The structures of the synthesized compounds were proven using PMR, IR, and mass spectra.
This reaction with other organolithium compounds is still being studied.
EXPERIMENTAL
IR spectra were obtained on a Model 2000 Fourier IR-spectrometer (Perkin–Elmer). PMR spectra were recorded in
CDCl on a Unity Plus instrument at operating frequency 400 MHz. Mass spectra were recorded on a Kratos MS-30 spectrometer
3
(England) at ionizing potential 70 eV and source temperature 220°C. The purity of products was monitored by TLC on Silufol
UV-254 plates (Czech Rep.).
Synthesis of 4-butyl-4-hydroxydeoxypeganine (3): A. A cold solution (–78°C) of deoxyvasicinone (1, 100 mg,
0.537 mmol) in THF (5 mL) was treated dropwise with a solution of n-BuLi (2.6 M, 0.644 mmol, 0.25 mL) under N , stirred
2
at –78°C for 1 h, and treated with MeOH (2 mL) to destroy the remaining n-BuLi. Solvent was distilled off. The solid was
separated over a column (petroleum ether:EtOAc, 7:3) to afford 3 (95 mg), yield 73%, R 0.86 (EtOAc:MeOH:petroleum
f
ether, 7:2:1), mp 116°C, C H N O.
15 20
2
B. Deoxyvasicinone (0.93 g, 5 mmol) was dissolved in anhydrous ether (100 mL), cooled to 0°C, and treated dropwise
under N with n-BuLi in hexane at a rate such that the temperature remained below 5°C. The addition took 30 min. After the
2
n-BuLi was added, the mixture was again cooled to 0°C, treated dropwise with MeOH (10 mL) from a dropping funnel, held
at this temperature for 8 h, left overnight, and treated with water (50 mL). The resulting crystals were filtered off, washed with
water until neutral, and recrystallized from hexane to afford a product (0.4 g, 33%) with mp 116°C, R 0.09 (acetone:CHCl ,
f
3
2:1). A mixed melting point with the sample obtained by method A was not depressed.
–1
IR spectrum (cm ): 3669, 3506, 3395, 3336, 3103. PMR spectrum (400 MHz, CDCl , ꢃꢄ, ppm): 0.8 (3H, t),
3
1.45–1.57 (2H, m), 1.76 (1H, br.s, OH), 2.13 (2H, t), 2.34–2.47 (2H, m), 2.79 (2H, t), 3.48–3.59 (2H, m), 4.39 (2H, t), 7.1 (1H,
+
+
d), 7.27 (2H, t), 7.6 (1H, d); HR-ES-MS, (m/z): 226 [M – 18] , 171 [M – 73] .
Reduction of Deoxyvasicinone by LiAlH . Deoxyvasicinone (1.86 g, 0.01 mol) in THF (25 mL) under N was
4
2
treated with LiAlH (1.52 g, 0.04 mol), refluxed for 8 h, treated with NaCl solution to destroy the remaining LiAlH , filtered,
4
4
and extracted with CHCl (3ꢅ). The organic layer was dried over anhydrous MgSO . The solvent was distilled off. The solid
3
4
was separated over a column (petroleum ether:EtOAc, 1:1) to afford 4 (0.612 g, 35.6%), mp 86–87°C (lit. mp 86–87°C) [6].
We also isolated 5 (0.929 g, 53.4%), mp 69–70°C (lit. mp 69–70°C) [7].
REFERENCES
1.
2.
3.
4.
5.
6.
7.
Kh. M. Shakhidoyatov and I. Kaisarov, Khim. Prir. Soedin., 79 (1998).
A. Sh. Abdurazakov, B. Zh. Elmuradov, and Kh. M. Shakhidoyatov, Khim. Prir. Soedin., 342 (2009).
Kh. M. Shakhidoyatov, G. P. Genzhemuratova, and E. Oripov, Khim. Prir. Soedin., 585 (2006).
B. Zh. Elmuradov, A. Sh. Abdurazakov, and Kh. M. Shakhidoyatov, Khim. Prir. Soedin., 383 (2008).
Kh. M. Shakhidoyatov, Dissertation, Tashkent, 1983.
Kh. N. Khashimov, M. V. Telezhenskaya, and S. Yu. Yunusov, Khim. Prir. Soedin., 456 (1969).
N. I. Koretskaya and L. M. Utkin, Zh. Obshch. Khim., 26, 1087 (1958).
599