5512 J . Org. Chem., Vol. 65, No. 18, 2000
Xiao et al.
158.5, 158.4, 157.0, 133.8, 128.2, 126.3, 123.1, 122.8, 122.7,
122.2, 122.1, 121.5, 118.7, 118.6, 118.0, 107.6, 104.8, 104.6,
104.4, 59.9, 37.5, 36.2, 36.1, 35.9, 34.8, 34.1, 14.1; MS (FAB)
m/z 636 (MH+); HRMS calcd for C29H34N9O8 (MH+) 636.2525,
found 636.2514.
J
C
) 7.2 Hz); MS (FAB) m/z 638 (MH+); HRMS calcd for
27H32N11O8 (MH+) 638.2430, found 638.2433.
PyPyPyPyγPyImImPyâOEt (29). To a mixture of 27a (0.40
g, 0.70 mmol) in 4 mL of DMF was added 0.7 mL of
N-methylpyrrolidone to make a clear solution. To this solution
was added HOBT (0.29 g, 2.2 mmol), followed by DCC (0.42
mg, 2.0 mmol). The reaction solution was stirred overnight.
Separately, to a solution of 28 (0.44 g, 0.70 mmol) in 9 mL of
DMF was added Pd/C catalyst (10%, 0.13 g), and the mixture
was stirred under a slight positive pressure of H2 at 70 °C for
6 h. The catalyst was removed by filtration through Celite,
and the filtrate was directed into the active ester solution and
stirred overnight. The mixture was filtered to remove the DCU,
and the filtrate was concentrated in vacuo. Column chroma-
tography of the residue (gradient elate 0-5% CH3OH in
CHCl3) provided 0.60 g of 29 (74% yield). IR (KBr)3305, 3125,
Sa p on ifica tion . 1-Methyl-4-(1-methylpyrrole-2-carboxami-
do)pyrrole-2-carboxylic Acid (PyPyCOOH) (21a ). To a solution
of PyPyCOOMe (2.61 g, 10 mmol) in 70 mL of ethanol was
added NaOH (1.20 g in 50 mL of water). The reaction solution
was stirred at room temperature overnight. After filtration,
the filtrate was concentrated in vacuo to remove the ethanol
solvent. The pH of the remaining aqueous solution was
adjusted to about 1 by adding 6 N HCl. The precipitate was
collected by filtration and was washed with water and dried
under an IR lamp to offer 2.34 g of 21a (95% yield). IR (KBr)
3463, 1665, 1581, 1418 cm-1; H1 NMR (DMSO-d6, 200 MHz) δ
12.16 (b, 1H), 9.81 (s, 1H), 7.42 (s, 1H), 6.93 (s, 1H), 6.89 (s,
1H), 6.81 (s, 1H), 6.05 (s, 1H), 3.86 (s, 3H), 3.82 (s, 3H); MS
(FAB) m/z 248 (MH+); HRMS calcd for C12H14N3O3 (MH+)
248.1030, found 248.1036. Anal. Calcd for C12H13N3O3: C,
58.29; H, 5.30; N, 17.00. Found: C, 58.27; H, 5.35; N, 16.97.
Syn th esis of P yP yP yP yγP yIm Im P yâDp . NO2ImImPyâ-
OEt (19). A synthetic procedure similar to that for 17 was
followed for the preparation of 19, and 3.23 g of product was
obtained (67% yield). IR (KBr) 3373, 3125, 1727, 1642, 1545,
1710, 1647, 1533, 1437, 1252 cm-1; H NMR (DMSO-d6, 400
1
MHz) δ 10.19 (s, 1H), 10.04 (s, 1H), 9.77 (s, 1H), 9.73 (s, 1H),
9.71 (s, 1H), 9.67 (s, 1H), 9.36 (s, 1H), 7.92 (t, 1H, J ) 5.6 Hz),
7.90 (t, 1H, J ) 5.6 Hz), 7.58 (s, 1H), 7.53 (s, 1H), 7.25 (d, 1H,
J ) 1.6 Hz), 7.20 (s, 3H), 7.15 (d, 1H, J ) 1.8 Hz), 7.05 (d, 1H,
J ) 1.8 Hz), 7.04 (d, 1H, J ) 1.8 Hz), 6.95 (t, 2H, J ) 1.7 Hz),
6.90 (d, 3H, J ) 1.8 Hz), 6.05 (t, 1H, J ) 2.6 Hz), 4.08 (q, 2H,
J ) 7.1 Hz), 4.02 (s, 3H), 4.01 (s, 3H), 3.89 (s, 3H), 3.86 (s,
3H), 3.85 (s, 3H), 3.85 (s, 3H), 3.82 (s, 3H), 3.81 (s, 3H), 3.42
(q, 2H, J ) 6.5 Hz), 3.25 (q, 2H, J ) 6.5 Hz), 2.53 (t, 2H, J )
7.0 Hz), 2.31 (t, 2H, J ) 7.3 Hz), 1.82 (m, 2H, J ) 7.2 Hz),
1.19 (t, 3H, J ) 7.1 Hz); 13C NMR(DMSO-d6, 100 MHz) δ 171.4,
169.4, 161.3, 161.2, 158.7, 158.6, 158.5, 155.5, 155.2, 136.6,
134.6, 134.5, 132.7, 128.1, 125.5, 123.0, 122.8, 122.2, 122.1,
121.7, 121.2, 119.3, 118.4, 118.2, 117.8, 115.4, 113.6, 112.6,
106.6, 104.8, 104.7, 104.5, 104.3, 59.9, 38.2, 36.2, 36.1, 36.0,
35.9, 35.2, 35.0, 34.8, 34.0, 33.3, 25.7, 14.1; MS (MALDI-TOF)
m/z 1188.5 (MNa+, 1188.5 calcd for C55H63N19O11 + Na); HRMS
calcd for C55H64N19O11 (MH+)1166.5033, found 1166.5026.
PyPyPyPyγPyImImPyâCOOH (29a ). A synthetic procedure
similar to that for 21a was followed for the preparation of 29a ,
and 185 mg of product was obtained (95% yield). IR (KBr)
1
1436 cm-1; H NMR (CDCl3, 200 MHz) δ 10.34 (s, 1H), 10.17
(s, 1H), 8.66 (s, 1H), 8.10 (t, 1H, J ) 5.4 Hz), 7.58 (s, 1H), 7.24
(s, 1H), 6.97 (s, 1H), 4.08 (q, 2H, J ) 7.2 Hz), 4.07 (s, 3H),
4.02 (s, 3H), 3.80 (s, 3H), 3.41 (q, 2H, J ) 6.4 Hz), 2.54 (t, 2H,
J ) 7.2 Hz), 1.20 (t, 3H, J ) 7.2 Hz); MS (FAB) m/z 516 (MH+);
HRMS calcd for C21H26N9O7 (MH+) 516.1950, found 516.1966.
PyPyPyPyγOEt (27). A synthetic procedure similar to that
for 26 was followed for the preparation of 27, and 2.13 g of
product was obtained (78% yield). IR (KBr) 3306, 3126, 1721,
1
1641, 1538, 1467 cm-1; H NMR (CDCl3, 200 MHz) δ 8.19 (s,
1H), 8.05 (s, 1H), 7.79 (s, 1H), 7.17 (s, 1H), 7.13 (s, 2H), 6.77
(s, 1H), 6.75 (s, 1H), 6.71 (s, 1H), 6.57 (s, 1H), 6.55 (s, 1H),
6.43 (t, 1H, J ) 5.4 Hz), 6.10 (t, 1H, J ) 3.2 Hz), 4.10 (q, 2H,
J ) 7.2 Hz), 3.95 (s, 3H), 3.86 (s, 3H), 3.82 (s, 6H), 3.39 (q,
2H, J ) 6.2 Hz), 2.38 (t, 2H, J ) 7.0 Hz), 1.88 (m, 2H, J ) 6.8
Hz), 1.21 (t, 3H, J ) 7.2 Hz); MS (FAB) m/z 605 (MH+); HRMS
calcd for C30H37N8O6 (MH+) 605.2831, found 605.2833.
PyPyPyPyγCOOH (27a ). A synthetic procedure similar to
that for 21a was followed for the preparation of 27a , and 1.50
g of product was obtained (84% yield). IR (KBr) 3314, 1714,
1640, 1541, 1467, 1256 cm-1; 1H NMR (DMSO-d6, 200 MHz) δ
12.08 (s, 1H), 9.96 (s, 1H), 9.91 (s, 1H), 9.85 (s, 1H), 8.05 (t,
1H, J ) 5.4 Hz), 7.25 (s, 2H), 7.19 (s, 1H), 7.06 (s, 2H), 6.95 (s,
1H), 6.93 (s, 1H), 6.88 (s, 1H), 6.07 (t, 1H, J ) 5.4 Hz), 3.89 (s,
3H), 3.86 (s, 6H), 3.80 (s, 3H), 3.19 (q, 2H, J ) 5.8 Hz), 2.26 (t,
2H, J ) 7.4 Hz), 1.71 (m, 2H, J ) 7.4 Hz); MS (FAB) m/z 577
(MH+); HRMS calcd for C28H33N8O6 (MH+) 577.2517, found
577.2485.
3393, 1643, 1538, 1437, 1256 cm-1; H NMR (DMSO-d6, 400
1
MHz) δ 10.20 (s, 1H), 10.02 (s, 1H), 9.78 (s, 1H), 9.74 (s, 1H),
9.72 (s, 1H), 9.68 (s, 1H), 9.38 (b, 1H), 7.91 (m, 2H), 7.58 (s,
1H), 7.53 (s, 1H), 7.26 (s, 1H), 7.20 (s, 3H), 7.15 (s, 1H), 7.05
(s, 1H), 7.04 (s, 1H), 6.95 (s, 1H), 6.94 (s, 1H), 6.90 (s, 3H),
6.05 (t, 1H, J ) 3.1 Hz), 4.02 (s, 3H), 3.89 (s, 3H), 3.86 (s, 3H),
3.85 (s, 3H), 3.85 (s, 3H), 3.82 (s, 3H), 3.81 (s, 3H), 3.57 (s,
3H), 3.39 (b, 2H), 3.25 (q, 2H, J ) 6.0 Hz), 2.44 (t, 2H, J ) 6.8
Hz), 2.31 (t, 2H, J ) 7.2 Hz), 1.82 (m, 2H, J ) 7.2 Hz); 13C
NMR(DMSO-d6, 100 MHz) δ 173.3, 169.4, 161.3, 161.2, 158.7,
158.6, 158.5, 155.5, 155.2, 136.6, 134.6, 134.4, 132.7, 128.1,
125.5, 123.1, 122.9, 122.8, 122.2, 122.1, 121.7, 121.2, 119.3,
118.4, 118.2, 117.8, 115.4, 113.6, 112.6, 106.6, 104.7, 104.4,
104.3, 38.2, 36.2, 36.1, 35.9, 35.1, 35.0, 34.5, 33.3, 25.7; MS
(FAB) m/z 1138 (MH+); HRMS calcd for C53H60N19O11 (MH+)-
1138.4719, found 1138.4683.
NO2PyImImPyâOEt (28). To a solution of 1-methyl-4-nitro-
pyrrole-2-carboxylic acid (0.77 g, 4.5 mmol) in 10 mL of DMF
was added HOBT (0.62 g, 4.6 mmol), followed by DCC (0.93 g,
4.5 mmol). The reaction mixture was stirred overnight at room
temperature. Separately, to a solution of 19 (2.33 g, 4.5 mmol)
in 25 mL of DMF was added Pd/C catalyst (10%, 0.52 g), and
the mixture was stirred under a slight positive pressure of H2
at 55 °C for 12 h. The catalyst was removed by filtration
through Celite, and the filtrate was directed into the active
ester and stirred overnight. After filtration, 100 mL of CHCl3
was added to the filtrate, and the organic layer was washed
with brine (40 mL×10) and dried over anhydrous MgSO4. The
desiccator was removed by filtration, and the filtrate was
concentrated in vacuo. After purification by column chroma-
tography with the mixed solvent of CHCl3 and CH3OH as
eluant, 2.13 g of 28 was obtained (74% yield) as a slight yellow
PyPyPyPyγPyImImPyâDp (30). To a solution of 29a (106 mg,
0.093 mmol) in 0.5 mL of DMF was added HOBT (40 mg, 0.30
mmol), followed by DCC (58 mg, 0.28 mmol). The reaction
solution was stirred overnight. N,N-Dimethylpropyldiamine
(40 µL) was added to the reaction solution, and the stirring
was continued for another 6 h. DCU was removed by filtration,
and the filtrate was concentrated in vacuo. Flash column
chromatography of the residue (CH3OH/CHCl3 ) 2:1 and CH3-
OH/CHCl3 ) 1:2) afforded 90 mg of the polyamide 30 (79%
yield). IR (KBr) 3392,1648, 1535, 1438, 1205 cm-1; H NMR
1
(DMSO-d6, 400 MHz) δ 10.40 (s, 1H), 10.26 (s, 1H), 9.94 (s,
1H), 9.91 (d, 2H, J ) 2.5 Hz), 9.84 (s, 1H), 9.43 (s, 1H), 8.06 (t,
1H, J ) 5.6 Hz), 8.04 (t, 1H, J ) 5.6 Hz), 7.90 (t, 1H, J ) 5.4
Hz), 7.63 (s, 1H), 7.58 (s, 1H), 7.31 (d, 1H, J ) 1.4 Hz), 7.24 (s,
2H), 7.23 (d, 1H, J ) 1.5 Hz), 7.19 (d, 1H, J ) 1.4 Hz), 7.07 (d,
1H, J ) 1.7 Hz), 7.06 (d, 1H, J ) 1.6 Hz), 6.96 (d, 1H, J ) 1.7
Hz), 6.95 (s, 2H), 6.93 (t, 2H, J ) 2.4 Hz), 6.06 (m, 1H), 4.02
(s, 3H), 4.01 (s, 3H), 3.89 (s, 3H), 3.86 (s, 3H), 3.85 (s, 3H),
3.85 (s, 3H), 3.82 (s, 3H), 3.81 (s, 3H), 3.37 (b, 2H), 3.23 (q,
2H, J ) 5.6 Hz), 3.07 (m, 4H), 2.33 (t, 2H, J ) 7.2 Hz), 2.26 (t,
2H, J ) 7.2 Hz), 2.16 (s, 6H), 1.80 (q, 2H, J ) 6.8 Hz), 1.56 (q,
1
solid. IR (KBr) 3371, 3132, 1726, 1650, 1543, 1474 cm-1; H
NMR (DMSO-d6, 200 MHz) δ 10.90 (s, 1H), 10.26 (s, 1H), 9.43
(s, 1H), 8.23 (s, 1H), 8.11 (t, 1H, J ) 5.4 Hz), 7.77 (s, 1H), 7.67
(s, 1H), 7.59 (s, 1H), 7.24 (s, 1H), 6.96 (s, 1H), 4.07 (q, 2H, J )
7.0 Hz), 4.02 (s, 3H), 4.01 (s, 3H), 3.97 (s, 3H), 3.81 (s, 3H),
3.42 (q, 2H, J ) 6.4 Hz), 2.54 (t, 2H, J ) 7.0 Hz), 1.19 (t, 3H,