186 Mloston et al.
Cq) ppm. 31P NMR (CDCl3, 121 MHz): δ 29.05 ppm.
MS-CI (NH3) m/z (%): 474 (5), 457 (7) [M + 1]+,
257 (100) [(M + 1) – SC6H3(NO2)2]+. Anal. Calcd for
C19H25O7N2PS (456.46): C, 50.00; H, 5.52; N, 6.14; S,
7.02; found: C, 49.74; H, 5.54; N, 6.16; S, 7.00.
Dimethyl ({8-[(2,4-Dinitrophenyl)sulfanyl]penta-
cyclo[5.4.0.02,6.03,10.05,9 ]undecan-8-yl}methyl)phos-
phonate (11c). The crude product was isolated as
a pale yellow oil, which after crystallization from of
hexane/CH2Cl2 gave 355 mg (76%) of 11c as yellow
crystals (mp 159◦C–160◦C). IR (KBr): v 3101, 2968,
2866, 1593, 1515, 1456, 1403, 1344, 1249, 1048,
1032, 918, 901, 833, 809, 736 cm−1. 1H NMR (CDCl3):
δ 1.09–1.15 (m, 1H), 1.31, 1.77 (AB, JAB = 10.8 Hz,
2H, CH2), 1.86–2.10 (m, 3H, CH, CH2), 2.36–3.00
Dimethyl {[8-(Methylsulfanyl)pentacyclo[5.4.0.02,6
.03,10.05,9]undecan-8-yl]methyl}phosphonate (11a).
After column chromatography (SiO2, dichlorome-
thane with an increasing amount of methanol), the
product was isolated as a pale yellow oil. Yield: 360
mg (76%). IR (film): v 2952, 2861, 1740, 1645, 1451,
1408, 1313, 1277, 1248, 1183, 1061, 1031, 888, 866,
3
(m, 9H, CH, CH2P); 3.58 [d, JH,P = 10.9 Hz, 3H,
3
(CH3O)2P], 3.60 [d, JH,P = 11.0 Hz, 3H, (CH3O)2P],
7.89–8.84 (m, 3 arom. H) ppm. 13C NMR (CDCl3): δ
1
1
794 cm−1. H NMR (CDCl3): δ 0.95–1.01 (m, 1H),
28.4, 32.8 (2CH2), 35.2 (d, JC,P = 144.9 Hz, CH2P),
3
36.5, 41.6, 44.3, 45.6, 45.8, 47.5 (6CH), 42.4 (d, JC,P
1.21, 1.67 (AB, JAB = 10.6 Hz, 2H, CH2), 1.86–2.74
3
= 4.7 Hz, CH), 50.5 (d, JC,P = 5.6 Hz, CH), 52.09,
(m, 10H, CH2, CH, CH2P), 2.13 (s, 3H, CH3S), 3.13
52.14 (2d, 2 JC,P = 6.6 Hz, (CH3O)2P), 57.3 (Cq), 121.0,
125.8, 131.7 (3CHar), 144.1, 144.4, 148.7 (3 arom.
Cq) ppm. 31P NMR (CDCl3, 121 MHz,): δ 28.98 ppm.
MS-CI (NH3): m/z (%): 484 (16), 467 (47) [M + 1]+,
267 (100) [(M + 1) – SC6H3(NO2)2]+, 253 (8). Anal.
Calcd for C20H23O7N2PS (466.45): C, 51.50; H, 4.97;
N, 6.01; S, 6.87; found: C, 51.30; H, 4.83; N, 5.89; S,
6.91.
1
3
(d, JH,P = 12.2 Hz, 1H), 3.73 (d, JH,P = 10.9 Hz,
3
3H, CH3O), 3.74 (d, JH,P = 10.9 Hz, 3H, CH3O)
ppm. 13C NMR (CDCl3): δ = 13.1 (CH3S), 28.3, 33.0
4
1
(2CH2), 36.8 (d, JC,P = 2.7 Hz, CH), 37.4 (d, JC,P
=
144.1 Hz, CH2P), 44.1 (d, 3 JC,P = 14.2 Hz, CH), 41.6,
3
42.3, 42.8, 45.4, 47.5 (5CH), 48.7 (d, JC,P = 6.4 Hz,
2
2
CH), 51.3 (d, JC,P = 3.4 Hz, Cq), 51.9 (d, JC,P = 6.7
2
Hz, 1 CH3O), 52.1 (d, JC,P = 6.6 Hz, 1 CH3O) ppm.
31P NMR (CDCl3, 121 MHz): δ 30.84 ppm. MS-CI
(NH3) m/z (%): 316 (18), 315 (100) [M + 1]+, 301
(7), 267 (42) [M – SCH3]+, 191 (6). Anal. Calcd for
C15H23O3PS (314.39): C, 57.31; H, 7.37; S, 10.20;
found: C, 57.26; H, 7.33; S, 10.15.
X-Ray Crystal-Structure Determination of 11c
(Fig. 1). All measurements were made on a Non-
ius KappaCCD diffractometer [19] using graphite-
˚
monochromated MoKα radiation (λ 0.71073 A) and
an Oxford Cryosystems Cryostream 700 cooler. Data
reduction was performed with HKL Denzo and
Scalepack [20]. The intensities were corrected for
Lorentz and polarization effects, and an absorp-
tion correction based on the multiscan method [21]
was applied. A view of the molecule is shown in
Fig. 1. The structure was solved by direct methods
using SIR92 [22], which revealed the positions of
all non-hydrogen atoms. There are two symmetry-
independent molecules in the asymmetric unit. The
atomic coordinates of the two molecules were tested
carefully for a relationship from a higher symme-
try space group using the program PLATON [23],
but none could be found. The non-hydrogen atoms
were refined anisotropically. All of the H-atoms were
placed in geometrically calculated positions and re-
fined using a riding model, where each H-atom was
assigned a fixed isotropic displacement parameter
with a value equal to 1.2Ueq of its parent C-atom
(1.5Ueq for the Me groups). Refinement of the struc-
ture was carried out on F2 using full-matrix least-
squares procedures, which minimized the function
ꢀw(Fo2– Fc2)2. A correction for secondary extinction
was not applied. One reflection, whose intensity was
considered to be extreme outliers, was omitted from
the final refinement. Neutral atom scattering factors
for non-hydrogen atoms were taken from [24], and
Dimethyl {[8-(Allylsulfanyl)pentacyclo[5.4.0.02,6
.03,10.05,9]undecan-8-yl]methyl}phosphonate (11b).
The crude product was isolated as a brownish oil,
which after crystallization from hexane (dry ice)
gave 250 mg (74%) of the analytically pure 11b (mp
46◦C–48◦C). IR (KBr): v 3079, 2998, 2972, 2963,
2934, 2860, 1635, 1452, 1425, 1415, 1277, 1250,
1237, 1189, 1060, 1045, 1033, 889, 866, 825, 811,
1
788 cm−1. H NMR (CDCl3): δ 0.95–1.02 (m, 1H),
1.21, 1.67 (AB, JAB = 10.6 Hz, 2H, CH2), 1.86–2.73
(m, 10H, CH, CH2), 3.12–3.32 (m, 3H), 3.58 [d, 3 JH,P
= 10.9 Hz, 3H, (CH3O)2P], 3.60 [3 JH,P = 11.0 Hz,
3H, (CH3O)2P], 5.04–5.22 (m, 2H, CH2), 5.38–5.96
(m, 1H, CH) ppm. 13C NMR (CDCl3): δ 28.3, 33.0
4
(2CH2), 33.9 (CH2S), 36.8 (d, JC,P = 2.9 Hz, CH),
1
38.0 (d, JC,P = 144.1 Hz, CH2P), 41.6, 42.3, 42.8,
3
45.2, 47.6 (5CH), 44.3 (d, JC,P = 14.4 Hz, CH), 49.1
(d, 3 JC,P = 6.1 Hz, CH), 51.9 (Cq), 52.0, 52.2 [2d, 2 JC,P
= 6.4 and 6.7 Hz, resp., (CH3O)2P], 116.9 ( CH2);
135.2 ( CH) ppm. 31P NMR (CDCl3, 121 MHz): δ
31.81 ppm. MS-CI (NH3) m/z (%): 331 (100) [M +
1]+, 315 (70), 267 (60) [(M + 1) – SCH2CH CH]+,
157 (6). Anal. Calcd for C17H25O3PS (340.42): C,
59.98; H, 7.40; S, 9.42; found: C, 59.73; H, 7.44; S,
9.44.
Heteroatom Chemistry DOI 10.1002/hc