Construction of Preorganized Polytopic Ligands
J . Org. Chem., Vol. 62, No. 5, 1997 1499
Bis[(2,2′:6′,2′′-ter p yr id in -4′-yl)p h en yl]bu ta d iyn e (9b).
Prepared following the general procedure (method 1), from 4′-
(4-ethynylphenyl)-2,2′:6′,2′′-terpyridine 6c (0.200 g, 0.600 mmol),
DMF (14 mL), CuCl (1.780 g, 17.980 mmol), CuCl2 (0.806 g,
6.00 mmol), oxygen, rt, during 1 week, and recrystallized in
mL (0.120 mmol) of TMEDA, and 18 mL of CH3CN to give
0.077 g (97%); mp >270 °C; H NMR (CDCl3) δ 7.36 (t, J )
1
6.5 Hz, 4H), 7.86 (m, 4H), 8.00 (ABq, J AB ) 8.2 Hz, ∆ν ) 114.9
Hz, 8H), 8.07 (d, J ) 7.9 Hz, 2H), 8.59 (s, 2H), 8.69 (m, 6H),
8.95 (s, 2H); IR (KBr, cm-1) 2922 (w), 1656 (w), 1582 (s), 1548
(s), 1470 (s), 1438 (m), 1392 (s), 1122 (s), 1046 (m), 774 (s);
FAB+ m/z 665 [M+ + H], 332 [M/2 + C]. Anal. Calcd for
C46H28N6: C, 83.11; H, 4.25; N, 12.64. Found: C, 82.89; H,
4.13; N, 12.41.
1
CH2Cl2 to give 0.092 g, 46%; mp >270 °C; H NMR (DMF-d7,
120 °C) δ 8.92 (m, 12H), 8.22 (td, J ) 7.7 Hz, J ) 1.7 Hz, 4H),
8.03 (AB q, J AB ) 8.6 Hz, ∆ν ) 21.8 Hz, 8H), 7.69 (ddd, J )
7.4 Hz, J ) 4.8 Hz, J ) 1.0 Hz, 4H); IR (KBr, cm-1) 2147 (w),
1605 (m), 1586 (s), 1583 (s), 1566 (m), 1467 (m), 1390 (m), 1264
(m), 790 (s); FAB+ m/z 665.2 (M+ + H), 432.2 (M+ - terpy).
Anal. Calcd for C46H28N6: C, 83.11; H, 4.25; N, 12.64.
Found: C, 82.89; H, 4.13; N, 12.56.
Bis(2,2′-bip yr id in -5-yl)eth yn e (13a ). Prepared following
exp. conditions 1 from 0.083 g (0.35 mmol) of 2a , 0.063 g (0.35
mmol) of 2c, 0.038 g (0.03 mmol) of [Pd(PPh3)4], 5 mL of
benzene, and 2 mL of diisopropylamine to give 0.086 g (73%);
mp 230-2 °C; 1H NMR (CDCl3) δ 8.85 (d, J ) 1.8 Hz, 2H),
8.70 (d, J ) 4.5 Hz, 2H), 8.44 (d, J ) 8.4 Hz, 4H), 7.97 (dd, J
) 8.3 Hz, J ) 2.1 Hz, 2H), 7.83 (pseudo td, J ) 7.7 Hz, J )
1.7 Hz, 2H), 7.32 (dd, J ) 6.5 Hz, J ) 4.9 Hz, 2H); 13C{1H}
NMR (CDCl3) δ 90.55, 119.73, 120.50, 121.53, 124.14, 137.08,
139.58, 149.43, 151.78, 155.38, 155.46; IR (KBr, cm-1) 3049
(w), 2976 (m), 1588 (w), 1570 (s), 1543 (s), 1496 (s), 1435 (m),
1370 (s), 1243 (s), 1091 (m), 798 (s); FAB+ MS m/z 335.2 [M +
H]+. Anal. Calcd for C22H14N4: C, 79.02; H, 4.22; N, 16.76.
Found: C, 78.94; H, 4.15; N, 16.71.
Bis(5,5′-d im eth yl-2,2′-bip yr id in -6-yl)eth yn e (10a ). Pre-
pared following exp. conditions 1 from 6-bromo-5,5′-dimethyl-
2,2′-bipyridine (0.126 g, 0.480 mmol), 6-ethynyl-5,5′-dimethyl-
2,2′-bipyridine (0.100 g, 0.480 mmol), 0.033 g (0.028 mmol) of
[Pd(PPh3)4], 30 mL of benzene, and 6 mL of diisopropylamine
1
to give 0.093 g (99%); mp 214-5 °C; H NMR (CDCl3) δ 2.38
(s, 6H), 2.62 (s, 6H), 7.61 (dd, J ) 8.1 Hz, 2H), 7.68 (d, J ) 8.1
Hz, 2H), 8.29 (d, J ) 8.1 Hz, 2H), 8.41 (d, J ) 8.1 Hz, 2H);
13C{1H} NMR (CDCl3) δ 18.3, 19.5, 90.5, 120.3, 120.8, 133.3,
136.1, 137.4, 138.0, 141.8, 149.4, 153.0, 154.4; Raman (neat,
cm-1) 2204/2218; GC-MS m/z 390 (M+, 100). Anal. Calcd for
C26H22N4: C, 79.97; H, 5.68; N, 14.35. Found: C, 79.69; H,
5.32; N, 14.17.
Bis(2,2′-bip yr id in -5-yl)bu ta d iyn e (13b). Prepared fol-
lowing the general procedure (method 3), from 0.090 g (0.50
mmol) of 2c, 0.050 g (0.50 mmol) of CuCl, and 20 mL of
1
Bis(5,5′-d im eth yl-2,2′-bip yr id in -6-yl)bu ta d iyn e (10b).
Prepared following the general procedure (method 2), from
CuCl (0.024 g, 0.24 mmol) and TMEDA (0.036 mL, 0.24 mmol)
in CH3CN (10 mL) and 6-ethynyl-5,5′-dimethyl-2,2′-bipyridine
(0.209 g, 1.003 mmol). Purification by flash chromatography
on silica gel, eluting with CH2Cl2/MeOH (97/3) to give 0.162 g
(78%); mp 244-6 °C; 1H NMR (2/3 CD2Cl2 + 1/3 CD3OD) δ
2.34 (s, 6H), 2.50 (s, 6H), 7.66 (dd, J ) 8.1 Hz, J ) 1.9 Hz,
2H), 7.72 (dd, J ) 8.1 Hz, J ) 0.6 Hz, 2H) 1H), 8.12 (d, J )
8.2 Hz, 2H), 8.18 (d, J ) 8.2 Hz, 2H), 8.39 (d, J ) 0.6 Hz, 2H);
13C{1H} NMR (CD2Cl2) δ 18.5, 19.4, 76.2, 81.3, 120.7, 121.3,
134.3, 137.9, 138.2, 138.6, 141.0, 150.0, 153.2, 155.1; Raman
(neat, cm-1) 2217; GC-MS m/z 414 (M+, 100). Anal. Calcd
for C28H22N4: C, 81.13; H, 5.35; H, 13.52. Found: C, 80.87;
H, 5.21; N, 13.29.
pyridine to give 0.064 g (72%); mp 260 °C dec; H NMR (D2O
t
+ 20%DCl + 1% BuOH) δ 8.94 (d, J ) 6.8 Hz, 2H), 8.93 (s,
2H), 8.72 (m, 4H), 8.33 (m, 4H), 8.12 (m, 2H); IR (KBr, cm-1
)
2922 (w), 1640 (w), 1582 (s), 1542 (s), 1458 (s), 1435 (m), 1370
(m), 1042 (m), 852 (s), 791 (s), 733 (s); FAB+ MS m/z 359.3 [M
+ H]+, 100%. Anal. Calcd for C24H14N4: C, 80.43; H, 3.94; N,
15.63. Found: C, 80.12; H, 3.69; N, 15.35.
4′-(2,2′-Bipyr idin -4-yleth yn yl)-2,2′:6′,2′′-ter pyr idin e (14).
Prepared following exp. conditions 1 from 4′-ethynyl-2,2′:6′,2′′-
terpyridine 7d (0.120 g, 0.466 mmol) and 4-bromo-2,2′-bipyr-
idine 1a (0.110 g, 0.466 mmol), benzene (20 mL), diisopropyl-
amine (5 mL), and 0.032 g (0.025 mmol) of [Pd(PPh3)4], 22 h
at 80 °C. Purified by chromatography (flash silica 2% MeOH/
CH2Cl2) and recrystallized from CH2Cl2/hexane to give 0.144
1
g, 75%; mp 198-9 °C; H NMR (CDCl3) δ 7.39 (m, 4H), 7.63
Bis(2,2′-bip yr id in -4-yl)eth yn e (11a ). Prepared following
exp. conditions 1 from 0.129 g (0.549 mmol) of 1a , 0.099 g
(0.549 mmol) of 1c, 0.039 g (0.034 mmol) of [Pd(PPh3)4], 27
mL of benzene, and 6 mL of diisopropylamine to give 0.147 g
(dd, J ) 7.7 Hz, J ) 1.8 Hz, 1H), 7.86 (m, 3H), 8.40 (d, J ) 7.9
Hz, 1H), 8.60 (m, 4H), 8.70 (m, 4H); 13C{1H} NMR (CDCl3) δ
90.8, 91.4, 121.1, 121.2, 123.0, 123.4, 124.1, 125.3, 128.3, 128.6,
131.5, 131.9, 132.0, 132.2, 136.9, 149.3, 155.2, 155.4, 155.7,
156.4; IR (KBr, cm-1) 3050 (m), 2926 (m), 2858 (m), 1582 (s),
1566 (m), 1460 (s), 1114 (s), 786 (s), 730 (s); FAB+ m/z 411 [M
+ H]+. Anal. Calcd for C27H17N5: C, 78.82; H, 4.16; N, 17.02.
Found: C, 78.75; H, 4.12; N, 16.97.
1
(80%); mp >270 °C; H NMR (CDCl3) δ 7.38 (t, J ) 7.1 Hz,
2H), 7.45 (d, J ) 4.8 Hz, 2H), 7.87 (td, J ) 7.1 Hz, J ) 1.0 Hz,
2H), 8.44 (d, J ) 8.0 Hz, 2H), 8.60 (s, 2H), 8.72 (d, J ) 4.8 Hz,
4H); GC-MS m/z 334 (M+, 100). Anal. Calcd for C22H14N4:
C, 79.02; H, 4.22; N, 16.76. Found: C, 78.78; H, 4.02; N, 16.53.
Bis(2,2′-bip yr id in -4-yl)bu ta d iyn e (11b). Prepared fol-
lowing the general procedure (method 2), from 0.147 g (0.816
mmol) of 1c, 0.297 g (0.408 mmol) of CuCl, 0.060 mL (0.408
mmol) of TMEDA, and 15 mL of MeCN to give 0.072 g (98%);
mp >270 °C; 1H NMR (CDCl3) δ 7.36 (t, J ) 7.2 Hz, 2H), 7.41
(d, J ) 4.9 Hz, 2H), 7.85 (d, J ) 7.2 Hz, 2H), 8.41 (d, J ) 7.9
Hz, 2H), 8.57 (s, 2H), 8.69 (d, J ) 4.9 Hz, 4H); Raman (neat,
cm-1) 2223; GC-MS m/z 358 (M+, 100). Anal. Calcd for
C24H14N4: C, 80.43; H, 3.94; N, 15.63. Found: C, 80.36; H,
3.83; N, 15.52.
5,5′-Bis(2,2′-bip yr id in -5-yleth yn yl)-2,2′-bip yr id in e (15).
Prepared following exp. conditions 1, from 0.115 g (0.64 mmol)
of 2c, 0.100 g (0.32 mmol) of 3a , 0.076 g (0.066 mmol) of [Pd-
(PPh3)4], benzene (10 mL), and diisopropylamine (4 mL) to give
0.110 g (67%); mp >300 °C; FAB+ m/z 513 [M + H]+; FT-IR
(KBr, cm-1) 3048 (m), 2976 (m), 1588 (m), 1569 (m), 1542 (m),
1463 (s), 1434 (m), 1368 (m), 1092 (m), 1050 (m), 1020 (m),
856 (m), 840 (s), 796 (s), 738 (s). Anal. Calcd for C34H20N6:
C, 79.51; H, 3.93; N, 16.40. Found: c, 79.51; H, 3.71; N, 16.27.
5,5′-Bis[(5,5′-d im eth yl-2,2′-bip yr id in -6-yl)eth yn yl]-2,2′-
bip yr id in e (16). Prepared following exp. conditions 1, from
0.100 g (0.32 mmol) of 3a , 0.133 g (0.64 mmol) of 6-ethynyl-
5,5′-dimethyl-2,2′-bipyridine, 0.076 g (0.066 mmol) of [Pd-
(PPh3)4], benzene (10 mL), and diisopropylamine (4 mL) to give
Bis[4-(2,2′:4′,2′′-t er p yr id in -6′-yl)p h en yl]et h yn e (12a ).
Prepared following exp. conditions 2 from 0.080 g (0.240 mmol)
of 5c, 0.093 g (0.240 mmol) of 5a , 0.017 g (0.015 mmol) of [Pd-
(PPh3)4], and 16 mL of n-propylamine to give 0.136 g (88%);
mp >270 °C; 1H NMR (CDCl3) δ 7.39 (t, J ) 6.4 Hz, 4H), 7.89
(m, 4H), 8.03 (AB q, J AB ) 8.3 Hz, ∆ν ) 116.2 Hz, 8 H), 8.11
(d, J ) 8.0 Hz, 2H), 8.62 (s, 2H), 8.77 (m, 6H), 8.99 (s, 2H); IR
(KBr, cm-1) 2926 (s), 2858 (m), 1656 (s), 1582 (s), 1548 (s),
1468 (s), 1440 (m), 1396 (s), 1264 (s), 1122 (m), 1074 (m), 842
(m), 778 (s); FAB+ m/z 641 [M+ + H], 332 [M - phenyl/bipy/
1
0.158 g (87%); mp 264-5 °C; H NMR (CDCl3) δ 2.40 (s, 6H),
2.60 (s, 6H), 7.63 (dd, J ) 8.2 Hz, J ) 2.0 Hz, 2H), 7.70 (d, J
) 8.2 Hz, 2H), 8.06 (dd, J ) 7.6 Hz, J ) 2.0 Hz, 2H), 8.29 (d,
J ) 8.0 Hz, 2H), 8.37 (d, J ) 8.0 Hz, 2H), 8.48 (s, 2H), 8.51 (d,
J ) 5.5 Hz, 2H), 8.94 (s, 2H); 13C{1H} NMR (D2O + 20%DCl
+ 1% tBuOH) δ 18.3, 19.2, 87.8, 83.7, 121.92-148.68 (aromat-
ics); FAB+ m/z 569 [M + H]+; FT-IR (KBr, cm-1) 3012 (s), 2916
(s), 2220 (w), 1582 (s), 1550 (s), 1465 (s), 1252 (s), 1132 (s),
1069 (s), 1023 (s), 824 (s), 736 (m), 652 (m), 495 (m). Anal.
Calcd for C38H28N6: C, 80.26; N, 4.96; N, 14.78. Found: C,
79.83; H, 4.72; N, 14.69.
py], 308 [M
- CtCphenyl/bipy/py]. Anal. Calcd for
C44H28N6: C, 82.48; H, 4.40; N, 13.12. Found: C, 82.19; H,
4.19; N, 12.88.
Bis[4-(2,2′:4′,2′′-ter p yr id in -6′-yl)p h en yl]bu ta d iyn e(12b).
Prepared following the general procedure (method 2), from
0.080 g (0.240 mmol) of 5c, 0.012 g (0.120 mmol) of CuCl, 0.018
6,6′-Bis[(5,5′-d im eth yl-2,2′-bip yr id in -6-yl)eth yn yl]-2,2′-
bip yr id in e (17). Prepared following exp. conditions 1, from