H+/g, we showed that the acids groups were accessible with
a high salt uptake.
product was purified by distillation (100 ꢀC at 2 ꢁ 10ꢂ2 mbar) to
1
give 5 as a colourless liquid (9.4 g, 25.4 mmol, 82% yield). H
3
NMR (d, 200 MHz, CDCl3): 0.61 (2 H, m), 1.26 (9 H, t, JH,H
¼
7.0 Hz), 1.30 (2 H, m), 1.32 (6 H, t, 3JH,H ¼ 7.0 Hz), 1.34 (2 H, m),
Experimental
1.66 (2 H, m), 1.82 (2 H, t, 3JH,H ¼ 6.4 Hz), 3.81 (6 H, q, 3JH,H
¼
3
7.0 Hz), 4.10 (4 H, q, JH,H ¼ 7.0 Hz). 13C NMR (d, 50 MHz,
CDCl3): 12.3, 16.7, 16.9, 23.0, 31.2, 61.7 and 65.0. 31P NMR (d,
100 MHz, CDCl3): 33.5. 29Si NMR (d, 40 MHz, CDCl3): ꢂ43.1.
General procedures
3-Cyanopropyltriethoxysilane, 3-chloropropyltriethoxysilane,
NaH, p-toluene sulfonyl chloride and NaCN were purchased
from Aldrich and used as supplied. 3-Cyanopropyltrichloro-
silane, 4-bromobutene, 5-bromopentene, 11-bromoundecene,
benzylbromide, triethoxysilane (HSi(OEt)3) and potassium
pentadionate were purchased from Alfa Aesar. Karstedt’s
catalyst was from ABCR. Diethyl malonate and triethylphosphite
were from Acros. 2-(4-Butenyl)propane-1,3-diol ditosylate was
prepared according to the procedure previously described10 for
2-(3-propenyl)propane-1,3-diol ditosylate. Cyanopentyltriiso-
propoxysilane and cyanoundecyltriisopropoxysilane were
prepared according to the procedure previously described.11 The
CP-MAS 29Si and 13C solid-state NMR spectra were recorded
on a BRUKER FTAM 300, in the latter case by using the TOSS
technique. The repetition time was 5 (for 13C) and 10 s (for 29Si)
with contact times of 3 (for 13C) and 5 (for 29Si) ms. The duration
of the 1H pulse was 4.2 (for 13C) and 4.5 (for 29Si) ms and the MAS
rate was 10 (for 13C) and 5 (for 29Si) kHz. Chemical shifts (d, ppm)
were referenced to Me4Si (13C and 29Si). Powder X-ray diffraction
experiments were carried out on a high resolution Bonse-Hart
camera with two germanium channel cuts for very small q values.
Synthesis of 6. 6 was prepared according to the procedure used
for 5 and was obtained in 80% yield after distillation (135 ꢀC at 2
ꢁ 10ꢂ2 mbar). 1H NMR (d, 200 MHz, CDCl3): 0.60 (2 H, m), 1.22–
1.40 (16 H, m), 1.26 (9 H, t, 3JH,H ¼ 7.9 Hz), 1.34 (6 H, t, 3JH,H
¼
7.0 Hz), 1.66 (2 H, m), 2.40 (2 H, m), 3.80 (6 H, q, 3JH,H ¼ 7.9 Hz),
4.10 (4 H, q, 3JH,H ¼ 7.0 Hz). 13C NMR (d, 50 MHz, CDCl3): 12.3,
16.7, 22.7–33.6, 61.8 and 65.1. 31P NMR (d, 100 MHz, CDCl3):
33.7. 29Si NMR (d, 40 MHz, CDCl3): ꢂ43.6.
Synthesis of 7. A mixture of 2-(4-butenyl)propane-1,3-diol
ditosylate10 (8.0 g, 18.0 mmol) and triethoxysilane (6.0 g,
36.0 mmol) in the presence of Karstedt’s catalyst (10 mol%)
was heated at 80 ꢀC for 24 h giving rise to 2-(4-triethoxysilyl-
butyl)propane-1,3-diol ditosylate. Subsequent isopropanolysis
was achieved to give 2-(4-trisopropoxysilylbutyl)propane-1,3-
diol ditosylate (8.2 g, 12.6 mmol, 70%) after distillation
(110 ꢀC at 2 ꢁ 10ꢂ2 mbar). The dinitrile was prepared by mixing
8.0 g (12.4 mmol) of ditosylate, NaCN (2.6 g, 53.0 mmol) and
DMSO (60 mL). The resulting solution was stirred at reflux
for 24 h. The reaction mixture was cooled to room temperature
and was taken up in water (50 mL) and Et2O (80 mL). After
extraction with Et2O (2 ꢁ 100 mL), the organic layer was dried
under MgSO4 and evaporated under vacuum. The crude product
was purified by distillation (110 ꢀC at 4 ꢁ 10ꢂ2 mbar) to give 4.1 g
(11.6 mmol, 92%) of 2-(4-trisopropoxysilylbutyl)glutaronitrile 7.
1H NMR (d, 200 MHz, CDCl3): 0.60 (2 H, m), 1.27 (18 H, d,
3JH,H ¼ 6.9 Hz), 1.40–1.80 (6 H, m), 2.16 (1 H, m), 2.57 (4 H,
˚
The wavelength used was 1.542 A (CuKa radiation). Elemental
analyses of Si, C, N, P, K and Eu were performed by the Service
Central d’Analyse (CNRS, Vernaison, France).
Syntheses
Synthesis of 2 and 3. 2 and 3 were prepared according to the
procedure previously described.11
3
3
Synthesis of 4. Triethoxysilylpropyldiethylphosphonate 4 was
prepared by Arbuzov reaction between 3-iodopropyltriethoxy-
silane12 and triethylphosphite. 3-Iodopropyltriethoxysilane
(16.6 g, 50 mmol) was added to P(OEt)3 (20.0 g, 120 mmol).
The mixture was heated at reflux for 24 h under Ar, then the
excess of P(OEt)3 was removed under vacuum. The crude product
was purified by distillation (120 ꢀC at 5 ꢁ 10ꢂ2 mbar) to give 4 as
a colourless liquid (12.0 g, 35 mmol, 70% yield). 1H NMR (d, 200
MHz, CDCl3): 0.63 (2 H, m), 1.25 (9 H, t, 3JH,H ¼ 7.0 Hz), 1.34
(6 H, t, 3JH,H ¼ 7.0 Hz), 1.81 (4 H, m), 3.80 (6 H, q, 3JH,H ¼ 7.0
d, JH,H ¼ 8.0 Hz), 4.21 (3 H, sept, JH,H ¼ 6.9 Hz). 13C NMR
(d, 50 MHz, CDCl3): 11.3, 13.8, 22.5, 25.7, 27.9, 29.0, 32.6,
56.5 and 117.0. 29Si NMR (d, 40 MHz, CDCl3): ꢂ44.0.
Synthesis of 8. To
a suspension of K2CO3 (15.0 g,
108.6 mmol), undecylenic acid (10.0 g, 54.3 mmol) in DMF
(200 mL), 7 mL (54.3 mmol) of benzylbromide were added at
room temperature. The resulting mixture was heated at 80 ꢀC
for 36 h. After cooling to room temperature, the mixture was
taken up in water (200 mL) and Et2O (100 mL). After extraction
with Et2O (2 ꢁ 100 mL), the organic layer was dried under
MgSO4 and evaporated under vacuum. 13.0 g (87%) of ester
were obtained as a colourless liquid. Subsequent hydrosilylation
was achieved as described above. 17.5 g (89%) of 8 were obtained
3
Hz), 4.12 (4 H, q, JH,H ¼ 7.0 Hz). 13C NMR (d, 50 MHz,
CDCl3): 10.3, 16.3, 16.9, 27.0, 29.4, 61.4 and 65.2. 31P NMR (d,
100 MHz, CDCl3): 32.7. 29Si NMR (d, 40 MHz, CDCl3): ꢂ43.0.
1
Synthesis of 5. A mixture of 5-bromopentene (10.0 g,
after distillation (180 ꢀC at 4 ꢁ 10ꢂ2 mbar). H NMR (d, 200
66.5 mmol) and triethoxysilane (22.0 g, 133.0 mmol) in the
ꢀ
MHz, CDCl3): 0.66 (2 H, m), 1.21–1.30 (14 H, m), 1.22 (9 H,
3
3
presence of Karstedt’s catalyst (10 mol%) was heated at 80 C
t, JH,H ¼ 7.9 Hz), 1.63 (2 H, m), 2.30 (2 H, t, JH,H ¼ 7.6 Hz),
3
for 24 h giving rise to 5-bromopentyltriethoxysilane in high yield
3.80 (6 H, q, JH,H ¼ 7.9 Hz), 5.40 (2 H, s), 7.38 (5 H, s). 13C
(80%) after distillation (90 C at 8 ꢁ 10ꢂ2 mbar). The Arbuzov
NMR (d, 50 MHz, CDCl3): 10.7, 18.7, 23.0–32.0, 34.7, 58.7,
59.5, 128.8, 174.0. 29Si NMR (d, 40 MHz, CDCl3): ꢂ44.1.
ꢀ
reaction was carried out by mixing 12.8 g of triethylphosphite
(77.0 mmol) and 5-bromopentyltriethoxysilane (10.0 g,
31.0 mmol). The resulting solution was stirred for 24 h at reflux.
The residual P(OEt)3 was evaporated under vacuum. The crude
Synthesis of 9. To a solution of silylated ester 8 (4.0 g,
9.1 mmol) in AcOEt (60 mL), 700 mg of Pd/C were added at
This journal is ª The Royal Society of Chemistry 2008
J. Mater. Chem., 2008, 18, 2028–2035 | 2029