The Journal of Organic Chemistry
Page 10 of 13
2
-Amino-5-benzoyl-4-(furan-2-yl)-4,5-dihydrothiophene-3- 9H), 3.51 (s, 3H), 4.21 (d, J = 2.0 Hz, 1H), 4.66 (d, J = 2.0 Hz,
1
3
1
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
carbonitrile(trans-3cf)
1H), 6.18 (br, 2H), 7.23-7.33 (m, 5H). C{ H} NMR (CDCl
3
,
100MHz) δ 26.5, 43.9, 50.5, 52.8, 53.2, 96.0, 126.8, 127.0,
128.6, 143.8, 160.6, 166.3, 209.9. MS (EI ) m/z 319 (M , 28),
f
Yellow solid (62.4 mg, 21% yield). R = 0.22 (hexane/EtOAc =
7
cm (CN), 1670 cm (C=O). H-NMR (CDCl
4.75 (2H, s), 5.11 (1H, d, J = 3.6 Hz), 5.19 (1H, J = 3.6 Hz),
6.34 (2H, m), 7.41 (1H, s), 7.51(2H, t, J = 7.7 Hz), 7.61 (1H, t,
J = 6.8 Hz), 7.90 (2H, d, J = 8.2 Hz). C{ H} NMR (CDCl
400MHz) δ 45.7, 54.3, 73.9, 107.3, 110.7, 116.5, 128.7, 129.0,
1
+
+
-1
:3). mp. 142-143 °C. IR (neat) 3416-3182 cm (NH
2
), 2201
-1
-1
1
286 (76), 262 (50), 234 (66), 230 (23), 202 (100), 175 (25).
3
, 400MHz) δ
+
+
HRMS (EI ) m/z : [M ] calcd. for C17
found: 319.1243. Anal. Calcd for C17
6.63; N, 4.39; S, 10.04, found: C, 63.79; H, 6.66; N, 4.44; S,
.93.
H
21NO
21NO
3
S: 319.1242,
H
3
S: C, 63.92; H,
1
3
1
3
,
9
+
Methyl 2-amino-4-phenyl-5-pivaloyl-4,5-dihydrothiophene-
34.0, 134.2, 142.7, 152.6, 160.0, 191.2. MS (EI) m/z 296 (M ,8
), 263 (39), 192 (14), 174 (11), 144 (21), 105 (100). HRMS (EI)
3-carboxylate (cis-3bi)
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
+
m/z : [M ] calcd. for C16
Anal. Calcd for C16
H 4.07, C 64.61, N 9.31.
-Amino-5-benzoyl-4-(furan-2-yl)-4,5-dihydrothiophene-3-
H
12
N
2
O
2
S: 296.0619, found: 296.0615.
f
White solid (8.8 mg, 5.4% yield). R = 0.21 (hexane/EtOAc =
H
12
N
2
O
2
S: H 4.08, C 64.85, N 9.45, found:
-1
7
1
:3). mp. 147.5-148.2 °C. IR (ATR) 3435, 3305 cm (NH
611, 1523 cm (C=O). H-NMR (CDCl
2
),
-1
1
3
, 400MHz) δ 1.03 (s,
2
9H), 3.54 (s, 3H), 4.64 (d, J = 7.9 Hz, 1H), 5.58 (d, J = 7.9 Hz,
1H), 6.27 (br, 2H), 7.17-7.27 (m, 3H), 7.35 (d, J = 7.1 Hz, 2H).
carbonitrile (cis-3cf)
1
3
1
C{ H} NMR (CDCl
3
, 100MHz) δ 26.3, 44.5, 50.5, 53.0,
Pale Yellow solid (51.0 mg, 17% yield). R
f
= 0.19
-1
60.7, 96.1, 127.4, 127.9, 128.3, 139.6, 162.4, 166.1, 208.9. MS
(EI ) m/z 319 (M , 42), 286 (64), 262 (27), 234 (86), 202 (100),
(hexane/EtOAc = 7:3). mp. 82-84 °C. IR (neat) 2176 cm (CN),
+
+
-1
1
1
=
(
679 cm (C=O). H-NMR (CDCl
7.8 Hz), 4.97 (2H, s), 5.93 (1H, J = 7.8 H), 6.10 (2H, m), 7.07
1H, s), 7.45-7.52(2H, m), 7.59-7.62 (2H, m), 7.79 (2H, d, J =
3
, 400MHz) δ4.85 (1H, d, J
+
+
1
87 (27), 175 (31), 156 (36), 57 (35). HRMS (EI ) m/z : [M ]
calcd. for C17 S: 319.1242, found: 319.1240. Anal. Calcd
for C17 S: C, 63.92; H, 6.63; N, 4.39; S, 10.04, found: C,
H
21NO
3
1
3
1
H21NO
3
7
1
1
3
.7 Hz). C{ H} NMR (CDCl , 400MHz) δ 47.9, 61.4, 72.6,
09.1, 110.5, 116.6, 128.2, 128.8, 133.7, 135.5, 142.4, 149.3,
62.7, 192.7. MS (EI) m/z 296 (M ,11 ), 263 (36), 191 (13), 174
63.63; H, 6.67; N, 4.41; S, 9.86.
+
Methyl 2-amino-5-benzoyl-4-phenyl-4,5-dihydrothiophene-
3-carboxylate (trans-3ci)
+
(10), 144 (15), 105 (100). HRMS (EI) m/z : [M ] calcd. for
16 12 2 2
C H N O
S: 296.0619, found: 296.0616.
Yellow solid (75.6 mg, 45% yield). R
f
= 0.23 (hexane/EtOAc =
-1
Methyl 5-acetyl-2-amino-4-phenyl-4,5-dihydrothiophene-3-
carboxylate (trans-3ai)
7:3). mp. 203.2-204.0 °C. IR (ATR) 3417, 3312 cm (NH
2
),
, 400MHz) δ 3.54 (s,
H), 4.73 (d, J = 1.6 Hz, 1H), 5.03 (d, J = 1.6 Hz, 1H), 6.14 (br,
2H), 7.26-7.38 (m, 5H), 7.46 (dd, J = 7.1, 7.5 Hz, 2H), 7.58 (t,
-1
1
1668, 1596 cm (C=O). H-NMR (CDCl
3
3
f
White solid. (63.4 mg, 46% yield). R = 0.18 (hexane/EtOAc =
-1
7
1
3
6
:3).mp. 97.2-97.5 °C. IR (ATR) 3386, 3281 cm (NH
2
), 1718,
, 400MHz) δ 2.32 (s, 3H),
.53 (s, 3H), 3.85 (d, J = 1.4 Hz, 1H), 4.78 (d, J = 1.4 Hz, 1H),
1
3
1
-1
1
3
J = 7.5 Hz, 1H), 7.85 (d, J = 7.1 Hz, 2H). C{ H} NMR (CDCl ,
100MHz) δ 50.6, 51.0, 56.0, 96.1, 127.1, 127.1, 128.6, 128.6,
128.8, 133.6, 134.5, 143.6, 160.6, 166.5, 193.0. MS (EI ) m/z
632 cm (C=O). H-NMR (CDCl
3
+
13
1
3
.32 (br, 2H), 7.23-7.30 (m, 5H). C{ H} NMR (CDCl ,
+
3
1
39 (M , 13), 306 (72), 274 (23), 234 (21), 20 (52), 156 (21),
100MHz) δ 26.5, 50.6, 51.1, 61.7, 95.0, 126.8, 127.0, 128.5,
143.1 , 161.1, 166.3, 202.5. MS (EI ) m/z 277 (M , 33), 244
(79), 234 (44), 212 (35), 202 (100), 176 (28), 175 (40), 130 (21),
126 (20), 115 (28). HRMS (EI ) m/z : [M ] calcd. for
C
C
+
+
28 (20), 105 (100), 77 (82), 51 (24). HRMS (EI ) m/z : [M ]
S: 339.0929, found: 339.0925. Anal. Calcd
S: C, 67.24; H, 5.05; N, 4.13; S, 9.45, found: C,
7.22; H, 5.04; N, 4.19; S, 9.40.
+
+
calcd. for C19
H17NO
3
for C19 17NO
H
3
+
+
6
14
H
H
15NO
15NO
3
S: 277.0773, found: 277.0769. Anal. Calcd for
S: C, 60.63; H, 5.45; N, 5.05; S, 11.56, found: C,
Methyl 2-amino-5-benzoyl-4-phenyl-4,5-dihydrothiophene-
3-carboxylate (cis-3ci) (CCDC; 1856497)
14
3
6
0.71; H, 5.50; N, 5.05; S, 11.44.
Methyl 5-acetyl-2-amino-4-phenyl-4,5-dihydrothiophene-3-
carboxylate (cis-3ai)
White solid (35.6 mg, 21% yield). R
f
= 0.18 (hexane/EtOAc =
-1
7:3). mp. 173.0-174.1 °C. IR (ATR) 3395, 3290 cm (NH
2
),
-1
1
1
639, 1504 cm (C=O). H-NMR (CDCl , 400MHz) δ 3.51 (s,
3
f
White solid. (28.5 mg, 21% yield). R = 0.15 (hexane/EtOAc =
-
1
3H), 4.75 (d, J = 8.3 Hz, 1H), 6.13 (d, J = 8.3 Hz, 1H), 6.36 (br,
2H), 6.91 (d, J = 6.7 Hz, 2H), 6.99-7.08 (m, 3H), 7.42 (dd, J =
7
1
3
1
:3). mp. 138.7-140.2 °C. IR (ATR) 3438, 3328 cm (NH
706, 1655 cm (C=O). H-NMR (CDCl
2
),
-
1
1
3
, 400MHz) δ 1.87 (s,
H), 3.55 (s, 3H), 4.66 (d, J = 8.5 Hz, 1H), 5.21 (d, J = 8.5 Hz,
H), 6.26 (br, 2H), 7.20-7.28 (m, 3H), 7.37 (d, J =6.5 Hz, 2H).
7
2
.5, 7.9 Hz, 2H), 7.57 (t, J = 7.5 Hz, 1H), 7.69 (d, J = 7.1 Hz,
H). C{ H} NMR (CDCl , 100MHz) δ 50.5, 53.1, 63.6, 96.1,
3
13
1
1
3
1
127.2, 127.7, 128.0, 128.1, 128.7, 133.4, 136.1, 138.3, 162.6,
C{ H} NMR (CDCl
3
, 100MHz) δ 28.5, 50.5, 52.0, 65.9,
+
+
1
66.1, 193.9. MS (EI ) m/z 339 (M , 17), 306 (58), 234 (22),
+
9
6.5, 127.6, 128.0, 128.3, 139.4, 162.0, 166.1, 202.3. MS (EI )
+
+
202 (42), 105 (100), 77 (74). HRMS (EI ) m/z : [M ] calcd. for
+
m/z 277 (M , 73), 244 (66), 234 (50), 218 (21), 212 (24), 22
C
C
19
H
H
17NO
17NO
3
S: 339.0929, found: 339.0935. Anal. Calcd for
S: C, 67.24; H, 5.05; N, 4.13; S, 9.45, found: C,
(100), 176 (29), 175 (50), 156 (32), 147 (20), 130 (29), 128 (23),
+
+
19
3
1
C
C
26 (21), 125 (22), 115 (30). HRMS (EI ) m/z : [M ] calcd. for
6
7.23; H, 5.18; N, 4.16; S, 9.34.
14
H
H
15NO
15NO
3
S: 277.0773, found: 277.0767. Anal. Calcd for
S: C, 60.63; H, 5.45; N, 5.05; S, 11.56, found: C,
4-Hydroxy-4-methyl-2-phenyldihydrothiophene-3,3(2H)-
dicarbonitrile (4aa)
14
3
60.68; H, 5.46; N, 5.12; S, 11.49.
o
Methyl 2-amino-4-phenyl-5-pivaloyl-4,5-dihydrothiophene-
3-carboxylate (trans-3bi)
Pale yellow solid (76.1 mg, 31% yield). mp. 103-109 C. IR
-1
1
3
(neat) 3440 cm (OH). H NMR (CDCl , 400 MHz): 7.71 (2H,
d, J = 3.1 Hz), 7.45 (3H, t, J = 3.0 Hz), 5.17 (1H, s), 3.61 (1H,
d, J = 12.1 Hz), 3.17 (1H, d, J = 12.1 Hz), 2.76 (1H, s), 1.86
f
White solid (19.5 mg, 12% yield). R = 0.28 (hexane/EtOAc =
7
-1
:3). mp. 150.5-151.2 °C. IR (ATR) 3443, 3325 cm (NH
2
),
1
3
1
3
(3H, s). C{ H} NMR (CDCl , 100 MHz): 131.7, 130.0, 129.0,
-1
1
1
664, 1612 cm (C=O). H-NMR (CDCl
3
, 400MHz) δ 1.15 (s,
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