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(5% Et3N, 5% EtOH, 90% EtOAc) affording C2 as a red solid
(204 mg, 64% yield). Rf =0.40 (5% Et3N, 5% EtOH, 90% EtOAc);
1H NMR (300 MHz, CDCl3): d=2.33 (s, 6H), 2.98 (d, J=12.8 Hz, 1H),
3.07 (s, 1H), 3.16 (s, 1H), 3.47 (quint, J=5.3 Hz, 1H), 3.75 (quint, J=
6.2 Hz, 1H), 3.88 (d, J=12.5 Hz, 2H), 4.06 (t, J=2.5 Hz, 1H), 4.11 (s,
5H), 4.14–4.17 (m, 1H), 4.19 (d, J=2.1 Hz, 1H), 6.32 (d, J=5.4 Hz,
1H), 7.25 (d, J=2.1 Hz, 1H), 7.83 (d, J=8.8 Hz, 1H), 7.96 (d, J=
2.1 Hz, 1H), 8.49 ppm (d, J=5.4 Hz, 1H); 13C{H} NMR (75 MHz,
CDCl3): d=38.3, 38.9, 44.2, 45.0, 57.8, 66.3, 69.2, 70.0, 71.2, 83.4,
98.3, 117.1, 122.1, 125.4, 127.9, 135.2, 150.3, 151.2, 148.2, 158.5,
162.5 ppm; IR (ATR): nmax =3292 brw, 1659 s (NÀC=O), 1611 w (7-
chloroquinoline), 1579 s (7-chloroquinoline), 1505 s (NÀC=O), 1141
7.35 (dd, J=8.8, 2.2 Hz, 1H), 7.67 (d, J=8. 8 Hz, 1H), 7.96 (d, J=
2.2 Hz, 1H), 8.54 ppm (d, J=5.5 Hz, 1H); 13C{H} NMR (75 MHz,
CDCl3): d=24.3, 28.4, 29.1, 38.2, 39.1, 43.1, 44.4, 58.0, 66.0, 69.2,
69.7, 71.1, 83.6, 84.2, 99.1, 117.1, 120.9, 125.3, 128.8, 134.9, 149.1,
149.7, 152.0, 159.0, 160.3 ppm; IR (ATR): nmax =3305 brw (NH), 1659
s (NÀC=O), 1609 w, 1578 s (7-chloroquinoline) 1505 s (NÀC=O),
1033 w, 1001 w (ferrocene); HRMS (EI) m/z [M+H]+ 590.1992,
C30H37ClFeN5O2 requires 590.1985.
N1-[6-(7-Chloroquinolin-4-ylamino)hexyl]-N6-{2-[(dimethylamino)-
methyl]ferrocenylmethyl}oxalamide (C6): Prepared in the same
manner as described for compound C2 using appropriate starting
materials. The product was purified by column chromatography
over silica gel (5% Et3N, 5% EtOH, 90% EtOAc) affording C6 as
a red solid (239 mg, 94% yield). Rf =0.51 (5% Et3N, 5% EtOH, 90%
w, 1001
w
(ferrocene); HRMS (EI) m/z [M+H]+ 548.1509,
C27H31ClFeN5O2 requires 548.1504.
N1-[3-(7-Chloroquinolin-4-ylamino)propyl]-N3-{2-[(dimethylami-
no)methyl]ferrocenylmethyl}oxalamide (C3): Prepared in the
same manner as described for compound C2 using appropriate
starting materials. The product was purified by column chromatog-
raphy over silica gel (5% Et3N, 5% EtOH, 90% EtOAc) affording C3
as a red solid (92 mg, 44% yield). Rf =0.42 (5% Et3N, 5% EtOH,
EtOAc); H NMR (400 MHz, CDCl3): d=1.38–1.46 (m, 2H), 1.49 (brs,
1
2H), 1.54–1.63 (m, 2H), 1.75 (t, J=7.0 Hz, 2H), 2.17 (s, 6H), 2.84 (d,
J=12.7 Hz, 1H), 3.26–3.35 (m, 4H), 3.75 (d, J=12.7 Hz, 1H), 4.02 (t,
J=2.4 Hz, 1H), 4.10 (s, 5H), 4.10–4.12 (m, 2H), 4.17–4.19 (m, 1H),
4.48 (d, J=8.6 Hz, 1H), 6.40 (d, J=5.5 Hz, 1H), 7.36 (dd, J=9.0,
2.2 Hz, 1H), 7.70 (d, J=9.0 Hz, 1H), 7.96 (d, J=2.2 Hz, 1H),
8.53 ppm (d, J=5.5 Hz, 1H); 13C{H} NMR (101 MHz, CDCl3): d=26.4,
28.6, 29.2, 30.9, 38.1, 39.1, 42.9, 44.4, 58.0, 65.9, 69.1, 69.6, 71.0,
83.6, 84.4, 99.1, 117.1, 120.9, 125.2, 128.9, 134.8, 149.1, 149.6, 152.1,
159.0, 160.2 ppm; IR (ATR): nmax =3303 brw, 2932 w (NH), 1659
s (NÀC=O), 1610 w, 1578 s (7-chloroquinoline), 1504 s (NÀC=O),
1032 w, 1011 w (ferrocene); HRMS (EI) m/z [M+H]+ 604.2128,
C31H39ClFeN5O2 requires 604.2142.
1
90% EtOAc); H NMR (400 MHz, CDCl3): d=1.85–1.93 (m, 2H), 2.24
(s, 6H), 2.88 (d, J=12.7 Hz, 1H), 3.37 (d, J=5.5 Hz, 2H), 3.42–3.50
(m, 2H), 3.81 (d, J=12.5 Hz, 1H), 4.05 (t, J=2.4 Hz, 1H), 4.11 (s,
5H), 4.12–4.17 (m, 2H), 4.20 (s, 1H), 4.53 (dd, J=14.3, 8.6 Hz, 1H),
6.39 (d, J=5.5 Hz, 1H), 7.32 (dd, J=8.9, 2.0 Hz, 1H), 7.88 (d, J=
8.9 Hz, 1H), 7.95 (d, J=2.0 Hz, 1H), 8.50 ppm (d, J=5.5 Hz, 1H);
13C{H} NMR (101 MHz, CDCl3): d=27.8, 36.4, 38.4, 38.8, 44.4, 57.9,
65.9, 69.2, 69.8, 71.2, 83.4, 84.3, 98.5, 117.6, 121.6, 125.1, 128.7,
134.8, 149.8, 151.9, 158.5, 161.5, 165.5 ppm; IR (ATR): nmax =3304
brw (NH), 1659 s (NÀC=O), 1610 w, 1578 s (7-chloroquinoline),
1505 s (NÀC=O), 1138 w, 1104 w (ferrocene); HRMS (EI) m/z [M+
H]+ 562.1675, C28H33ClFeN5O2 requires 562.1672.
N1-[2-(7-Chloroquinolin-4-ylamino)ethyl]-N2-{2-[(dimethylamino)-
methyl]benzyl}oxalamide (D2): Compounds 15 (70.0 mg,
0.217 mmol) and 8 (70.6 mg, 0.43 mmol) were dissolved in 3 mL
dry EtOH and stirred at 408C for 18 h in a dry 50 mL round-bot-
tomed flask under nitrogen. The solvent was then removed, and
the resulting residue was dissolved in CH2Cl2. The product was pu-
rified by column chromatography over silica gel. The product was
purified by column chromatography over silica gel (5% Et3N, 5%
EtOH, 90% EtOAc) affording D2 as a white powder (48 mg, 50%
yield). Rf =0.36 (5% Et3N, 5% EtOH, 90% EtOAc); 1H NMR
(300 MHz, CDCl3): d=2.35 (s, 6H), 3.43–3.51 (m, 2H), 3.53 (s, 2H),
3.73–3.82 (m, 2H), 4.49 (d, J=5.9 Hz, 2H), 6.31 (d, J=5.6 Hz, 1H),
7.21–7.29 (m, 4H), 7.32–7.36 (m, 1H), 7.82 (d, J=9.0 Hz, 1H), 7.97
(d, J=2.1 Hz, 1H), 8.47 ppm (d, J=5.4 Hz, 1H); 13C{H} NMR
(75 MHz, CDCl3) 38.9, 43.0, 44.4, 45.2, 62.9, 98.2, 116.9, 122.1, 125.4,
127.5, 127.5, 128.0, 128.5, 130.5, 131.5, 135.4, 137.0, 137.5, 150.6,
150.7, 158.6, 162.8 ppm; IR (ATR): nmax =3295 brw, 2924 w (NH),
1656 s (NÀC=O), 1610 w, 1582 s (7-chloroquinoline) 1537 s (NÀC=
O), 1514 s (aromatic C=C); HRMS (EI) m/z [M+H]+ 440.1853,
C23H27ClFeN5O2 requires 440.1842.
N1-[4-(7-Chloroquinolin-4-ylamino)butyl]-N4-{2-[(dimethylamino)-
methyl]ferrocenylmethyl}oxalamide (C4): Prepared in the same
manner as described for compound C2 using appropriate starting
materials. The product was purified by column chromatography
over silica gel (5% Et3N, 5% EtOH, 90% EtOAc) affording C4 as
a red solid (142 mg, 63% yield). Rf =0.44 (5% Et3N, 5% EtOH, 90%
1
EtOAc); H NMR (400 MHz, CDCl3): d=1.71–1.76 (m, 2H), 1.77–1.83
(m, 2H), 2.19 (s, 6H), 2.85 (d, J=12.7 Hz, 1H), 3.32–3.38 (m, 2H),
3.41 (d, J=6.8 Hz, 2H), 3.77 (d, J=12.7 Hz, 1H), 4.03 (t, J=2.4 Hz,
1H), 4.10 (s, 5H), 4.12 (d, J=2.2 Hz, 2H), 4.19 (s, 1H), 4.51 (dd, J=
14.4, 8.5 Hz, 1H), 6.40 (d, J=5.5 Hz, 1H), 7.35 (dd, J=8.9, 2.3 Hz,
1H), 7.75 (d, J=8.9 Hz, 1H), 7.96 (d, J=2.3 Hz, 1H), 8.53 ppm (d,
J=5.5 Hz, 1H); 13C{H} NMR (101 MHz, CDCl3): d=25.6, 27.6, 38.2,
39.0, 43.2, 44.4, 57.9, 65.9, 69.1, 69.7, 71.1, 83.6, 84.3, 99.1, 117.2,
121.1, 125.3, 128.8, 134.8, 149.1, 149.7, 152.0, 158.9, 160.5 ppm; IR
(ATR): nmax =3303 brw (NH), 1659 s (NÀC=O), 1610 w, 1578 s (7-
chloroquinoline), 1505 s (NÀC=O), 1032 w, 1001 w (ferrocene);
HRMS (EI) m/z [M+H]+ 576.1831, C29H35ClFeN5O2 requires
576.1829.
N1-[3-(7-Chloroquinolin-4-ylamino)propyl]-N3-{2-[(dimethylami-
no)methyl]benzyl}oxalamide (D3): Prepared in the same manner
as described for compound D2 using appropriate starting materi-
als. The product was purified by column chromatography over
silica gel (5% Et3N, 5% EtOH, 90% EtOAc) affording D3 as a white
powder (37 mg, 22% yield). Rf =0.37 (5% Et3N, 5% EtOH, 90%
EtOAc); 1H NMR (400 MHz, CDCl3): d=1.93 (quint, J=5.9 Hz, 2H),
2.31 (s, 6H), 3.40–3.45 (m, 2H), 3.45–3.50 (m, 2H), 3.52 (s, 2H), 4.51
(d, J=5.9 Hz, 2H), 6.41 (d, J=6.1 Hz, 1H), 7.23–7.25 (m, 1H), 7.27–
7.38 (m, 4H), 8.03 (d, J=2.2 Hz, 1H), 8.07 (d, J=9.0 Hz, 1H),
8.41 ppm (d, J=5.9 Hz, 1H); 13C{H} NMR (101 MHz, CDCl3): d=30.1,
36.7, 39.5, 43.2, 44.7, 63.0, 98.3, 117.2, 122.7, 126.1, 126.3, 128.3,
128.8, 130.8, 131.7, 136.5, 137.2, 137.7, 149.1, 151.8, 153.5, 159.1,
161.8 ppm; IR (ATR): nmax =3309 brw, 2935 w (NH), 1650 s (NÀC=O),
1611 w, 1578 s (7-chloroquinoline), 1544 s (NÀC=O), 1510 s (aromat-
N1-[5-(7-Chloroquinolin-4-ylamino)pentyl]-N5-{2-[(dimethylami-
no)methyl]ferrocenylmethyl}oxalamide (C5): Prepared in the
same manner as described for compound C2 using appropriate
starting materials. The product was purified by column chromatog-
raphy over silica gel (5% Et3N, 5% EtOH, 90% EtOAc) affording C5
as a red solid (90 mg, 58% yield). Rf =0.49 (5% Et3N, 5% EtOH,
90% EtOAc); 1H NMR (400 MHz, CDCl3): d=1.47–1.57 (m, 2H),
1.59–1.71 (m, 2H), 1.80 (quint, J=7.4 Hz, 2H), 2.19 (s, 6H), 2.86 (d,
J=12.5 Hz, 1H), 3.28–3.32 (m, 2H), 3.33–3.37 (m, 2H), 3.76 (d, J=
12.7 Hz, 1H), 4.04 (t, J=2.5 Hz, 1H), 4.10 (s, 5H), 4.11–4.13 (m, 2H),
4.19 (s, 1H), 4.50 (dd, J=14.3, 8.6 Hz, 1H), 6.40 (d, J=5.5 Hz, 1H),
ChemMedChem 2015, 10, 2099 – 2110
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