828 J . Org. Chem., Vol. 66, No. 3, 2001
Okubo and Yamaguchi
(P ,P ,P ,P ,P )-[5 + 6]Dia m in e. Yield 85%. Mp >300 °C
(toluene-methanol). Anal. Calcd for C242H240N12O10‚6H2O: C;
81.08, H; 7.09, N; 4.69%. Found: C; 81.18, H; 6.98, N; 5.14%.
Found: C; 81.01, H; 6.83, N; 5.08%. Found: C; 80.88, H; 6.99,
at 90 °C) δ 1.45-1.65 (60H, m), 1.92 (54H, s), 2.07 (12H, s),
2.10-2.37 (52H, m), 2.39 (96H, s), 4.07 (4H, br), 6.80 (4H, s),
7.04 (4H, s), 7.17 (32H, s), 7.52 (18H, d, J ) 7 Hz), 7.69 (18H,
t, J ) 8 Hz), 8.28 (18H, s), 8.36 (18H, d, J ) 8 Hz), 9.76 (18H,
br). 13C NMR (100 MHz, CDCl3) δ 18.1, 19.4, 23.1, 23.4, 26.5,
37.3, 45.1, 45.6, 66.9, 121.4, 122.7, 123.8, 126.9, 127.1, 128.3,
129.1, 129.3, 129.7, 131.1, 131.1, 134.1, 134.6, 134.9, 136.8,
137.4, 139.9, 147.6, 148.8, 167.6. CD (CHCl3) λext (∆ꢀ) 356 nm
(+165), 305 (-133), 283 (+194).
N; 4.73%. [R]28D +64 (c 2.0, CHCl3). MS (TOF, dithranol) Calcd
12
for
λ
C
13C3H240N12O10: 3476.9. Found: 3478. UV-vis (CHCl3)
239
max (ꢀ) 303 nm (2.5 × 105). IR (CHCl3) 3411, 3400-3200, 1666
cm-1 1H NMR (400 MHz, CDCl3, 2 mM) δ 1.40-1.70 (36H,
.
m), 1.90 (30H, s), 2.12 (12H, s), 2.20-2.35 (24H, m), 2.38 (12H,
s), 2.40 (48H, s), 3,40 (4H, br), 6.88 (4H, s), 7.08 (4H, s), 7.15
(16H, s), 7.40-7.55 (20H, m), 7.55-7.70 (10H, m), 8.05-8.10
(10H, m), 8.35-8.45 (10H, m). 13C NMR (100 MHz, CDCl3, 2
mM) δ 18.1, 19.3, 23.1, 23.3, 26.5, 37.3, 45.0, 45.6, 121.3,
122.7, 123.8, 126.9, 127.1, 128.2, 129.0, 129.2, 129.7, 130.6,
131.0, 134.0, 134.5, 134.9, 136.7, 137.3, 139.8, 147.5, 148.7,
167.5. CD (CHCl3) λext (∆ꢀ) 356 nm (+97), 306 (-77), 284
(+110).
P r otected (P ,P )-[2 + 3]Dia m in e, (P ,P )-5 (n ) 1). Yield
94%. Mp >300 °C (toluene). Anal. Calcd for C126H126N6O8: C;
81.70, H; 6.86, N; 4.54%. Found: C; 82.31, H; 6.56, N; 4.62%.
[R]23 +59 (c 0.69, CHCl3). MS (FAB, NBA) Calcd for
D
12
C
13C1H126N6O8: 1852.0. Found: 1852. UV-vis (CHCl3) λmax
125
(ꢀ) 304 nm (9.6 × 104). IR (KBr) 3500-3200, 1717, 1661 cm-1
.
1H NMR (400 MHz, CDCl3, 28 mM) δ 1.40-1.70 (18H, m), 1.84
(6H, s), 1.85 (6H, s), 2.14 (12H, s), 2.20-2.30 (8H, m), 2.34
(24H, s), 5.06 (4H, s), 6.08 (2H, s), 7.00 (4H, s), 7.08 (4H, s),
7.15 (4H, s), 7.26-7.35 (10H, m), 7.38 (4H, d, J ) 7 Hz), 7.53
(2H, t, J ) 7 Hz), 7.55 (2H, t, J ) 7 Hz), 7.60 (2H, br), 7.62
(2H, br), 8.00 (2H, s), 8.01 (2H, s), 8.35 (2H, d, J ) 8 Hz), 8.37
(2H, d, J ) 8 Hz). 13C NMR (100 MHz, CDCl3, 28 mM) δ 18.7,
19.3, 22.9, 23.3, 26.4, 37.1, 45.4, 45.6, 66.8, 122.6, 123.8, 126.8,
127.0, 127.1, 127.8, 127.9, 128.2, 128.3, 129.0, 129.2, 129.7,
130.9, 130.9, 131.0, 134.0, 134.8, 134.9, 135.0, 136.2, 136.7,
146.9, 147.5, 154.1, 167.5.
P r otected (P ,P ,P ,P ,P ,P ,P )-[7 + 8]Dia m in e. Yield 86%.
Mp >300 °C (toluene-methanol). Anal. Calcd for
C
346H336N16O18: C; 83.00, H; 6.76, N; 4.48%. Found: C; 83.20,
H; 6.94, N; 4.29%. [R]21 +62 (c 0.46, CHCl3). MS (TOF,
D
12
dithranol) Calcd for
C
13C4H336N16O18+Na: 5029.6.
342
Found: 5029. UV-vis (CHCl3) λmax (ꢀ) 303 nm (3.1 × 105). IR
(KBr) 3400-3200, 1720, 1660 cm-1 1H NMR (400 MHz,
.
DMSO-d6 at 90 °C) δ 1.40-1.65 (48H, m), 1.93 (42H, s), 2.14
(12H, s), 2.20-2.35 (32H, m), 2.36 (12H, s), 2.40 (72H, s), 5.09
(4H, s), 7.04 (4H, s), 7.10 (4H, s), 7.17 (24H, s), 7.25-7.40 (12H,
m), 7.50-7.55 (14H, m), 7.69 (14H, t, J ) 7 Hz), 8.28 (14H,
br), 8.36 (14H, d, J ) 8 Hz), 9.77 (14H, br). 13C NMR (100
MHz, CDCl3) δ 18.9, 19.4, 23.0, 23.1, 23.4, 26.4, 26.5, 37.2,
45.5, 45.6, 67.0, 122.8, 123.9, 126.9, 127.2, 128.0, 128.4, 129.2,
129.3, 129.8, 131.0, 131.2, 134.2, 134.8, 134.9, 135.0, 136.9,
147.6, 167.6.
(P ,P )-[2 + 3]Dia m in e, (P ,P )-4 (n ) 3). Yield 91%. Mp
>300 °C (toluene). Anal. Calcd for C110H114N6O4: C; 83.40, H;
7.25, N; 5.31%. Found: C; 82.93, H; 7.45, N; 5.27%. [R]26D +68
12
(c 1.1, CHCl3). MS (FAB, NBA) Calcd for
C
13C1H114N6O4:
109
1583.9. Found: 1585. UV-vis (CHCl3) λmax (ꢀ) 303 nm (7.6 ×
105). IR (KBr) 3382, 3280, 1657 cm-1 1H NMR (400 MHz,
.
CDCl3, 40 mM) δ 1.40-1.70 (18H, m), 1.93 (12H, s), 2.15 (12H,
s), 2.20-2.35 (8H, m), 2.40 (12H, s), 2.42 (12H, s), 3.43(4H,
br), 6.88 (4H, s), 7.08 (4H, s), 7.15 (4H, s), 7.43 (2H, s), 7.46
(4H, d, J ) 8 Hz), 7.48 (2H, s), 7.64 (2H, t, J ) 8 Hz), 7.64
(2H, t, J ) 7 Hz), 8.11 (4H, s), 8.43 (2H, d, J ) 8 Hz), 8.44
(2H, d, J ) 8 Hz). 13C NMR (100 MHz, CDCl3, 40 mM) δ 18.2,
19.4, 19.4, 23.1, 23.4, 26.6, 37.2, 37.3, 45.1, 45.6, 121.4, 122.8,
123.8, 123.9, 127.0, 127.0, 127.2, 127.2, 128.4, 129.2, 129.3,
129.8, 130.5, 130.9, 131.2, 134.2, 134.3, 134.6, 134.9, 136.9,
137.3, 139.9, 147.5, 148.9, 167.5, 167.6. CD (CHCl3) λext (∆ꢀ)
356 nm (+47), 307 (-42), 284 (+57).
(P ,P ,P ,P ,P ,P ,P )-[7 + 8]Dia m in e. Yield 85%. Mp >300 °C
(toluene-methanol). Anal. Calcd for C330H324N16O14‚10H2O: C;
80.59, H; 7.05, N; 4.56%. Found: C; 80.67, H; 6.98, N; 4.35%.
Found: C; 80.94, H; 7.14, N; 4.39%. Found: C; 80.70, H; 7.03,
N; 4.22%. [R]24D +67 (c 1.7, CHCl3). MS (TOF, dithranol) Calcd
12
for
C
13C4H324N16O14: 4738.5. Found: 4738. UV-vis (CHCl3)
326
λmax (ꢀ) 303 nm (3.3 × 105). IR (KBr) 3450-3150, 1716, 1654
cm-1 1H NMR (400 MHz, DMSO-d6 at 90 °C) δ 1.45-1.65
.
(48H, m), 1.93 (42H, s), 2.07 (12H, s), 2.10-2.30 (16H, m),
2.30-2.38 (28H, m), 2.40 (72H, s), 4.10 (4H, br), 6.80 (4H, s),
7.05 (4H, s), 7.17 (24H, s), 7.52 (14H, d, J ) 7 Hz), 7.69 (14H,
t, J ) 8 Hz), 8.21 (2H, s), 8.27 (2H, s), 8.28 (10H, s), 8.33-
8.40 (14H, m), 9.70-9.80 (14H, m). 13C NMR (100 MHz, CDCl3)
δ 18.2, 19.4, 23.1, 23.4, 26.5, 26.6, 37.3, 37.3, 45.1, 45.6, 121.4,
122.7, 123.8, 125.1, 127.0, 127.0, 127.1, 128.1, 128.3, 128.9,
129.1, 129.3, 129.8, 130.6, 131.0, 131.1, 134.1, 134.2, 134.6,
134.9, 136.8, 137.4, 139.9, 147.6, 148.8, 167.6. CD (CHCl3) λext
(∆ꢀ) 356 nm (+126), 305 (-132), 283 (+136).
P r otected (P ,P ,P ,P )-[4 + 5]Dia m in e. Yield 97%. Mp >300
°C (toluene-methanol). Anal. Calcd for C214H210N10O12
: C;
82.54, H; 6.79, N; 4.50%. Found: C; 82.49, H; 7.22, N; 4.41%.
[R]28 +54 (c 0.83, CHCl3). MS (TOF, dithranol) Calcd for
D
12
C
13C3H210N10O12+Na: 3137.6. Found: 3138. UV-vis (CHCl3)
211
λmax (ꢀ) 302 nm (1.8 × 105). IR (KBr) 3450-3150, 1718, 1654
cm-1
.
1H NMR (400 MHz, CDCl3, 7 mM) δ 1.40-1.70
(30H, m), 1.92 (6H, s), 1.93 (18H, s), 2.19 (12H, s), 2.20-2.38
(20H, m), 2.39 (12H, s), 2.42 (36H, s), 5.13 (4H, s), 6.00 (2H,
br), 7.00 (4H, s), 7.08 (4H, s), 7.15 (12H, s), 7.25-7.40 (10H,
m), 7.40-7.50 (20H, m), 7.60-7.70 (10H, m), 8.05-8.15 (10H,
m), 8.40-8.50 (10H, m). 13C NMR (100 MHz, CDCl3, 7 mM) δ
18.7, 19.3, 23.0, 23.3, 26.4, 37.1, 45.4, 45.6, 66.9, 122.7, 123.8,
126.8, 127.1, 127.8, 128.2, 128.3, 129.1, 129.2, 129.7, 130.9,
131.0, 134.0, 134.8, 134.9, 136.1, 136.7, 147.0, 147.5, 154.3,
167.5.
P r otected (P ,P ,P ,P ,P ,P ,P ,P ,P )-[9 + 10]Dia m in e. Yield
68%. Mp >300 °C (toluene-methanol). Anal. Calcd for
C
434H420N20O22‚9H2O: C; 81.06, H; 6.87, N; 4.36%. Found: C;
80.87, H; 7.21, N; 4.22%. Found: C; 81.25, H; 7.11, N; 4.22%.
Found: C; 81.09, H; 7.12, N; 4.33%. [R]21 +68 (c 1.0, CHCl3).
D
12
MS (TOF, dithranol) Calcd for
C
13C5H420N20O22: 6268.2.
429
Found: 6269. UV-vis (CHCl3) λmax (ꢀ) 303 nm (4.1 × 105). IR
(CHCl3) 3411, 3350-3150, 1731, 1665 cm-1 1H NMR (400
.
MHz, DMSO-d6 at 90 °C) δ 1.40-1.65 (60H, m), 1.93 (54H, s),
2.14 (12H, s), 2.20-2.37 (52H, m), 2.40 (96H, s), 5.09 (4H, s),
7.04 (4H, s), 7.10 (4H, s), 7.17 (32H, s), 7.25-7.37 (12H, m),
7.52 (18H, d, J ) 7 Hz), 7.69 (18H, t, J ) 8 Hz), 8.28 (18H,
br), 8.36 (18H, d, J ) 8 Hz), 9.77 (18H, br). 13C NMR (100
MHz, CDCl3) δ 18.7, 19.3, 23.0, 23.3, 26.4, 37.1, 45.5, 45.6,
66.9, 122.8, 124.0, 127.0, 127.2, 128.0, 128.4, 129.2, 129.4,
129.9, 131.1, 131.2, 134.2, 135.0, 136.9, 147.7, 167.9.
(P ,P ,P ,P )-[4 + 5]Dia m in e. Yield 94%. Mp >300 °C (tolu-
ene-methanol). Anal. Calcd for C198H198N10O8‚6H2O: C; 80.51,
H; 7.17, N; 4.74%. Found: C; 80.59, H; 6.83, N; 4.96%.
Found: C; 80.76, H; 6.95, N; 4.79%. [R]25 +64 (c 2.0, CHCl3).
D
12
MS (FAB, NBA) Calcd for
C
13C2H198N10O8: 2845.5.
196
Found: 2846. UV-vis (CHCl3) λmax (ꢀ) 302 nm (2.1 × 105). IR
(KBr) 3400-3100, 1654 cm-1 1H NMR (400 MHz, CDCl3, 5
.
mM) δ 1.40-1.70 (30H, m), 1.90 (24H, s), 2.13 (12H, s), 2.20-
2.35 (20H, m), 2.38 (12H, s), 2.41 (36H, s), 3,42 (4H, br), 6.87
(4H, s), 7.07 (4H, s), 7.15 (12H, s), 7.40-7.55 (16H, m), 7.55-
7.65 (8H, m), 8.05-8.15 (8H, m), 8.35-8.45 (8H, m). 13C NMR
(100 MHz, CDCl3, 5 mM) δ 18.1, 19.3, 23.1, 23.3, 26.5, 37.3,
45.0, 45.6, 121.3, 122.6, 123.7, 126.9, 127.1, 128.2, 129.0, 129.2,
129.7, 130.6, 131.0, 134.0, 134.5, 134.9, 136.7, 137.3, 139.8,
147.5, 148.7, 167.5. CD (CHCl3) λext (∆ꢀ) 356 nm (+76), 306
(-55), 284 (+86).
(P ,P ,P ,P ,P ,P ,P ,P ,P )-[9 + 10]Dia m in e. Yield 72%. Mp
>300 °C (toluene-methanol). Anal. Calcd for C418H408N20O18
‚
14H2O: C; 80.30, H; 7.03, N; 4.48%. Found: C; 80.27, H; 7.19,
N; 4.36%. Found: C; 80.03, H; 7.31, N; 4.31%. Found: C; 80.40,
H; 6.83, N; 4.31%. [R]25 +75 (c 1.4, CHCl3). MS (TOF,
D
12
dithranol) Calcd for
C
13C5H408N20O18
:
6000.2. Found:
413
6001. UV-vis (CHCl3) λmax (ꢀ) 303 nm (4.0 × 105). IR (CHCl3)
3410, 3350-3150, 1666 cm-1 1H NMR (400 MHz, DMSO-d6
.