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#129 METHYL-K
2-METHYLAMINO-1-(3,4-METHYLENEDIOXYPHENYL)PENTANE; N-METHYL-1-(1,3-BENZODIOXOL-5-YL)-2-PENTYLAMINE
SYNTHESIS: The Grignard reagent of butyl
bromide was prepared in
anhydrous Et2O by the dropwise addition of 68 g n-butyl
bromide to a
well-stirred suspension of 14 g
magnesium turnings in 500 mL
anhydrous
Et2O. When the exothermic reaction had stopped, there was added a
solution of 60 g
piperonal in about 100 mL
Et2O, over the course of 1
h. After the exothermic addition was complete, the reaction mixture
was held at reflux for several h, then cooled and decomposed by the
addition of dilute HCl. The
phases were separated, and the aqueous
phase extracted with 2x75 mL
CH2Cl2. The organics were combined and
gave, after the removal of the
solvents under vacuum, 84 g of
1-hydroxy-1-(3,4-methylenedioxyphenyl)pentane as a yellow liquid.
This was used in the following
dehydration step without further
purification.
A mixture of 52 g of the crude
1-hydroxy-1-(3,4-methylenedioxyphenyl)pentane and 2 g powdered
KHSO4
was heated with a flame until there was no more apparent generation of
H2O. The resulting dark, fluid oil was
distilled at 100-110 °C at 0.3
mm/
Hg to give 29.5 g of
1-(3,4-methylenedioxyphenyl)-1-pentene as a
light yellow liquid. This was employed in the following
oxidation
step without further purification.
To 120 mL of 90%
formic acid there was added, with good stirring, 15
mL H2O, followed by 23 mL of 35% H2O2 To this mixture, cooled with an
external ice bath, there was added a
solution of 24 g crude
1-(3,4-methylenedioxyphenyl)-1-pentene in 120 mL
acetone at a rate
slow enough to keep the internal tem
perature from exceeding 35 °C. At
the end of the addition, the tem
perature was brought up to 45 °C by
heating briefly on the steam bath, and then the reaction mixture was
allowed to stand and stir at ambient tem
perature for several h. All
volatiles were removed under vacuum, with a bath tem
perature
maintained at 45 °C. The residue was
dissolved in 30 mL MeOH, then
there was added 200 mL 15% H2SO4 and the mixture held on the steam
bath for 1.5 h. There was then added an additional 300 mL H2O, and
this was extracted with 2x250 mL of a petroleum
ether/
EtOAc (5:1)
mixture. The extracts were pooled, and the
solvents removed under
vacuum to give a residue that was
distilled at 115-120 °C at 0.3
mm/
Hg. This light yellow liquid weighed 13.5 g and was substantially
pure
1-(3,4-methylenedioxyphenyl)-2-pentanone by TLC.
To 5.0 g of
aluminum foil cut into 1 inch squares, there was added a
solution of 150 mg
HgCl2 in 200 mL H2O. The mixture was heated
briefly until there were clear signs of active
amalgamation, such as
fine bubbling for the
aluminum surfaces and the beginning of the
formation of a gray,
amorphous solid
phase. The
HgCl2
solution was
decanted off and the
aluminum was washed with 2x200 mL additional H2O.
After shaking as dry as possible, there was added, in sequence and
with good swirling agitation between each addition, 10 g
methylamine
hydrochloride in 10 mL H2O, 27 mL IPA, 22 mL of 25%
NaOH, 5.0 g
1-(3,4-methylenedioxyphenyl)-2-pentanone, and finally an additional 50
mL IPA. The mixture was heated on the steam bath periodically to
maintain the reaction rate at a vigorous boil. When all of the
aluminum had been consumed, the cooled mixture was filtered and the
solids washed with MeOH. The combined filtrate and washings were
stripped of
solvent under vacuum. The residue was
dissolved in dilute
H2SO4 and washed with 2x75 mL
CH2Cl2. After making basic again with
25%
NaOH, this was extracted with 2x100 mL
CH2Cl2, and the pooled
extracts were stripped of
solvent under vacuum. The residue was
distilled at 105-110 °C at 0.3 mm/
Hg to give 2.7 g of a colorless
liquid. This was
dissolved in 15 mL IPA, neutralized with
concentrated HCl, and diluted with 75 mL
anhydrous Et2O which allowed
a delayed appearance of a fine white
crystal. This was removed by
filtration,
Et2O washed, and air dried to give 2.45 g
2-aminomethyl-1-(3,4-methylenedioxyphenyl)pentane hydrochloride
(METHYL-K) as a white product with a mp of 155-156 °C. Anal.
(
C13H20ClNO2) C,H.
DOSAGE: greater than 100 mg.
DURATION: unknown.
QUALITATIVE COMMENTS: (with 100 mg) There were no effects. I was
busy and totally wound up and didn't sleep until 3 AM, but this was
probably unrelated to the Me-K.
EXTENSIONS AND COMMENTARY: The well appears to be running dry, with a
pentane chain as a basic skeleton. METHYL-J, at this level, was
already showing a number of hints and clues, largely physical such as
coldness in the feet and a slight
mastoidal pressure, that activity
was right around the corner. But METHYL-K gave no such hints. The
un
methylated homologue,
2-amino-1-(3,4-methylenedioxyphenyl)pentane
(K), was also made, by the reductive
amination of
1-(3,4-methylene-dioxyphenyl)-2-pentanone with
ammonium acetate and
sodium cyanoborohydride in
methanol. It was a white
crystalline
solid, mp 202-203 °C, but is given here in the comments only, as its
human assaying had never even been initiated. Anal. (
C12H18ClNO2)
C,H. The N-
ethyl homologue,
2-ethylamino-1-(3,4-methylene-dioxyphenyl)pentane (ETHYL-K), is
entered with its own recipe, on the other hand, since testing had been
started with it.
And the longest chain that has been explored in this Muni Metro series
is the six-
carbon hexyl chain which is, quite logically, the L-series,
sort of the end of the Taraval line (see under METHYL-J for an
explanation). The central compound for all the L-compounds was the
ketone 1-(3,4-methylenedioxyphenyl)-2-hexanone, which was prepared by
the Grignard reagent of (n)-amyl
bromide with
piperonal to give
1-hydroxy-1-(3,4-methylenedioxyphenyl)hexane,
dehydration of this with
potassium bisulfate to the olefin, and
oxidation of this with hydrogen
peroxide and
formic acid to the L-
ketone which was an orange-colored
liquid with a bp of 125-135 °C at 0.3 mm/
Hg. This
ketone was
reductively
aminated with
ammonium acetate and
sodium cyanoborohydride
in
methanol to produce
2-amino-1-(3,4-methylenedioxyphenyl)hexane
hydrochloride (L) as a white
crystalline product with a mp of 157-158
°C. Anal. (
C13H20ClNO2) C,H. And this
ketone was reductively
aminated with
methylamine hydrochloride and
amalgamated
aluminum in
isopropanol to produce
2-methylamino-1-(3,4-methylenedioxyphenyl)hexane hydrochloride
(METHYL-L) as a white
crystalline product with a mp of 139-141 °C.
Anal. (
C14H22ClNO2) C,H. The reduction of this
ketone in a similar
manner with
ethylamine hydrochloride produced
2-ethylamino-1-(3,4-methylenedioxyphenyl)hexane (ETHYL-L). None of
this series has yet been explored either as
psychedelic or
entactogenic materials.
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