1
554
N. Sato, N. Narita
PAPER
1H NMR (400 MHz): = 2.74 (s, 3 H), 7.46–7.61 (m, 8 H), 8.11–
.13 (m, 2 H), 9.15 (s, 1 H).
13C NMR(100.6 MHz): = 8.0, 23.8, 32.9, 127.3, 129.1, 130.5,
135.8, 137.6, 144.6, 153.1, 153.6, 203.6.
8
13C NMR (67.8 MHz):
= 28.5, 126.9, 128.5, 129.0, 129.1, 129.4,
30.3, 135.3, 137.2, 142.0, 148.2, 148.9, 150.9, 201.0.
MS: m/z (%) = 227 (MH , 100).
+
1
Anal. Calcd for C H N O: C, 74.31; H, 6.24; N, 12.38. Found: C,
1
4
14
2
+
MS: m/z (%) = 275 (MH , 100).
73.98; H, 6.19; N, 12.03.
Anal. Calcd for C H N O: C, 78.81; H, 5.14; N, 10.21. Found: C,
18
14
2
5
,6-Diphenyl-2-propionylpyrazine (5d)
7
8.78; H, 5.10; N, 10.15.
Colorless needles; mp 105–106 °C (EtOH).
2
-Acetyl-3,5,6-triphenylpyrazine (3g)
IR (KBr): = 1698 (C=O), 1356, 1267, 1168, 1102, 966, 771, 696
cm .
–
1
Colorless needles; mp 156–157 °C (EtOH).
–
1
1H NMR (400 MHz): = 1.26 (t, 3 H, J = 7.2 Hz), 3.31 (q, 2 H,
J = 7.2 Hz), 7.30–7.37 (m, 6 H), 7.49–7.52 (m, 4 H), 9.20 (s, 1 H).
13C NMR (100.6 MHz): = 7.8, 31.4, 128.2, 128.3, 128.4, 129.0,
129.3, 129.6, 129.7, 138.0, 140.3, 144.6, 151.1, 155.3, 202.1.
IR (KBr): = 1704 (C=O), 1395, 1122, 771, 692 cm .
1H NMR (400 MHz): = 2.77 (s, 3 H), 7.31–7.35 (m, 6 H), 7.45–
.47 (m, 3 H), 7.59–7.63 (m, 4 H), 7.69–7.71 (m, 2 H).
7
13C NMR (100.6 Mz):
1
= 28.5, 128.3, 128.4, 129.0, 129.3, 129.5,
29.7, 129.9, 137.3, 137.6, 137.7, 144.8, 147.9, 149.5, 151.8, 200.9.
+
MS: m/z (%) = 289 (MH , 100).
+
MS: m/z (%) = 351 (MH , 100).
Anal. Calcd for C H N O: C, 79.14; H, 5.59; N, 9.72. Found: C,
1
9
16
2
7
9.13; H, 5.86; N, 9.93.
Anal. Calcd for C H N O: C, 82.26; H, 5.18; N, 7.99. Found: C,
24
18
2
8
1.85; H, 5.13; N, 7.80.
3
,5-Diphenyl-2-propionylpyrazine (5e)
Colorless needles; mp 97.5–98.5 °C (EtOH).
2
-Acetylpyridine (7)
1
4
Colorless oil; bp (Kugelrohr) 50 °C/9 Torr (Lit. bp 78–80 °C/11
Torr).
IR (KBr): = 1701 (C=O), 1543, 1520, 1374, 1257, 1029, 955, 752,
–
1
687 cm .
1H NMR (400 MHz): = 2.73 (s, 3 H), 7.45–7.48 (m, 1 H), 7.81–
1H NMR (400 MHz): = 1.18 (t, 3 H, J = 7.2 Hz), 3.06 (q, 2 H,
J = 7.2 Hz), 7.47–7.53 (m, 6 H), 7.63–7.64 (m, 2 H), 8.15 (d, 2 H,
J = 6.8 Hz), 8.97 (s, 1 H).
7
.85 (m, 1 H), 8.04 (t, 1 H, J = 5.0, 2.9 Hz), 8.69 (d, 1 H, J = 3.6 Hz).
13C NMR (100.6 MHz):
= 25.7, 121.6, 127.0, 136.8, 149.0, 153.6,
2
00.1.
13C NMR (100.6 MHz): = 8.0, 34.1, 127.4, 128.4, 129.1, 129.4,
1
30.5, 135.6, 137.7, 138.0, 147.4, 152.2, 152.3, 204.0.
5
-Phenyl-2-propionylpyrazine (5a)
+
MS: m/z (%) = 289 (MH , 100).
Colorless needles; mp 145–147 °C (EtOH).
Anal. Calcd for C H N O: C, 79.14; H, 5.59; N, 9.72. Found: C,
1
9
16
2
IR (KBr): = 1697 (C=O), 1449, 1367, 1239, 1015, 779, 747, 691
cm .
7
8.92; H, 5.57; N, 9.56.
–
1
1H NMR (270 MHz): = 1.26 (t, 3 H, J = 7.3 Hz), 3.24 (q, 2 H,
J = 7.3 Hz), 7.53–7.56 (m, 3 H), 8.08–8.12 (m, 2 H), 9.06 (d, 1 H,
J = 1.3 Hz), 9.27 (d, 1 H, J = 1.3 Hz).
3,6-Diphenyl-2-propionylpyrazine (5f)
Colorless needles; mp 120–121 °C (EtOH).
IR (KBr): = 1703 (C=O), 1431, 960, 763, 692 cm–1.
1H NMR (400 MHz): = 1.22 (t, 3 H, J = 7.2 Hz), 3.15 (q, 2 H,
J = 7.2 Hz), 7.46–7.60 (m, 8 H), 8.10–8.12 (m, 2 H), 9.15 (s, 1 H).
13C NMR (67.8 MHz):
40.4, 143.0, 145.6, 155.1, 201.7.
= 7.7, 31.3, 127.4, 129.2, 130.8, 135.6,
1
+
MS: m/z (%) = 213 (MH , 100).
13C NMR (100.6 MHz):
= 7.8, 34.1, 127.0, 128.5, 128.9, 129.1,
Anal. Calcd for C H N O: C, 73.56; H, 5.70; N, 13.20. Found: C,
129.4, 130.2, 135.4, 137.2, 141.8, 148.7, 149.0, 150.8, 204.1.
13
12
2
7
3.53; H, 5.67; N, 13.13.
+
MS: m/z (%) = 289 (MH , 100).
Anal. Calcd for C H N O: C, 79.14; H, 5.59; N, 9.72. Found: C,
3
-Phenyl-2-propionylpyrazine (5b)
19 16
2
7
8.79; H, 5.58; N, 9.58.
Pale yellow needles; mp 63–64 °C (EtOH).
–
1
IR (KBr): = 1707 (C=O), 1397, 1248, 1094, 956, 759, 698 cm .
3
,5,6-Triphenyl-2-propionylpyrazine (5g)
1H NMR (400 MHz): = 1.15 (t, 3 H, J = 7.3 Hz), 3.00 (q, 2 H,
J = 7.3 Hz), 7.45–7.48 (m, 3 H), 7.52–7.56 (m, 2 H), 8.55 (d, 1 H,
J = 2.2 Hz), 8.72 (d, 1 H, J = 2.2 Hz).
Pale yellow needles; mp 134–135 °C (EtOH).
IR (KBr): = 1704, (C=O), 1401, 1340, 1102, 1010, 963, 771, 695
cm .
1H NMR (400 MHz): = 1.22 (t, 3 H, J = 7.2 Hz), 3.21 (q, 2 H,
J = 7.2 Hz), 7.31–7.35 (m, 6 H), 7.45–7.46 (m, 3 H), 7.58–7.62 (m,
–1
13C NMR (100.6 MHz):
41.3, 144.9, 150.0, 152.9, 204.0.
= 7.7, 34.1, 128.5, 128.8, 129.5, 137.2,
1
+
MS: m/z (%) = 213 (MH , 100).
4 H), 7.68–7.69 (m, 2 H).
Anal. Calcd for C H N O: C, 73.56; H, 5.70; N, 13.20. Found: C,
13C NMR (100.6 MHz): = 8.0, 34.0, 128.3, 128.36, 128.42, 129.0,
129.2, 129.4, 129.7, 129.9, 137.3, 137.7, 137.8, 145.2, 148.1, 149.4,
13
12
2
7
3.35; H, 5.71; N, 13.22.
1
51.7, 203.9.
3
-Methyl-5-phenyl-2-propionylpyrazine (5c)
+
MS: m/z (%) = 365 (MH , 100).
Colorless needles; mp 77–78 °C (EtOH).
Anal. Calcd for C H N O: C, 82.39; H, 5.53; N, 7.69. Found: C,
2
5
20
2
IR (KBr): = 1698 (C=O), 1527, 1306, 1255, 1175, 959, 781, 691
cm .
8
2.36; H, 5.51; N, 7.61.
–
1
1H NMR (400 MHz): = 1.22 (t, 3 H, J = 7.3 Hz), 2.89 (s, 3 H), 3.23
2-Propionylpyridine (8)
Colorless oil; bp (Kugelrohr) 50 °C/4 Torr (Lit. bp 91–92 °C/10
Torr).
1
5
(
(
q, 2 H, J = 7.3 Hz), 7.51–7.52 (m, 3 H), 8.08–8.09 (m, 2 H), 8.89
s, 1 H).
Synthesis 2001, No. 10, 1551–1555 ISSN 0039-7881 © Thieme Stuttgart · New York