Tripodands with Phenyl and Thiophenyl Rings and Nitrogen Bridgehead Atoms
FULL PAPER
Car), 125.0 (d, Car), 126.0 (d, Car), 128.6 (d, Car), 129.1 (d, Car),
calcd. C 68.60, H 7.14, N 3.20, S 14.65; found C 68.58, H 7.19, N
3.37, S 14.77.
132.7 (d, Car), 141.1 (s, Car), 146.2 (s, Car) ppm. HRMS (FAB+):
12
calcd. for
C
27
1H3414N132S128Si1 432.2181; found 432.2187.
2-[4-(Trimethylsilylethynyl)phenyl]-N,N-bis(2-phenylethyl)ethyl-
amine (38): Starting materials: 34 (1.73 g, 3.80 mmol), ethynyltri-
methylsilane (1.16 g, 4.74 mmol, 40% solution in THF), tetrakis-
(triphenylphosphane)palladium(0) (254 mg, 0.22 mmol), copper(I)
iodide (84 mg, 0.44 mmol), diethylamine (40 mL); column
chromatography: silica gel, petroleum ether/diethyl ether (10:1).
Yield: 1.6 g (95%) of 38 as a colorless oil. 1H NMR (300 MHz,
CD2Cl2): δ = 0.24 (s, 9 H, CH3), 2.71 (m, 6 H, CH2), 2.80 (m, 6
N,N-Bis{2-[5-(trimethylsilylethynyl)-2-thienyl]ethyl}-2-phenylethyl-
amine (26): Starting materials: 23 (2.32 g, 3.91 mmol), ethynyltri-
methylsilane (1.74 g, 17.67 mmol, 44% solution in THF), tetrakis-
(triphenylphosphane)palladium(0) (444 mg, 0.38 mmol), copper(I)
iodide (146 mg, 0.77 mmol), diethylamine (50 mL); column
chromatography: deactivated silica gel, petroleum ether/diethyl
ether (5:1). Yield: 2.1 g (99 %) of 26 as a yellow oil. 1H NMR
(300 MHz, CD2Cl2): δ = 0.23 (s, 18 H, Si-CH3), 2.74–2.80 (m, 4 H,
CH2), 2.81–2.84 (m, 4 H, CH2), 2.86–2.94 (m, 4 H, CH2), 6.64 (d,
3J = 3.5 Hz, 2 H, CHar), 7.04 (d, 3J = 3.5 Hz, 2 H, CHar), 7.18 (m,
3
3
H, CH2), 7.10 (d, J = 7.1 Hz, 2 H, CHar), 7.17 (d, J = 7.5 Hz, 4
H, CHar), 7.20 (t, 3J = 7.5 Hz, 2 H, CHar), 7.28 (t, 3J = 7.4 Hz, 4 H,
CHar), 7.36 (d, J = 8.1 Hz, 2 H, CHar) ppm. 13C NMR (75 MHz,
3
4
3 H, CHar), 7.27 (t, 3J = 9.2 Hz, J = 5.5 Hz, 2 H, CHar) ppm. 13C
CD2Cl2): δ = 0.0 (q, CH3), 34.1 (t, CH2), 34.2 (t, CH2), 55.9 (t, N-
CH2), 56.2 (t, N-CH2), 93.7 (s, CϵC), 105.4 (s, CϵC), 120.1 (s,
Car), 126.0 (d, Car), 128.6 (d, Car), 129.1 (d, Car), 129.2 (d, Car),
NMR (75 MHz, CD2Cl2): δ = –0.1 (q, Si-CH3), 28.7 (t, CH2), 34.0
(t, CH2), 55.5 (t, N-CH2), 56.1 (t, N-CH2), 98.2 (s, CϵC), 98.3 (s,
CϵC), 121.3 (s, CHar), 125.0 (d, CHar), 126.3 (d, CHar), 128.7 (d,
132.0 (d, Car), 141.2 (s, Car), 142.2 (s, Car) ppm. HRMS (FAB+):
12
calcd. for
C
29
1H3614N128Si1 426.2617; found 426.2596; calcd. for
CHar), 129.1 (d, CHar), 132.8 (d, CHar), 140.8 (s, CHar), 146.0 (s,
12
1H4014N132S228Si2
C
29
1H3414N128Si 424.2461; found 424.2467. IR (film): ν = 3026
˜
1
12
CHar) ppm. HRMS (FAB+): calcd. for
534.2141; found 534.2138; calcd. for
C
30
1H3814N132S228Si2
12
(s), 2954 (vs), 2861 (m), 2803 (s), 2156 (vs), 1506 (s), 1496 (s), 1453
(s), 1249 (s), 1223 (m), 1121 (s). C29H35NSi (425.68): C 81.82, H
8.29, N 3.29; found C 81.97, H 8.41, N 3.54.
C
30
532.1984; found 532.2029. IR (KBr): ν = 3441 (m), 3025 (w), 2953
˜
(s), 2815 (s), 2141 (vs), 1943 (w), 1532 (m), 1497 (m), 1453 (s), 1439
(m), 1248 (s) cm–1. C30H39NS2Si2 (533.94): calcd. C 67.48, H 7.36,
N 2.62; found C 67.48, H 7.52, N 2.86.
N,N-Bis{2-[4-(trimethylsilylethynyl)phenyl]ethyl}-2-phenylethyl-
amine (39): Starting materials: 35 (4.71 g, 8.10 mmol), ethynyltri-
methylsilane (4.60 g, 18.83 mmol, 44% solution in THF), tetrakis-
(triphenylphosphane)palladium(0) (468 mg, 0.41 mmol), copper(I)
iodide (154 mg, 0.81 mmol), diethylamine (50 mL); column
chromatography: deactivated silica gel, petroleum ether/diethyl
Tris{2-[5-(trimethylethylsilylethynyl)-2-thienyl]ethyl}amine (27):
Starting materials: 24 (1.81 g, 2.50 mmol), ethynyltrimethylsilane
(2.01 g, 8.23 mmol, 44% solution in THF), tetrakis(triphenylphos-
phane)palladium(0) (372 mg, 0.32 mmol), copper(I) chloride
(158 mg, 0.83 mmol), diethylamine (85 mL); column chromatog-
raphy: deactivated silica gel, petroleum ether/diethyl ether (5:1).
Yield: 1.56 g (99%) of 27 as a white solid; m.p. 94 °C. 1H NMR
1
ether (5:1). Yield: 4.11 g (97%) of 39 as a colorless oil. H NMR
(500 MHz, CD2Cl2): δ = 0.23 (s, 18 H, Si-CH3), 2.67 (m, 6 H, CH2),
3
3
2.76 (m, 6 H, CH2), 7.06 (d, J = 8.1 Hz, 4 H, CHar), 7.14 (d, J =
3
3
7.0 Hz, 2 H, CHar), 7.17 (t, J = 7.3 Hz, 1 H, CHar), 7.27 (t, J =
7.0 Hz, 2 H, CHar), 7.35 (d, 3J = 8.1 Hz, 4 H, CHar) ppm. 13C
NMR (125 MHz, CD2Cl2): δ = 0.0 (q, Si-CH3), 34.1 (t, CH2), 34.2
(t, CH2), 55.2 (t, N-CH2), 55.9 (t, N-CH2), 93.6 (s, CϵC), 105.3 (s,
CϵC), 120.9 (s, CHar), 126.0 (d, CHar), 128.6 (d, CHar), 129.1 (d,
3
(500 MHz, CDCl3): δ = 0.24 (s, 27 H, CH3), 2.81 (t, J = 7.1 Hz,
3
3
6 H, CH2), 2.91 (t, J = 7.1 Hz, 6 H, CH2), 6.60 (d, J = 3.4 Hz, 3
H, CHar), 7.05 (d, 3J = 3.4 Hz, 3 H, CHar) ppm. 13C NMR
(125 MHz, CDCl3): δ = 0.1 (q, Si-CH3), 28.7 (t, CH2), 55.4 (t,
CH2), 98.0 (s, CϵC), δ = 98.2 (s, CϵC), 121.4 (s, Car), 124.9 (d,
CHar), 129.2 (d, CHar), 132.0 (d, CHar), 141.2 (s, CHar), 142.0 (s,
Car), 132.6 (d, Car), 145.1 (s, Car) ppm. HRMS (FAB+): calcd. for
12
CHar) ppm. HRMS (FAB+): calcd. for
522.3012; found 522.2976; calcd. for
found 520.2818.
C
1H4414N128Si2
C
C
1H4614N132S328Si3 636.2100; found 636.2070; calcd. for
12
34
33
12
C
1H4214N128Si2 520.2856;
34
12
1H4414N132S328Si3 634.1944; found 634.1923. IR (KBr): ν =
˜
33
3451 (b), 2955 (m), 2924 (m), 2824 (w), 2140 (s), 1533 (w), 1459 (m),
1248 (s), 1172 (m), 1158 (m) cm–1. C33H45NS3Si3 (636.17): calcd. C
62.31, H 7.13, N 2.20, S 15.12; found C 62.52, H 7.29, N 2.37, S
15.11.
Tris{2-[4-(phenylethynyl)phenyl]ethyl}amine (16): Compound 36
(1.34 g, 1.90 mmol), tetrakis(triphenylphosphane)palladium(0)
(134 mg, 0.108 mmol), and copper(I) iodide (54 mg, 0.28 mmol)
were suspended in triethylamine (60 mL) and 1-ethynylbenzene
(1.16 g, 11.36 mmol) was added. The reaction mixture was heated
at 80 °C for 1 h. For work up the solvent was evaporated under
reduced pressure and the residue was purified by column
chromatography [deactivated silica gel, petroleum ether/diethyl
ether (3:1)]. Yield: 1.13 g (94%) of 16 as a white solid; m.p. 106 °C.
1H NMR (500 MHz, CDCl3): δ = 2.73 (m, 6 H, CH2), 2.82 (m, 6
H, CH2), 7.12 (d, 3J = 8.0 Hz, 6 H, CHar), 7.30–7.35 (m, 9 H,
2-[4-(Trimethylsilylethynyl)phenyl]-N,N-bis[2-(2-thienyl)ethyl]ethyl-
amine (37): Starting materials: 33 (5.00 g, 10.71 mmol), ethynyltri-
methylsilane (3.04 g, 13.39 mmol, 44% solution in THF), tetrakis-
(triphenylphosphane)palladium(0) (309 mg, 0.27 mmol), copper(I)
iodide (102 mg, 0.54 mmol), diethylamine (60 mL); column
chromatography: deactivated silica gel, petroleum ether/diethyl
1
ether (5:1). Yield: 4.6 g (98%) of 37 as a pale yellow oil. H NMR
(300 MHz, CD2Cl2): δ = 0.28 (s, Si-CH3), 2.72–2.92 (m, 8 H, CH2),
2.94–3.05 (m, 4 H, CH2), 6.82 (d, 3J = 3.0 Hz, 2 H, CHar), 6.94
(dd, 3J = 5.1 Hz, 3J = 3.0 Hz, 2 H, CHar), 7.14 (m, 4 H, CHar), 7.40
3
3
4
CHar) 7.46 (d, J = 8.0 Hz, 6 H, CHar), 7.53 (dd, J = 7.1 Hz, J
= 2.0 Hz, 6 H, CHar) ppm. 13C NMR (125 MHz, CDCl3): δ = 34.0
(t, CH2), 55.7 (t, CH2), 89.0 (s, CϵC), 89.5 (s, CϵC), 121.0 (s, Car),
123.6 (s, Car), 128.3 (d, Car), 128.5 (d, Car), 129.0 (d, Car), 131.6 (d,
3
(d, J = 8.0 Hz, 2 H, CHar) ppm. 13C NMR (75 MHz, CD2Cl2): δ
= 0.1 (q, Si-CH3), 28.6 (t, CH2), 34.2 (t, CH2), 55.8 (t, N-CH2),
56.0 (t, N-CH2), 93.7 (s, CϵC), 105.6 (s, CϵC), 121.0 (s, Car), 123.6
(d, Car), 125.0 (d, Car), 127.0 (d, Car), 129.2 (d, Car), 132.0 (d, Car),
Car), 131.8 (d, Car), 141.2 (s, Car) ppm. HRMS (FAB+): calcd. for
12
C
48
1H4014N 630.3161; found 630.3145. IR (KBr): ν = 3447 (b),
˜
1
3028 (w), 2949 (w), 2791 (w), 2214 (w), 1639 (m), 1510 (s), 1441
(m), 1121 (s). C48H39N (629.83): C 91.53, H 6.24, N 2.22; found C
91.36, H 6.31 N 2.45.
142.0 (s, Car), 143.5 (s, Car) ppm. HRMS (FAB+): calcd. for
12
C
C
1H3214N132S228Si1 438.1745; found 438.1723; calcd. for
25
12
1H3014N132S228Si1 436.1589; found 436.1604. IR (film): ν =
˜
25
3069 (m), 2954 (s), 2808 (s), 2157 (s), 1506 (s), 1461 (m), 1439 (s),
General Procedure for Removal of the TMS Group − Synthesis of
1399 (m), 1353 (m), 1249 (s), 1223 (m) cm–1. C25H31NS2Si (437.36): 28–30: The TMS-protected compounds were dissolved in tetra-
Eur. J. Org. Chem. 2006, 5264–5278
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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