A. I. Khalaf et al. / Tetrahedron 56 (2000) 5225±5239
5237
HOBT (26 mg, 0.1926 mmol) and dry DMF (1.0 mL). The
resultant mixture was placed under nitrogen, and stirred and
cooled in an ice bath. A solution of diisopropylcarbodiimide
(54.5 mg, 0.4325 mmol) in dry DMF (0.5 mL) was added,
and the resultant solution was allowed to come to room
temperature. After 18 h, water (2 drops) was added. The
required linked oligomer was isolated as described above
(49% yield).
pyrrole); 3.88 (6H, s, 2£NMe pyrrole); 6.95 (2H, s, pyrrole);
7.12 (2H, s, pyrrole); 7.16 (2H, s, pyrrole); 7.34 (2H, s,
pyrrole); 7.90 (2H, s, ArH); 7.92 and 7.94 (2H, d, J
8.4 Hz, ArH); 8.04 and 8.06 (4H, d, J8.4 Hz, ArH and t,
J5.4 Hz, CONH exch.); 9.94 (2H, s, CONH exch.); 10.36
(2H, s, CONH exch.).
9,10-Dihydrophenanthrene-2,7-dicarboxamido{3-[1-meth-
yl-4-(4-amino-1-methyl-pyrrole-2-carboxamido) pyrrole-
2-carboxamido]-morpholine} (23). (morphp pyrr pyrr
H2phen pyrr pyrr morph) In 67% yield from 5e and dihy-
drophenanthrene-2,7-dicarboxylic acid 14 using HBTU
coupling. (Found: ES-MS: 1010.0 and 505.0; C54H64N12O8
requires (free base) 1010.18 (M11) and 505.60 [(M12)/2]);
The following compounds were prepared similarly.
9,10-Dihydrophenanthrene-2,7-dicarboxamido{3-[1-meth-
yl-4-(4-amino-1-methyl-pyrrole-2-carboxamido)pyrrole-
2-carboxamido]-dihydroxyethylaminopropane}
(20).
(dheap pyrr pyrr H2phen pyrr pyrr dheap) In 45% yield
from 5d and dihydrophenanthrene-2,7-dicarboxylic acid
using HBTU coupling. (Found: ES-MS: 1046.1, 523.9
C54H68N12O10 requires (free base) 1046.2 (M11) and
523.6 [(M12)/2]); nmax/cm21 (KBr) 1682, 1640, 1585,
1432, 1270, 1202; dH (DMSO-d6) d 1.91 (4H, m, 2£CH2±
CH2±CH2), 2.97 (4H, s, Ar±CH2±CH2±Ar), 3.17±3.24
(16H, m, 8£CH2), 3.75 (8H, m, 4£CH2), 3.82 (6H, s, 2£
pyrrole NMe), 3.88 (6H, s, 2£pyrrole NMe), 5.30 (4H, bs,
exch., 4£OH), 6.94 (2H, d, J1.6 Hz, 2£pyrrole ArH), 7.13
(2H, d, J1.6 Hz, 2£pyrrole ArH), 7.18 (2H, d, J1.6 Hz,
2£pyrrole ArH), 7.34 (2H, d, J1.6 Hz, 2£pyrrole ArH),
7.90±7.94 (4H, m, 4£benzene ArH), 8.04±8.06 (2H, m,
2£benzene ArH), 8.15 (2H, t, J5.6 Hz, exch.,
2£CONH±CH2), 9.07 (2H, bs, exch., 2£TFA), 9.95 (2H,
s, exch., 2£CONH), 10.34 (2H, s, exch., 2£CONH).
n
max/cm21 (KBr) 1677, 1642, 1534, 1440, 1265, 1201; dH
(DMSO-d6) d 1.89 (4H, m, 2£CH2±CH2±CH2), 2.97 (4H, s,
Ar±CH2±CH2±Ar), 2.97±3.14 (8H, m, 4£CH2), 3.25 (4H,
m, 2£CH2), 3.40 (4H, m, 2£CH2), 3.63 (4H, m, 2£CH2),
3.83 (6H, s, 2£NMe), 3.88 (6H, s, 2£NMe), 3.98 (4H, m,
2£CH2), 6.96 (2H, d, J1.6 Hz, 2£ArH), 7.12 (2H, d,
J1.6 Hz, 2£ArH), 7.18 (2H, d, J2.0 Hz, 2£ArH), 7.34
(2H, d, J2.0 Hz, 2£ArH), 9.6±9.8 (2H, bs, exch., 2£TFA)
9.95 (2H, s, exch., 2£CONH), 10.37 (2H, s, exch.,
2£CONH).
9,10-Dihydrophenanthrene-2,7-dicarboxamido{3-[1-meth-
yl-4-(4-amino-1-methyl-pyrrole-2-carboxamido)pyrrole-
2-carboxamido]-propanamidine} (24). (amidp pyrr pyrr
H2phen pyrr pyrr amidp) In 35% yield from 5f and dihy-
drophenanthrene-2,7-dicarboxylic acid 14 using HBTU
coupling. (Found: ES-MS: 895.86 and 447.84;
C46H50N14O6 (free base) requires: 895.99 (M11) and
448.50 [(M12)/2]); nmax/cm21 (KBr) 1682, 1640, 1585,
1540, 1270, 1202, 1134; dH (DMSO-d6) d 2.61 (4H, t,
2£CH2±CH2±C NH14 ), 2.97 (4H, s, CH2±CH2 bridge),
3.51 (4H, q, J6.0 Hz, becoming t, J6.2 Hz after D2O,
2£NH±CH2±CH2), 3.82 (6H, s, 2£pyrrole NCH3), 3.88
(6H, s, 2£pyrrole NCH3), 6.97 (2H, d, J1.6 Hz, 2£pyrrole
ArH), 7.12 (2H, d, J1.6 Hz, 2£pyrrole ArH), 7.18 (2H, d,
J1.6 Hz, 2£pyrrole ArH), 7.34 (2H, d, J1.6 Hz, 2£
pyrrole ArH), 7.90 (2H, s, 2£ArH), 7.93 (2H, d,
J8.4 Hz, 2£ArH), 8.05 (2H, d, J8.4 Hz, 2£ArH), 8.20
(2H, t, J5.6 Hz, exch., 2£CONH±CH2), 8.53 (4H, s, exch.,
amidine), 8.90 (4H, exch., amidine), 9.95 (2H, s, 2£CONH),
10.37 (2H, s, 2£CONH).
9,10-Dihydrophenanthrene-2,7-dicarboxamido{3-[1-meth-
yl-4-(4-amino-1-methyl-pyrrole-2-carboxamido)pyrrole-
2-carboxamido]-N-pyrrolidinylpropane} (21). (pyrp
pyrr pyrr H2phen pyrr pyrr pyrp) In 65% yield from 5b
and dihydrophenanthrene 2,7-dicarboxylic acid using
HBTU coupling. (ES-MS: found 978.0, and 488.94;
C54H66N12O6 requires (M11) 979.1 and [(M12)/2]
489.59.); nmax/cm21 (KBr) 1679, 1648, 1535, 1439, 1266,
1201; dH (DMSO-d6): 1.82±1.91 (8H, m, 4£CH2); 2.02±
2.04 (4H, m, 2£CH2); 2.97±3.02 (8H, m and s, 2£CH2 and
dihydrophenanthrene 2£CH2); 3.13±3.18 (4H, m, 2£CH2);
3.24±3.27 (4H, m, 2£CH2); 3.56±3.57 (4H, m, 2£CH2);
3.82 (6H, s, 2£NMe pyrrole); 3.88 (6H, s, 2£NMe pyrrole);
6.96 and 6.97 (2H, d, J1.6 Hz, pyrrole); 7.12 and 7.13 (2H,
d, J1.6 Hz, pyrrole); 7.17 and 7.18 (2H, d, J1.6 Hz,
pyrrole); 7.33 and 7.34 (2H, d, J1.6 Hz, pyrrole); 7.90
(2H, s, ArH); 7.92 and 7.94 (2H, d, J1.6 Hz, ArH); 8.09
and 8.07 (2H, d, J1.6 Hz, ArH); 8.14±8.17 (2H, t, J
5.6 Hz, CONH exch.); 9.4 (2H, broad, TFA exch.); 9.95
(2H, s, 2£CONH exch.); 10.37 (2H, s, 2£CONH exch.).
Phenanthrene-3,6-dicarboxamido{3-[1-methyl-4-(4-amino-
1-methyl-pyrrole-2-carboxamido)pyrrole-2-carboxamido]-
dimethylaminopropane} (25). (dmap pyrr pyrr phen pyrr
pyrr dmap) In 69% yield from 5a and phenanthrene-3,6-
dicarboxylic acid 15a using HBTU coupling. (Found: ES-
MS: 924.2 and 462.9 C50H58N12O6 (free base) requires 924.1
(M11) and 462.5 [(M12)/2]); nmax/cm21 (KBr) 1682,
1649, 1535, 1270, 1201; dH (DMSO-d6) 1.85 (4H, qt,
J8.0 Hz, 2£CH2±CH2±CH2), 2.80 (12H, d, J2.8 Hz,
becoming s after D2O, 2£NH1(CH3)2), 3.08 (4H, m,
becoming t, J5.6 Hz after D2O, 2£NH±CH2±CH2), 3.26
(4H, q, J6.8 Hz, becoming t, J5.6 Hz after D2O, 2£NH±
CH2±CH2), 3.83 (6H, s, 2£pyrrole NCH3), 3.91 (6H, s,
2£pyrrole NCH3), 6.97 (2H, d, J1.6 Hz, 2£pyrrole
ArH), 7.18 (2H,d, 2£pyrrole ArH), 7.19 (2H, d, J1.6 Hz,
2£pyrrole ArH), 7.40 (2H, d, J1.6 Hz, 2£ pyrrole
ArH), 8.06 (2H,s, ArH), 8.17 (2H, t, J5.6 Hz, exch.,
9,10-Dihydrophenanthrene-2,7-dicarboxamido{3-[1-Meth-
yl-4-(4-amino-1-methyl-pyrrole-2-carboxamido)pyrrole-
2-carboxamido]-(4-methylpiperazinyl)propane}
(22).
(mpip pyrr pyrr H2phen pyrr pyrr mpip) In 43% yield
from 5c and dihydrophenanthrene 2,7-dicarboxylate using
HBTU coupling. (ES-MS: Found: 1036.1, 518.1
C56H70N14O6 requires (M11) 1036.2 and [(M12)/2]
518.6; nmax/cm21 (KBr) 1680, 1641, 1538, 1437, 1267,
1200; dH (DMSO-d6): 1.77 (4H, m, 2£CH2); 2.72 (6H, s,
2£NMe); 2.97 (4H, s, dihydro); 3.23±3.24 (4H, q, J
5.6 Hz, 2£CH2); 3.53 (20H, broad); 3.82 (6H, s, 2£NMe