of the fermentation
mixture to force the yeast to the bottom. I'm sure
that works well for them, because once the centrifuge
is installed, no materials need be purchased
from then on to settle the yeast. The centrifuge
pays for itself.
Chapter Seventeen
Brewing Your Own Ephedrine
Brewers approach unsettled yeast in two ways.
On a small scale, they will add a material called
"finings" to the brew mixture, and it settles the
yeast. On a larger scale, they will filter the brew.
Yeast is some gummy stuff. It will plug a filter
paper in no time flat, so in addition to the filter
paper, they use filter aid.
Filter aid is stuff like Celite (diatoms), powdered
cellulose, or even a bed of sand to catch
those gummy yeast particles before they get to
the filter paper and plug it up.
Once the yeast has been removed from the
brew mixture, the phenylpropanol-l-one-2 can be
extracted out of the solution. The original references
used ether to do the extraction. I would
suggest substituting hardware store toluene. Several
extractions with a few hundred ml portions of
toluene should be enough to completely remove
the product from a 5 gallon pail fermenter.
Next the combined extracts should be distilled
to remove the toluene. Once the toluene is mostly
all gone, the residue should be fractionally distilled
under a vacuum. The product, also called
phenylacetylcarbinol, distills over the range of
100° C to 150° C under a vacuum of 14 torr. A
really good aspirator using nice cold water will
pull a vacuum this strong. Weaker vacuums will
result in higher boiling ranges. The yield of distilled
product amounts to around 70% of the
amount of benzaldehyde added to the fermentation
mixture.
An alternative to vacuum distillation is to isolate
the phenylpropanol-l-one-2 by means of the
bisulfite addition product. Take a volume of water
roughly equal to the toluene extracts. Dissolve
about 10 to 20% by weight of sodium bisulfite
into the water, then cool it down to around 10° C.
Sodium bisulfite is commonly sold at brewing
supply shops. Now pour the toluene extracts into
a sep funnel or other glass container, and then add
the sodium bisulfite solution. Shake the two of
them together for a few minutes, then let the layers
settle. The product will be in the water layer
on the bottom, so drain it off and save it. The
toluene layer can be thrown away.
175
To recover the product, prepare a 10% by
weight solution of sodium bicarbonate in water.
Arm and Hammer bicarb is the most convenient
source of sodium bicarbonate. With stirring, drip
in the bicarb solution to the bisulfite solution containing
the product until no more bubbles of CO2
are given off. The bisulfite addition product of the
phenylpropanol-l-one-2 has just been broken,
and the product can be extracted with solvent.
Toluene or ether starting fluid are suitable
extracting solvents. With ether, simply extract,
separate the ether layer, and allow the ether to
evaporate away. With toluene, a source of vacuum
to aid the evaporation of the solvent would
be helpful.
Now the phenylpropanol-l-one-2 can be reductively
alkylated to give 1-ephedrine. Any one of
several methods can be used, just as in the case of
reductively alkylating phenylacetone to meth.
Method number one has to be catalytic hydrogenation
using platinum catalyst.
In the example taken from US Patent
1,956,950, the chemists place 300 ml of the distilled
phenylpropanol-l-one-2 in the hydrogenation
bomb along with one gram of platinum catalyst,
and 85 grams of 33% methylamine solution.
They state that it's advantageous to add some
ether to the hydrogenation solution. How much is
some, they don't say. They then hydrogenate the
solution in the usual manner, with up to 3 atmospheres
of hydrogen pressure, and magnetic stirring
of the contents of the hydrogenation bomb.
When absorption of hydrogen stops in two or
three hours, the platinum catalyst is filtered out.
Then the ether hydrogenation mixture is shaken
with a volume or two of 10% HC1 solution to pull
the ephedrine out of the ether and into the acid
water, forming the HC1 salt of ephedrine. The
ether layer is separated off with a sep funnel, then
the dilute acid is boiled away. The residue is diluted
with a little alcohol, and then a lot more
ether. Passing dry HC1 through this mixture then
gives crystals of pure ephedrine hydrochloride.
Their yield was around 110 grams.
My commentary on this hydrogenation? That
yield is awfully low. Using phenylacetone as a
Secrets of Methamphetamine Manufacture
Seventh Edition
176
guide, one should be expecting a yield around
300 grams of ephedrine. What's up? Check out
the amount of methylamine used. There are about
two moles of the phenylacetone derivative, but
they don't even use one mole of methylamine. It
should be the other way around, an excess of methylamine.
Perhaps this is how they only get 1-
ephedrine from the phenylacetone derivative. In
any case, I'd much rather have 300 grams of racephedrine
than 110 grams of 1-ephedrine. My
thoughts are that one would be better served just
going to Chapter Eleven, and just plug in this
phenylacetone derivative for the regular
phenylacetone. That means two or three moles of
methylamine for each mole of phenylacetone, alcohol
as solvent, and a bit more platinum catalyst
in the mixture.
In the patent, they give another reductive alkylation
example. They use amalgamated aluminum
as the reducer, just like in Method Three in Chapter
Twelve. They take 120 grams of the undistilled
fermentation product containing the 1-
phenylpropanol-l-one-2, and drip it over the
course of two hours into a solution of 10 grams of
methylamine in 500 ml of ether in the presence of
20 grams of activated aluminum amalgam. Simultaneously,
they drip into the mixture 20 to 30 ml
of water. Stirring of the mixture is required.
The vigorous reaction that sets in is moderated
by periodic cooling. When the reaction is complete
after a few hours, they filter the mixture to
remove the aluminum. Then they shake the ether
solution with 10% HC1 solution to draw the
ephedrine into the water. The ether layer is separated,
then the dilute acid boiled off. The residue
is thinned with a little alcohol, then dissolved in a
lot more ether. Bubbling with dry HC1 gives 25 to
45 grams of 1-ephedrine hydrochloride crystals.
My commentary on this procedure is identical
to the last one. So little methylamine used! I haven't
tried this, but I would be surprised to say
the least if more methylamine didn't greatly increase
the yield of product. I would also think
that any one of the activated aluminum procedures
given in Chapter Twelve could be used, just
by plugging in this phenylacetone derivative for
the regular phenylacetone. Also the use of ether is
to be avoided when possible. One could also use
one of the reduction methods from Chapter
Twelve, which make use of sodium cyanoborohydride
or sodium borohydride to reduce a mixture
of methylamine plus 1-phenylpropanol-lone-
2 to ephedrine. Of the two choices, sodium
borohydride would be best because it is easily
available and produces good yields of product.
See The Journal of Chemical Technology and
Biotechnology Volume 77, pages 137 to 140
(2002) for a sample recipe using sodium borohydride
to do this reduction. Note that they
zapped the reaction mixture in a microwave oven
to kick start the reduction.
You don't like that recipe? Check out this one
taken from Chemical Abstracts, Volume 47, column
3347. Twenty grams of N-methyl-d,l-alanine
and 50 grams of benzaldehyde are placed in a
flask and heated on an oil bath at 150-160° C until
the mixture stops fizzing off carbon dioxide.
The mixture is then cooled and mixed with a
few hundred ml of toluene. Whatever doesn't dissolve
in the toluene is thrown away. The product,
which is a mixture of ephedrine and pseudoephedrine,
is then extracted out of the toluene
by shaking the toluene with about an equal volume
of 10% HC1. The toluene can be distilled to
recover unused benzaldehyde, if there is any in it.
The dilute hydrochloric acid solution which
contains the products should be boiled down to
concentrate it. The steam will also carry off some
byproducts, so vent this steam outside.
Once the dilute acid has boiled down to a volume
of 50-100 ml, allow it to cool. Then add a little
activated carbon, and stir it around for a while.
Then filter it out. This will decolorize the solution.
Add lye pellets a little bit at a time with stirring
until the water solution is strongly alkaline. Extract
the alkaline water a few times with toluene.
The combined toluene extracts should next be
bubbled with dry HC1 gas to give a crystalline
product amounting to about 12 grams. The prodChapter
Seventeen
Brewing Your Own Ephednne
uct will be about 8 grams of d,l-pseudoephedrine,
and 4 grams of d,l-ephedrine. It will yield racemic
meth upon reduction.
Take note that recovering ephedrine from water
solutions is a bit different than recovering meth.
That's because ephedrine free base dissolves well
in water, while meth doesn't. So for recovery of
the ephedrine we take the dilute acid solution of
the ephedrine and boil it down, just like in the pill
extraction procedure using water. Once it is concentrated,
then it is made alkaline with lye, and
the ephedrine extracted out. hi this way you get
good recovery of the ephedrine. Use too much
water, and it's difficult to extract it all out.
This recipe is pretty easy to scale up to larger
size batches, but it suffers from a really serious
flaw. N-methyl alanine is just about impossible to
find, and if one could find it, the cost charged for
it is astronomical. It's also not so easy to make
from the common amino acid alanine.
The way around these problems is to substitute
alanine for the N-methyl alanine in the example
batch just given. The product obtained then
would be phenylpropanolamine (PPA). Reduction
of that PPA by any of the methods given in this
chapter would then give one Benzedrine if d,lalanine
was used, or Dexedrine if food grade 1-
alanine was used.
The reaction using alanine rather than Nmethyl
alanine works exactly the same. The yield
of product can be increased if one uses a larger
amount of alanine than would be called for if one
copied the sample batch exactly. One could double
the amount of alanine used, keep the other ingredients
the same as in the sample batch and get
a much higher amount of PPA than was obtained
from the sample batch. Alanine is really cheap, so
this is a good strategy. Researchers have found
that taking alanine daily helps shrink swollen
prostate glands. This is a great excuse for anyone
getting the amino acid through health food stores.
People who have tried this reaction using
alanine have found that it is best to grind the
alanine down to a nice fine powder before adding
it to the batch. It doesn't dissolve very well. It is
also advisable to add the alanine slowly without
177
stirring as the batch warms up because it has a
tendency to clump together in the reaction mixture.
Clumped up alanine will not be able to react
to make PPA. All things considered, this reaction
is a good alternative to scrounging for pills that
get more difficult to buy and harder to extract
every day.
Chapter Eighteen
MDA, Ecstasy (XTC), and Other Psychedelic Amphetamines
179
Chapter Eighteen
MDA, Ecstasy (XTC), and
Other Psychedelic Amphetamines
The psychedelic amphetamines are a fascinating
and largely ignored group of drugs. They all
have the basic amphetamine carbon skeleton
structure, but show effects that are more akin to
LSD than to the amphetamines. The LSD-like effect
is due to the presence of a variety of "add
ons" to the benzene ring of the basic amphetamine
structure. Generally, these "add ons" are
ether groupings on the 3, 4, or 5 positions on the
benzene ring. Because of these "add ons" one can
consider these compounds more closely related to
mescaline than to amphetamine. Consider the
mescaline molecule pictured below.
Mescaline should by all rights be considered an
amphetamine derivative. It has the basic
phenethylamine structure of the amphetamines
with methyl ether groupings on the benzene ring
at the 3, 4, 5 positions. To be a true amphetamine,
it would only need its side chain extended by one
carbon, putting the nitrogen atom in the central,
isopropyl position. Such a compound does in fact
exist. It is called trimethoxyamphetamine, or
TMA for short. Its effects are very similar to
mescaline in much lower dosage levels than the 1/2
gram required for pure mescaline. Its chemical
cousin, TMA-2 (2,4,5 trimethoxyamphetamine)
has similar awe-inspiring characteristics. More on
this later.
The most popular and, in my opinion, the best
of the psychedelic amphetamines are the members
of the MDA family. This family consists of
MDA, and its methamphetamine analog, XTC, or
Ecstasy, or MDMA. MDA (3,4 methylenedioxyamphetamine)
gives by far the best high of
this group. Its effects can best be described as being
sort of like LSD without the extreme excited
state caused by that substance. It was popularly
known as "the love drug" because of the calm
state of empathy so characteristic of its effect. It
could also be a powerful aphrodisiac under the
right circumstances.
This substance gradually disappeared during
the early 80s due to an effective crimping upon
the chemicals needed for its easy manufacture.
This crimping, and the drug laws in effect at
the time, gave rise to a bastard offspring of MDA.
This substance was XTC, or MDMA, the socalled
Ecstasy of the drug trade. This material
was a designer variant of MDA, and so was legal.
The chemicals needed to make it could be obtained
without fear of a bust. It also lacked the
best qualities of its parent. While the addition of a
methyl group of the nitrogen of the amphetamine
molecule accentuates its power and fine effect,
the addition of a methyl group to the MDA molecule
merely served to make it legal. As fate
would have it, the hoopla surrounding the subsequent
outlawing of this bastard child served to
make it a more desired substance than MDA. This
is typical of black-market, prohibition-driven demand.
To understand the various routes which can be
followed to make these substances, note the structures
of MDA and MDMA shown below:
Secrets of Methamphetamine Manufacture
Seventh Edition
180
To make these substances, and the rest of the
psychedelic amphetamines for that matter, the
manufacturer has a choice of two starting materials.
He can use the appropriately substituted benzaldehyde,
which in the case of MDA or MDMA
is piperonal (heliotropin), or he can use the correspondingly
substituted allylbenzene, which in this
case is safrole. These substances are pictured below:
Piperonal was the favored starting material for
making MDA, as were the other substituted benzaldehydes
for making other psychedelic amphetamines.
The supply of these raw materials
was effectively shut off. Piperonal does find legitimate
use in making perfumes, but considerable
determination is needed to divert significant
amounts of the stuff into clandestine operations.
Once obtained, these substituted benzaldehydes
could be converted into amphetamines by an interesting
variant of the Knoevenagel reaction as
described in Chapter Nine. They could be reacted
in a mixture of nitroethane and ammonium acetate
to form the appropriately substituted 1-
phenyl-2-nitropropene. This nitropropene could
then be reduced to the amphetamine by using lithium
aluminum hydride. For this recipe, see
PIHKAL under MDA. The nitroalkene obtained
by the reaction of piperonal and nitroethane can
also be reduced by the hydrogenation methods
given in the Knoevenagal reaction section of this
book in a yield of around 50%. Similarly, the
electric reduction method given in that section
can also be used. Now that both piperonal and
nitroethane are List I chemicals, we would have
to concede that the narcoswine have won this
round, and that this pathway can be considered
for all practical purposes to be dead.
This left safrole, and the other substituted allylbenzenes,
as starting materials for psychedelic
amphetamine manufacture. This route had the advantage
of having a raw material source that was
nearly impossible to shut down if you are lucky
enough to have a grove of sassafras trees nearby.
For instance, sassafras oil consists of 80-90% safrole.
One merely has to distill the oil under a
vacuum to get very pure safrole. Similarly, other
psychedelic amphetamines can be made using essential
oils that contain the appropriately substituted
allylbenzene or propenylbenzene as a major
substituent. For instance, calamus oil contains a
large proportion of B-asarone, the starting material
for TMA-2. Nutmeg contains a mixture of
myristicin (potential MMDA) and elemicin (potential
TMA). These oils, with the exception of
sassafras oil, are all available from herbal supply
shops and dealers in the occult. Even without this
source, the oils can be easily obtained from the
plants.
Calamus oil is some interesting stuff! Its composition
depends upon the country the oil comes
from. Luckily, most of the oil on the market
comes from India. The vast majority of oil from
that country contains about 80% B-asarone, although
there are reports (see Journal of Indian
Chemical Society, Volume 16, page 583, 1939)
that some oils from that country contain around
80% allylasarone.
Chapter Eighteen
MDA, Ecstasy (XTC), and Other Psychedelic Amphetamines
Other major sources of commercial calamus oil
are Japan and Europe. These oils contain lesser
and variable amounts of a-asarone. This is the cistrans
isomer of B-asarone. It differs in that aasarone
is a solid at room temperature, and may
precipitate out of oils upon cooling in a freezer. It
reacts in the same manner as B-asarone. Both can
be obtained in a pure form from the oil by fractional
vacuum distillation.
On the topic of purifying essential oils, it has
been proposed by other underground sources that
sassafras oil can be purified by putting it in a
freezer, allowing the safrole to solidify, and then
filtering out the solid safrole. Let me fill you in
on the facts of the matter. Sassafras oil is very
stable in a supercooled state. You can put a bottle
in a freezer for months, and never see a crystal of
solid safrole form. Believe me, I've tried it. To
get crystals to form, a seed crystal of solid frozen
safrole would have to be added to the supercooled
sassafras oil. Where do you get this seed crystal
to start with? And at 80-90% pure safrole, the oil
will then freeze into a virtual solid block, so what
would filter out except the safrole that begins
melting during the filtering process? This whole
line of pursuit is a waste of time. Moreover, the
small amount of impurities are actually beneficial
if the HBr route is chosen for production of MDA
or MDMA from the sassafras oil.
Starting with essential oils, how does one make
the desired amphetamine from them? Let's take
the conversion of sassafras oil to MDA or
MDMA as the example to illustrate the various
processes which can be used. If we go to
PIHKAL, and read the recipe for MDA, you get
the old classical procedure. Safrole obtained from
sassafras oil is first converted to isosafrole (a
propenylbenzene). This is done by putting safrole
into a flask, adding some 10% alcoholic KOH,
181
and then warming the mixture up to 243° C for 3
minutes. This isomerization works just fine so
long as absolute alcohol is used, and the alcohol
is allowed to distill off. You know that you have
gotten isomerization, because the boiling point of
safrole is 233° C.
The isosafrole is then mixed with acetone, formic
acid and hydrogen peroxide to give the glycol
mentioned in Chapter Ten. The reaction mixture
is evaporated away under a vacuum, then the
residue in the flask is heated with sulfuric acid in
alcohol solvent to give the phenylacetone. The
phenylacetone is then used to make the amphetamine
by any of the methods given in this book.
My opinion on this method? It's a lot of work,
the yields are on the low side, and that evaporation
of the reaction mixture under the vacuum
will destroy your aspirator. Peroxyformic acid is
rough on metal. Let's use the more direct approach.
The first problem which confronts the chemist
in the process of turning sassafras oil into MDA
or MDMA is the need to obtain pure safrole from
it. In spite of the fact that crude sassafras oil consists
of 80-90% safrole, depending on its source,
it is a good bet that the impurities will lower the
yield of the desired product. The axiom "garbage
in, garbage out" was custom made for organic
chemistry reactions. It is simplicity itself to turn
crude sassafras oil into pure safrole, and well
worth the effort of underground chemists bent on
MDA production.
Sassafras oil is an orange-colored liquid with a
smell just like licorice. It is a complex mixture of
substances which is easily purified by distilling.
To obtain pure safrole from sassafras oil, the
glassware is set up as shown in Figure 13 in
Chapter Three. The distilling flask is filled about
2/3 full of sassafras oil, along with a few boiling
chips, and then vacuum is applied to the system.
A little bit of boiling results due to water in the
oil, but heat from the buffet range is required to
get things moving. Water along with eugenol and
related substances distill at the lower temperatures.
Then comes the safrole fraction. The safrole
fraction is easily spotted because the "oil
Secrets of Methamphetamine Manufacture
Seventh Edition
182
mixed with water" appearance of the watery forerun
is replaced with a clear, homogenous run of
safrole. When the safrole begins distilling, the
collecting flask is replaced with a clean new one
to receive it. The chemist is mindful that the safrole
product is 80-90% of the total volume of the
sassafras oil. Under a vacuum, it boils at temperatures
similar to phenylacetone and methamphetamine.
When all the safrole has distilled, a
small residue of dark orange-colored liquid remains
in the distilling flask. The distilled safrole
is watery in appearance, and smells like licorice.
With a liberal supply of safrole obtained by distilling
sassafras oil, work can then commence on
converting it into 3,4 methylenedioxyphenylacetone.
This is done in exactly the same manner as
described in Chapter Ten. Any one of the three
Wacker oxidations of the allylbenzene (safrole) to
the phenylacetone (m-d-phenylacetone) can be
used. When the essential oil contains a propenyl
benzene, such as the B-asarone in calamus oil,
then the electric cell discussed in Chapter Ten
and Practical LSD Manufacture should be used to
get the phenylacetone in high yield.
With the methylenedioxyphenylacetone obtained
in this manner, the chemist proceeds to
make it into XTC by one of the methods used to
turn phenylacetone into meth. Of all the methods
to choose from, the most favored one would have
to be reductive alkylation using the bomb and
platinum catalyst. The free base is converted into
crystalline hydrochloride salt in exactly the same
manner as for making meth crystals. It is interesting
to note here that XTC crystals will grow in
the form of little strings in the ether solution as
the HC1 gas is bubbled through it. Once filtered
and dried, it bears a remarkable resemblance to
meth crystals. It generally has a faint odor which
reminds one of licorice.
To make MDA from the methylenedioxyphenylacetone,
one has three good choices.
Choice number one is to use the reductive animation
method with a bomb, with Raney nickel catalyst
and ammonia. See Journal of the American
Chemical Society, Volume 70, pages 2811-12
(1948). Also see Chemical Abstracts from 1954,
column 2097. This gives a yield around 80% if
plenty of Raney nickel is used. The drawback to
this method is the need for a shaker device for the
bomb, and also a heater.
A complete discussion of these two methods
can be found in Chapter Twelve. The only difference
is that the substituted phenylacetone is used
instead of regular phenylacetone, and a substituted
amphetamine is produced as a result. One
should also see Advanced Techniques of Clandestine
Psychedelic & Amphetamine Manufacture
for a Convenient Tabletop MDA recipe using a
Raney nickel cathode to do the hydrogenation,
and also for a convenient method of making ammonia-
saturated alcohol. MDA distills at about
150° C at aspirator vacuum of 20 torr, and
MDMA will distill at around 160° C under the
same vacuum. Poorer vacuum will result in
higher boiling temperatures.
Another method for converting methylenedioxyphenylacetone
to MDA is the Leuckardt reaction.
My experience with mixing formamide with
phenylacetone to get amphetamine is that using
anything other than 99% formamide is a waste of
time. You just get that red tar. Two ways have
been found around that. These variations use the
much more easily available 98% formamide. See
Chemical Abstracts from 1953, column 11246,
and Austrian patent 174,057. In this variation, 40
ml of methylenedioxyphenylacetone is mixed
with 110 ml of freshly vacuum-distilled formamide,
2 ml glacial acetic acid, and 20 ml water.
This mixture is heated up to about 130° C, at
which point bubbling should begin. Then the
temperature is slowly raised to keep the bubbling
going, as described in Chapter Five, until a temperature
of 150° C is reached. This should take at
least 5 hours. The yield is 70%, according to the
patent.
Processing is then done just as in the case of
meth. The formamide is destroyed by boiling
with lye solution. In this case, the ammonia gas
which is produced is led away in plastic tubing.
The formyl amide is then separated, and hydroChapter
Eighteen
MDA, Ecstasy (XTC), and Other Psychedelic Amphetamines
lyzed by refluxing in a mixture of 60 grams of
KOH, 200 ml alcohol, and 50 ml water for an
hour. After the reflux, the mixture is made acid
with HC1, and the alcohol evaporated away under
a vacuum. The residue is then diluted with water,
and the free base obtained by making the solution
strongly alkaline to litmus by adding lye solution.
The free base is then extracted out with some
toluene, and distilled.
Most people don't get close to the 70% yield
claimed in the patent for this method.
Another choice is to use the European Variation
of the Leuckardt reaction, given in Chapter
Five. The last I heard from Geert, the heat was
closing in on him, but he was going to pass along
an XTC recipe that is very popular over there. He
says that they do it in an icebox! I haven't heard
from him since, and that was nearly 4 years ago.
This space is dedicated to him.
The last choice is a very simple, but also very
time-consuming (several days!) reaction. Sodium
cyanoborohydride in methanol with ammonium
acetate and methylenedioxyphenylacetone at pH
6 react to give disappointing yields of MDA. See
PIHKAL by Dr. Shulgin in the section under
MDA, for full cooking instructions.
Reference
Psychedelics Encyclopedia, by Peter Stafford.
The recommended dosage of MDA or XTC is
about a tenth of a gram of pure material. TMA-2
is 40 milligrams.
The other good synthetic route of making
MDA, MDMA and related psychedelic amphetamines
from the substituted allylbenzenes
found in essential oils such as sassafras oil is a
two-step procedure involving first reacting the
substituted allylbenzene (e.g., safrole from sassafras
oil) with HBr to make the corresponding
phenyl-substituted 2-bromopropane. Then this
substance is mixed with an alcohol solution containing
excess ammonia or methylamine to yield
MDA or MDMA from, for example, safrole.
Heating is required to get a good yield of product.
183
Details on this procedure are found in the chapter
covering the production of meth or benzedrine
from benzene and allyl chloride (Chapter Twenty
One). The reason why it is in that chapter is because
the final step of heating the 2-
bromopropane compound with ammonia or methylamine
solution is pretty much identical. Some
further commentary on this route not found in
that chapter is called for.
The addition of HX (HC1, HBr, HI) to a double
bond is a general reaction, meaning most all double
bonds, other than those found in benzene
rings, will add HX. Of these three acids, HBr
adds most easily to double bonds. It is also the
only one that will add abnormally, meaning that
one can get, besides the 2-bromopropane, the 3-
bromopropane also. Exposure to strong light or
oxidizing substances promotes the abnormal addition,
so this reaction shouldn't be done in full
sunlight.
The strength of the HBr used in reaction has a
great effect upon the yield and speed of the reaction
with safrole. The less free water floating
around in the acid, the better it reacts with safrole.
So dry HBr gas will react best with safrole, followed
closely by 70% HBr, while the ACS reagent
48% HBr is practically useless as is.
Another point to be aware of is cleavage of the
methylenedioxy ether by HX. HI is much better at
cleaving this ether than is HBr, which is better
than HC1. It is because of "ether" cleavage that
the temperature during this reaction must not be
allowed to rise above the stated limits in the procedures
given in this book. If your magnetic stirrer
gets warm while working, the batch must be
insulated from this source of heat.
An obvious variation upon this procedure
which would pop into the head of any thinking
chemist reading this tract would center around
adding dry HC1 to safrole by bubbling dry HC1
through a toluene solution of sassafras oil to get
the 2-chloropropane, and reacting this substance
with ammonia or methylamine like the other
phenyl-2-chloropropanes listed in the Journal of
the American Chemical Society article cited in the
meth or benzedrine from benzene and allyl chloSecrets
of Methamphetamine Manufacture
Seventh Edition
184
ride chapter in this book. My observations on this
route will be useful if someone is contemplating
this procedure.
First of all, dry HC1 adds only slowly to safrole
at room temperature. A toluene solution of sassafras
oil literally reeking with HC1, sealed up and
kept at an average temperature of 90° F for three
weeks, resulted in only about 10% conversion of
the safrole to chlorosafrole. No doubt, some further
heat must be applied to the mixture to get
reasonably complete conversion of the safrole to
chlorosafrole. HC1 doesn't cleave ethers very
well, so this can be considered safe.
How does this observation jibe with the Journal
of the American Chemical Society article in
which they postulate that when allyl chloride adds
to benzene or substituted benzene, the 2-chlorophenylpropanes
are the result of HC1 adding to
the double bond of the allylbenzene? Either the
theory was mistaken, or iron chloride is a catalyst
for adding HC1 to the double bond. I haven't yet
checked this out personally, but it's worth a try.
Further, once one has chlorosafrole, what good
is it? See the above-cited Journal of the American
Chemical Society article. You will note that the
yields obtained converting similar phenylsubstituted
ether 2-chloropropanes is pretty low,
down near 10%. That's why bromosafrole is used
to make MDA or MDMA. The bromine atom is
much more easily replaced with ammonia than is
chlorine. It's termed a better leaving group. The
iodine atom is a much better leaving group than is
the bromine atom, so even better results should be
had reacting iodosafrole with ammonia or methylamine.
One would expect that lower temperatures
could be used, maybe even room temperature.
This would avoid all the tar formed as a byproduct
when heating bromosafrole.
Chlorosafrole can be converted to iodosafrole
by refluxing one mole of chlorosafrole with 2
moles of sodium iodide in a saturated solution in
acetone for about 15 minutes to lA hour. After
cooling this reaction mixture, the sodium chloride
that precipitates out of solution is filtered. Then
the acetone is taken off under a vacuum. The resulting
residue of iodosafrole and Nal crystals is
extracted with toluene to remove the product
from the Nal crystals, which can be reused. This
toluene extract is shaken with water containing
some sodium thiosulfate and a little HC1. This destroys
iodine formed by decomposition of the
Nal. Snorting iodine really sucks. Exposure to
light speeds the decomposition of Nal to iodine,
especially in solution. Experimenters using this
procedure are invited to write in with their results.
A final word needs to be said about the Ritter
reaction. Since safrole and related allylbenzenes
from essential oils are all allylbenzenes, one
would assume that the Ritter reaction would be
directly applicable to them. Such is not the case.
See Chemical Abstracts, Volume 22, page 86, for
an article titled "Cleavage of the Methylenedioxy
Group." Here they detail how concentrated sulfuric
acid quickly cleaves the methylenedioxy
group. As a consequence, brave experimenters
wishing to use the Ritter reaction to make MDA
must use the substitutes for sulfuric acid which
are listed in the Journal of the American Chemical
Society article cited in Chapter Fourteen. Substitutes
include methanesulfonic acid and polyphosphoric
acid. Directions for how to make the
latter from phosphoric acid and P2O5 are to be
found in the Merck Index. A final caveat for those
trying to make chlorosafrole is also to be found in
that article. The article states that fuming HC1,
heated to 100° to 130° C in a sealed tube, is a potent
cleaver of the methylenedioxy group. Heating
of safrole with dry HC1 must be held well below
this level.
Know Your Essential Oils
Sassafras Oil contains about 80-90% safrole.
This is purified by fractional vacuum distillation.
Boiling point of safrole is 234° C at
normal pressure, about 120° C with an aspirator,
and 105° at 6 torr. Yields MDA with ammonia,
or MDMA (XTC) with methylamine.
Dosage 1/10 gram.
Chapter Eighteen
MDA, Ecstasy (XTC), and Other Psychedelic Amphetamines
Calamus Oil that of Indian origin contains
80% B-asarone. Oil from other areas contains
much less asarone. Boiling point is 296° C at
normal pressure, and 167° C at 12 torr. Yields
TMA-2. Dosage is 40 mg.
Indian Dill Seed Oil contains up to 53% dill
apiol (3,4-methylene-dioxy-5,6-dimethoxyallyl-
benzene). Boiling point is 296° C with
decomposition at normal pressure. Aspirator
vacuum will distill it at about 170° C. Yields
DMMDA-2, dosage about 50 mg.
Nutmeg Oil contains 0-3% safrole, and 0-13%
myristicin (3,4-methylene-dioxy-5-methoxy
allylbenzene). The boiling point at 15 torr is
150° C. Yield MMDA, dosage 80 mg.
Mace Oil contains 10% myristicin.
Parsley Seed Oil contains 0-80% parsley
apiol (2-methoxy-3,4-methylene-dioxy-5-
methoxy-allylbenzene). Its boiling point is
292° C at normal pressure, and 179° C at 34
torr. It yields DMMDA, dosage about 75 mg.
This oil may also contain 10-77% myristicin.
Oil of Bitter Almonds contains around 95%
benzaldehyde. This is a precursor to
phenylacetone or amphetamine.
Oil of Cinnamon contains 80-90% cinnamaldehyde.
This can be reduced to allylbenzene
with borohydride.
185
mixtures containing List One chemicals. They
simply decide by themselves if the List One
chemical is "easily obtained" from the mixture.
Buying retail is still completely safe, if you are
lucky enough to find sassafras oil on any retail
shelves. Be warned!
References
PIHKAL, by Dr. Shulgin
The Essential Oils, by Ernest Guenther
Psychedelics Encyclopedia, by Peter Stafford
WARNING!! Some wholesale distributors of
essential oils are being leaned upon to give up
their customer lists. The heat wants to know who
is buying sassafras oil, and oil of bitter almonds.
They will soon want to know who is getting cinnamon
oil, after this book hits the streets. Oils fall
under the definition of "mixture" in the chemical
division act, and so did not used to be subject to
regulation. In the latest version of CFR 21, the
DEA has decided that it now has control over
Chapter Nineteen
Ice
187
Chapter Nineteen
Ice
At the time of the writing of the second
edition, the latest drug craze was the
smokable form of methamphetamine called
"ice." At the writing of this seventh edition,
this material was still popular, with most usage
being confined to those with serious
drug problems.
I'm not going to endorse or encourage the
foolhardy practice of smoking meth. Seeing
firsthand what this stuff does to rubber stoppers,
corks, and razor blades, I can only
imagine what it does to lung tissue. My
opinion on this practice is similar to my
opinion on injecting the substance. If snorting
the hydrochloride salt doesn't get you as
wired as you could ever want to get, it is
time to give up and find something else to
fill your spare time with.
I have never made nor used "ice" as such,
but I can tell you how to get smokable forms
of meth. Since the godless importers of this
stuff have already created a market for it,
it's only right that I help American technology
catch up.
The regular hydrochloride salt is not ideally
suited for smoking, as a lot of the product
will get charred during the heating. The
free base is quite smokable, but it is a liquid,
and as such is not easily sold, as it is unfamiliar.
I will cover this matter from two angles:
a home technique that works well to
base your personal stash for smoking, and a
more large-scale procedure for commercial
use.
To base your stash and smoke it, mix your
stash with an equal amount of bicarb, and
then with a dropper, drip a little water onto it
with stirring to make a paste. Now take
some aluminum foil, and with your finger
indent a well into it about an inch deep. Into
this well put some of the paste, and heat it
from underneath with a lighter. Suck up the
smoke with a straw.
For making a crystalline yet volatile derivative
of meth similar to crack rocks, one
first needs meth free base. All of the production
methods in this book yield meth free
base. Then to this free base, add dry ice.
This will convert the free base to the carbonate,
which can be chipped and scraped
out of the beaker when the dry ice has
evaporated. Use of a solvent during this
conversion will be helpful.
Crank rocks similar to crack rocks are
pretty simple to make also
Originally Posted by DiverDan88
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