[ Pobierz całość w formacie PDF ]
nitrite is not held in solution very well on account of its very low
boiling point. If ethyl nitrite was used instead, then only three or four
moles would be needed.
While the reaction is being done, the mixture takes on the
appearance of mud if palladium bromide is being used. A fizzing also
Practical LSD Manufacture
82
occurs, which gives the reaction mixture the appearance of freshly
poured Coke. Note above that a bit of acid is required to get
hydrolysis of the intermediate dialkoxyphenylpropane to the phenyl-
acetone. The best pH for this reaction is between 4-7. If palladium
chloride or the mixed catalyst PdCh-CuCla is being used, the pH of
the reaction mixture can be adjusted to this range by adding a small
amount of HC1. If PdBr2, is used, it is best to wait until the catalyst is
filtered out before adding HC1, as the HC1 could form PdCh and
complicate catalyst recovery. The pH of the reaction mixture is best
measured by first dampening some indicating pH paper with distilled
water, then putting a drop of reaction mixture on the paper. The
preferred temperature for this reaction is about 25° C throughout.
When all the methyl nitrite has been bubbled into the reaction
mixture, stirring should be continued for another hour. Then, if
palladium bromide was used, it should be filtered out. Repeated
filtrations will be needed to remove all of the catalyst, because it gets
quite finely divided during the course of the reaction. This leaves a
clear light-reddish solution. If palladium bromide was used, now
adjust pH to 4-7, and allow another hour to complete the hydrolysis.
If palladium chloride or the mixed catalyst was used, these
substances are soluble in alcohol. In this case, the catalyst will be
recovered later. Here, check the pH of the solution again to be sure it is
in the proper range before proceeding.
Now the alcohol solvent must be removed. This is best done by
pouring the reaction mixture into a large filtering flask, stoppering the
top of the flask, and removing the solvent under a vacuum. Use of a
hot-water bath to speed evaporation is highly recommended for this
process. It is not OK to distill off the alcohol at normal pressure, as
the heat will cause the nitrite and NO in solution to do bad things to the
product.
To the residue left in the flask after removal of the alcohol, add
some toluene to rinse the product out of the flask into a sep funnel.
Next, put 300 ml of water into the flask to dissolve the catalyst if
PdCla or the mixed catalyst was used. Add the water solution to the
sep funnel to dissolve carried-over catalyst there, then drain this water
12 Studies On The Production OfTMA-2
83
solution of catalyst into a dark bottle and store in the dark until the
next batch. If PdBr2 was used, this step can be skipped. Just store the
filtered-out PdBra under water in the dark.
Now the toluene-phenylacetone solution should be distilled
through a Claisen adapter packed with some pieces of broken glass to
effect fractionation. The first of the toluene should be distilled at
normal pressure to remove water from solution azeotropically. The
b.p. of the azeotrope is 85° C, while water-free toluene boils at 110° C.
When the water is removed from solution, turn off the heat on the
distillation, and carefully apply a vacuum to remove the remainder of
the toluene. Then with the vacuum still on, resume heating the flask,
and collect the substituted phenylacetone. Methylenedioxyphenyl-
acetone distills at about 140° C and 160° C using a good aspirator
with cold water. A poor vacuum source leads to much higher
distillation temps and tar formation in the distilling flask. The yield
from the reaction is close to 150 ml of phenylacetone. Its color should be
clear to a light yellow. The odor of methylenedioxyphenylacetone is
much like regular phenylacetone, with a trace of the candy shop odor
of the safrole from which it was made.
A higher-boiling phenylacetone like 2,4,5-trimethyloxyphenyl-
acetone is better purified as the bisulfite addition product, unless a
vacuum pump giving high vacuum is available. To make the bisulfite
addition product, take the residue from the filtering flask, dissolved in
some toluene and freed from catalyst as described above, and pour it in
a beaker. Next, add 3 volumes of sodium bisulfite solution prepared by
adding sodium bisulfite or metabisulfite to water until no more
dissolves. Shake or vigorously stir for a couple of hours to convert the
phenylacetone to the solid bisulfite addition product. Filter out the
solid, then regenerate pure phenylacetone by putting the solid into a
round-bottom flask, adding an excess of saturated solution of sodium
bicarbonate in water, and refluxing for a couple hours. After cooling,
the phenylacetone should be extracted out with some toluene. The
toluene should then be removed under a vacuum, and the residue
stored in a freezer until conversion to the amphetamine. All
Practical LSD Manufacture
84
phenylacetones are sensitive to light, and should be stored in the
freezer.
The above cooking procedure is the best way to process
allylbenzenes to the corresponding phenylacetones. Sassafras oil, as
previously mentioned, is 80-90% safrole. Calumus oil, if its country of
origin is India, consists of about 80% of the allyl isomer of asarone:
It too can be purified by distillation under a vacuum to yield fairly
pure allyl-asarone. Its boiling point is 296° C at normal pressure and
about 170° C with aspirator vacuum. More details on this Indian
calamus oil can be found in Chetn. Abstracts column 6585 (1935),
also Current Science, Volume 3, page 552 (1935).
My search for calamus oil of Indian origin came up empty. In fact,
the health-food store in my town, which is well-stocked with various
oils for use in aromatherapy, had never heard of the stuff, nor was it
listed for sale in their catalogs. This left one alternative: dig up the
roots of North American calamus, and steam-distill the oil out of
them.
While searching for calamus in my area's swamps, bogs and
ponds, the damaging effects of the spread of purple loosestrife was
obvious. This imported plant from Europe has taken over much of the
former habitat of the calamus plant. Here in America, the loosestrife is
free from the insect that keeps it under control in Europe by feeding [ Pobierz całość w formacie PDF ]
zanotowane.pl doc.pisz.pl pdf.pisz.pl aikidobyd.xlx.pl
nitrite is not held in solution very well on account of its very low
boiling point. If ethyl nitrite was used instead, then only three or four
moles would be needed.
While the reaction is being done, the mixture takes on the
appearance of mud if palladium bromide is being used. A fizzing also
Practical LSD Manufacture
82
occurs, which gives the reaction mixture the appearance of freshly
poured Coke. Note above that a bit of acid is required to get
hydrolysis of the intermediate dialkoxyphenylpropane to the phenyl-
acetone. The best pH for this reaction is between 4-7. If palladium
chloride or the mixed catalyst PdCh-CuCla is being used, the pH of
the reaction mixture can be adjusted to this range by adding a small
amount of HC1. If PdBr2, is used, it is best to wait until the catalyst is
filtered out before adding HC1, as the HC1 could form PdCh and
complicate catalyst recovery. The pH of the reaction mixture is best
measured by first dampening some indicating pH paper with distilled
water, then putting a drop of reaction mixture on the paper. The
preferred temperature for this reaction is about 25° C throughout.
When all the methyl nitrite has been bubbled into the reaction
mixture, stirring should be continued for another hour. Then, if
palladium bromide was used, it should be filtered out. Repeated
filtrations will be needed to remove all of the catalyst, because it gets
quite finely divided during the course of the reaction. This leaves a
clear light-reddish solution. If palladium bromide was used, now
adjust pH to 4-7, and allow another hour to complete the hydrolysis.
If palladium chloride or the mixed catalyst was used, these
substances are soluble in alcohol. In this case, the catalyst will be
recovered later. Here, check the pH of the solution again to be sure it is
in the proper range before proceeding.
Now the alcohol solvent must be removed. This is best done by
pouring the reaction mixture into a large filtering flask, stoppering the
top of the flask, and removing the solvent under a vacuum. Use of a
hot-water bath to speed evaporation is highly recommended for this
process. It is not OK to distill off the alcohol at normal pressure, as
the heat will cause the nitrite and NO in solution to do bad things to the
product.
To the residue left in the flask after removal of the alcohol, add
some toluene to rinse the product out of the flask into a sep funnel.
Next, put 300 ml of water into the flask to dissolve the catalyst if
PdCla or the mixed catalyst was used. Add the water solution to the
sep funnel to dissolve carried-over catalyst there, then drain this water
12 Studies On The Production OfTMA-2
83
solution of catalyst into a dark bottle and store in the dark until the
next batch. If PdBr2 was used, this step can be skipped. Just store the
filtered-out PdBra under water in the dark.
Now the toluene-phenylacetone solution should be distilled
through a Claisen adapter packed with some pieces of broken glass to
effect fractionation. The first of the toluene should be distilled at
normal pressure to remove water from solution azeotropically. The
b.p. of the azeotrope is 85° C, while water-free toluene boils at 110° C.
When the water is removed from solution, turn off the heat on the
distillation, and carefully apply a vacuum to remove the remainder of
the toluene. Then with the vacuum still on, resume heating the flask,
and collect the substituted phenylacetone. Methylenedioxyphenyl-
acetone distills at about 140° C and 160° C using a good aspirator
with cold water. A poor vacuum source leads to much higher
distillation temps and tar formation in the distilling flask. The yield
from the reaction is close to 150 ml of phenylacetone. Its color should be
clear to a light yellow. The odor of methylenedioxyphenylacetone is
much like regular phenylacetone, with a trace of the candy shop odor
of the safrole from which it was made.
A higher-boiling phenylacetone like 2,4,5-trimethyloxyphenyl-
acetone is better purified as the bisulfite addition product, unless a
vacuum pump giving high vacuum is available. To make the bisulfite
addition product, take the residue from the filtering flask, dissolved in
some toluene and freed from catalyst as described above, and pour it in
a beaker. Next, add 3 volumes of sodium bisulfite solution prepared by
adding sodium bisulfite or metabisulfite to water until no more
dissolves. Shake or vigorously stir for a couple of hours to convert the
phenylacetone to the solid bisulfite addition product. Filter out the
solid, then regenerate pure phenylacetone by putting the solid into a
round-bottom flask, adding an excess of saturated solution of sodium
bicarbonate in water, and refluxing for a couple hours. After cooling,
the phenylacetone should be extracted out with some toluene. The
toluene should then be removed under a vacuum, and the residue
stored in a freezer until conversion to the amphetamine. All
Practical LSD Manufacture
84
phenylacetones are sensitive to light, and should be stored in the
freezer.
The above cooking procedure is the best way to process
allylbenzenes to the corresponding phenylacetones. Sassafras oil, as
previously mentioned, is 80-90% safrole. Calumus oil, if its country of
origin is India, consists of about 80% of the allyl isomer of asarone:
It too can be purified by distillation under a vacuum to yield fairly
pure allyl-asarone. Its boiling point is 296° C at normal pressure and
about 170° C with aspirator vacuum. More details on this Indian
calamus oil can be found in Chetn. Abstracts column 6585 (1935),
also Current Science, Volume 3, page 552 (1935).
My search for calamus oil of Indian origin came up empty. In fact,
the health-food store in my town, which is well-stocked with various
oils for use in aromatherapy, had never heard of the stuff, nor was it
listed for sale in their catalogs. This left one alternative: dig up the
roots of North American calamus, and steam-distill the oil out of
them.
While searching for calamus in my area's swamps, bogs and
ponds, the damaging effects of the spread of purple loosestrife was
obvious. This imported plant from Europe has taken over much of the
former habitat of the calamus plant. Here in America, the loosestrife is
free from the insect that keeps it under control in Europe by feeding [ Pobierz całość w formacie PDF ]