R. Koschabek, R. Gleiter, F. Rominger
FULL PAPER
3
carbonate (4.9 g, 35 mmol) in acetonitrile (200 mL). The mixture
was stirred intensively and refluxed for 2 d until the starting mate-
rial was consumed. The mixture was filtered and the solvent evapo-
rated. The residue was purified by column chromatography on alu-
mina.
CarH), 7.60 (d, J = 8.5 Hz, 4 H, CarH) ppm. 13C NMR (75 MHz,
CD2Cl2): δ = 33.9 (s, CH2), 34.2 (s, CH2), 56.2 (s, CH2), 56.3 (s,
CH2), 126.2 (t, Car), 127.3 (t, Car), 127.3 (t, Car), 127.5 (t, Car),
128.7 (t, Car), 129.1 (t, Car), 129.2 (t, Car), 129.7 (t, Car), 135.4 (q,
C ), 139.1 (q, C ), 140.6 (q, C ), 141.4 (q, C ) ppm. IR (KBr): ν
˜
ar
ar
ar
ar
= 3440, 3057, 3027, 2943, 2859, 2808, 1486, 1452, 1408 cm–1. UV/
Vis (CH2Cl2): λmax (lg ε) = 258 (4.6) nm. HRMS (FAB) calcd. for
C36H36N 482.2848; found 482.2881. C36H35N (482.28): calcd. C
89.77, H 7.32, N 2.91; found C 89.54, H 7.39, N 3.03.
Tris(2-phenylethyl)amine (28): 945 mg (58%); m.p. 31 °C; cyclohex-
ane/ethyl acetate, 50:1. 1H NMR (300 MHz, CD2Cl2): δ = 2.75–
2.81 (m, 6 H, CH2), 2.84–2.90 (m, 6 H, CH2), 7.21–7.24 (m, 9 H,
3
CarH), 7.32 (t, J = 7.2 Hz, 6 H, CarH) ppm. 13C NMR (75 MHz,
CD2Cl2): δ = 34.2 (s, CH2), 56.4 (s, CH2), 126.2 (t, Car), 128.7 (t,
Tris[2-(biphenyl-4-yl)ethyl]amine (33): 405 mg (15%); m.p. 75 °C;
hexane/diethyl ether, 20:1. 1H NMR: (300 MHz, CD2Cl2): δ =
2.79–2.85 (m, 6 H, CH2), 2.88–2.93 (m, 6 H, CH2), 7.26 (d, 3J =
C ), 129.2 (t, C ), 141.4 (q, C ) ppm. IR (KBr): ν = 3480, 3086,
˜
ar
ar
ar
3028, 2957, 2933, 2864, 2798, 1946, 1873, 1809, 1751, 1600, 1491,
1452 cm–1. UV/Vis (CH2Cl2): λmax (lg ε) = 258 (3.0) nm. HRMS
(FAB) calcd. for C24H28N 330.2221; found 330.2207. C24H27N
(330.22): calcd. C 87.49, H 8.26, N 4.25; found C 87.44, H 8.22, N
4.40.
3
8.1 Hz, 6 H, CarH), 7.30–7.35 (m, 3 H, CarH), 7.43 (t, J = 7.5 Hz,
3
3
6 H, CarH), 7.52 (d, J = 8.1 Hz, 6 H, CarH), 7.59 (d, J = 7.6 Hz,
6 H, CarH) ppm. 13C NMR (75 MHz, CD2Cl2): δ = 33.8 (s, CH2),
56.2 (s, CH2), 127.3 (t, Car), 127.3 (t, Car), 127.4 (t, Car), 129.1 (t,
Car), 129.7 (t, Car), 139.0 (q, Car), 140.6 (q, Car), 141.4 (q, Car) ppm.
(But-3-ynyl)bis(2-phenylethyl)amine (29): 305 mg (22%) colorless li-
quid; hexane/diethyl ether, 10:1. 1H NMR (300 MHz, CD2Cl2): δ
= 2.01 (m, 1 H, ϵCH), 2.30 (m, 2 H, CH2), 2.72–2.84 (m, 10 H,
CH2), 7.15–7.21 (m, 4 H, CarH), 7.25–7.31 (m, 6 H, CarH) ppm.
13C NMR (75 MHz, CD2Cl2): δ = 17.7 (s, CH2), 34.4 (s, CH2), 53.2
(s, CH2), 56.3 (s, CH2), 69.1 (t, ϵCH), 83.6 (q, ϵC), 126.3 (t, Car),
IR (KBr): ν = 3440, 3027, 2924, 2854, 1486, 1461, 1450 cm–1. UV/
˜
Vis (CH2Cl2): λmax (lg ε) = 258 (4.7) nm. HRMS (FAB) calcd. for
C42H40N 558.3160; found 558.3134. C42H39N (558.32): calcd. C
90.44, H 7.05, N 2.51; found C 90.09, H 7.32, N 2.65.
General Procedure for the Cyclization of α,ω-Diamines with 1,6-Di-
bromo-3-hexyne (16) to the Bicyclic Diynes 4–8: 1,6-Dibromo-3-
hexyne (17) (1.5 g, 6.25 mmol) and the corresponding α,ω-diamines
(2 mmol) were added together to a suspension of finely powdered
potassium carbonate (4.5 g, 33 mmol) in acetonitrile (125 mL). The
mixture was stirred intensively and refluxed for 3 d until the start-
ing material was consumed. The mixture was filtered and the sol-
vent evaporated. The residue was purified by column chromatog-
raphy on alumina.
128.7 (t, C ), 129.2 (t, C ), 141.2 (q, C ) ppm. IR (KBr): ν =
˜
ar
ar
ar
3294, 3026, 2948, 2860, 2812, 2117, 1946, 1868, 1805, 1742, 1602,
1496, 1453 cm–1. UV/Vis (CH2Cl2): λmax (lg ε) = 260 (2.5) nm.
HRMS (FAB) calcd. for C20H23N 278.1909; found 278.1918.
C20H23N (278.19): calcd. C 86.59, H 8.36, N 5.05; found C 86.64,
H 8.33, N 5.27.
[2-(Biphenyl-4-yl)ethyl]bis(2-phenylethyl)amine (30): 940 mg (47%);
m.p. 54 °C; hexane/diethyl ether, 10:1. 1H NMR (500 MHz,
3
CD2Cl2): δ = 2.74–2.87 (m, 12 H, CH2), 7.18 (d, J = 8.0 Hz, 6 H,
4-Thia-1,7-diazabicyclo[5.6.6]nonadeca-10,16-diyne
(4):
Yield:
3
CarH), 7.26 (m, 6 H, CarH), 7.31–7.34 (m, 1 H, CarH), 7.43 (t, J
227 mg of 4 (41%), column chromatography with cyclohexane/ethyl
3
3
= 7.7 Hz, 2 H, CarH), 7.53 (d, J = 8.0 Hz, 2 H, CarH), 7.60 (d, J
= 7.5 Hz, 2 H, CarH) ppm. 13C NMR (125 MHz, CD2Cl2): δ = 33.7
(s, CH2), 34.1 (s, CH2), 56.1 (s, CH2), 56.2 (s, CH2), 126.1 (t, Car),
127.2 (t, Car), 127.2 (t, Car), 127.3 (t, Car), 128.5 (t, Car), 129.0 (t,
Car), 129.1 (t, Car), 129.6 (t, Car), 139.0 (q, Car), 140.5 (q, Car),
1
acetate, 20:1, m.p. 69 °C. H NMR (500 MHz, CD2Cl2): δ = 2.24–
3
2.35 (m, 8 H, CH2), 2.52–2.56 (m, 8 H, CH2), 2.76 (t, J = 6.0 Hz,
4 H, CH2), 2.98 (t, 3J = 6.0 Hz, 4 H, CH2) ppm. 13C NMR
(125 MHz, CD2Cl2): δ = 19.5 (s, CH2), 30.6 (s, CH2), 53.4 (s, CH2),
56.5 (s, CH2), 80.6 (q, Calkyne) ppm. IR (KBr): ν = 3447, 2900,
˜
141.3 (q, C ) ppm. IR (KBr): ν = 3025, 2946, 1597, 1495, 1486,
˜
ar
2835, 2801, 2781, 2731, 1449, 1432 cm–1. Raman: ν = 2228,
˜
1453 cm–1. UV/Vis (CH2Cl2): λmax (lg ε) = 256 (4.4) nm. HRMS
(EI+) calcd. for C30H31N 405.2457; found 405.2448. C30H31N
(405.24): calcd. C 88.84, H 7.70, N 3.45; found C 88.44, H 7.84, N
3.57.
2291 cm–1. HRMS (FAB) calcd. for C16H25N2S 277.1738; found
277.1731. C16H24N2S (272.17): calcd. C 69.52, H 8.75, N 10.13, S
11.60; found C 69.31, H 8.77, N 10.04, S 11.43.
4-Selena-1,7-diazabicyclo[5.6.6]nonadeca-10,16-diyne (5): Yield:
212 mg of 5 (33%), column chromatography with cyclohexane/ethyl
acetate, 20:1, m.p. 107 °C. 1H NMR (300 MHz, CD2Cl2): δ = 2.26–
2.33 (m, 8 H, CH2), 2.52–2.56 (m, 8 H, CH2), 2.89 (t, 3J = 6.1 Hz, 4
H, CH2), 3.01 (t, 3J = 6.1 Hz, 4 H, CH2) ppm. 13C NMR (75 MHz,
CD2Cl2): δ = 19.5 (s, CH2), 22.2 (s, CH2), 53.3 (s, CH2), 57.4 (s,
Bis[2-(biphenyl-4-yl)ethyl]but-3-ynylamine (31): 553 mg (25%) col-
orless oil; hexane/diethyl ether, 10:1. 1H NMR: (500 MHz,
4
3
CD2Cl2): δ = 2.04 (t, J = 2.6 Hz, 1 H, ϵCH), 2.37 (dt, J = 4.8,
4J = 2.6 Hz, 2 H, CϵCCH2), 2.82–2.87 (m, 10 H, CH2), 7.29 (d,
3J = 8.1 Hz, 4 H, CarH), 7.34 (pt, 3J = 7.4 Hz, 2 H, CarH), 7.44
(pt, 3J = 7.7 Hz, 4 H, CarH), 7.54 (d, 3J = 8.1 Hz, 4 H, CarH), 7.61
(d, 3J = 7.2 Hz, 4 H) ppm. 13C NMR: (125 MHz, CD2Cl2): δ =
17.6 (s, CH2), 33.9 (s, CH2), 53.10 (s, CH2), 56.1 (s, CH2), 69.10 (t,
ϵCH), 83.6 (q, ϵC), 127.2 (t, Car), 127.3 (t, Car), 127.4 (t, Car),
129.1 (t, Car), 129.6 (t, Car), 139.1 (q, Car), 140.3 (q, Car), 141.3
CH2), 80.6 (q, Calkyne) ppm. IR: (KBr): ν = 3445, 2951, 2903, 2790,
˜
2728, 1453, 1428 cm–1. Raman: ν = 22278, 22891 cm–1. HRMS
˜
(FAB) calcd. for C16H25N282Se 327.1184; found 327.1144.
C16H24N2Se (327.12): calcd. C 59.43, H 7.48, N 8.66; found C
59.28, H 7.55, N 8.58.
(q, C ) ppm. IR (KBr): ν = 3441, 3307, 3055, 3026, 1487, 1449,
˜
ar
1407 cm–1. UV/Vis (CH2Cl2): λmax (lg ε) = 258 (4.6) nm. HRMS
(FAB) calcd. for C32H31N 430.2534; found 430.2534. C32H31N
(430.25): calcd. C 89.47, H 7.27, N 3.26; found C 89.08, H 7.25, N
3.32.
4,7-Dithia-1,10-diazabicyclo[8.6.6]docosa-13,19-diyne (6): Yield:
291 mg of 6 (43%), column chromatography with cyclohexane/ethyl
1
acetate, 50:1, m.p. 134 °C. H NMR (300 MHz, CD2Cl2): δ = 2.26
(mt, 8 H, CH2), 2.44–2.48 (m, 8 H, CH2), 2.61–2.65 (m, 8 H, CH2),
2.74 (s, 4 H, SCH2CH2S) ppm. 13C NMR (75 MHz, CDCl3): δ =
18.7 (s, CH2), 30.4 (s, CH2), 31.8 (s, CH2), 53.2 (s, CH2), 54.3 (s,
Bis[2-(biphenyl-4-yl)ethyl](2-phenylethyl)amine (32): 566 mg (56%);
m.p. 82 °C; hexane/diethyl ether, 10:1. 1H NMR (300 MHz,
3
CD2Cl2): δ = 2.78–2.92 (m, 12 H, CH2), 7.20 (d, J = 7.6 Hz, 3 H, CH2), 79. 5 (q, Calkyne) ppm. IR (KBr): ν = 3440, 2956, 2900, 2801,
˜
CarH), 7.26 (d, 3J = 8.2 Hz, 6 H, CarH), 7.31–7.36 (m, 2 H, 2730, 1630, 1455, 1421 cm–1. Raman: ν = 22368, 2300 cm–1. HRMS
˜
3
3
CarH),7.44 (t, J = 8.0 Hz, 4 H, CarH), 7.53 (d, J = 8.2 Hz, 4 H,
(FAB) calcd. for C18H29N2S2 337.1772; found 337.1735.
618
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Eur. J. Inorg. Chem. 2006, 609–620