Pickaert et al.
3,5-Bis(3,5-d ih exa d ecyloxyb en zoyla m in o)-4-m et h yl-
ben zoic Acid (6b). The compound was prepared from 1.228
g (0.9 mmol) of 5b, 1.800 g (45 mmol) of NaOH, and THF/H2O
(50/50) as described for 6a to give 0.975 g of 6b (81%). 1H NMR
(CDCl3): δ 0.87 (m, 12H), 1.24 (br, 104H), 1.70 (br, 8H), 2.24
(s, 3H), 3.87 (m, 8H), 6.57 (t, J ) 2.1 Hz, 2H), 6.96 (d, J )
2.1 Hz, 4H), 7.96 (m, 2H), 8.12 (m, 2H). FAB+ m/z (nature of
the peak, relative intensity): 1111.2 ([M + H]+, 80), 1065.2
([M - COOH], 20). Anal. Calcd for C86H146N2O8: C, 77.31; H,
11.01; N, 2.10. Found: C, 76.98; H, 10.74; N, 1.82.
13C NMR (CDCl3): δ 14.1, 56.7, 68.5, 105.2, 105.6, 119.0, 120.0,
121.5, 123.9, 124.4, 127.6, 133.5, 136.0, 136.6, 136.9, 147.5,
149.4, 155.6, 155.3, 156.0, 160.2, 165.5, 166.6. EI-HRMS: calcd
739.772, found 739.773. Anal. Calcd for C42H37N5O8: C, 68.19;
H, 5.04; N, 9.47. Found: C, 67.84; H, 4.82; N, 9.03.
4
4
Liga n d 10b. The compound was prepared from 0.100 g
(0.075 mmol) of 6b, 0.018 g (0.068 mmol) of 4′-(hydroxymethyl)-
2,2′;6′2′′-terpyridine 9, 0.028 g (0.149 mmol) of EDC‚HCl,0.018
g (0.149 mmol) of DMAP, and 30 mL of distilled CH2Cl2 as
described for 10a to afford 0.070 g of 10b (65%). Clearing
point: 155 °C. FT-IR (KBr): 3400 (shoulder), 3270 (m), 2923
(vs), 2853 (s), 1726 (m),1661 (shoulder), 1644 (m), 1591 (s),
1525 (shoulder), 1511 (m), 1459 (m), 1407 (w), 1384 (w), 1348
Liga n d 8a . A Schlenk flask equipped with a septum and
an argon inlet was charged with 6a (0.100 g, 0.202 mmol),
0.041 g (0.184 mmol) of 2-(hydroxymethyl)-9-methyl-1,10-
phenanthroline 7, 0.077 g (0.404 mmol) of EDC‚HCl, 0.050 g
(0.404 mmol) of DMAP, and distilled CH2Cl2/THF (20 mL/20
mL). The solution was stirred overnight. After evaporation of
the solvent, the purification of the ligand was performed by
flash chromatography on silica gel with CH2Cl2/methanol
(100/0 to 99/1) as eluant, followed by crystallization from
CH2Cl2/CH3CN to afford 0.074 g of 8a (57%). Mp: 272-273
°C. FT-IR (KBr): 3400 (shoulder), 3232 (m), 2940 (m), 2836
(m), 2358 (w), 1718 (m), 1649 (s), 1593 (vs), 1535 (shoulder),
1510 (s), 1456 (m), 1427 (m), 1350 (m), 1319 (s), 1251 (w), 1211
(w), 1267 (w), 1220 (w), 1163 (s), 1051 (m) cm-1 1H NMR
.
(CDCl3): δ 0.87 (t, 3J ) 6.7 Hz, 12H), 1.25 (m, 104H), 1.69 (m,
3
8H), 2.13 (s, 3H), 3.85 (t, J ) 6.4 Hz, 8H), 5.41 (s, 2H), 6.50
4
4
(t, J ) 1.9 Hz, 2H), 6.96 (d, J ) 1.9 Hz, 4H), 7.29 (m, 4H),
8.10 (s, 2H), 8.31 (s, 2H), 8.57 (m, 6H). 13C NMR (CDCl3): δ
13.0, 14.0, 14.1, 22.5, 22.7, 26.0, 29.0, 29.2, 29.4, 29.5, 29.6,
29.7, 29.7, 31.9, 53.4, 65.0, 68.3, 105.0, 105.7, 118.9, 119.1,
121.4, 123.9, 124.2, 127.8, 133.7, 136.1, 136.8, 136.8, 147.1,
149.0, 155.5, 155.6, 155.9, 160.3, 165.2, 166.5. FAB+ m/z
(nature of the peak, relative intensity): 1581.2 ([M + H]+, 100),
1317.2 ([M - terpyCH2O + H]+, <5). Anal. Calcd for
1
(vs), 1157 (s), 1105 (w), 1066 (m), 1045 (w), 999 (w) cm-1. H
NMR (DMSO-d6): δ 2.19 (s, 3H), 2.78 (s, 3H), 3.81 (s, 12H),
C102H157N5O8: C, 77.47; H, 10.01; N, 4.43. Found: C, 77.32; H,
9.91; N, 4.29.
5.75 (s, 2H), 6.72 (t, 4J ) 2.1 Hz, 2H), 7.17 (d, 4J ) 2.1 Hz,
3
3
4H), 7.66 (d, J ) 8.3 Hz, 1H), 7.85 (d, J ) 8;3 Hz, 1H), 7.94
(d, 4J ) 1.9 Hz, 2H), 7.97 (s, 2H), 8.38 (d, 3J ) 8.0 Hz, 1H),
Liga n d 12. A Schlenk flask equipped with a septum and
an argon inlet was charged with 0.110 g (0.082 mmol, 1 equiv)
of the acid 6b, distilled CH2Cl2, and 0.020 g (0.165 mmol, 2
equiv) of DMAP, and the mixture was stirred until complete
solubilization of the acid. Finally, 0.031 g (0.165 mmol, 2 equiv)
of EDC‚HCl and 0.020 g (0.075 mmol, 0.9 equiv) of (4′R)-2-
(4′,5′-dihydro-4′-phenyl-2′-oxazolyl)-6-(hydroxymethyl)pyri-
dine 11 were added to the solution, which was stirred over-
night. After evaporation of the solvent, the purification of the
ligand was performed by flash chromatography on silica gel
with CH2Cl2/methanol (100/0 to 99/1) as eluant, followed by
crystallization from CH2Cl2/CH3CN to afford 0.073 g of 12
(62%). Clearing point: 131 °C. FT-IR (KBr): 3218 (w), 2918
(vs), 2848 (s), 1720 (m), 1647 (m), 1590 (s), 1519 (m), 1452 (s),
1330 (m), 1216 (m), 1162 (s), 1053 (w), 844 (w), 756 (w), 696
8.53 (d, J ) 8.3 Hz, 1H), 8.68 (s, 2H). 13C NMR (DMSO-d6):
3
δ 14.9, 25.9, 56.4, 68.8, 104.5, 106.5, 121.9, 124.6, 126.2, 126.2,
127.6, 127.7, 128.8, 137.0, 137.3, 138.0, 138.2, 138.4, 145.5,
156.5, 159.5, 161.3, 166.0. FAB+ m/z (nature of the peak,
relative intensity): 701.2 ([M + H]+, 100). Anal. Calcd for
.
C40H36N4O8 H2O: C, 68.56; H, 5.18; N, 8.00. Found: C, 68.37;
H, 5.08; N, 7.83.
Liga n d 8b. The compound was prepared from 0.150 g
(0.113 mmol) of 6b, 0.025 g (0.113 mmol) of 2-(hydroxymethyl)-
9-methyl-1,10-phenanthroline 7, 0.043 g (0.226 mmol) of EDC‚
HCl, 0.014 g (0.113 mmol) of DMAP, and 30 mL of distilled
CH2Cl2 to afford 0.130 g of 8b (75%). Clearing point: 124 °C.
FT-IR (KBr): 3400 (shoulder), 3224 (m), 2919 (vs), 2850 (s),
1720 (m), 1655 (shoulder), 1645 (s), 1593 (s), 1520 (shoulder),
1508 (m), 1465 (m), 1442 (m), 1384 (w), 1350 (w), 1321 (m),
1256 (w), 1217 (w), 1190 (vw), 1168 (s), 1056 (w) cm-1. 1H NMR
(CDCl3): δ 0.87 (m, 12H), 1.25 (br, 104H), 1.71 (m, 8H), 2.14
(s, 3H), 2.86 (s, 3H), 3.90 (t, 3J ) 6.4 Hz, 8H), 5.69 (s, 2H),
1
3
(w) cm-1. H NMR (CDCl3): δ 0.87 (t, J ) 6.7 Hz, 12H), 1.25
(m, 104H), 1.78 (m, 8H), 2.25 (s, 3H), 3.98 (t, 3J ) 6.7 Hz, 8H),
3
3
2
4.39 (t, J ) 8.4 Hz, 1H), 4.89 (dd, J ) 8.6 Hz, J ) 1.8 Hz,
3
2
1H), 5.43 (dd, J ) 8.6 Hz, J ) 1.8 Hz, 1H), 5.57 (s, 2H), 6.62
4
4
(t, J ) 2.1 Hz, 2H), 7.00 (d, J ) 2.1 Hz, 4H), 7.30 (m, 5H),
4
4
3
3
3
3
6.56 (t, J ) 2.1 Hz, 2H), 7.06 (d, J ) 2.1 Hz, 4H), 7.48 (d, J
) 8.0 Hz, 1H), 7.60 (m, 3H), 8.10 (m, 4H), 8.43 (m, 2H). 13C
NMR (CDCl3): δ 13.9, 14.1, 22.7, 25.6, 26.0, 29.2, 29.4, 29.7,
31.9, 68.1, 68.3, 105.2, 105.7, 121.3, 123.8, 125.5, 126.5, 126.9,
128.1, 132.9, 136.1, 136.4, 136.7, 137.2, 145.2, 156.4, 159.5,
160.5, 165.3, 166.1. FAB+ m/z (nature of the peak, relative
intensity): 1542.6 ([M + H]+, 100), 940.5 ([M - C39H70NO3 +
7.56 (d, J ) 7.8 Hz, 1H), 7.80 (t, J ) 7.8 Hz, 1H), 7.88 (d, J
) 7 Hz, 1H), 8.09 (s, 2H), 8.25 (s, 2H). 13C NMR (CDCl3): δ
13.8, 14.1, 22.7, 26.05, 29.2, 29.4, 29.4, 29.6, 29.7, 29.7, 29.7,
31.9, 67.1, 68.4, 70.3, 105.4, 105.6, 123.4, 123.6, 123.8, 126.9,
127.8, 128.2, 128.8, 136.1, 136.6, 137.6, 141.7, 146.2, 156.4,
160.6, 163.7, 165.1, 166.1. FAB+ m/z (nature of the peak,
relative intensity): 1572.1 ([M + H]+, 100), 1320.1 ([M -
pyoxCH2O]+, 20). Anal. Calcd for C101H158N4O9: C, 77.15; H,
10.13; N, 3.56. Found: C, 76.84; H, 9.92; N, 3.43.
.
H]+, 25). Anal. Calcd for C100H156N4O8 H2O: C, 76.98; H, 10.21;
N, 3.59. Found: C, 76.69; H, 10.05; N, 3.38.
Liga n d 10a . A Schlenk flask equipped with a septum and
an argon inlet was charged with the acid 6a 0.050 g (0.101
mmol), 0.024 g (0.092 mmol) of 4′-(hydroxymethyl)-2,2′;6′2′′-
terpyridine 9, 0.039 g (0.202 mmol) of EDC‚HCl 0.022 g (0.202
mmol) of DMAP, and distilled CH2Cl2/THF (15 mL/15 mL).
The solution was stirred overnight. After evaporation of the
solvent, the purification of the ligand was performed by flash
chromatography on silica gel with CH2Cl2/methanol (100/0 to
99/1) as eluant, followed by crystallization from CH2Cl2/
CH3CN to afford 0.031 g of 10a (45%). Mp: 286-287 °C.
FT-IR (KBr): 3400 (shoulder), 3259 (m), 2948 (w), 2834 (w),
2358 (m), 2331 (m), 1720 (m), 1666 (shoulder), 1647 (s), 1594
(vs), 1512 (s), 1461 (m), 1421 (w), 1348 (m), 1309 (s), 1249 (m),
Liga n d 14. A Schlenk flask equipped with a septum and
an argon inlet was charged with the acid 6b (0.200 g, 0.149
mmol), 0.018 g (0.075 mmol) of 2,9-(hydroxymethyl)-1,10-
phenantroline 13, 0.115 g (0.6 mmol) of EDC‚HCl, 0.019 g (0.15
mmol) of DMAP, and 30 mL of distilled CH2Cl2. The solution
was stirred overnight. After evaporation of the solvent, the
purification of the ligand was performed by flash chromatog-
raphy on silica gel with CH2Cl2/methanol (100/0 to 99/1) as
eluant followed by crystallization from CHCl3/CH3CN to afford
0.145 g of 14 (67%). Mp: 215-216 °C. FT-IR (KBr): 3436
(shoulder), 3247 (m), 2922 (vs), 2852 (s), 1737 (w), 1654
(shoulder), 1645 (m), 1595 (s), 1525 (shoulder), 1511 (w), 1455
(w) 1443 (m), 1384 (m), 1351 (w), 1319 (w), 1260 (w), 1215 (w),
1
1211 (s), 1155 (s), 1120 (w), 1068 (m) cm-1. H NMR (CDCl3):
1167 (s), 1058 (m) cm-1 1H NMR (CDCl3): δ 0.87 (m, 24H),
.
4
δ 2.10 (s, 3H), 3.73 (s, 12H), 5.42 (s, 2H), 6.50 (t, J ) 2.2 Hz,
1.24 (m, 208H), 1.67 (m, 16H), 2.09 (s, 6H), 3.85 (m, 16H), 5.54
4
3
2H), 6.98 (d, J ) 2.2 Hz, 4H), 7.3 (m, 2H), 7.83 (dt, J ) 7.7
(s, 4H), 6.53 (t, 4J ) 1.9 Hz, 4H), 7.01 (d, 4J ) 1.9 Hz, 8H),
4
3
Hz, J ) 1.8 Hz, 2H), 8.12 (s, 2H), 8.32 (s, 2H), 8.57 (m, 6H).
7.69 (m, 4H), 8.02 (s, 4H), 8.19 (d, J ) 8.3 Hz, 2H), 8.46 (m,
5340 J . Org. Chem., Vol. 69, No. 16, 2004