478
H.-C. Song, Y.-W. Chen, J.-H. Yao, Z.-L. Xu, J. S. Bradshaw, P. B. Savage and R. M. Izatt
Vol. 40
in vacuum. The product was extracted with chloroform and the
solvent was evaporated under reduced pressure. The residue was
separated by chromatography on a silica gel column using
nmr: δ 1.95 (t, J = 6.5 Hz, 4H), 2.37 (s, 6H), 2.81-2.63 (m, 24H),
3.65 (t, J = 5.5 Hz, 4H), 4.06 (t, J = 5.9 Hz, 4H), 6.10 (s, 2H),
6.77 (d, J =2.5 Hz, 2H), 6.82 (dd, J = 8.8, J = 2.5 Hz, 2H), 7.46
1
2
13
CHCl :CH OH:NH .H O = 100:5:0.5 as eluent to give 2.56 g
(d, J = 8.8 Hz, 2H); C nmr: δ 20.4, 28.6, 31.7, 34.1, 34.2, 52.8,
3
3
3
2
1
(70%) of viscous liquid 9; H nmr: δ 2.29 (s, 2H), 2.71-2.82 (m,
16H), 3.58 (t, J = 4.8 Hz, 4H), 3.69 (t, J = 5.4 Hz, 4H); C nmr:
55.5, 56.6, 68.0, 71.3, 103.0, 113.5, 114.2, 115.2, 127.2, 154.3,
13
+
156.9, 163.0, 163.7; ms (fab) for C
727.3, found 726.3.
H
N O S (M+H) calcd.
38 51
2
8
2
,
δ 32.1, 33.2, 48.5, 49.1, 70.1, 71.9; hrms for C
(M+H) , calcd. 295.1566, found 295.1515.
H N O S
12 27 2 2 2
+
Anal. Calcd. for C
H N O S : C, 62.78; H, 6.93; N, 3.85.
38 50 2 8 2
Found C, 62.65; H, 6.57; N,3.68.
1,13-Diaza-4,7,10,19-tetraoxa-16-22-dithiacyclotetracosane (10)
(Scheme 1).
1,7-Bis(3-coumarinylaminoformylmethyl)-1,7-diaza-4,13-dioxa-
10,16-dithiacyclooctadecane (14) (Scheme 2).
Macrocyclic diamine 10, (2.69 g, 70%), was prepared as a vis-
cous liquid from 4.10 g (10.0 mmole) of macrocyclic diamide 8 as
above; H nmr: δ 2.80 (t, J = 5.9 Hz, 4H), 3.31 (s, 4H), 3.50 (q,
Ligand 14 (0.15 g, 31%) was obtained from 0.20 g (0.7
mmole) of 9 and 0.50 g (2.1 mmole) of 23, according to the gen-
1
1
J =5.1 Hz, 4H), 3.57-3.61 (m, 4H), 3.63-3.71 (m, 16H), 7.48 (s,
eral procedure; H nmr: δ 2.82 (t, J = 6.5 Hz, 4H), 2.90 (m, 8H),
13
2H); C nmr: δ 34.2, 38.1, 41.2, 71.5, 72.0, 72.2, 72.3, 73.6; ms
3.00 (s, 4H), 3.33 (s, 4H), 3.61 (t, J = 4.5 Hz, 4H), 3.74 (t, J = 6
Hz, 4H), 7.27 (t, J = 7.5 Hz, 2H), 7.29 (d, J = 8.0 Hz, 2H), 7.42 (t,
J = 8.1 Hz, 2H), 7.49 (d, J = 7.5 Hz, 2H), 8.68 (s, 2H), 10.05 (s,
+
(fab) for C H N O S (M+H) , calcd. 383.2, found 383.2; hrms
16 35
2 4 2
+
for C H N O S (M+H) , calcd. 383.2038, found 383.2035.
16 35
2 4 2
13
2H); C nmr δ: 30.0, 31.4, 54.7, 55.8, 59.7, 69.6, 71.9, 116.2,
General Procedure for the Preparation of 11-20 (Scheme 2).
119.8, 123.3, 123.9, 124.9?127.6, 129.5, 150.2, 158.2, 171.2; ms
+
The macrocyclic diamine (2.0 mmole) and 3.0 mmole of the
appropriate alkyl halide were dissolved in 100 mL of methanol
and 6.0 mmole of triethylamine was added. The mixture was
refluxed for 5 days and the solvent was evaporated under reduced
pressure. The residue was chromatographed on silica gel using
(fab) for C
H
N O S (M+H) calcd. 697.2, found 697.2.
34 41
4
8
2
,
Anal. Calcd. for C
H N O S •CH OH: C, 58.13; H, 5.94;
34 40 4 8 2 3
N, 7.86. Found C, 58.16;H, 5.53; N, 7.62.
1,7-Bis(1-naphthylaminoformylmethyl)-1,7-diaza-4,13-dioxa-
10,16-dithiacyclooctadecane (15) (Scheme 2).
CHCl :MeOH:NH .H O = 100:2:0.2 as eluent to obtain the
3
3
2
desired products.
Macrocyclic amine 9 (0.20 g, 0.7 mmole) was treated with 2.1
mmole (0.46 g) of chloroacetamide 24 in methanol to give 15
(0.18 g, 39%) as a viscous yellow liquid; H nmr: δ 2.63 (s, 4H),
1,7-Bis[2-(4-methyl-7-coumarinyl)oxyethyl]-1,7-diaza-4,13-
dioxa-10,16-dithiacyclooctadcane (11) (Scheme 2).
1
2.73 (t, J = 5.6 Hz, 4H), 2.80 (d, J = 4.9 Hz, 4H), 2.84 (d, J = 4.8
Hz, 4H), 3.27 (s, 4H), 3.49 (t J = 5.5 Hz, 4H), 3.67 (t, J = 5.6 Hz,
4H), 7.27-7.55 (m, 6H), 7.67 (d, J = 8.2 Hz, 2H), 7.84 (d, J = 8.2
According to the general procedure, 0.15 g (31%) of 11 was
separated as a yellow viscous liquid from 0.2 g (0.7 mmole) of 9
and 0.50 g (2.1 mmole) of 21; H nmr: δ 2.37 (s, 6H), 2.72-2.81
1
13
Hz, 2H), 8.07 (t, J = 8.2 Hz, 4H), 10.00 (s, 2H); C nmr: δ 31.5,
(m, 8H), 2.85 (t, J = 5.5 Hz, 4H), 2.94 (t, J = 5.7 Hz, 4H), 3.01 (t,
J = 5.7 Hz, 4H), 3.60 (t, J = 5.5 Hz, 4H), 3.67 (t, J= 6.1 Hz, 4H),
4.10 (t, J = 5.7 Hz, 4H), 6.11 (s, 2H), 6.78 (d, J = 2.4 Hz, 2H),
6.85 (dd, J = 8.8 Hz, J = 2.5 Hz, 2H), 7.47 (d, J = 8.8 Hz, 2H);
32.2, 54.7, 55.2, 59.6, 68.8, 71.8, 119.5, 121.4, 125.2, 125.8,
125.9, 126.8, 128.6, 132.6, 134.1, 169.8; ms (fab) for
+
C
H
N O S (M+H) calcd. 661.3, found 661.2.
36 45
4
4
2
,
Anal. Calcd. for C
H
N O S . H O: C, 64.55; H, 6.77; N,
1
2
36 44
4
4
2
2
13
C nmr: δ 20.3, 31.7, 33.2, 55.3, 55.9, 57.1, 68.8, 71.6, 73.5,
8.36. Found C, 64.84; H, 5.87; N,8.06.
103.1, 113.5, 114.1, 115.2, 127.3, 154.3, 156.8, 162.8, 163.4; ms
1,13-Bis[2-(4-methyl-7-coumarinyl)oxyethyl]-1,13-diaza-
4,7,10,19-tetraoxa-16,22-dithiacyclotetracosane (16).
+
(fab) for C
H
N O S (M+H) , calcd. 699.3, found 699.3.
36 47
2 8 2
Anal. Calcd. for C
H N O S : C, 61.87; H, 6.63; N, 4.01.
36 46 2 8 2
Found C, 61.68; H, 6.32; N, 3.92.
According to the general procedure, 0.20 g (0.5 mmole) of
macrocyclic diamine 10 was treated with 1.5 mmole (0.36 g) of
21 to give 0.22 g (56%) of viscous liquid 16; H nmr: δ 2.39 (s,
6H); 2.89 (m, 4H), 2.73-2.79 (m, 8H), 2.95 (t, J = 2.0 Hz, 4H),
3.06 (s, 4H), 3.59-3.67 (m, 16H), 4.1 (t, J = 5.0 Hz, 4H), 6.12 (d,
1-[2-(4-Methyl-7-coumarinyl)oxyethyl]-1,7-diaza-4,13-dioxa-
10,16-dithiacyclooctadecane (12) (Scheme 2).
1
According to the general procedure, compound 15 was isolated
as a minor product from the reaction residue in which ligand 11
J = 1.0 Hz, 2H), 6.81 (d, J = 2.5 Hz, 2H), 6.85-6.87 (dd, J = 8.5
1
1
13
was obtained; H nmr: δ 2.38 (s, 3H), 2.71-2.84 (m, 14H), 2.90 (t,
Hz, J = 2.5 Hz, 2H), 7.48 (d, J = 8.5 Hz, 2H); C nmr: δ 20.3,
2
J = 5.4 Hz, 2H), 2.98 (t, J = 5.5 Hz, 2H), 3.60-3.66 (m, 6H), 3.82
(t, J = 4.4 Hz, 2H), 4.09 (t, J = 5.42 Hz, 2H), 6.11 (s, 1H), 6.81 (d,
J = 2.4 Hz, 1H), 6.86 (dd, J = 8.8 Hz, J = 2.5 Hz, 1H), 7.48 (d,
J = 8.8 Hz, 1H); C nmr: δ 20.4, 31.3, 32.8, 33.2, 34.0, 49.4,
50.0, 54.7, 55.4, 56.1, 67.8, 68.5, 70.5, 72.5, 73.7, 103.4, 113.6,
31.3, 31.5, 33.4, 55.0, 55.8, 57.2, 68.7, 71.3, 72.3, 73.0, 103.2,
113.6, 114.2, 115.3, 127.7, 154.3, 156.8, 162.9, 163.3; ms (fab)
for C
H N O S , calcd. 787.3, found 787.3; hrms for
1
2
40 55 2 10 2
13
+
C
H N O S (M+H) , calcd. 787.3298, found 787.3301.
40 55 2 10 2
1,13-Bis[3-(4-methyl-7-coumarinyl)oxypropyl]-1,13-diaza-
4,7,10,19-tetraoxa-16,22-dithiacyclotetracosane (17).
114.1, 115.4, 127.4,154.4, 156.8, 163.0, 163.3; ms (fab) for
+
C
C
H
N O S (M+H) calcd. 497.2; found 497.2. hrms for
24 37
2
5
2
,
+
H
N O S (M+H) , calcd. 497.2144, found 497.2141.
Ligand 17 (0.22 g, 54%) was obtained as a viscous liquid from
0.20 g (0.5 mmole) of macrocyclic diamine 10 and 0.45 g (1.5
24 37
2 5 2
1,7-Bis[3-(4-methyl-7-coumarinyl)oxypropyl]-1,7-diaza-4,13-
dioxa-10,16-dithiacyclooctadecane (13) (Scheme 2).
1
mmole) of 22, according to the general procedure; H nmr: δ 2.04
(s, 4H), 2.40 (s, 6H), 2.73 (t, J = 6.0 Hz, 4H), 2.75 (m, 4H), 2.81
(t, J = 2.0 Hz, 4H), 2.84 (t, J = 0.9 Hz, 4H), 3.40 (t, J = 1.5 Hz,
4H), 3.58 (t, J = 3.5 Hz, 4H), 3.62 (t, J = 6.0 Hz, 4H), 3.65 (t, J =
Compound 13 (0.22 g, 43%) was obtained as a viscous liquid
1
from 0.20 g (0.7 mmole) of 9 and 0.62 g (2.1 mmole) of 22; H