7
6.8, 32.9, 24.6 (quaternary Ar–C could not be detected due
aqueous phase was extracted with 2 × 10 ml chloroform. The
organic extracts were dried over Na SO , filtered and the sol-
to low solubility); m/z (CI) Found: 655.269 (M ϩ H).
2
4
C H N S requires: 655.2706.
vent removed in vacuo. The residue was recrystallised from
toluene to give the trianglamine (38) as a white solid. Mp
36
43
6 3
2
5
Ϫ1
1
95–198 ЊC; [α]
D
ϩ190 (CHCl , c = 0.1); ν
(Nujol)/cm
(
(
2R,3R,11R,12R,20R,21R)-1,4,10,13,19,22-Hexaaza-
2,3:11,12:20,21)-tributano-(6,8:15,17:24,26)-tris(cyclo-
3
max
3
331 (N–H); δ (500 MHz; CDCl ) 7.07 (6H, s, Ar–H), 3.85
H
3
(
6H, d, J 12.9, CH H N), 3.55 (6H, d, J 12.9, CH H N),
A B A B
heptatrieno)-(2H,3H,11H,12H,20H,21H)-hexahydro-(27)-
annulene (34) and (2R,3R,11R,12R)-1,4,10,13-tetraaza-
2
.28 (18H, s, Me), 1.01–1.86 (36H, CH , CHN and NH);
2
δ (CDCl ) 137.4, 133.9, 130.5, 61.9, 49.0, 32.0, 25.6, 18.9; m/z
(
(
2,3:11,12)-dibutano-(6,8:15,17)-bis(cycloheptatrieno)-
2H,3H,11H,12H)-tetrahydro-(18)-annulene (35)
C
3
(
CI) (Found: 732.583. C H N requires: 732.5818).
48 72 6
In the same way as for compound (27) 228 mg (1R,2R)-
diaminocyclohexane (22) (2 mmol) and 368 mg 1,3-
diformylazulene (2 mmol) in 20 ml dichloromethane gave an
inseparable 4 : 1 mixture of trianglimine (34) and macrocycle
(
2R,3R,11R,12R,20R,21R)-1,4,10,13,19,22-Hexaaza-(7,16,25)-
trimethyl-(2,3:11,12:20,21)-tributano-(6,8:15,17,24,26)-tri-
propeno-(1H,2H,3H,4H,5H,9H,10H,11H,12H,13H,14H,18H,
1
(
9H,20H,21H,22H,23H,27H)-octadecahydro-(27)-annulene
39)
25
(
35) as a black glassy solid. Mp 180–183 ЊC; [α]
D
(could not
be determined since solution completely absorbs polarised
Ϫ1
In the same way as for compound (38) 100 mg trianglimine (23)
1.47 mmol) and 34 mg NaBH4 (8.8 mmol) gave the tri-
anglamine (39) as a colourless oil that turned solid upon stand-
light); νmax (Nujol)/cm
1644 (C᎐N); δ (500 MHz; d -
H 6
(
DMSO) 9.00 (6H, d, J 9.7, Ar–H, trimer), 8.58 (6H, s, HC᎐
᎐
N, trimer), 8.49 (4H, s, HC᎐N, dimer), 8.27 (2H, s, Ar–H,
᎐
2
5
ing (95 mg, 94%). Mp 182–184 ЊC; [α] ϩ192 (CHCl , c = 0.1);
νmax (Nujol)/cm 3334 (N–H); δ (500 MHz; CDCl ) 7.10 (6H,
D
dimer), 8.19 (4H, d, J 9.7, Ar–H, dimer), 8.09 (3H, s, Ar–H,
trimer), 7.47 (2H, t, J 9.7, Ar–H, dimer), 7.11 (6H, t, J 9.7,
Ar–H, trimer), 6.56 (4H, t, J 9.7, Ar–H, dimer), 6.33 (3H, t,
J 9.7, Ar–H, trimer), 3.50 (4H, m, HCN, dimer), 3.44 (6H,
3
Ϫ1
H
3
d, J 8.1, Ar–H), 7.02 (3H, t, J 8.1, Ar–H), 3.78 (6H, d, J 12.9,
CH H N), 3.55 (6H, d, J 12.9, CH H N), 2.17 (18H, s, Me),
0
1
6
A
B
A
B
.96–1.86 (36H, CH , CHN and NH); δ (CDCl ) 137.2, 133.9,
m, HCN, trimer), 1.12–2.15 (24H, m, CH , dimer and tri-
2 C 3
2
30.5, 128.2, 62.2, 49.1, 32.1, 25.6, 18.9; m/z (CI) (Found:
mer); m/z (LSIMS) 788.0 (M ϩ H, trimer, 80%), 526.4 (M,
ϩ
90.535 (M ). C H N requires: 690.5349).
2
0%, dimer); CHN (Found: C, 81.8; H, 7.63; N, 10.6.
45 66
6
C H N requires: C, 81.1; H, 7.43; N, 9.24%).
59
60
6
(
2R,3R,11R,12R,20R,21R)-1,4,10,13,19,22-Hexaaza-
(
2,3:11,12:20,21)-tributano-(6,8:15,17:24,26)-tris(2-methyl-
(
2R,3R,11R,12R)-1,4,10,13-Tetraaza-7,16-dimethyl-
2,3:11,12)-dibutano-(6,8:15,17)-dipropeno-(2H,3H,11H,12H)-
propeno)-(1H,2H,3H,4H,5H,9H,10H,11H,12H,13H,14H,
8H,19H,20H,21H,22H,23H,27H)-octadecahydro-(27)-
(
1
tetrahydro-(18)-annulene (36)
annulene (40)
A solution of 50 mg (0.74 mmol) of trianglimine (24) in 5 ml
dichloromethane was heated under reflux for 12 hours. The sol-
vent was removed in vacuo and the residue recrystallised from
ethyl acetate–toluene (1 : 1) to give the title compound as a
In the same way as for compound (38) 60 mg of trianglimine
(
24) (0.88 mmol) and 20 mg NaBH (5.3 mmol) gave the tri-
4
anglamine (40) as a white solid (54 mg, 89%). Mp over 200 ЊC;
25
Ϫ1
2
5
[α]
D
3
Ϫ192 (CHCl , c = 0.1); νmax(Nujol)/cm 3420 (br, NH),
white powder (50 mg, 99%). Mp 206–208 ЊC; [α]
D
ϩ196
1
604, 1463, 815; δ (500 MHz; CDCl ) 7.11 (3H, s, CH), 6.97
Ϫ1
H
3
(
CHCl , c = 0.1); ν (Nujol)/cm 1640 (C᎐N); δ (500 MHz;
3
max
H
(
6H, s, CH), 3.79 (6H, d, J 13.1, CH H N), 3.56 (6H, d, J 13.1,
A B
CDCl ) 8.36 (4H, s, CH᎐N), 7.50 (4H, d, J 8.0, Ar–H), 7.12
3
CH H N), 2.29 (9H, s, Me), 2.13 (6H, br s, exchanges with
A
B
(
2H, t, J 8.0, Ar–H), 3.35 (4H, m, N᎐CH), 2.29 (6H, s, Me),
᎐
D O, NH), 2.03 (6H, m, CHN), 1.20–1.88 (24H, m, CH );
2
2
1
.26–2.17 (12H, m, CH ); δ (CDCl ) 162.3, 136.9, 130.3, 126.3,
2 C 3
δ (125 MHz; CDCl ) 141.8, 138.2, 127.9, 124.9, 61.4, 51.4, 32.2,
C
3
1
25.5, 74.5, 32.8, 25.0, 21.5; m/z (CI) 425 (M ϩ H); CHN
2
9
5.7, 21.7; m/z (CI) 691.2 (M ϩ H); CHN (Found: C, 77.6; H,
(
Found: C, 79.8; H, 8.03; N, 12.4. C H N requires: C, 79.6; H,
30 36 4
.81; N, 11.9. C H N requires: C, 78.2; H, 9.63; N, 12.2%).
45
66
6
8
.02; N, 12.4%).
(
(
(
2R,3R,12R,13R,22R,23R)-1,4,11,14,21,24-Hexaaza-
7,8,17,18,27,28)-hexamethoxy-(2,3:12,13:22,23)-tributano-
6,9:16,19:26,29)-trietheno-(1H,2H,3H,4H,5H,9H,10H,11H,
(
(
2R,3R,11R,12R)-1,4,10,13-Tetraaza-(2,3:11,12)-dibutano-
6,8:15,17)-bis(2Ј-methylpropeno)-(2H,3H,11H,12H)-
tetrahydro-(18)-annulene (37)
1
2H,13H,14H,18H,19H,20H,21H,22H,23H,27H)-
octadecahydro-(30)-annulene (41)
In the same way as for compound (36) 50 mg (0.74 mmol) of
trianglimine (25) gave after 72 hours under reflux the title com-
Trianglimine (26) (0.1 g, 0.16 mmol), was dissolved in 2 ml of
THF–MeOH (1 : 1) at 0 ЊC. NaBH (0.12 g, 3.21 mmol) was
2
5
pound as a white powder (50 mg, 99%). Mp 188 ЊC; [α]
D
ϩ181
4
Ϫ1
(
CHCl , c = 0.1); ν (Nujol)/cm 1641 (C᎐N); δ (500 MHz;
3
max
H
added slowly. After the addition the reaction was stirred for 2 h
at rt. Finally the solvent was removed and the solid was
extracted with dichloromethane and water. The solvent was
evaporated to give the trianglamine (41) (20 mg, 15%) as an oil.
CDCl ) 8.18 (4H, s, CH᎐N), 7.74 (2H, br s, Ar–H), 7.36 (4H, br
3
s Ar–H), 3.43 (4H, m, N᎐CH), 2.28 (6H, s, Me), 1.50–2.08
᎐
(
18H, m, CH ); δ (CDCl ) 160.5, 138.9, 136.8, 126.3, 125.4,
2 C 3
7
4.9, 33.5, 24.9, 21.4; m/z (CI) (Found: 453.2942 (M ϩ H).
25
D
Ϫ1
[α]
Ϫ200 (CHCl , c = 0.1); ν
(Nujol)/cm 3415 (N–H);
3
max
C H N requires: 453.2940).
30
30
4
δ (300 MHz; CDCl ) 6.93 (6H, s, Ar–H), 3.77 (18H, s, CH O),
H 3 3
3
.52 (12H, AB quartet, J 13.3, CH H N), 0.95–2.08 (36H, m,
A B
(
(
(
2R,3R,12R,13R,22R,23R)-1,4,11,14,21,24-Hexaaza-
7,8Ј,17,18Ј,27,28Ј)-hexamethyl-(2,3:12,13:22,23)-tributano-
6,9:16,19:26,29)-trietheno-(1H,2H,3H,4H,5H,10H,11H,12H,
CHN, CH and NH); δ (CDCl ) 152.3, 124.6, 77.7, 61.3, 46.1,
2 C 3
32.1, 31.7, 25.5; m/z (CI) 831.0 (M ϩ 3H); C H N O requires:
48
72
6
6
828.5508, found: 828.54419.
1
3H,14H,15H,20H,21H,22H,23H,24H,25H,29H)-
octadecahydro-(30)-annulene (38)
(2R,3R,11R,12R,20R,21R)-1,4,10,13,19,22-Hexaaza-(7,16,25)-
trimethoxy-(2,3:11,12:20,21)-tributano-(6,8:15,17:24,26)-
tris(1Ј,3Ј-dimethoxypropeno)-(1H,2H,3H,4H,5H,9H,10H,11H,
To a solution of 100 mg (1.3 mmol) trianglimine (23) in 5 ml
THF–MeOH (1 : 1) was slowly added 30 mg (7.9 mmol) of
1
2H,13H,14H,18H,19H,20H,21H,22H,23H,27H)-
octadecahydro-(27)-annulene (42)
NaBH at 0 ЊC. The solution was stirred for 2 hours at this
4
temperature. To the solution was added 10 ml of H O and 10
2
ml of chloroform. The organic phase was separated and the
Trianglimine (27) (16 mg, 0.02 mmol), was dissolved in 0.6 ml
1
168
O r g . B i o m o l . C h e m . , 2 0 0 3 , 1, 1 1 5 7 – 1 1 7 0