568W. Wysocka
et al. · III. Thioanalogs of Sparteine Lactams
Experimental Section
(+)-17-Thionosparteinium perchlorate (I·HClO )
4
52.8mg (0.2 mmol) of I were dissolved in 1.5 ml
of methanol and 0.96 ml (0.22 mmol) of 60% per-
chloric acid solution in methanol (1:39 v/v) were
added. A white powder was precipitated. Recrys-
tallization from ethanol gave 55 mg (75%) of
transparent crystals, m.p. 231 ∞C. Ð IR (KBr): ν =
General techniques
Melting points were determined on a Boetius
apparatus (PHMK 05 VEB Wägetechnik Rapido,
Radebeul). The IR spectra were recorded by
means of a FT-IR Bruker IFS 113v spectrometer
(KBr pellets technique). Electron-impact mass
spectra were taken on an AMD 402 spectrometer
1494, 2954Ð2783 cmÐ1
.
at standard parameters. The H NMR, 13C NMR,
1
X-ray crystal structure determination of I
1HÐ1H COSY, 13CÐ1H COSY and DEPT spectra
(in C6D6, c = 0.06 M) were measured on a Varian
Gemini 300 spectrometer at a frequency of 75.462
Single crystals were obtained by slow evapora-
tion of saturated hexane solution. A colourless
transparent crystal was selected for the X-ray in-
vestigation. To check the possibility of phase tran-
sitions, the unit cell parameters were measured as
a function of decreasing temperature down to
100(2) K. No phase transition was observed in the
temperature range of 293Ð100 K and the data col-
lection was carried out at 100(2) K on a KUMA
KM4 diffractometer [13] using MoÐKα radiation.
The accurate unit cell parameters were obtained
by the least-square fit of setting angles of 26 reflec-
tions (2Θ range 6.3∞Ð31.3∞). In the data collection
the 2ΘÐΘ scan method was applied with a vari-
able scan rate ranging from 0.02∞/s to 0.25∞/s, de-
pending on reflection intensity. One control reflec-
tion (2 1 3) was measured every 100 current
measurements. The data were corrected for Lo-
rentz and polarization effects, but not for absorp-
tion [13]. The structure was solved by direct meth-
ods using SHELXS-97 program [14] and refined
by full-matrix least-squares method with
SHELXL-97 [15]. The function Σw(|Fo |2 Ð |Fc |2)2
was minimized, with wÐ1 = [σ2(F2o) + (0.036P)2 +
1.27P] where P = (F2o + 2F2c)/3.
All non-hydrogen atoms were refined anisotropi-
cally. The positions of hydrogen atoms at C15 and
C15A were refined. The remaining H atoms were
calculated in their theoretical positions and refined
as a “riding model”. The isotropic displacement
parameters Ui of all hydrogen atoms were set at 1.2
times of their carrier atoms. The absolute configura-
tion was assigned according to the previous determi-
nation of the naturally occurring sparteine deriva-
tives [16].
MHz for 13C NMR and 300 MHz for H). Thin
1
layer chromatography (TLC) was carried out on
silica gel sheets (Merck) in the system acetoneÐ
methanolÐammonia (4:1:0.05).
(Ð)-17-Oxosparteine
420 mg of (Ð)-sparteine sulfate pentahydrate
(Aldrich Chemical Company) were dissolved in
3 ml of a water-dioxane mixture (1:2). To the solu-
tion were added 7 ml of alkaline potassium ferri-
cyanide (5 ml of 1 N aqueous solution of potas-
sium ferricyanide in 2 ml of 20% aq. NaOH) and
10 g of diatomaceous earth. The mixture was sett-
led in a column and eluated with ethyl ether. After
evaporation 210 mg of white crystalline powder of
(Ð)-17-oxosparteine were obtained. Recrystalliza-
tion from hexane (5 ml) afforded 189 mg (77%) of
(Ð)-17-oxosparteine, m.p. 86Ð87 ∞C, [α]2D0 = Ð11.6o
(c 0.5, C2H5OH). Ð IR (KBr): ν = 2795Ð2700,
1632 cmÐ1. Ð MS: m/z (%) = 248(60) [M ], 220
(58), 97 (100). Ð C15H24N2O (248.4): calcd. C
72.54, H 9.74, N 11.28; found C 71.97, H 9.58,
N 11.06.
+
(+)-17-Thionosparteine (I)
124 mg of (Ð)-17-oxosparteine were dissolved in
5 ml of toluene and 162 mg of solid Lawesson’s
reagent were added. The reaction mixture was
stirred continuously at 100 ∞C for 13 h. The excess
of Lawesson’s reagent was removed on a column
filled with neutral alumina oxide (Woelm, activity
II, 11 g) using dichloromethane. Subsequent elu-
tion of I and crystallization from hexane gave
92 mg (70%) of (+)-17-thionosparteine, m.p. 89Ð
X-ray structure determination of I·HClO
4
Single crystals were obtained by slow evapora-
91 ∞C, [α]20 = +85.8∞ (c 0.5, C2H5OH). Ð IR (KBr): tion of saturated ethanol solution. A colourless
ν = 2805Ð2650, 1491, 1140 cmÐ1. Ð MS: m/z (%) = transparent crystal was selected for the X-ray in-
264 (74) [M+], 265 (15) [M+1], 266 (4) [M+2], 231 vestigation. The data collection was carried out on
(100). Ð C15H24N2S (264.4): calcd. C 68.13, H 9.15, a KUMA KM4 CCD diffractometer [17] using
N 10.59; found C 68.16, H 9.02, N 10.60.
MoÐKα radiation at 293(2) K. The intensity data