662
Yu. M. Yutilov et al.
EXPERIMENTAL PART
2-CH2); 2.87 t (2H, 1-CH2); 3.79 sec (2H, 4-CH2; 5.32 sec
(2H, N–CH2); 7.00 – 7.82 m (9H, aromatic protons).
g-Carboline (V). A mixture of 7.0 g (35 mmoles)
1-(4-pyridyl)benzotriazole (VI) and 25.0 g paraffin were
heated for 1 h at 300°C, and then the temperature was raised
up to 350°C and held there for 10 minutes. The mass was
cooled down and washed with petroleum ether. The residue
was dissolved in a solution of 2 N hydrochloric acid, heated
with activated charcoal and neutralized with a 25% aqueous
solution of ammonia. The light gray crystals that precipitated
were filtered off and dried. Yield of g-carboline: 4.25 g
(70%), m.p. 223 – 225°C. According to data in [6], m.p.
225°C.
The PMR spectra were recorded on a Gemini-200 spec-
trometer with operating frequency 200 MHz, in CD3OD,
CDCl3; internal standard, HMDS. The purity of the synthe-
sized compounds was monitored by TLC on Silufol UV-254
plates; the eluent was alcohol (detection with iodine vapors
and in UV light).
Elemental analysis data for the compounds obtained cor-
respond to the empirical formulas.
3-Methyl-g-carboline (II). 1.14 g of 2-methyl-g-carboli-
nium methylsulfate (I) was dissolved with heating in 20 mL
water, and 20 ml of a 50% KOH solution was added to the
hot solution. The light yellow precipitate of II was filtered
off, washed with 3 ml of cold water, and recrystallized from
2-propanol. Obtained: 0.65 g (93%) of compound II, m.p.
1-(4-Pyridyl)benzotriazole (VI). A mixture of 13.0 g
(110 mmoles) 1,2,3-benzotriazole (VII) and 50.0 g (220
mmoles) of the hydrochloride of N-(4-pyridyl)pyridinium
chloride was heated at a temperature of 150 – 160°C for
3 – 4 h. The mass was cooled down. It was dissolved in wa-
ter and the solution was neutralized with a 25% aqueous so-
lution of ammonia. The precipitate of VI was filtered off,
dried, and recrystallized from heptane. Obtained: 14.0 g
(65%) of compound VI, m.p. 112°C. According to data in
[6], m.p. 113°C.
79 – 81°C. C12H10N2. PMR spectrum (CDCl3), d, ppm: 3.82
sec (3H, N–CH3); 7.24 – 7.61 m (4H, aromatic protons);
7.89 – 8.04 m and 9.56 sec (3H, aromatic protons).
3-Methyl-9-benzyl-g-carbolinium chloride (III). 0.4
ml (3.8 mmoles) benzyl chloride were added to a solution of
0.4 g (2 mmoles) of 3-methyl-g-carboline (II) in 5 ml of
2-propanol, and the mixture was boiled for 3.0 – 3.5 h. The
mixture was cooled down, the precipitate of III was filtered
off and recrystallized from alcohol. Yield: 0.6 g (88%), m.p.
REFERENCES
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337 – 340°C. C19H17ClN2. PMR spectrum (CD3OD), d, ppm:
4.46 sec (3H, N–CH3); 4.96 sec (2H, N–CH2); 7.55 – 7.86 m
(5H, C6H5); 8.05 d (J 7.2 Hz, 1H, 1-H); 8.31 – 8.40 m (4H,
aromatic protons); 8.64 d (J 7.2 Hz, 1H, 2-H); 9.96 sec (1H,
4-H).
3-Methyl-9-benzyl-1,2,3,4-tetrahydrocarboline (IV).
0.12 g (3.16 mmoles) of sodium borohydride was added in
portions over a 0.5 h period with vigorous stirring at room
temperature to a solution of 0.4 g (1.3 mmoles) 3-methyl-9-
7. A. P. Gray, J. Am. Chem. Soc., 77(22), 5930 – 5932 (1955).
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benzyl-g-carbolinium chloride (III) in 15 ml of 70% ethanol.
After 24 h, the solution was evaporated down and the reac-
tion product was extracted from the dry residue with ben-
zene. After purification from hexane, we obtained 0.25 g
(73%) of compound IV, m.p. 72 – 73°C. C19H20N2. PMR
spectrum (CDCl3), d, ppm: 2.61 sec (3H, CH3); 2.87 t (2H,