5
04 Journal of Medicinal Chemistry, 2008, Vol. 51, No. 3
Li et al.
1
H NMR (d-TFA): δ 9.66 (br, 8H, Ar-H), 8.98 (br, 8H, Py-H),
SiPc (13). Pc 8 (35 mg, 0.02 mmol) and CH
described above for Pc 10, and the title compound was obtained as
3
I (8 mL) reacted as
1
3
8
.73 (br, 8H, Py-H), 8.58 (br, 8H, Py-H), 8.21 (br, 8H, Py-H).
C
NMR (d-TFA): δ 158.95, 152.09, 151.43, 139.324, 137.64, 136.40,
a green solid (28 mg, 96%); mp > 250 °C. UV–vis (H
2
O): λmax
1
1
1
34.08, 131.48, 120.53 (Ar-C, Py-C). MS (MALDI-TOF) m/z
(log ε) 677 (4.84), 648 (4.05), 610 (4.07), 356 (4.45) nm. H NMR
(d-DMF): δ 9.99 (s, 8H, Ar-H), 9.70 (s, 8H, Py-H), 9.22 (d, 8H, J
) 5.5 Hz, Py-H), 8.88 (d, 8H, J ) 7.4 Hz, Py-H), 8.48–8.46 (m,
+
319.82 [M - Cl] , calcd. for C72
8
H40ClN16O Si 1319.27.
SiPc (6). A mixture of Pc 5 (0.45 g, 0.33 mmol) and sodium
methoxide (1.5 g, 27 mmol) in 60 mL of water/ethanol (5:1) was
heated to reflux for 5 h. The solvent was removed under reduced
pressure, and the product was isolated by precipitation upon addition
of 10 mL of water. The slurry solid was filtered and washed
thoroughly with water. The final product was dried under vacuum
at 40 °C for 2 days to afford the title compound as a dark green
8H, Py-H), 4.73 (s, 24H, N-CH
CH ), -1.99 to -2.06 (m, 6H, CH). C NMR (d-DMF): δ 156.30,
149.94, 148.96, 142.92, 138.75, 135.08, 134.49, 130.02, 117.56 (Ar-
C, Py-C), 49.49 (N-CH ), 16.24, 11.33 (CH(CH ). MS (MALDI-
3
), -1.07 (d, 36H, J ) 7.4 Hz,
13
3
3
3 2
)
+
TOF) m/z 1457.69 [M - 8MeI - OSi(C
3
H
7
)
3
] , 1472.70 [M -
+
+
7
7
C
MeI - OSi(C
3
H
7
)
3
] , 1630.80 [M - 8MeI] , 1645.82 [M -
MeI] , calcd. for C81 Si 1457.44, C82 Si 1472.46,
1630.57, C91 10Si 1645.59. HRMS-ESI
+
H
61
N
16
O
9
2
H
64
N
16
O
9
2
solid (0.35 g) in 81% yield; mp > 250 °C. UV–vis (DMSO): λ max
1
90
H
82
N
16
O10Si
3
H
85
N
16
O
3
(
log ε) 677 (4.11), 609 (3.64), 364 (3.94) nm. H NMR (d-TFA):
3
+
3+
m/z 795.4410 [M - 3I] , 752.8038 [M - 4I - H] , 564.6037
δ 9.72 (br, 8H, Ar-H), 9.03 (br, 8H, Py-H), 8.81 (br, 8H, Py-H),
4
+
4+
1
3
[
[
[
M
C
C
-
106
4I]
,
532.6259 [M
-
795.6001, [C98
564.5941, [C98
5I
-
H]
, calcd. for
8
1
1
8
1
1
.64 (br, 8H, Py-H), 8.29 (br, 8H, Py-H). C NMR (d-TFA): δ
59.11, 152.24, 151.58, 139.46, 137.78, 136.55, 134.20, 131.61,
20.67 (Ar-C, Py-C). FTIR (solid): 3382.3 (O-H), 1209.5 (C-O),
3
+
+
3+
98
H
I
I
5
N
N
16
O
10Si
10Si
3
]
]
H
105
I
I
4
N
N
16
O
O
10Si
10Si
3
]
]
752.8038,
532.6161.
4
4+
98
H
106
4
16
O
3
H
105
3
16
3
-1
+
SiPc (9). Pc 6 (0.2 g, 0.15 mmol) and tert-butyldiphenylchlo-
rosilane (0.8 mL, 3.0 mmol) reacted as described above for Pc 7
and the title compound was obtained as a dark green solid (99 mg,
44.6 (Si-O) cm . MS (MALDI-TOF) m/z 1301.81 [M - OH] ,
+
318.63 [M] , calcd. for C72
318.30.
41 16 9 42 16
H N O Si 1301.30, C72H N O10Si
3
7%); mp 185–187 °C. UV–vis (DMF):λ max (log ε) 680 (5.09),
SiPc (7). Pc 6 (0.17 g, 0.125 mmol) was dissolved in 10 mL of
1
6
50 (4.29), 612 (4.36), 363 (4.59) nm. H NMR (d-DMF): δ 9.19
dry pyridine at 115 °C under an argon atmosphere. Chlorotripro-
pylsilane (0.7 mL, 3.2 mmol) was added dropwise to the reaction
solution via syringe. After 8 h, another portion of chlorotripropyl-
silane (0.5 mL, 2.2 mmol) was added. The reaction solution was
refluxed for another 9 h. The solvent was evaporated to dryness,
and 10 mL of pentane was added. After sonication for 5 min, the
crude product was obtained by centrifugation. The solid was further
purified using a short silica column and THF for elution. The title
compound was dried under vacuum at 40 °C and obtained as a
(
s, 8H, Ar-H), 8.75 (d, J ) 2.6 Hz, 8H, Py-H), 8.60 (d, J ) 4.5
Hz, 8H, Py-H), 7.92–7.90 (m, 8H, Py-H), 7.70–7.66 (m, 8H, Py-
H), 6.99 (t, J ) 7.3 Hz, 4H, Ar-H), 6.57 (t, J ) 7.4 Hz, 8H, Ar-H),
1
3
4
.91 (d, J ) 7.1 Hz, 8H, Ar-H), -1.22 (s, 18H, C(CH
3
)
3
).
C
NMR (d-DMF): δ 154.44, 151.27, 148.62, 146.13, 141.19, 133.79,
133.30, 133.21, 128.94, 126.94, 126.39, 125.78, 115.95 (Ar-C, Py-
+
C), 24.99, 17.00 (C(CH ) ). MS (MALDI-TOF) m/z 1794.37 [M ],
3 3
t
+
1
C
539.26 [M - (OSiPh
Si 1539.42.
SiPc (14). Pc 9 (20 mg, 0.01 mmol) and CH
described above for Pc 10, and the title compound was obtained as
2 78 16 3
Bu)] , calcd for C104H N O10Si 1794.54,
88
H
59
N
16
O
9
2
dark green solid (0.11 g, 52%); mp > 250 °C. UV–vis (CH
2 2
Cl ):
1
3
I (4 mL) reacted as
λ
max (log ε) 674 (5.34), 644 (4.54), 607 (4.60), 360 (4.92) nm. H
NMR (d-THF): δ 9.30 (s, 8H, Ar-H), 8.58 (d, J ) 2.7 Hz, 8H,
Py-H), 8.46 (dd, J ) 1.0, 4.5 Hz, 8H, Py-H), 7.63–7.59 (m, 8H,
a green solid (29 mg, 91%); mp 217–219 °C. UV–vis (H
2
O): λmax
1
(
(
log ε) 679 (4.81), 649 (3.96), 612 (4.01), 352 (4.29) nm. H NMR
Py-H), 7.45–7.41 (q, 8H, Py-H), -0.15 (t, J ) 7.2 Hz, 18H, CH
3
),
).
d-DMF): δ 9.79 (s, 8H, Ar-H), 9.71 (s, 8H, Py-H), 9.25 (d, J )
-
0.99 to -1.07 (m, 12H, CH ), -2.29 to -2.34 (m, 12H, CH
2
2
5
8
8
.3 Hz, 8H, Py-H), 8.88 (d, J ) 7.8 Hz, 8H, Py-H), 8.57–8.54 (m,
1
3
C NMR (d-THF): δ 154.75, 151.75, 149.04, 146.15, 141.46,
H, Py-H), 7.04 (t, J ) 7.3 Hz, 4H, Ar-H), 6.68 (t, J ) 7.4 Hz,
1
33.91, 125.48, 125.09, 116.40 (Ar-C, Py-C), 17.84, 16.42, 15.87
H, Ar-H), 4.89 (d, J ) 7.0 Hz, 8H, Ar-H), 4.76 (s, 24H, N-CH
3
),
). C NMR (d-DMF): δ 156.47, 149.87,
48.76, 143.06, 138.95, 135.06, 134.24, 133.70, 133.05, 130.17,
29.32, 127.36, 117.61 (Ar-C, Py-C), 49.61 (N-CH ), 25.24, 17.04
). MS (MALDI-TOF) m/z 1810.95 [M - 7MeI - I +
H] , calcd. for C105 1810.57. HRMS-ESI m/z 850.0984
(
(
CH
2
CH
2
CH
3
). MS (MALDI-TOF) m/z 1457.88 [M - OSi-
13
-
3 3
1.24 (s, 18H, C(CH )
+
C
3
H
7
)
3
] , calcd. for C81 Si 1457.44.
H
61
N
16
O
9
2
1
1
SiPc (12). Pc 7 (20 mg, 0.01 mmol) and CH
described above for Pc 10, and the title compound was obtained as a
green solid (27 mg, 95%); mp > 250 °C. UV–vis (H O): λ max (log ε)
74 (5.03), 644 (4.31), 607 (4.35), 356 (4.68) nm. H NMR (d-DMF):
3
I (7 mL) reacted as
3
(
3 3
C(CH )
2
+
H
82
N
16
O
10Si
3
1
6
t
3+
t
[
2
M - (OSiPh
2
Bu) - I + 2H] , 606.0964 [M - (OSiPh Bu) -
2
δ 10.10 (s, 8H, Ar-H), 9.67 (s, 8H, Py-H), 9.21 (d, 8H, J ) 5.6 Hz,
Py-H), 8.81 (d, 8H, J ) 8.3 Hz, Py-H), 8.48–8.43 (m, 8H, Py-H),
4+
t
4+
I + 2H] , 573.6194 [M - (OSiPh
2
Bu) - 3I + H] , 541.6409
t
4+
3+
[
8
5
M - (OSiPh
2
Bu) - 4I] , calcd. for [C96
H
85
I
7
N
16
O
O
9
Si
Si
2
]
]
4
-
(
1
(
.71 (s, 24H, N-CH
1.08 (m, 12H, CH
d-DMF): δ 156.57, 150.05, 148.78, 142.99, 138.67, 135.09, 134.51,
30.06, 117.89 (Ar-C, Py-C), 49.56 (N-CH ), 17.80, 16.07, 15.57
CH CH CH ). MS (MALDI-TOF) m/z 1644.87 [M - 7CH
456.46 [M - OSi(C
645.59, C81
3
), -0.12 (t, 18H, J ) 7.0 Hz, CH
3
), -0.99 to
4+
4+
49.9846, [C98
73.7842, [C96
H
H
85
I
6
N
N
16
O
9
Si
2
]
]
606.1078, [C96
541.8062.
H
84
5
I N
16
9
2
13
2
), -2.31 to -2.37 (m, 12H, CH
2
). C NMR
4+
83
I
4
16
O
9
Si
2
SiPc (15). Pc 9 (45 mg, 0.025mmol) and CH
3
(OCH
2
CH
2
)
3
I (2.2
3
g, 8.2 mmol) reacted as described above for Pc 11, and the title
compound was obtained as a dark green solid (94 mg, 94%); mp
+
2
2
3
3
- 8I] ,
+
1
1
3
3
H
7
)
2
3
- 8CH
3
85 16 3
- 8I] , calcd. for C91H N O10Si
8
2–84 °C. UV–vis (H O): λ max (log ε) 678 (4.76), 649 (3.90), 610
2
H
N
61 16
O
9
Si
1457.44. HRMS-ESI m/z 795.1072 [M -
1
(
3.96), 353 (4.25) nm. H NMR (CD
3
CN): δ 9.58 (s, 8H, Ar-H),
.43 (s, 8H, Py-H), 8.97 (d, J ) 5.3 Hz, 8H, Py-H), 8.63 (d, J )
.7 Hz, 8H, Py-H), 8.29 (t, J ) 7.6 Hz, 8H, Py-H), 6.98 (t, J ) 7.3
3
+
4+
4+
I] , 564.8538 [M - 4I] , 532.6256 [M - 5I - H] , 525.8209
9
7
4
+
3+
[M - 5I - (CH
3
)
2
+ H] , calcd. for [C98
H
106
I
I
3
5
N
N
16
O
3
10Si ]
4
+
4+
795.0936, [C98
H
106
I
I
4
N
16
O
10Si
3
]
564.9740, [C98H
105
525.9824.
16
O
3
10Si ]
Hz, 4H, Ar-H), 6.57 (t, J ) 7.3 Hz, 8H, Ar-H), 5.02 (br, 16H,
OCH ), 4.84 (d, J ) 7.1 Hz, 8H, Ar-H), 4.14 (br, 16H, OCH ),
.70 (br, 16H, OCH ), 3.55–3.47 (m, 48H, OCH ), 3.28 (s, 24H,
OCH ), -1.26 (s, 18H, C(CH ) ). C NMR (CD CN): δ 156.50,
4
+
532.6161, [C96
H
101
3
N
16
O
10Si
3
]
2
2
SiPc (8). Pc 6 (0.12 g, 0.088 mmol) and chlorotriisopropylsilane
0.4 mL, 1.8 mmol) reacted as described above for Pc 7 and the
title compound was obtained as a dark green solid (94 mg, 64%);
mp > 250 °C. UV–vis (CH Cl ): λ max (log ε) 677 (5.13), 646 (4.21),
3
2
2
1
3
(
3
3 3
3
149.97, 148.87, 142.63, 138.42, 136.02, 134.40, 133.96, 133.15,
130.39, 129.55, 127.50, 117.49 (Ar-C, Py-C), 72.48, 71.16, 70.88,
70.79, 69.38, 62.73 (OCH ), 59.01 (OCH ), 25.37, 17.20 (C(CH ) ).
2
2
1
6
09 (4.28), 359 (4.63) nm. H NMR (d-DMF): δ 9.43 (s, 8H, Ar-
2
3
3 3
+
H), 8.68 (s, 8H, Py-H), 8.57 (d, J ) 4.4 Hz, 8H, Py-H), 7.84 (d, J
MS (MALDI-TOF) m/z 3985.42 [M - H] , 3603.91 [M -
t + t +
)
8.4 Hz, 8H, Py-H), 7.64–7.59 (m, 8H, Py-H), -1.06 (d, J ) 8.0
OSiPh Bu - I - H] , 3476.98 [M - OSiPh Bu - 2I - H] ,
2
2
13
t
2
+
t
2
Hz, 36H, CH
3
), -1.94 to -2.01 (m, 6H, CH). C NMR (d-DMF):
3348.09 [M - OSiPh Bu - 3I - 2H] , 3221.20 [M - OSiPh Bu
+
δ 154.36, 151.52, 148.90, 146.18, 141.22, 133.22, 126.15, 125.68,
-
4I
-
2H] , calcd. for
C
H
60 197 8 16 34
I N O Si 3985.58,
I N O Si
2
1
3
116.01(Ar-C, Py-C), 16.11, 11.42 (CH(CH ). MS (MALDI-TOF)
)
3 2
C
C
144H I N O Si
3603.56, C144
3348.74, C144
ESI m/z 1202.3092 [M - (OSiPh Bu) - I + 2H] , 870.0024 [M
H
3476.66,
178 7
16 33
16
2
178 6 16 33
+
+
m/z 1631.23 [M + H] , 1457.42 [M - OSi(C
C
3
H
7
)
3
] , calcd. for
144
H
177
5
I N
O
33Si
2
H
2
177
I
4
N
16
O
33Si
2
3221.84. HRMS-
t
3+
90
H
83
N
16
O10Si
3
1631.58, C81 Si 1457.43.
H
61
N
16
O
9
2