B.P. Pichon et al. / Journal of Organometallic Chemistry 691 (2006) 1126–1130
1129
1
compound 2a as a colorless liquid (4.77 g, 70%); H NMR
(CDCl3): d = 0.59 (t, 2H, J = 7.0 Hz, CH2Si), 1.18 (t, 9H,
J = 6.9 Hz, CH3), 1.40 (m, 4H, CH2), 1.81 (m, 2H, CH2),
3.33 (t, 2H, J = 6.8 Hz, CH2Br), 3.77 (q, 6H, J = 6.9 Hz,
OCH2); 13C NMR (CDCl3): d = 10 (CH2Si), 18 (CH3),
22, 31 and 32 (3CH2), 34 (CH2Br), 58 (CH2O); 29Si
NMR (CDCl3): d = À45.4; m/e MS FAB+ 314/312 (M+,
32); IR (CHCl3): m = 2976, 2929, 2891, 1102, 1077, 958,
night at 80 ꢁC. Distillation under reduced pressure (90 ꢁC
at 4 · 10À2 bar) afforded compound 2b as a colorless liquid
(6.35 g, 80%). 1H NMR (CDCl3): d = 0.59 (t, 2H,
J = 7.2 Hz, CH2Si), 1.18 (t, 9H, J = 6.9 Hz, CH3), 1.22
(m, 16H, CH2), 1.81 (m, 2H, CH2), 3.36 (t, 2H,
J = 6.8 Hz, CH2Br), 3.77 (q, 6H, J = 6.9 Hz, OCH2); 13C
NMR (CDCl3): d = 10 (CH2Si), 18 (CH3), 22 (CH2), 28–
33 (8CH2), 34 (CH2Br), 58 (CH2O); 29Si NMR (CDCl3):
d = À45.4; m/e MS FAB+ 398/396 (M+, 10); IR (CHCl3):
792 cmÀ1
.
2976, 2928, 2856, 1102, 1077, 908, 737 cmÀ1
.
4.1.2. 5-Azidopentyltriethoxysilane (3a)
1.7 g of sodium azide (28.5 mmol) was added to 3.56 g
of 5-bromopentyltriethoxysilane (11.4 mmol) in acetoni-
trile (40 mL) under nitrogen atmosphere. The solution
was stirred under reflux for 48 h. After removal of the sol-
vent under vacuum, the crude mixture was diluted in pen-
tane and the suspension was filtered. Solvent was removed
from the resulting filtrate and the crude oil obtained was
distilled under reduced pressure (65 ꢁC at 3 · 10À2 bar) to
4.1.5. 11-Azidoundecyltriethoxysilane (3b)
To a solution of 5.96 g of 11-bromoundecyltriethoxysi-
lane (15.0 mmol) in acetonitrile (40 mL) placed under
nitrogen atmosphere, was added 2.46 g of sodium azide
(37.8 mmol). The solution was stirred under reflux for
48 h. The solvent was removed under vacuum, the crude
mixture was diluted in pentane and the suspension was fil-
tered. Solvent was removed from the obtained filtrate and
the crude oil obtained is distilled under reduced pressure
(111 ꢁC at 5 · 10À2 bar) to give compound 3b as a colorless
1
give compound 3a as a colorless liquid (2.66 g, 84%). H
NMR (CDCl3): d = 0.60 (t, 2H, J = 7.0 Hz, CH2Si), 1.18
(t, 9H, J = 6.9 Hz, CH3), 1.25 (m, 2H, CH2), 1.38 (m,
2H, CH2), 1.58 (m, 2H, CH2), 3.20 (t, 2H, J = 6.7 Hz,
NCH2), 3.77 (q, 6H, J = 6.9 Hz, OCH2); 13C NMR
(CDCl3): d = 10 (CH2Si), 18 (CH3), 22, 28 and 29
(3CH2), 51 (CH2N), 58 (CH2O); 29Si NMR (CDCl3):
d = À45.4; m/e MS FAB+ 275 (M+, 15); IR (CHCl3):
2976, 2930, 2887, 2099, 1102, 1077, 959, 793 cmÀ1; Anal.
Calc. for C11H25N3O3Si: C, 47.97; H, 9.15; N, 15.26.
Found: C, 47.69; H, 9.24; N, 15.46%.
1
liquid (4.80 g, 89%). H NMR (CDCl3): d = 0.61 (t, 2H,
CH2Si), 1.17 (t, J = 6.9 Hz, 9H, CH3), 1.25 (m, 16H,
CH2), 1.58 (m, 2H, CH2), 3.23 (t, 2H, J = 6.7 Hz,
NCH2), 3.78 (q, 6H, J = 6.9 Hz, OCH2); 13C NMR
(CDCl3): d = 0 (CH2Si), 18 (CH3), 23 (CH2), 27–33
(8CH2), 51 (CH2N), 58 (CH2O); 29Si NMR (CDCl3):
d = À45.4; m/e MS FAB+ 314 [(M À EtO), 27]; IR
(CHCl3): 2927, 2856, 2098, 1102, 1078, 909, 738 cmÀ1
;
Anal. Calc. for C17H37N3O3Si: C, 56.78; H, 10.37; N,
11.69. Found: C, 56.95; H, 10.42; N, 11.39%.
4.1.3. 5-Aminopentyltriethoxysilane (4a)
The synthesis of 5-aminopentyl triethoxysilane (4a) has
been already described [23]. 1.63 g of 5-azidopentyltrieth-
oxysilane (5.9 mmol) and ethanol (40 mL) were placed in
an autoclave. Palladium on activated carbon, wt. 10%
(50 mg) was added and a pressure of hydrogen (1 bar)
was applied and the mixture was stirred during 20 min at
room temperature. The solution was filtered to eliminate
the charcoal and the solvent was removed under vacuum.
The crude oil obtained was distilled under reduced pressure
to give compound 4a (67 ꢁC at 3 · 10À2 bar) as a colorless
4.1.6. 11-Aminoundecyltriethoxysilane (4b)
The synthesis of 11-aminoundecyltriethoxysilane (4a)
has been already described [20]. A solution of 1 g of 11-azi-
doundecyltriethoxysilane (2.76 mmol) in ethanol (40 mL)
was placed in an autoclave. 50 mg of palladium catalyst
on activated carbon (10 wt%) was added and a pressure
of hydrogen (1 bar) was applied. The reaction mixture
was stirred during 20 min at room temperature. The char-
coal was eliminated by filtration and the solvent was
removed under vacuum. The crude oil obtained was dis-
tilled under reduced pressure (136 ꢁC at 4 · 10À2 bar) to
1
liquid (1.15 g, 78%). H NMR (CDCl3): d = 0.60 (t, 2H,
1
J = 7.0 Hz, CH2Si), 1.18 (t, 9H, J = 6.8 Hz, CH3), 1.36
(m, 8H, CH2, NH2), 2.63 (t, 2H, J = 6.5 Hz, NCH2), 3.77
(q, 6H, J = 6.8 Hz, OCH2); 13C NMR (CDCl3): d = 10
(CH2Si), 18 (CH3), 23, 30–33 (3CH2), 42 (CH2N), 58
(CH2O); 29Si NMR (CDCl3): d = À45.4; m/e MS FAB+
249 (M+, 100); IR (CHCl3): 3323, 2976, 2930, 2887, 1102,
give compound 4b as a colorless liquid (1.15 g, 78%). H
NMR (CDCl3): d = 0.61 (t, 2H, J = 7.0 Hz, CH2Si), 1.18
(t, 9H, J = 6.9 Hz, CH3), 1.25 (m, 18H, CH2), 2.66 (t,
2H, J = 6.8 Hz, NCH2), 3.80 (q, 6H, J = 6.9 Hz, OCH2);
13C NMR (CDCl3): d = 10 (CH2Si), 18 (CH3), 23 (CH2),
27–33 (8 CH2), 42 (CH2N), 58 (CH2O); 29Si NMR:
d = À45.4; IR (CHCl3): 3300, 2976, 2927, 2856, 1102,
1077, 959, 793 cmÀ1
.
1078, 909, 738 cmÀ1
.
4.1.4. 11-Bromoundecyltriethoxysilane (2b)
The synthesis of 11-bromoundecyltriethoxysilane (2b)
has already been described [24]. To 4.66 mL of 1-bromoun-
decene (20 mmol), were added 5.5 mL of triethoxysilane
(30 mmol) and 44.5 mL of Karstedt catalyst (1 mmol)
under nitrogen atmosphere. The reaction was stirred over-
4.1.7. 1,4-Bis[(triethoxysilyl)pentylureido]benzene (P)
To a solution of 96 mg of 1,4-diisocyanatobenzene
(0.6 mmol) in dichloromethane (10 mL), was added drop-
wise 385 mg of 5-aminopentyltriethoxysilane (1.55 mmol)
and the reaction was stirred overnight. The solvent was