EXPERIMENTAL
NMR spectra were recorded on a DRX-500 (Bruker) instrument at working frequency500.13 MHz with TMS internal
standard; mass spectra, in an SSQ-710 (Finnigan MAT) spectrometer at 70 eV ionizing-electron energy. Elemental analyses
agreed with those calculated.
β-Phenyltryptamine (3). A mixture of 3-(2-nitro-1-phenylethyl)indole (26.6 g, 0.1 mol) in alcohol (94%, 100 mL)
and freshly prepared Raney nickel (1 g) was treated over 60 h with hydrazine hydrate (50 mL) in alcohol (100 mL). If the
boiling stopped, a new portion of catalyst was added. The mixture was filtered. The filtered catalyst was washed with hot
alcohol (3 × 10 mL). The filtrate was evaporated. The solid was dissolved in anhydrous ether and treated with ether saturated
with HCl. The resulting hydrochloride was filtered off, suspended in ether, and shaken with aqueous base. The ether solution
was dried over MgSO and evaporated. Yield 21 g (90%), mp 131-132°C (lit. mp 131-132°C [15]) (from ethylacetate).
4
4-Phenyl-3,4-dihydro-β-carboline (5)(monohydrate). Compound3(10mmol)was dissolved in distilledformicacid
(20 mL). The solution was heated on an oil bath to distill off the solvent over 30 min, adjusting the temperature of the mixture
to 145°C. After cooling, water (30 mL) and CHCl (20 mL) were added. The organic layer was separated and washed with
3
water. The solvent was vacuum distilled to afford 4 (2.40 g) as a slowly crystallizing oil. The product was treated with freshly
distilled phosphoryl chloride (7 mL) with stirring to dissolve it and placed on an oil bath. The temperature was increased over
1.5 h to 120°C to distill simultaneouslythe POCl . The mixture was held at 120-121°C for another 30 min, cooled, and poured
3
into icewater (50 g). After the exothermic reaction subsided, the solution was filtered. The solid was treated twice with HCl
(50 mL each, 5%). The combined filtrates were made basic with ammonia (25%). The resulting precipitate was filtered off
and washed with water. The product was purified bydissolving in HCl (10 mL, 5%), separating the insoluble part, and making
the solution basic with ammonia to afford 5 (0.52 g, 22%) as the monohydrate, mp 116°C (dec.).
PMR spectrum (CDCl , δ, ppm): 3.87 and 4.23 (m, ab system, 1H+1H, CH CH), 4.39 (m, 1H, CH), 6.95-7.70 (m, 9H,
3
2
+
H
), 8.69 (br.s, 1H, NH). Mass spectrum (EI, 70 eV) m/z (I , %): 246 (15) [M] .
rel
arom
REFERENCES
1.
2.
3.
Sh. I. Khan, E. A. Abourashed, I. A. Khan, and L. A. Walker, Chem. Pharm. Bull., 52, No. 4, 394 (2004).
G. Zetler, G. Back, and H. Iven, Naunyn-Schmiedeberg's Arch. Pharmacol., 285, 273 (1974).
B. Grella, M. Dukat, R. Young, M. Teitler, K. Herrick-Davis, C. B. Gauthier, and R. A. Glennon, Drug Alcohol
Depend., 50, 99 (1998).
4.
5.
6.
M. J. Chan-Bacab and L. M. Pena-Rodriguez, Nat. Prod. Rep., 18, 674 (2001).
C. W. Wright and J. D. Phillipson, Phytother. Res., 4, 127 (1990).
V. Mahiou, F. Roblot, R. Hocquemiller, A. Cave, A. Rojas de Arias, G. Yalu, A. Fournet, and A. Angelo, J. Nat.
Prod., 57, 890 (1994).
7.
8.
C. C. Shi, J. F. Liao, and C. F. Chen, Jpn. J. Pharmacol., 85, 299 (2001).
O. Curet, G. Damoiseau, N. Aubin, N. Sontag, V. Rovei, and F.-X. Jarreau, J. Pharmacol. Exp. Ther., 277, 253
(1996).
9.
10.
11.
D. L. Nelson, A. Herbet, Y. Petillot, L. Pichat, J. Glowinski, and M. Hamon, J. Neurochem., 32, 1817 (1979).
R. W. Fuller, C. J. Wong, and S. K. Hemrick-Luecke, Life Sci., 38, 409 (1986).
B. T. Ho, V. Estevez, G. E. Fritchie, L. W. Tansey, J. Idanpaan-Heikkila, and W. M. McIsaac, Biochem.
Pharmacol., 20, 1313 (1971).
12.
13.
14.
A. Villeneuve and T. L. Sourkes, Rev. Can. Biol., 25, 231 (1966).
K. A. Krasnov, V. G. Kartsev, and M. N. Yurova, Zh. Org. Khim., 39, No. 4, 632 (2003).
V. I. Dulenko, I. V. Komissarov, A. T. Dolzhenko, and Yu. A. Nikolyukin, β-Carbolines. Chemistry and
Neurobiology [in Russian], Naukova Dumka, Kiev (1992).
15.
E. P. Styngach, K. I. Kuchkova, and T. M. Efremova, Khim. Geterotsikl. Soedin., 1523 (1973).
592