The Journal of Organic Chemistry
Article
150.5, 146.4, 130.7, 129.9, 123.3, 50.3, 43.3, 33.8, 25.6, 24.9, 23.3, 20.8;
TOF-HRMS calcd for C17H28N3 [M + H]+ 274.2283, found 274.2286.
3-Cyclohexyl-2-((4-nitrophenyl)imino)imidazolidin-4-one
(Scheme 4, 4a). Yellow solid (0.0722 g, 85% yield); mp 191−192 °C;
5.04 (br s, 1H), 4.74 (s, 2H), 4.18 (dd, J = 6.8, 4.4 Hz, 1H), 3.10 (dd, J
= 14.0, 4.4 Hz, 1H), 2.96 (dd, J = 14.0, 6.8 Hz, 1H); 13C{1H} NMR
(100 MHz, CDCl3) δ 172.8, 149.5, 146.3, 136.0, 135.1, 129.5, 129.4,
128.7, 128.5, 128.3, 128.2, 127.5, 127.3, 123.7, 58.4, 42.5, 38.0; TOF-
HRMS calcd for C23H2135ClN3O (M + H+) 390.1373, found 390.1376;
calcd for C23H2137ClN3O [M + H]+ 392.1343, found 392.1347.
3,5-Dibenzyl-2-(phenylimino)imidazolidin-4-one (Scheme 4, 4i).
Colorless solid (0.0678 g, 68% yield); mp 77−78 °C; Rf 0.27 (20%
EtOAc/hexanes); 1H NMR (400 MHz, CDCl3) δ 7.78−7.73 (m, 1H),
7.57−7.45 (m, 2H), 7.35−7.24 (m, 7H), 7.14−7.11 (m, 2H), 7.06 (d, J
= 7.6 Hz. 1H), 6.89 (d, J = 7.6 Hz, 2H), 4.79 (s, 2H), 4.20 (dd, J = 7.2,
4.4 Hz, 1H), 3.14 (dd, J = 9.6, 4.4 Hz, 1H), 2.97 (dd, J = 14.0, 7.2 Hz,
1H); 13C{1H} NMR (100 MHz, CDCl3) δ 172.8, 149.0, 136.2, 135.3,
132.3, 131.6, 129.53, 129.47, 128.8, 128.7, 128.53, 128.50, 127.6,
127.3, 123.3, 122.3, 58.6, 42.6, 38.2; TOF-HRMS calcd for C23H22N3O
[M + H]+ 356.1763, found 356.1759.
3,5-Dibenzyl-2-(p-tolylimino)imidazolidin-4-one (Scheme 4, 4j).
Yellow solid (0.0582 g, 56% yield); mp 162−163 °C; Rf 0.32 (20%
EtOAc/hexanes); 1H NMR (400 MHz, CDCl3) δ 7.31−7.25 (m, 8H),
7.12 (d, J = 7.6 Hz, 4H), 6.78 (d, J = 8.4 Hz, 2H), 4.78 (s, 2H), 4.19
(dd, J = 6.8, 4.4 Hz, 1H), 3.12 (dd, J = 14.0, 4.4 Hz, 1H), 2.95 (dd, J =
14.0, 6.8 Hz, 1H), 2.32 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ
172.9, 149.3 136.2, 135.3, 132.6, 130.0, 129.5, 128.7, 128.5, 128.4,
127.5, 127.3, 122.1, 58.6, 42.5, 38.1, 20.8; TOF-HRMS calcd for
C24H24N3O [M + H]+ 370.1919, found 370.1926.
1
Rf 0.21 (20% EtOAc/hexanes); H NMR (400 MHz, CDCl3) δ 8.05
(d, J = 8.8 Hz, 2H), 7.02 (d, J = 8.8 Hz, 2H), 5.10 (s, 1H), 4.15−4.07
(m, 1H), 3.86 (s, 2H), 2.33−2.22 (m, 2H), 1.86−1.62 (m, 5H), 1.39−
1.16 (m, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 171.2, 155.4,
151.3, 142.8, 125.3, 123.0, 52.6, 46.8, 28.9, 26.0, 25.2; TOF-HRMS
calcd for C15H19N4O3 [M + H]+ 303.1457, found 303.1458.
3-Cyclohexyl-5-methyl-2-((4-nitrophenyl)imino)imidazolidin-4-
one (Scheme 4, 4b). Yellow solid (0.0755 g, 85% yield); mp 161−162
1
°C; Rf 0.31 (50% EtOAc/hexanes); H NMR (400 MHz, CDCl3) δ
8.01 (dd, J = 8.8 Hz, 2H), 7.00 (d, J = 8.8 Hz, 2H), 5.62 (s, 1H), 4.09−
4.01 (m, 1H), 3.92 (q, J = 6.8 Hz, 1H), 2.27−2.16 (m, 2H), 1.81−1.58
(m, 5H), 1.35−1.12 (m, 3H), 1.32 (d, J = 6.8 Hz, 3H); 13C{1H} NMR
(100 MHz, CDCl3) δ 174.7, 155.6, 150.3, 142.5, 125.1, 123.0, 52.9,
52.3, 28.8, 25.9, 25.1, 17.9; TOF-HRMS calcd for C16H21N4O3 [M +
H]+ 317.1614, found 317.1617.
3-Cyclohexyl-5-isopropyl-2-((4-nitrophenyl)imino)imidazolidin-4-
one (Scheme 4, 4c). Yellow oil (0.0782 g, 81% yield); Rf 0.30 (30%
EtOAc/hexanes); 1H NMR (400 MHz, CDCl3) δ 8.34 (d, J = 9.2 Hz,
2H), 7.45 (d, J = 8.4 Hz, 2H), 4.09 (d, J = 4.0 Hz, 1H), 3.79−3.69 (m,
2H), 2.36−2.25 (m, 1H), 2.17−1.91 (m, 2H), 1.72−1.66 (m, 2H),
1.64−1.58 (m, 1H), 1.46−1.33 (m, 2H), 1.21−1.12 (m, 3H), 1.10 (d, J
= 6.8 Hz, 3H), 0.96 (d, J = 6.8 Hz, 3H); 13C{1H} NMR (100 MHz,
CDCl3) δ 173.0, 149.6, 138.2, 132.2, 127.6, 125.4, 117.3, 50.6, 33.4,
33.2, 31.8, 25.7, 24.9, 24.8, 18.9; TOF-HRMS calcd for C18H25N4O3
[M + H]+ 345.1927, found 345.1923.
5-Benzyl-3-butyl-2-(phenylimino)imidazolidin-4-one (Scheme 4,
4k). Yellow oil (0.0462 g, 51% yield); Rf 0.34 (20% EtOAc/hexanes);
1H NMR (400 MHz, CDCl3) δ 7.32−7.25 (m, 5H), 7.15 (d, J = 7.2
Hz, 2H), 7.02 (t, J = 7.2 Hz, 1H), 6.87 (d, J = 7.2 Hz, 2H), 4.63 (s,
1H), 4.15 (dd, J = 7.6, 4.0 Hz, 1H), 3.58 (td, J = 7.2, 1.6 Hz, 2H), 3.13
(dd, J = 14.0, 4.0 Hz, 1H), 2.92 (dd, J = 14.0, 7.6 Hz, 1H), 1.54 (qui,
7.2 Hz, 2H), 1.30−1.21 (m, 2H), 0.91 (t, J = 7.2 Hz, 3H); 13C{1H}
NMR (100 MHz, CDCl3) δ 173.0, 149.5, 147.8, 135.5, 129.6, 129.5,
128.8, 127.4, 123.2, 122.4, 58.5, 39.1, 38.5, 29.8, 20.1, 13.9; TOF-
HRMS calcd for C20H24N3O [M + H]+ 322.1919, found 322.1921.
Methyl 2-(5-oxo-2-(phenylimino)imidazolidin-1-yl)propanoate
(Scheme 4, 4l). Yellow oil (0.0492 g, 67% yield); Rf 0.23 (20%
EtOAc/hexanes); 1H NMR (400 MHz, CDCl3) δ 7.51−7.43 (m, 1H),
7.32−7.25 (m. 2H), 7.05 (t, J = 7.2 Hz, 1H), 6.97−6.94 (m, 1H), 4.42
(s, 2H), 4.11 (q, J = 6.8 Hz, 1H), 3.77 (s, 3H), 1.41 (d, J = 6.8 Hz,
3H); 13C{1H} NMR (100 MHz, CDCl3) δ 174.2, 167.9, 148.8, 129.5,
128.4, 123.5, 122.5, 53.6, 52.6, 40.1, 18.2; TOF-HRMS calcd for
C13H16N3O3 [M + H]+ 262.1192, found 262.1195.
Methyl 3-methyl-2-(5-oxo-2-((4-(trifluoromethyl)phenyl)imino)-
imidazolidin-1-yl)butanoate (Scheme 4, 4m). Yellow oil (0.0743 g,
74% yield); Rf 0.43 (20% EtOAc/hexanes); 1H NMR (400 MHz,
CDCl3) δ 7.57 (d, J = 8.4 Hz, 2H), 7.07 (d, J = 8.4 Hz, 2H), 4.45 (s,
2H), 4.01 (d, J = 3.6 Hz, 1H), 3.77 (s, 3H), 2.28−2.20 (m, 1H), 1.01
(d, J = 7.2 Hz, 3H), 0.99 (d, J = 6.8 Hz, 3H); 13C{1H} NMR (100
MHz, CDCl3) δ 172.7, 167.7, 150.2, 128.9, 126.8 (q, JC−F = 3.7 Hz),
123.0, 121.8, 63.2, 52.7, 40.1, 30.9, 18.9, 16.3; TOF-HRMS calcd for
C16H19F3N3O3 [M + H]+ 358.1379, found 358.1376.
5-Benzyl-3-cyclohexyl-2-((4-nitrophenyl)imino)imidazolidin-4-on
(Scheme 4, 4d). Yellow oil (0.0903 g, 82% yield); Rf 0.51 (30%
EtOAc/hexanes); 1H NMR (400 MHz, CDCl3) δ 8.09 (d, J = 9.0 Hz,
2H), 7.36−7.18 (m, 5H), 6.90 (d, J = 9.0 Hz, 2H), 5.01 (s, 1H), 4.20
(t, J = 5.2 Hz, 1H), 4.01−3.95 (m, 1H), 3.11−3.09 (m, 2H), 2.24−
2.15 (m, 2H), 1.85−1.79 (m, 2H), 1.67−1.60 (m, 2H), 1.48−1.20 (m,
4H).; 13C{1H} NMR (100 MHz, CDCl3) δ 172.9, 155.5, 150.0, 142.9,
134.9, 129.8, 128.7, 127.5, 125.4, 123.0, 57.9, 52.4, 38.0, 28.85, 28.59,
26.00, 25.96, 25.2; TOF-HRMS calcd for C22H25N4O3 [M + H]+
393.1927, found 393.1925.
2-Cyclohexyl-3-((4-nitrophenyl)imino)hexahydro-1H-pyrrolo[1,2-
c]imidazol-1-one (Scheme 4, 4e). Yellow oil (0.0769 g, 80% yield); Rf
0.37 (20% EtOAc/hexanes); 1H NMR (400 MHz, CDCl3) δ 8.13 (d, J
= 9.2 Hz, 2H), 7.05 (d, J = 9.2 Hz, 2H), 4.08−4.01 (m, 2H), 2.92−
2.87 (m, 1H), 2.80−2.75 (m, 1H), 2.36−2.15 (m, 3H), 2.00−1.60 (m,
8H), 1.38−1.14 (m, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 173.4,
155.4, 154.4, 142.2, 125.0, 122.6, 64.4, 53.1, 50.1, 28.9, 28.7, 28.4, 27.3,
26.01, 25.94, 25.2; TOF-HRMS calcd for C18H23N4O3 [M + H]+
343.1770, found 343.1765.
3,5-Dibenzyl-2-((4-nitrophenyl)imino)imidazolidin-4-one
(Scheme 4, 4f). Yellow solid (0.0968 g, 86% yield); mp 159−160 °C;
1
Rf 0.45 (30% EtOAc/hexanes); H NMR (400 MHz, CDCl3) δ 8.05
(d, J = 8.8 Hz, 2H), 7.26−7.10 (m, 10H), 6.89 (d, J = 8.8 Hz, 2H),
4.71 (d, J = 14.8 Hz, 1H), 4.67 (d, J = 14.8 Hz, 1H), 4.28 (t, J = 4.8
Hz, 1H), 3.13−3.01 (m, 2H), 2.93 (s, 1H); 13C{1H} NMR (100 MHz,
CDCl3) δ 173.0, 155.1, 149.8, 142.7, 135.7, 134.7, 129.6, 128.5, 128.4,
128.0, 127.5, 127.3, 125.1, 122.9, 58.5, 42.5, 37.5; TOF-HRMS calcd
for C23H21N4O3 [M + H]+ 401.1614, found 401.1612.
3,5-Dibenzyl-2-((4-fluorophenyl)imino)imidazolidin-4-one
(Scheme 4, 4g). Yellow oil (0.0849 g, 81% yield); Rf 0.36 (20%
EtOAc/hexanes); 1H NMR (400 MHz, CDCl3) δ 7.34−7.25 (m, 8H),
7.14−7.10 (m, 2H), 7.02−6.98 (m, 2H), 6.83−6.80 (m, 2H), 4.78 (s,
2H), 4.21 (dd, J = 7.2, 4.0 Hz, 1H), 3.15 (dd, J = 13.8, 4.0 Hz, 1H),
2.97 (dd, J = 13.8, 7.2 Hz, 1H); 13C{1H} NMR (100 MHz, CDCl3) δ
172.7, 159.1 (d, JC−F = 240.0 Hz), 149.5, 136.2, 135.3, 129.5, 128.8,
128.6, 128.52, 128.47, 127.6, 127.4, 123.4 (d, JC−F = 7.8 Hz), 116.1(d,
JC−F = 22.0 Hz), 58.6, 42.6, 38.2; TOF-HRMS calcd for C23H21FN3O
[M + H]+ 374.1669, found 374.1664.
Methyl 2-(4-benzyl-2-((4-nitrophenyl)imino)-5-oxoimidazolidin-
1-yl)acetate (Scheme 4, 4n). Yellow oil (0.0838 g, 78% yield); Rf
0.36 (30% EtOAc/hexanes); 1H NMR (400 MHz, CDCl3) δ 8.06 (d, J
= 9.2 Hz, 2H), 7.35−7.17 (m, 5H), 6.93 (d, J = 9.2 Hz, 2H), 5.10 (br
s, 1H), 4.38−4.35 (m, 1H), 4.35 (s, 2H), 3.76 (s, 3H), 3.28 (dd, J =
14.0, 4.0 Hz, 1H), 2.97 (dd, J = 14.0, 8.0 Hz, 1H); 13C{1H} NMR
(100 MHz, CDCl3) δ 172.3, 167.6, 154.4, 148.9, 143.2, 135.4, 129.0,
127.6, 125.4, 124.3, 122.9, 59.2, 52.7, 40.1, 38.4; TOF-HRMS calcd for
C19H19N4O5 [M + H]+ 383.1355, found 383.1348.
Methyl 2-(5-oxo-2-(phenylimino)imidazolidin-1-yl)-3-phenylpro-
panoate (Scheme 4, 4o). Yellow oil (0.0579 g, 61% yield); Rf 0.22
1
(20% EtOAc/hexanes); H NMR (400 MHz, CDCl3) δ 7.33−7.24
(m, 5H), 7.17 (d, J = 7.2 Hz, 2H), 7.03 (t, J = 7.2 Hz, 1H), 6.89 (d, J =
7.2 Hz, 2H), 4.38 (s, 2H), 4.27 (dd, J = 8.4, 4.0 Hz, 1H), 3.75 (s, 3H),
3.25 (dd, J = 14.0, 4.0 Hz, 1H), 2.91 (dd, J = 13.6, 8.4 Hz, 1H);
13C{1H} NMR (100 MHz, CDCl3) δ 172.7, 167.7, 148.7, 135.7, 129.5,
129.4, 128.9, 127.4, 123.7, 122.5, 59.1, 52.6, 40.1, 38.5; TOF-HRMS
calcd for C19H20N3O3 [M + H]+ 338.1505, found 338.1502.
3,5-Dibenzyl-2-((4-chlorophenyl)imino)imidazolidin-4-one
(Scheme 4, 4h). Colorless solid (0.0856 g, 78% yield); mp 128−129
1
°C; Rf 0.31 (20% EtOAc/hexanes); H NMR (400 MHz, CDCl3) δ
7.30−7.23 (m, 10H), 7.10−7.08 (m, 2H), 6.79 (d, J = 8.8 Hz, 2H),
H
J. Org. Chem. XXXX, XXX, XXX−XXX