Table 4 X-Ray data and structural refinement details for compounds
3, 14 and 16
contain exclusively 9 and traces of 1,3-bis(ethoxydimethyl-
1
silyl)benzene were detected in the H and 13C NMR spectrum
(between 5 to 8%). Unfortunately, further attempts to purify
9 by distillation led to a partial decomposition of the com-
pound. Yield: 19 g (62%). 1H NMR (CDCl3): d 0.41 (s, 18
H, SiMe2), 1.21 [t, 9 H, 3J(H–H) ¼ 6.98, Me], 3.71 [q, 6 H,
3J(H–H) ¼ 6.98, OCH2], 7.85 (s, 3 H, H of C6H3). 13C {1H}
NMR (CDCl3): d ꢁ1.6 (s, SiMe2), 18.5 (s, Me of OEt), 58.8
(s, OCH2), 136.3 (s, C1,3,5 of C6H3), 139.8 (s, CH of C6H3).
MS: m/z (%): 384 (2) [M ꢁ 1], 368 (100) [M ꢁ CH3], 324 (20)
[M ꢁ CH3 ꢁ OC2H5], 281 (18) [M ꢁ Si(CH3)2OC2H5], 267
Compound
3
14
16
Molecular formula
C
24H42O3Si6 C16H28O2S2Si4 C18H32Br2N2O2Si4ꢃC4H8O
FW
T/K
547.12
150.0(10)
0.71069
428.86
150.0(10)
0.71069
652.74
150.0(10)
0.71069
Orthorhombic
Pnma
˚
l/A
Crystal system
Monoclinic
P21/c
Triclinic
Pꢁ1
Space group
˚
a/A
˚
17.0411(3)
12.0953(2)
16.9900(2)
90.00
6.7411(2)
8.2744(2)
11.44040(10)
72.939(2)
23.444(5)
12.699(5)
10.521(5)
90.00
b/A
˚
c/A
(40)
[M ꢁ Si(CH3)2OC2H5 ꢁ CH3],
177
(60)
[M ꢁ 2
a/deg
b/deg
g/deg
Si(CH3)2OC2H5].
114.0700(10) 72.984(2)
90.00
90.00
90.00
3197.43(9)
4
73.3800(10)
569.18(2)
1
1,3,5-Tris(chlorodimethylsilyl)benzene (12). Compound 9 (5 g,
13 mmol) and acetyl chloride (10 mL), which was used both as
reagent and solvent, were heated at 80 ꢀC for 15 h. After
evaporation of the excess acetyl chloride and ethyl acetate,
compound 12 was recovered as a brownish oil. After disti-
llation, 12 was recovered as a colourless oil (purity 95%). Yield:
4.62 g ( > 99%). For spectroscopic charcaterizations, see ref. 11.
3
˚
U/A
3132(2)
4
Z
m(MoKa)/cmꢁ1
Reflect. measured
Indep. reflect.
Reflections used
Rint
0.283
15394
9244
0.452
4544
2.765
6591
3296
2782
3592
2757
7331
0.0212
0.0388
0.1104
0.0277
0.0346
0.0967
0.0249
0.0455
0.1388
a
R1 [I > 2s(i)]
b
wR2 [I > 2s(I)]
2,5-Bis(chlorodimethylsilyl)thiophene(13). The 2,5-bis(chloro-
dimethylsilyl)thienyl derivative was obtained through the
reaction of the dilithium salt with Me2SiCl2 in excess. A solu-
tion of butyllithium (1.6 M in hexane; 40 mmol, 25 mL) was
added dropwise at room temperature to a solution of thio-
phene (1.64 g, 20 mmol) and TMEDA (4.64 g, 40 mmol).
The resulting mixture was then heated under reflux for 90
min. After cooling to ꢁ20 ꢀC, Me2SiCl2 (51.84 g, 400 mmol)
was added and the resulting solution was heated under reflux
for 2 h. After evaporation of the excess Me2SiCl2 , the orange
residue obtained was distilled. Compound 13 was recovered as
a colourless oil. Yield: 3.77 g (70%). For spectroscopic charac-
terizations, see ref. 14.
a
b
2
R1 ¼ S|F0| ꢁ |Fc|/S|F0|. wR2 ¼ (SwkF0| ꢁ |Fck /Sw|F0|2)1/2
.
dichloromethane was added and the resulting solution was fil-
tered on celite. The pink powder obtained was successively
washed with hexane (5 mL) and Et2O (2 ꢂ 5 mL), after eva-
poration of the solvent. After drying, pyridinophane 17 was
recovered as a slightly coloured pink solid. Yield: 0.17 g
(78%); mp > 260 ꢀC. 1H NMR (CDCl3): d 0.61 (s, 24H,
3
SiMe2), 7.4 [d, 4 H, J (H–H) ¼ 7.6 Hz, H3 of C5H3N], 7.65
[t, 2 H, J (H–H) ¼ 7.8 Hz, H4 of C5H3N]. 13C {1H} NMR
3
(CDCl3): d 0.6 (s, SiMe2), 127.7 (s, C3 of C5H3N), 132.8 (s,
C4 of C5H3N), 171.23 (s, C2 of C5H3N). MS (m/z, %): 429
(M, 100). Anal. calcd for C18H30N2O2Si4 : C, 51.62; H, 7.22;
found: C, 51.50; H, 7.29%.
1,1,3,3,9,9,11,11-Octamethylsilyl-2,10-oxa[3.3](2,5)thiopheno-
phane (14). 13 (4 g, 15 mmol) was dissolved in THF (1.5 L) and
water (1.35 g, 65 mmol) was added in one portion at room
temperature. The resulting solution was stirred for 1 week.
After evaporation of the solvent, the orange residue obtained
was crystallized in methanol (10 mL) at room temperature.
After filtration, compound 14 was recovered as a white solid.
Yield: 0.20 g (7%); mp 175 ꢀC. 1H (CDCl3): d 0.36 (s, 24H,
4 ꢂ SiMe2), 7.26 (s, 4H, H of C4H2S). 13C {1H} NMR
(CDCl3): d 0.3 (s, SiMe2), 134.1 (s, CH of C4H2S), 158.1 (s,
Cipso of C4H2S). MS (m/z, %): 429 (M, 100). Anal. calcd for
C16H28O2S2Si4 : C, 44.81; H, 6.58; found: C, 44.70; H, 6.63%.
X-Ray structural determination
Single crystals of compound 3 suitable for X-ray crystallogra-
phy were obtained by recrystallization from hexane. Single
crystals of compound 14 were obtained by diffusing methanol
into a toluene solution of the compound. Single crystals of
compound 16 were obtained by diffusing THF into a benzoni-
trile solution of the compound. Data were collected on a Non-
ius Kappa CCD diffractometer using an Mo Ka (l ¼ 0.71073
˚
A) X-ray source and a graphite monochromator. Experimental
Precursor 16. The 2,6-bis(bromodimethylsilyl)pyridine
hydrobromide salt (15; 5 g, 11.5 mmol) was dissolved in
THF (700 mL) and water (0.4 g, 22.2 mmol) was added in
one portion at room temperature. After 5 days of stirring,
macrocycle 16 was collected by filtration and washed with
ether (20 mL). After drying, 16 was recovered as a white solid.
details are described in Table 4. The crystal structures were
solved using SIR 9719 and SHELXL-97.20 ORTEP drawings
were made using ORTEP III for Windows.21
rsc.org/suppdata/nj/b2/b211045h/ for crystallographic data
in CIF or other electronic format.
1
Yield: 2.66 g (80%); mp > 260 ꢀC. H NMR (CD3CN): d 0.88
(s, 24H, SiMe2), 8.19 [dd, 4 H, 3J(H–H) ¼ 7.8 Hz, 4J(H–H) ¼
1.3 Hz, H3 of C5H3N], 8.48 [t, 2 H, 3J(H–H) ¼ 7.8, H4 of
C5H3N]. 13C {1H} NMR (CD3CN): d 0.0 (s, SiMe2), 134.0
(s, C3 of C5H3N), 143.5 (s, C4 of C5H3N), 160.3 (s, C2 of
C5H3N). MS (m/z, %): 419 (100) [M ꢁ 1], 282 (75)
[M ꢁ C5H5NSiMe2]. Anal. calcd for C18H32Br2N2O2Si4 : C,
37.24; H, 5.56; found: C, 37.30; H, 5.65%.
Acknowledgements
The authors thank the CNRS and the Ecole Polytechnique for
the financial support of this work.
References
1,1,3,3,10,10,12,12-Octamethylsilyl-2,11-oxa[3.3](2,6)pyridino-
phane (17). Compound 16 (0.30 g, 0.519 mmol) was suspended
in hexane (15 mL). Methyllithium in ether (1.6 M; 0.66 mL,
1.056 mmol) was then added to this solution at 0 ꢀC. After
warming up to room temperature, the solution was stirred
at room temperature for 3 h. After evaporation of the solvent,
1
2
C. J. Brown and A. C. Farthing, Nature (London), 1949, 164,
915–916.
(a) F. Vo¨gtle, Top. Curr. Chem., 1983, 113, 16–19; (b) F.
Diederich, Cyclophanes, Royal Society of Chemistry, Cambridge,
1991; (c) D. J. Cram and J. M. Cram, Container Molecules and
Their Guests, Royal Society of Chemistry, Cambridge, 1994.
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