C, 43.03; H, 7.74; S, 49.23%). IR (KBr, cmꢁ1): 2956 (s), 2908
(s), 2548 (m), 1424 (s), 1370 (m), 1344 (m), 1296 (s), 1252 (s),
1204 (m), 866 (m), 754 (m). 1H-NMR (300 MHz, CDCl3): d =
1.05 (s, 3 H), 1.36 (t, J = 8 Hz, 3 H), 1.85 (tt, J = 7 Hz,
6 H), 2.57–2.65 (m, 18 H). 13C-NMR (75 MHz, CDCl3):
d = 23.2, 23.8, 32.1, 33.4, 40.3, 41.5. EI-MS: m/z 390.0
(11.3%).
as eluent. Yield 15%. Mp 78–81 1C. (Found C, 51.05; H, 8.33;
S, 32.68%, C25H50OSiS6 (M 587.12) requires C, 51.14; H, 8.58;
S, 32.77%). IR (KBr, cmꢁ1): 2952 (s), 2924 (s), 2854 (m), 1464
1
(m), 1414 (m), 1250 (m), 1092 (s) 844 (w), 742 (w). H-NMR
(300 MHz, CDCl3): d = 0.05 (s, 6H), 0.89 (s, 9 H), 1.09 (s, 3
H), 1.99 (t, J = 6.6 Hz, 6 H), 2.73 (t, J = 6.6 Hz, 6 H), 2.73 (t,
J = 6.6 Hz, 6 H), 2.87 (s, 6 H), 2.92 (s, 6 H), 3.57 (s, 2 H). 13C-
NMR (75 MHz, CDCl3): d = ꢁ5.71, 18.11,, 24.1, 25.8, 28.4, ,
31.6, 31.8, 38.0, 40.7, 42.1, 45.9, 66.8. FAB-MS: m/z 587.3
(100%).
1,9-Dimethyl-3,7,11,15,18,22-hexathiabicyclo[7.7.7]tricosane
(9). Caesium carbonate (2.84 g, 8.7 mmol) was suspended in
dry DMF (270 ml) under nitrogen. 4 (2.98 g, 5.12 mmol) and 8
(2 g, 5.12 mmol) each dissolved in dry DMF (320 ml) were
added at the same time dropwise under stirring over 72 hours
at 60 1C in a nitrogen atmosphere. After complete addition the
reaction mixture was stirred for an additional day. The solvent
was removed in vacuum and the remaining solid was extracted
several times with dichloromethane. Evaporation of the
solvent gave a brownish semisolid. Column chromatography
over silica with dichloromethane as eluent yielded the
product as a white, crystalline solid. Yield 0.24 g (10%).
Mp. 104–105 1C. (Found C, 49.96; H, 7.76; S, 42.22%,
C19H36S6 (M 456.85) requires: C, 49.95; H, 7.94; S, 42.11%).
IR (KBr, cmꢁ1): 2912 (s), 1430 (m), 1254 (m), 844 (m).
1H-NMR (300 MHz, CDCl3): d = 1.09 (s, 6 H), 1.99 (q, J
= 6.6 Hz, 6 H), 2.75 (t, J = 6.6 Hz, 12 H), 2.87 (s, 12 H).
13C-NMR (75 MHz, CDCl3): d = 24.1, 28.4, 21.6, 40.8, 42.2.
EI-MS: m/z 456.1 (23.34%).
1,1,1-Tris(6-mercapto-2-thiahexanyl)-ethane (13). The com-
pound was prepared from 1,4-butanedithiole and 4 in analogy
to 8. The residue after evaporation of the solvent was sub-
jected to column chromatography on silica (CH2Cl2 : hexane
= 2 : 1). Yield 60%. Found C, 47.20; H, 8.42%, C17H36S6
(M 432.83) requires: C, 47.17; H, 8.38%). IR (KBr, cmꢁ1):
2928 (s), 2848 (m), 2548 (w), 1450 (m), 1370 (m), 1280 (m),
1244 (m), 1202 (w), 860 (w), 738 (w). 1H-NMR (300 MHz,
CDCl3): d = 1.06 (s, 3 H), 1.35 (t, J = 7.9 Hz, 3 H), 1.67–1.71
(m, 12 H), 2.49–2.56 (m, 12 H), 2.63 (s, 6 H). 13C-NMR
(75 MHz, CDCl3): d = 23.7, 24.1, 28.3, 33.3, 32.8, 40.3, 41.6.
FAB-MS: m/z 432.0 (100%).
1-Hydroxymethyl-10-methyl-3,8,12,17,20,25-hexathiabicyclo
[8.8.8]hexacosane (14). The compound was prepared starting
from 13 and 6 in analogy to 9. Column chromatography over
silica with dichloromethane : acetonitrile = 9 : 1 as eluent gave
the product as a white, crystalline solid. Yield 29%. M.p.:
80–82 1C. (Found C, 51.47; H, 8.26; O, 3.29; S, 37.11%,
C22H42OS6 (M 514.93) requires C, 51.31; H, 8.22; O, 3.11; S,
37.36%). IR (KBr, cmꢁ1): 3438 (m, br), 2914 (s), 2848 (m),
1420 (m), 1372 (w), 1280 (m), 1240 (m), 1052 (m), 858 (w), 750
(w). 1H-NMR (300 MHz, CDCl3): d = 1.09 (s, 3 H), 1.78–1.83
(m, 12 H), 2.60–2.65 (m, 12 H), 2.77 (s, 6 H), 2.87 (s, 6 H), 3.67
(s, 2 H). 13C-NMR (75 MHz, CDCl3): d = 23.7, 27.0, 27.2,
32.9, 32.9, 37.4, 40.0, 41.4, 44.2, 68.0. FAB-MS: m/z (%) =
514.2 (69.46%).
1-Nitro-9-methyl-3,7,11,15,18,22-hexathiabicyclo[7.7.7]tricosane
(10). The compound was prepared from 5 and 8 in analogy to
the cage 9. The purification was achieved by column chroma-
tography on silica with dichloromethane : iso-hexane = 8 : 1.
Yield 12%. Mp. 117–119 1C. (Found C, 44.40; H, 6.95; N,
2.90; O, 6.45; S, 39.31%, C18H33NO2S6 (M 487.82) requires C,
44.32; H, 6.82; N, 2.87; O, 6.56; S, 39.44%). IR (KBr, cmꢁ1):
2908 (m), 1538 (s), 1406 (m), 1374 (w), 1344 (m). 1H-NMR
(300 MHz, CDCl3): d = 1.10 (s, 3 H), 2.02 (tt, JAB = JBC 6.7
Hz, 6 H), 2.74 (t, J = 6.7 Hz, 6 H), 2.83 (s, 6 H), 3.43 (s, 6 H).
13C-NMR (75 MHz, CDCl3): d = 23.9, 28.4, 31.7, 32.3, 38.3,
40.7, 42.1, 95.6. EI-MS: m/z 487.0 (33.43%), 441.1 (33.29%,
M-NO2).
Tris(3-chloropropanyl)nitromethane (16).
A mixture of
tris(3-hydroxypropanyl)nitromethane 15 (10 g, 43 mmol) and
thionyl chloride (16 ml, 216 mmol) was stirred at rt for one
hour. Excess thionyl chloride was evaporated and the mixture
chromatographed on silica with CH2Cl2 as eluent. The pro-
duct was isolated as a yellow oil. Yield 10.7 g (86%). (Found
C, 41.59; H, 6.26; N, 4.64; O, 11.20%, C10H18Cl3NO2 (M
290.62) requires: C, 41.33; H, 6.24; N, 4.82; O, 11.01%). IR
(KBr, cmꢁ1): 2964 (s), 2872 (m), 1537 (s), 1448 (m), 1354 (m),
1316 (m), 1116 (w), 842 (w), 782 (w), 732 (w), 652 (m).
1H-NMR (300 MHz, CDCl3): d = 1.66–1.75 (m, 6 H),
2.06–2.12 (m, 6 H), 3.56 (t, J = 6.1 Hz, 6 H). 13C-NMR (75
MHz, CDCl3): d = 26.5, 32.8, 44.2, 93.0. EI-MS: m/z 243.0
(12.35%).
1-Hydroxymethyl-9-methyl-3,7,11,15,18,22-hexathiabicyclo
[7.7.7]tricosane (11). The compound was prepared from 8 and
6 in analogy to 9. Purification was achieved by column
chromatography over silica with dichloromethane : aceto-
nitrile = 9 : 1 as eluent. Yield 22%. Mp. 164 1C. (Found C,
48.11; H, 7.61; O, 3.67; S, 40.76%, C19H36OS6 (M 472.85)
requires: C, 48.26; H, 7.67; O, 3.38; S, 40.69%). IR (KBr,
cmꢁ1): 3448 (w), 2950 (m), 2912 (s), 1448 (m), 1430 (m), 1400
(m), 1290 (m), 1254 (m), 1188 (w), 844 (w), 742 (w). 1H-NMR
(300 MHz, CDCl3): d = 1.09 (s, 3 H), 2.00 (tt, J = 6.6 Hz, 6
H), 2.76 (t, J = 6.6 Hz, 12 H), 2.88 (s, 6 H), 2.98 (s, 6 H), 3.65
(s, 2 H). 13C-NMR (75 MHz, CDCl3): d = 24.1, 28.2, 31.5,
31.7, 38.3, 40.9, 42.4, 45.6, 68.0. EI-MS: m/z 472.2 (100%).
Tris(7-mercapto-4-thiaheptanyl)nitromethane (17). The com-
pound was prepared starting from 16 and 1,3-propanedithiole
in analogy to 8. The residue was subjected to column chro-
matography on silica (CH2Cl2 : hexane = 3 : 1). The com-
pound was isolated as a colourless oil. Yield 53%. (Found
C, 45.07; H, 7.74; N, 2.67; O, 6.17; S 38.25%, C19H39NO2S6
1-(tert-Butyl-dimethylsilyloxymethyl)-9-methyl-3,7,11,15,18,
22-hexathia[7.7.7]tricosane (12). The compound was prepared
in analogy to 9 starting from 7 and 8. Purification was
achieved by column chromatography on silica with CH2Cl2
ꢀc
This journal is the Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2007
New J. Chem., 2007, 31, 409–417 | 415