27.7, 27.1, 27.0, 22.8, 22.7, 14.2, 8.0; m/z (FAB) 1406.7613
([M þ K]1 C81H116N3O9P3K requires 1406.7562).
MHz; CDCl3) 7.84–7.96 (12 H, m, Ph), 7.42–7.54 (18 H, m,
Ph), 3.80–3.91 (3 H, m, NCH(CH2CH3)2), 3.70 (6 H, d, JP–H
15.6, CH2P(O)), 3.01–3.10 (6 H, m, NCH2CH2Ph), 2.81 (6 H,
q, J 7.8, CH3CH2Ph), 2.37–2.46 (6 H, m, NCH2CH2Ph),
1.42–1.70 (12 H, m, NCH(CH2CH3)2), 0.79–1.00 (27 H, m,
CH3); dC(75 MHz; CDCl3) 166.4, 166.3, 141.3, 133.3, 133.2,
132.2, 131.9, 131.6, 131.4, 128.8, 128.6, 62.4, 42.8, 40.1, 39.2,
27.9, 26.6, 22.6, 15.7, 11.3; m/z (FAB) 1266.6274 ([M þ K]1
C75H96N3O6P3K requires 1266.6149).
CMPO ligand 9d. Reaction of tripodal amine 3d (0.93 g,
1.80 mmol), chloroacetyl chloride (1.3 mL, 16.2 mmol) and
K2CO3 (2.8 g, 20 mmol) and subsequently diphenyl ethyl
phosphinite (2.5 mL, 11.6 mmol) gave ligand 9d (1.87 g,
83%). dH(300 MHz; CDCl3) 7.76–7.89 (12 H, m, Ph),
7.39–7.47 (18 H, m, Ph), 3.98–4.08, 3.56–3.74, 3.03–3.42 (27
H, m, CH2O, CH2NCH, CH2P(O)), 1.72–1.84, 1.18–1.62 (20
H, m, CH3CH2C, NCH(CH2CH3)2, OCH2CH2CH2N),
0.62–0.90 (21 H, m, CH3); dC(75 MHz; CDCl3) 166.2, 166.1,
166.0, 165.9, 133.8, 133.6, 132.4, 132.2, 132.1, 131.5, 131.4,
128.7, 128.6, 71.6, 69.7, 68.7, 62.3, 58.8, 53.6, 43.3, 42.1, 39.6,
38.5, 38.2, 31.4, 29.1, 26.5, 26.0, 23.5, 11.3, 8.0; m/z (FAB)
1280.6150 ([M þ K]1 C72H98N3O9P3K requires 1280.6153).
CMPO ligand 12. Reaction of tripodal amine 5 (0.62 g, 1.34
mmol), chloroacetyl chloride (0.9 mL, 11.3 mmol) and K2CO3
(1.8 g, 13 mmol) and subsequently diphenyl ethyl phosphinite
(2 mL, 9.26 mmol) gave ligand 12 (0.51 g, 32%). dH(300 MHz;
CDCl3) 7.85–7.92 (12 H, m, Ph), 7.44–7.57 (18 H, m, Ph),
4.45–4.67 (6 H, m, PhCH2N), 3.66–3.80 (6 H, m, C(O)CH2-
P(O)), 2.35–2.73 (9 H, m, NHCH(CH2CH3)2, PhCH2CH3),
1.42–1.62 (12 H, m, NHCH(CH2CH3)2), 0.40–1.25 (27 H, m,
CH3); dC(75 MHz; CDCl3) 165.8, 146.5, 133.5, 132.3, 132.2,
131.4, 131.3, 131.2, 128.9, 128.8, 128.6, 61.7, 47.8, 40.9, 40.1,
24.0, 22.8, 16.1, 11.6, 11.5; m/z (FAB) 1224.5672 ([M þ K]1
C72H90N3O6P3K requires 1224.5680).
CMPO ligand 9e. Reaction of tripodal amine 3e (0.86 g, 1.67
mmol), chloroacetyl chloride (1.2 mL, 15 mmol) and K2CO3
(2.2 g, 16 mmol) and subsequently diphenyl ethyl phosphinite
(1.5 mL, 6.9 mmol) gave ligand 9e (0.27 g, 13%). dH(300 MHz;
CDCl3) 7.81–7.86 (12 H, m, Ph), 7.40–7.52 (18 H, m, Ph), 3.65
(6 H, d, JP–H 15.3, CH2P(O)), 3.20–3.60 (12 H, m,
OCH2CH2CH2N), 3.06 (6 H, s, CCH2O), 2.20–2.32 (6 H, m,
OCH2CH2CH2N), 1.68–1.71 (8 H, m, CH2CH3), 1.26 (18 H, s,
CCH3), 0.65 (12 H, t, J 7.4, CH2CH3); dC(75 MHz; CDCl3)
165.7, 165.6, 133.8, 132.5, 131.9, 131.5, 131.3, 128.7, 128.5,
71.7, 68.6, 61.4, 44.2, 43.2, 41.0, 40.2, 32.5, 32.1, 27.0, 23.2, 8.9,
8.0; m/z (FAB) 1280.5921 ([M þ K]1 C72H98N3O9P3K
requires 1280.6153).
CMP ligand 13b. Reaction of tripodal amine 3b (0.91 g, 1.91
mmol), chloroacetyl chloride (1.2 mL, 15.3 mmol) and K2CO3
(2.2 g, 16 mmol) and subsequently triethyl phosphite (4.0 mL,
24.1 mmol) gave ligand 13b (1.31 g, 68%). dH(300 MHz;
CDCl3), 4.11–4.21 (12 H, m, POCH2CH3), 3.24–3.48 (24 H,
m, CH2O, CH2N), 2.97–3.09 (6 H, m, C(O)CH2P(O)),
1.72–1.85,
1.25–1.61
(38
H,
m,
CH3CH2C,
CH3CH2CH2CH2N,
OCH2CH2CH2N,
P(O)CH2CH3),
CMPO ligand 10a. Reaction of tripodal amine 7a (0.67 g,
2.69 mmol), chloroacetyl chloride (2.03 mL, 25.6 mmol) and
K2CO3 (3.6 g, 26 mmol) and subsequently diphenyl ethyl
phosphinite (2 mL, 9.3 mmol) gave ligand 10a (1.18 g, 45%)
(Found: C, 68.29; H, 5.99; N, 3.80. Calc. for
C57H60N3O6P3 ꢃ 0.33CH2Cl2: C, 68.58; H, 6.09; N, 4.18%);
mp 4 221 1C (melting with decomposition); dH(300 MHz;
CDCl3) 7.71–7.78, 7.42–7.58 (33 H, m, NH, Ph), 3.31 (6 H, d,
JH–P 12.3, C(O)CH2P(O)), 3.15–3.23, 2.64–2.70 (12 H, m,
PhCH2CH2N), 2.21 (9 H, s, CH3); dC(75 MHz; CDCl3)
164.91, 164.85, 133.9, 133.6, 132.7, 132.6, 132.5, 131.1, 131.0,
130.9, 129.2, 129.0, 39.4, 39.3, 38.6, 30.9, 16.0.
0.80–0.97 (12 H, m, CH3CH2C, CH3CH2CH2CH2N); dC(100
MHz; CDCl3) 164.7, 164.6, 164.5, 71.7, 68.9, 67.9, 62.7, 62.6,
49.3, 46.0, 45.8, 44.1, 43.2, 34.2, 34.0, 32.8, 32.7, 31.3, 29.8,
29.3, 28.1, 23.4, 20.3, 20.2, 16.6, 16.5, 14.0, 8.0; m/z (FAB)
1008.5818 ([M þ H]1 C45H93N3O15P3 requires 1008.5820).
CMP ligand 13c. Reaction of tripodal amine 3c (1.40 g, 2.18
mmol), chloroacetyl chloride (1.5 mL, 18.5 mmol) and K2CO3
(2.6 g, 19 mmol) and subsequently triethyl phosphite (5.0 mL,
29.2 mmol) gave ligand 13c (0.82 g, 32%). dH(300 MHz;
CDCl3) 4.09–4.19 (12 H, m, POCH2CH3), 3.20–3.47 (24 H,
m, CH2O, CH2N), 2.95–3.07 (6 H, m, C(O)CH2P(O)),
1.72–1.82, 1.17–1.58 (62 H, m, CH3CH2C, CH3C6H12CH2N,
OCH2CH2CH2N, POCH2CH3) 0.79–0.88 (12 H, m,
CH3CH2C, CH3C6H12CH2N); dC(75 MHz; CDCl3) 164.8,
164.6, 164.5, 71.6, 69.0, 68.0, 62.7, 62.6, 62.5, 49.6, 46.3,
45.8, 44.1, 43.3, 34.5, 32.7, 32.5, 32.0, 31.9, 29.6, 29.5, 29.4,
29.3, 28.2, 27.8, 27.2, 27.1, 23.5, 22.8, 16.6, 16.5, 14.2, 8.1; m/z
(FAB) 1214.7168 ([M þ K]1 C57H116N3O15P3K requires
1214.7256).
CMPO ligand 10b. Reaction of tripodal amine 7b (0.76 g,
2.62 mmol), chloroacetyl chloride (1.5 mL, 18.3 mmol) and
K2CO3 (2.6 g, 19 mmol) and subsequently diphenyl ethyl
phosphinite (2.3 mL, 10.6 mmol) gave ligand 10b (0.96 g,
36%) (Found: C, 70.05; H, 6.40; N, 4.23. Calc. for
C60H66N3O6P3 ꢃ 0.1CH2Cl2: C, 70.08; H, 6.48; N, 4.08%);
mp 143 1C; dH(300 MHz; CDCl3) 7.72–7.79, 7.42–7.57 (33
H, m, CH2NHCO, Ph), 3.32 (6 H, d, JH–P 12.3, C(O)CH2-
P(O)), 3.15–3.26, 2.52–2.64 (18 H, m, PhCH2CH2N CH2CH3),
1.02 (9 H, t, J 9.2, CH2CH3); dC(100 MHz; CDCl3) 164.81,
164.77, 140.5, 132.7, 132.6, 132.4, 132.2, 131.1, 131.0, 130.9,
129.2, 129.0, 41.0, 39.4, 38.8, 29.5, 22.5, 15.9.
CMP ligand 13d. Reaction of tripodal amine 3d (0.87 g, 1.68
mmol), chloroacetyl chloride (1.2 mL, 15.1 mmol) and K2CO3
(2.2 g, 16 mmol) and subsequently triethyl phosphite (3.0 mL,
29.1 mmol) gave ligand 13d (0.37 g, 21%). dH(300 MHz;
CDCl3) 4.09–4.19 (12 H, m, POCH2CH3), 3.00–3.08,
3.14–3.63 (27 H, m, CH2O, CH2PO, CH2NCH), 1.75–1.88,
1.35–1.59 (20 H, m, CH3CH2C, NCH(CH2CH3)2,
CMPO ligand 11. Reaction of tripodal amine 8 (0.72 g, 1.44
mmol), chloroacetyl chloride (1.0 mL, 12.6 mmol) and K2CO3
(1.8 g, 13 mmol) and subsequently diphenyl ethyl phosphinite
(4.57 mL, 21.1 mmol) gave ligand 11 (1.22 g, 69%). dH(300
OCH2CH2CH2N), 1.30 (16 H, t,
J 3.5, POCH2CH3),
ꢀc
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New J. Chem., 2007, 31, 109–120 | 117