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PAPER
1105 (w), 1051 (w), 1028 (w), 993 (w), 916 (m), 888 (w), 845 (s),
770 (w), 638 (w), 607 (w) cm–1.
addition of [PdCl2(PPh3)2] (15.1 mg, 21.3 mmol) and copper(I) io-
dide (20.0 mg, 106 mmol) the mixture was heated at 80 °C for 24 h.
The color changed from yellow to dark red. The solvent was re-
moved and the residue was dissolved in CH2Cl2 (50 mL). After
washings with an aq solution of KCN (2 × 20 mL, 2%) and water
(3 × 20 mL), the organic layer was dried (Na2SO4), filtered, and con-
centrated. Purification of the product by column chromatography
(CH2Cl2, Rf 0.25) and recrystallization from CHCl3–hexane fur-
nished an orange solid. Yield: 19.4 mg (17.1 mmol, 28%); mp > 300
°C.
1H NMR (400 MHz, CDCl3): d = 1.90 (s, 12 H, 7¢-H, 10¢-H), 1.98
(s, 12 H, 7¢¢-H, 10¢¢-H), 2.04 (s, 12 H, 7¢¢¢-H, 9¢¢¢-H), 2.08 (s, 12 H,
7¢¢¢¢¢-H, 9¢¢¢¢¢-H), 2.23 (s, 6 H, 8¢¢¢-H), 2.28 (s, 6 H, 8¢¢¢¢¢-H), 2.38 (s,
12 H, 8¢¢-H, 9¢¢-H), 2.52 (s, 12 H, 8¢-H, 9¢-H), 6.91 (s, 4 H, 5¢¢¢-H,
3¢¢¢-H), 7.01 (s, 4 H, 3¢¢¢¢¢-H, 5¢¢¢¢¢-H), 7.47 (d, J = 8.0 Hz, 2 H, 8-H),
7.72 (s, 2 H, 5¢¢¢¢-H, 6¢¢¢¢-H) 7.84 (dd, J1 = 9.8 Hz, J2 = 1.8 Hz, 4 H,
5-, 6-H), 8.28 (d, J = 8.0 Hz, 2 H, 7-H), 8.38 (d, J = 2.3 Hz, 2 H, 4-
H), 8.47 (s, 2 H, 4¢¢¢¢-H, 7¢¢¢¢-H).
IR (KBr): 2950 (s), 2914 (s), 2858 (s), 2212 (w), 1610 (m), 1583
(w), 1535 (w), 1507 (s), 1452 (s), 1410 (s), 1249 (m), 1144 (w),
1108 (w), 1060 (w), 1035 (w), 993 (w), 923 (m), 875 (w), 840 (s),
779 (w), 635 (w), 615 (w) cm–1.
1H NMR (400 MHz, CDCl3): d = 1.92 (s, 12 H, 10¢-H, 11¢-H), 2.01
(s, 12 H, 7¢¢-H, 9¢¢-H), 2.13 (s, 6 H, 8¢¢-H), 2.30 (s, 12 H, 9¢-H, 12¢-
H), 6.90 (s, 4 H, 3¢¢-H, 5¢¢-H), 7.65 (dd, J1 = 8.0 Hz, J2 = 4.4 Hz, 2
H, 8¢¢¢-H), 7.80 (d, J = 8.4 Hz, 2 H, 6¢¢¢-H), 7.85 (s, 2 H, 5-H, 6-H),
7.89 (d, J = 8.4 Hz, 2 H, 5¢¢¢-H), 8.26 (dd, J1 = 8.0 Hz, J2 = 1.8 Hz,
2 H, 7¢¢¢-H), 8.38 (d, J = 1.9 Hz, 2 H, 4¢¢¢-H), 8.42 (s, 2 H, 4-H, 7-
H), 9.19 (dd, J1 = 4.4 Hz, J2 = 1.8 Hz, 2 H, 9¢¢¢-H), 9.27 (d, J = 1.9
Hz, 2 H, 2¢¢¢-H).
13C NMR (100 MHz, CDCl3): d = 17.8 (C-7¢), 19.1 (C-8¢), 20.0 (C-
7¢¢, C-10¢¢), 20.3 (C-7¢¢¢, C-9¢¢¢), 20.5 (C-7¢¢¢¢¢, C-9¢¢¢¢¢), 20.7 (C-8¢¢,
C-9¢¢), 21.2 (C-8¢¢¢¢¢), 21.2 (C-8¢¢¢), 87.2 (C-9¢), 88.3 (C-2¢), 94.4 (C-
10¢), 95.0 (C-1¢), 119.6 (C-8¢¢¢¢) 119.7, 122.4, 122.8, 123.2, 123.9,
124.5, 125.6, 126.0, 126.8, 127.0, 127.4, 127.6, 127.9, 128.2, 128.5,
128.9, 131.2, 131.9, 134.6, 134.9, 135.2, 135.4, 136.0, 136.5, 136.8,
137.0, 137.2, 137.4, 137.6, 137.7, 138.2, 144.2, 144.9, 145.8, 146.5,
150.2, 151.9, 160.4 (C-9), 161.9 (C-2).
MS (ESI): m/z (%) = 1793.1 (100) [M + H]+.
Anal. Calcd for C120H106N6Br2·2H2O: C, 78.84; H, 6.07; N, 4.60.
Found: C, 78.79; H, 6.13; N, 4.49.
13C NMR (100 MHz, CDCl3): d = 17.5 (C-9¢, C-12¢), 19.3 (C-10¢,
C-11¢), 20.0 (C-7¢¢, C-9¢¢), 21.2 (C-8¢¢), 87.7 (C-7¢), 88.3 (C-2¢), 94.6
(C-1¢), 95 (C-8¢), 119.2, 119.6, 121.8, 122.3, 122.7, 123.3, 124.6,
125.2, 126.8, 127.3, 127.4, 127.6, 127.9, 128.3, 128.5, 128.9, 131.1,
131.9, 135.8, 135.9, 137.2, 137.4, 137.6, 137.8, 138.0, 138.5, 144.8,
144.9, 145.8, 145.9, 150.5, 151.9, 160.4, 161.9 (C-2).
3,8-Bis{4-[2-(4-bromo-2,3,5,6-tetramethylphenyl)-9-(2,4,6-tri-
methylphenyl)-[1,10]phenanthrolin-3-ylethynyl]-(2,3,5,6-tet-
ramethylphenylethynyl)}-[1,10]phenanthroline (T3)
Under N2 atmosphere, 13 (75.0 mg, 100 mmol) and 6b (107 mg, 200
mmol) were dissolved in benzene (25 mL) and Et3N (10 mL). After
adding [PdCl2(PPh3)2] (30.0 mg, 42.6 mmol) and copper(I) iodide
(47.6 mg, 106 mmol) the mixture was heated at 80 °C for 24 h. The
color changed from yellow to dark red. The solvents were removed
and the residue was dissolved in CH2Cl2 (100 mL). Thereafter, it
was washed with an aq solution of KCN (2 × 50 mL, 2%) and water
(3 × 50 mL). The organic layer was dried (MgSO4), filtered, and
concentrated. Separation of the residue was achieved by column
chromatography (CH2Cl2, Rf 0.22). An orange solid was furnished
after recrystallization from CHCl3–hexane. Yield: 41.1 mg (26.5
mmol, 27%); mp > 300 °C.
MS (ESI): m/z (%) = 1134.6 (100) [M + H+].
Anal. Calcd for C82H64N6·1 H2O: C, 85.53; H, 5.78; N, 7.30. Found:
C, 85.41; H, 5.69; N, 7.19.
3,8-Bis{2,5-bisdodecyloxy-4-([1,10]phenanthrolin-3-ylethynyl)-
phenylethynyl}-[1,10]phenanthroline (T5)
Under N2 atmosphere, 9 (51.0 mg, 223 mmol) and 16 (348 mg, 449
mmol) were dissolved in benzene (20 mL) and Et3N (15 mL). After
addition of [PdCl2(PPh3)2] (15 mg, 21.5 mmol) and copper(I) iodide
(20.0 mg, 106 mmol) the mixture was heated at 80 °C for 24 h. The
color changed from yellow to dark red. The solvents were removed
and the residue was dissolved in CH2Cl2. After washings with an aq
solution of KCN (2 × 20 mL, 2%) and water (3 × 20 mL), the organ-
ic layer was dried (Na2SO4), filtered, and concentrated. Separation
of the residue was accomplished by column chromatography
(CH2Cl2–EtOAc, 90:10; Rf 0.12). Yield: 102 mg (67 mmol, 30%); a
light orange solid; mp > 300 °C.
IR (KBr): 2951 (s), 2917 (s), 2855 (s), 2207 (w), 1612 (m), 1579
(w), 1534 (w), 1505 (s), 1455 (s), 1401 (s), 1249 (m), 1144 (w),
1105 (w), 1064 (w), 1031 (w), 991 (w), 913 (m), 885 (w), 845 (s),
778 (w), 638 (w), 609 (w) cm–1.
1H NMR (400 MHz, CDCl3): d = 1.92 (s, 12 H, 7¢-H, 10¢-H), 1.98
(s, 12 H, 7¢¢-H, 10¢¢-H), 2.06 (s, 12 H, 7¢¢¢-H, 9¢¢¢-H), 2.23 (s, 6 H,
8¢¢¢-H), 2.38 (s, 12 H, 8¢¢-H, 9¢¢-H), 2.52 (s, 12 H, 8¢-H, 9¢-H), 6.91
(s, 4 H, 3¢¢¢-H, 5¢¢¢-H), 7.47 (d, J = 8.0 Hz, 2 H, 8-H), 7.72 (s, 2 H,
5¢¢¢¢-H, 6¢¢¢¢-H), 7.84 (dd, J1 = 9.8 Hz, J2 = 1.8 Hz, 4 H, 5-H, 6-H),
8.28 (d, J = 8.0 Hz, 2 H, 7-H), 8.38 (d, J = 2.3 Hz, 2 H, 4¢¢¢¢-H, 7¢¢¢¢-
H), 8.47 (s, 2 H, 4-H), 9.18 (d, J = 2.3 Hz, 2 H, 2¢¢¢¢-H, 9¢¢¢¢-H).
13C NMR (100 MHz, CDCl3): d = 17.8 (C-7¢, C-10¢), 19.7 (C-8¢, C-
9¢), 20.0 (C-7¢¢, C-10¢¢), 20.4 (C-7¢¢¢, C-9¢¢¢), 20.9 (C-8¢¢, C-9¢¢), 21.2
(C-8¢¢¢), 87.2 (C-9¢), 88.3 (C-2¢), 94.4 (C-10¢), 95.0 (C-1¢), 119.6,
119.7, 122.4, 122.8, 123.2, 124.5, 125.6, 126.0, 126.8, 127.0,
127.4, 127.6, 127.9, 128.2, 128.5, 128.9, 131.2, 131.9, 134.9, 135.2,
135.4, 136.0, 137.0, 137.2, 137.4, 137.6, 137.7, 138.2, 144.2, 144.9,
145.8, 146.5, 150.2, 152.4, 162.1 (C-9), 165.2 (C-2).
IR (KBr): 2208 (w), 1592 (m), 1477 (s), 1415 (s), 1268 (m), 1209
(s), 1095 (m), 1050 (m), 944 (m), 818 (s), 731 (s) cm–1.
1H NMR (400 MHz, CDCl3): d = 0.85 (t, J = 7.1 Hz, 12 H, CH3),
1.23–1.78 (m, 80 H, CH2), 4.09 (t, J = 6.1 Hz, 8 H, OCH2), 7.03 (s,
2 H, 4¢-H), 7.05 (s, 2 H, 9¢-H), 7.60 (dd, J1 = 8.0 Hz, J2 = 4.3 Hz, 2
H, 8-H), 7.68 (d, J = 8.8 Hz, 2 H, 5-H), 7.70 (s, 2 H, 5¢¢-H, 6¢¢-H),
7.74 (d, J = 8.8 Hz, 2 H, 6-H), 8.15 (dd, J1 = 8.0 Hz, J2 = 1.3 Hz, 2
H, 7-H), 8.20 (d, J = 1.8 Hz, 2 H, 4-H), 8.35 (d, J = 1.8 Hz, 2 H, 4¢¢-
H, 7¢¢-H), 9.16 (dd, J1 = 4.3 Hz, J2 = 1.3 Hz, 2 H, 9-H), 9.20 (d, J =
1.8 Hz, 2 H, 2-H), 9.22 (d, J = 1.8 Hz, 2 H, 2¢¢-H, 9¢¢-H).
MS (ESI): m/z (%) = 1556.6 (100) [M + H+].
13C NMR (100 MHz, CDCl3): d = 10.9 (CH2-CH3), 14.5, 23.6, 26.8,
29.5 and 29.6 (overlapping signals), 30.2, 32.2, 46.5 (CH2), 69.8
(CH2O), 87.2 (C-7¢), 88.3 (C-2¢), 94.4 (C-8¢), 95.0 (C-1¢), 119.6,
119.7, 122.4, 122.8, 123.2, 126.8, 127.0, 127.4, 127.6, 127.9, 128.2,
128.6, 128.9, 131.2, 131.6, 131.9, 139.4, 139.5, 138.1, 138.2, 145.2,
145.5, 145.8, 146.2, 150.2, 152.4, 152.6, 155.2.
Anal. Calcd for C102H86N6Br2·2H2O: C, 76.97; H, 5.70; N, 5.28.
Found: C, 76.79; H, 5.63; N, 5.19.
3,8-Bis{2,3,5,6-tetramethyl-4-([1,10]phenanthrolin-3-ylethy-
nyl)-phenylethynyl}-2,9-bis-(2,4,6-trimethylphenyl)-
[1,10]phenanthroline (T4)
MS (ESI): m/z (%) = 1523.3 (100) [M + H+].
Under N2 atmosphere, 14 (60.0 mg, 61.2 mmol) and 4 (25.5 mg, 125
mmol) were dissolved in benzene (10 mL) and Et3N (5 mL). After
Anal. Calcd for C104H124N6O4: C, 82.06; H, 8.21; N, 5.52. Found: C,
82.09; H, 8.23; N, 5.59.
Synthesis 2005, No. 3, 367–373 © Thieme Stuttgart · New York