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#9 ASB
ASYMBESCALINE; 3,4-DIETHOXY-5-METHOXYPHENETHYLAMINE
SYNTHESIS: To a
solution of 32 g of 5-
bromobourbonal in 150 mL DMF
there was added 31 g
ethyl iodide and 32 g of finely ground 85% KOH
pellets. There was the formation of a purple color and a heavy
precipitate. On gradual heating to reflux, the color faded to a pale
yellow and the
precipitate dissolved over the course of 1 h. The
heating was continued for an additional 1 h. The reaction mixture was
added to 1 L H2O, and extracted with 2x150 mL of petroleum
ether. The
extracts were pooled, washed with 2x200 mL 5%
NaOH and finally with
H2O. After drying over
anhydrous K2CO3 the
solvents were removed
under vacuum to yield 36 g of crude
3-bromo-4,5-diethoxybenzaldehyde
as an amber liquid. This was used without purification for the
following step. Distillation at 105-115 °C at 0.3 mm/
Hg provided a
white sample which did not
crystallize. Anal. (
C11H13BrO3 ) C,H.
A mixture of 36 g
3-bromo-4,5-diethoxybenzaldehyde and 17 mL
cyclohexylamine was heated with an open flame until it appeared to be
free of H2O. The residue was put under a vacuum (0.4 mm/
Hg) and
distilled at 135-145 °C, yielding 42 g
3-bromo-N-
cyclohexyl-4,5-
diethoxybenzylidenimine as a viscous light
greenish oil. This slowly set to a
crystalline glass with a mp of
60-61 °C. Re
crystallization from hexane gave a white
crystalline
product without any improvement in the mp. Anal. (
C17H24BrNO2) C,H.
This is a chemical intermediate to a number of active bases, taking
advantage of the available
bromine atom. This can be exchanged with a
sulfur atom (leading to
5-TASB and
3-T-TRIS) or with an oxygen atom as
described below.
A
solution of 18 g 3-bromo-N-
cyclohexyl-4,5-
diethoxybenzylidenimine in
250 mL
anhydrous Et2O was placed in an
atmosphere of He, stirred
magnetically, and cooled with an external dry ice/
acetone bath. Then
36 mL of a 1.5 M
solution of
butyllithium in hexane was added over 2
min, producing a clear yellow
solution. This was stirred for 10 min.
There was then added 30 mL of butyl
borate at one time, the stirring
continued for 5 min. The stirred
solution was allowed to return to
room tem
perature. There was added 150 mL of saturated aqueous
ammonium sulfate. The
Et2O layer was separated, and the aqueous
phase
extracted with another 75 mL
Et2O. The combined organic
phases were
evaporated under vacuum. The residue was
dissolved in 100 mL MeOH,
diluted with 20 mL H2O, and then treated with 15 mL 35% H2O2 added
over the course of 2 min. This mildly exothermic reaction was allowed
to stir for 15 min, then added to 500 mL H2O. This was extracted with
2x100 mL
CH2Cl2 and the
solvent removed under vacuum. The residue was
suspended in 150 mL dilute HCl and heated on the steam bath for 0.5 h.
Stirring was continued until the reaction was again at room
tem
perature, then it was extracted with 2x75 mL
CH2Cl2. These
extracts were pooled and extracted with 3x100 mL dilute aqueous KOH.
The aqueous extracts were washed with
CH2Cl2, reacidified with HCl,
and reextracted with 2x75 mL
CH2Cl2. These extracts were pooled, and
the
solvent removed under vacuum to yield a brown residue. This was
distilled at 107-127 °C at 0.4 mm/
Hg to yield 8.3 g of
3,4-diethoxy-5-hydroxybenzaldehyde as an oil that set to a tan solid.
Re
crystallization from
cyclohexane gave a white product with a mp of
70.5-71.5 °C. Anal. (
C11H14O4) C,H.
A
solution of 8.3 g of
3,4-diethoxy-5-hydroxybenzaldehyde and 3.0 g
KOH in 75 mL
EtOH was treated with 5 mL
methyl iodide and stirred at
room tem
perature for 5 days. The reaction mixture was added to 400 mL
H2O and extracted with 2x50 mL
CH2Cl2. The extracts were pooled,
washed with 2x150 mL dilute
NaOH, and the
solvent removed under
vacuum. The
residual oil was
distilled at 95-110 °C at 0.3 mm/
Hg to
yield 8.2 g of
3,4-diethoxy-5-methoxybenzaldehyde as a pale yellow
liquid. This product was a
crystalline solid below 20 °C but melted
upon coming to room tem
perature. It was analyzed, and used in further
reactions as an oil. Anal. (
C12H16O4) C,H.
To a
solution of 6.4 g
3,4-diethoxy-5-methoxybenzaldehyde in 40 mL
nitromethane there was added about 0.5 g
anhydrous ammonium acetate,
and this was held at reflux for 1 h. The excess
solvent/reagent was
removed under vacuum, producing a red oil which set up to
crystals.
These were re
crystallized from 40 mL boiling MeOH to yield 3.0 g of
3,4-diethoxy-5-methoxy-beta-nitrostyrene as yellow plates, with a mp of
89-90 °C. Anal. (
C13H17NO5) C,H.
A
solution of 3.0 g LAH in 150 mL
anhydrous THF under He was cooled to
0 °C and vigorously stirred. There was added, dropwise, 2.1 mL of
100% H2SO4, followed by the dropwise addition of a
solution of 3.5 g
3,4-diethoxy-5-methoxy-beta-nitrostyrene in 30 mL
anhydrous THF, over the
course of 10 min. The addition was exothermic. The mixture was held
at reflux on the steam bath for 30 min. After cooling again, the
excess
hydride was destroyed with IPA, followed by the addition of 10%
NaOH sufficient to covert the
aluminum oxide to a white, granular
form. This was removed by filtration, the filter cake washed with
IPA, the mother liquor and filtrates combined, and the
solvents
removed under vacuum to provide a yellow oil. This residue was added
to 100 mL dilute H2SO4 producing a cloudy suspension and some yellow
in
soluble gum. This was washed with 2x75 mL
CH2Cl2. The aqueous
phase was made basic with 25%
NaOH, and extracted with 2x75 mL
CH2Cl2.
The
solvent was removed from these pooled extracts and the residue
distilled at 110-135 °C at 0.4 mm/
Hg to provide 2.0 g of a colorless
liquid. This was
dissolved in 7 mL IPA, neutralized with about 40
drops of concentrated HCl, followed by 50 mL
anhydrous Et2O with
stirring. The initially clear
solution spontaneously
deposited a
white
crystalline solid. This was diluted with an additional 30 mL
Et2O, let stand for 1 h, and the solids removed by filtration. After
Et2O washing, the product was air-dried to yield 1.25 g of
3,4-diethoxy-5-methoxyphenethylamine hydrochloride (ASB) with a mp of
142-143 °C. Anal. (
C13H22ClNO3) C,H.
DOSAGE: 200 - 280 mg.
DURATION: 10 - 15 h.
QUALITATIVE COMMENTS: (with 240 mg) There was a pleasant and easy
flow of day-dreaming thoughts, quite friendly and somewhat erotic.
There was a gentle down-drift to my starting baseline mental status by
about midnight (I started at 9:00 AM). I never quite made it to a
+++, and rather regretted it.
(with 280 mg) The plateau of effect was evident by hour two, but I
found the experience lacking the visual and interpretive richness that
I had hoped for. Sleep was very fitful after the effects had largely
dropped--it was hard to simply lie back and relax my guard--and even
while being up and about the next day I felt a
residual plus one.
Over all, there were few if any of the open interactions of
2C-B or
LSD. Some negative side seemed to be present.
(with 280 mg) The entire session was, in a sort of way, like being in
a corridor outside the lighted halls where a beautiful mescaline
experience is taking place, sensing the light from behind a grey door,
and not being able to find my way in from the dusky underside
passageways. This is sort of a gentle sister of mescaline, but with a
tendency to emphasize (for me, at this time) the negative, the sad,
the struggling. Sleep was impossible before the fifteenth hour. When
I tried, I got visions of moonlight in the desert, with figures around
me which were the
vampire-werewolf aspect of the soul, green colored
and evil. I had to sit quietly in the living room and wait patiently
until they settled back to wherever they belonged and stopped trying
to take over the scene. During the peak of the experience, my pulse
was thready, somewhat slowed, and uneven. There was a faint feeling
of physical weirdness.
EXTENSIONS AND COMMENTARY: This specific
amine was a target for a
single study in cats many years ago, in
Holland, using material
obtained from
Hoffman La Roche in Basel. Their findings are hard to
evaluate, in that 200 milligrams was injected into a 3.75 kilogram cat
(53 mg/Kg), or about twice the dosage that they used in their studies
with
metaescaline. Within 5 minutes there were indications of
catatonia, and within a half hour the animal was unable to walk. This
condition persisted for two days, at which time the animal died.
Although this dose was many times that used in man, perhaps hints of
the physical unease and long action are there to be gleaned. The
consensus from over a half dozen experiments is that there is not
enough value to be had to offset the body load experienced.
A comment is needed on the strange name a
symbescaline! In the
marvelous world of chemical
nomenclature, bi- (or di-) usually means
two of something, and tri- and tetra- quite reasonably mean three and
four of something. But occasionally there can be an ambiguity with bi
(or tri or tetra) in that bi some-thing-or-other might be two
something-or-others hooked tog
ether or it might be two things hooked
onto a something-or-other. So, the former is called bi- and the
latter is called bis-. This compound is not two escalines hooked
tog
ether (bi-escaline) but is only one of them with two
ethyl groups
attached (bis-escaline or bescaline). And since there are two ways
that this can be done (either symmetrically or asymmetrically) the
symmetric one is called
symbescaline (or SB for short) and this one is
called a
symbescaline (or ASB for short). To complete the terminology
lecture, the term tri- becomes tris- (the name given for the drug with
all three ethoxy groups present in place of the methoxys of mescaline)
and the term tetra- mutates into the rather incredible tetrakis-!
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