The Journal of Organic Chemistry
Page 6 of 9
1
3
13
J = 8.2 Hz, 2H), 2.31 (s, 3H), 2.24 (s, 3H); C NMR (CDCl 100
7.6 Hz, 2H), 1.25 (t, J = 7.6 Hz, 3H); C NMR (CDCl 100 MHz,
3,
3,
1
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3
4
5
6
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8
9
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MHz, ppm) δ 168.0, 145.0, 135.1, 133.3, 129.9, 127.0, 125.5,
24.4, 123.2, 120.3, 117.0, 115, 6, 114.3, 23.9, 21.7; MS (ESI,
ppm) δ 172.1, 138.1, 129.1, 124.3, 119.9, 30.9, 9.8.MS (ESI, posiꢀ
+
1
tive) m/z calcd for C H NO [M+H]: 150.09, Found 150.10.
9
12
+
positive) m/z calcd for C H N O S [M+H]: 329.10, Found
5)
1
1
7
17
2
3
Nꢀphenylisobutyramide (3y) . White solid (mg, 95%). H
3
29.10.
Nꢀ(benzo[b]thiophenꢀ2ꢀyl)acetamide (3p)
NMR (CDCl3, 400 MHz, ppm) δ 7.87 (br, 1H), 7.54 (d, J = 8.0
Hz, 2H), 7.27 (t, J = 8.0 Hz, 2H), 7.07 (t, J = 7.3 Hz, 1H), 2.53
3
2)
. White solid
61.2 mg, 64%). H NMR ((CD ) CO. 400 MHz, ppm) δ 10.4 (br,
1
13
(
(sept, J = 6.9 Hz, 1H), 1.21 (d, J = 6.9 Hz, 6H); C NMR (CDCl3,
3
2
1
1
H), 7.78 (d, J = 8.1 1H), 7.61 (d, J = 8.1, 2H), 7.28 (t, J = 7.1,
H), 7.21 (t, J = 7.1, 1H), 6.91 (s, 3H), 2.16 (s, 3H); C NMR
100 MHz, ppm) δ 175.4, 138.2, 129.1, 124.3, 119.9, 36.8, 19.7;
13
+
MS (ESI, positive) m/z calcd for C H NO [M+H]: 164.11,
10
14
(
100 MHz, (CD ) CO, ppm) δ 167.8, 141.4, 138.4, 136.1, 125.1,
Found 164.20.
3
2
123.4, 122.6, 122.5, 106.4, 106.3, 23.0; MS (ESI, positive) m/z
36)
Nꢀphenylcyclopropanecarboxamide (3z) . White solid (74.2
+
calcd for C H NOS [M+H]: 192.05, Found 192.10.
1
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
10 10
mg, 91%). H NMR (CDCl 400 MHz, ppm) δ 7.63 (br, 1H), 7.50
3,
8
)
1
Nꢀphenylbenzamide (3q) . White solid (94.6 mg, 96%).
NMR (CDCl3, 400 MHz, ppm) δ 7.88 (d, J = 7.1 Hz, 2H), 7.79
br, 1H), 7.65 (d, J = 7.9 Hz, 2H), 7.57 (t, J = 7.3 Hz, 1H), 7.50 (t,
H
(d, J = 7.6 Hz, 2H), 7.28 (dd, J = 7.6, 8.0 Hz, 2H), 7.08 (t, J = 7.2
Hz, 1H) 1.51ꢀ1.50 (m, 1H), 1.09ꢀ1.05 (m, 2H), 0.84ꢀ0.79 (m, 2H);
1
3
(
C NMR (CDCl3, 100 MHz, ppm) δ 172.5, 138.3, 129.0, 124.1,
+
J = 7.1 Hz, 2H), 7.39 (t, J = 7.9 Hz, 2H), 7.16 (t, J = 7.4 Hz, 1H);
120.0, 15.6, 8.0; MS (ESI, positive) m/z calcd for C H NO
10 12
13
C NMR (CDCl3, 100 MHz, ppm) δ 166.0, 138.1, 135.1, 132.0,
[M+H]: 162.09, Found 162.10.
1
29.2, 128.9, 127.2, 124.7, 120.4; MS (ESI, positive) m/z calcd
37)
Nꢀphenylcyclohexanecarboxamide (3aa) . White solid (78.3
+
for C H NO [M+H]: 198.09, Found 198.10.
1
13
12
mg, 77%). H NMR (400 MHz, CDCl ) δ 7.65 (br, 1H), 7.54 (d, J
3
33)
Nꢀ(phenethyl)acetamide (3r) . White solid (69.3 mg, 85%).
H NMR (CDCl 400 MHz, ppm) δ 7.31 (t, J = 7.0 Hz, 2H), 7.27ꢀ
= 8.2 Hz, 2H), 7.29 (t, J = 7.6 Hz, 2H), 7.07 (t, J = 7.6 Hz, 1H),
1
2.28ꢀ2.20 (m, 1H), 1.99ꢀ1.91 (m, 2H), 1.82ꢀ1.79 (m, 2H), 1.69ꢀ
3,
1
3
7.18 (m, 3H), 5.67 (br, 1H), 3.50 (q, J = 6.7 Hz, 2H), 2.81 (t, J =
1.67 (m, 1H), 1.57ꢀ1.48 (m, 2H), 1.31ꢀ1.16 (m, 3H); C NMR
1
3
6
1
.7 Hz, 2H), 1.93 (s, 3H); C NMR (CDCl3, 100 MHz, ppm) δ
(CDCl , 100 MHz, ppm) δ 174.8, 138.3, 129.0, 124.1, 120.0, 46.5,
3
+
70.2, 139.0, 128.9, 128.8, 126.6, 40.8, 35.7, 23.4; MS (ESI, posiꢀ
29.7, 25.75, 25.73; MS (ESI, positive) m/z calcd for C H NO
1
3
18
+
tive) m/z calcd for C H NO [M+H]: 164.10, Found 164.20.
[M+H]: 204.14, Found 204.10.
1
0
13
3
4)
1
39)
Nꢀnonylacetamide (3s) . White solid (88.9 mg, 96%). H
NMR (CDCl3, 400 MHz, ppm) δ 5.61 (br, 1H), 3.23 (q, J = 6.0
Nꢀ(4ꢀmethoxyphenyl)benzamide (3ab) . White solid (64.8
1
mg, 57%). H NMR (CDCl 400 MHz, ppm) δ 7.85 (d, J = 8.8
3,
Hz, 2H), 1.97 (s, 3H), 1.51ꢀ1.47 (m, 2H), 1.30ꢀ1.26 (m, 12H),
Hz, 2H), 7.75 (br, 1H), 7.63 (d, J = 7.7 Hz, 2H), 7.37 (t, J = 7.7
Hz, 2H), 7.14 (t, J = 7.4 Hz, 1H), 6.98 (d, J = 8.8 Hz, 2H), 3.88 (s,
13
0
1
.88 (t, J = 6.6 Hz, 3H); C NMR (CDCl3, 100 MHz, ppm) δ
13
70.1, 39.8, 32.0, 29.7, 29.6, 29.42, 29.39, 27.0, 23.5, 22.8, 14.2;
MS (ESI, positive) m/z calcd for C H NO [M+H]: 186.18,
3H); C NMR (CDCl3, 100 MHz, ppm) δ 165.8, 156.8, 135.1,
+
131.8, 131.1, 128.9, 127.1, 122.3, 114.3, 55.6; MS (ESI, positive)
1
1
24
+
Found 186.20.
m/z calcd for C H NO [M+H]: 228.10, Found 228.10.
14 14
2
8
)
1
40)
ɛꢀCaprolactam (3t) . White solid (45.8 mg, 81%). H NMR
4,5ꢀDihydroꢀ1Hꢀbenzo[b]]azepinꢀ2(3H)ꢀone (3ac) . White
solid (57.2 mg, 71%). H NMR (CDCl 400 MHz, ppm) δ 7.71
1
(
2
CDCl 400 MHz, ppm) δ 6.47 (br, 1H), 3.23ꢀ3.19 (m, 1H), 2.48ꢀ
.45 (m, 1H), 1.79ꢀ1.62 (m, 3H); C NMR (CDCl3, 100 MHz,
3,
3,
1
3
(dd, J = 1.4, 7.4 Hz, 1H), 7.41 (dt, J = 1.4, 7.4 Hz, 1H), 7.34 (dt, J
= 1.2, 7.5 Hz, 1H), 7.19 (d, J = 7.5 Hz, 1H), 6.76 (br, 1H), 3.13
(q, J = 6.8 Hz, 2H), 2.87 (t, J = 7.1 Hz, 2H), 2.03 (quin, J = 7.1
ppm) δ 179.3, 43.0 36.8, 30.7, 29.9, 23.4; MS (ESI, positive) m/z
+
calcd for C H NO [M+H]: 114.09, Found 114.20.
6
12
13
5)
Hz, 2H); C NMR (CDCl 100 MHz, ppm) δ 175.9, 138.1, 134.4,
Azacyclododecanꢀ2ꢀone (3u)
4%). H NMR (CDCl 400 MHz, ppm) δ 6.13 (br, 1H), 3.33ꢀ3.29
.
White solid (86.1 mg,
3,
1
129.9, 127.6, 125.7, 122.0, 32.9, 30.4, 28.7; MS (ESI, positive)
9
3
,
+
m/z calcd for C H NO [M+H]: 162.09, Found 162.10.
(
m, 2H), 2.25ꢀ2.22 (m. 2H), 1.73ꢀ1.67 (m, 2H), 1.59ꢀ1.57 (m,
10 12
1
3
41)
2H), 1.46ꢀ1.34 (m, 12H); C NMR (CDCl3, 100 MHz, ppm) δ
7ꢀmethylazepanꢀ2ꢀone (3ad) . White solid (40.0 mg, 63%).
H NMR (CDCl 400 MHz, ppm) δ 5.72 (br, 1H), 3.54ꢀ3.46 (m,
1
173.7, 39.3, 36.4, 25.9, 25.3, 25.2, 24.7, 24.6, 24.21, 24.19, 23.3;
3,
+
MS (ESI, positive) m/z calcd for C H NO [M+H]: 184.17,
1H), 2.50ꢀ2.42 (m, 2H), 2.05ꢀ1.74 (m, 4H), 1.61ꢀ1.48 (m, 1H),
11 22
13
Found 184.20.
1.42ꢀ1.32 (m, 1H), 1.21 (d, J = 6.7 Hz, 3H); C NMR (CDCl3,
100 MHz, ppm) δ 177.9, 49.5, 37.6, 37.0, 29.9, 23.1, 22.7; MS
8)
Azacyclotridecanꢀ2ꢀone (3v)
.
White solid (92.7 mg,
+
1
(ESI, positive) m/z calcd for C H NO [M+H]: 128.11, Found
9
4%). H NMR (CDCl 400 MHz, ppm) δ 6.01 (br, 1H), 3.32ꢀ3.27
7
14
3
,
1
28.20.
(
2
m, 2H), 2.25ꢀ2.20 (m. 2H), 1.71ꢀ1.65 (m, 2H), 1.55ꢀ1.48 (m,
H), 1.37ꢀ1.30 (m, 14H); C NMR (CDCl3, 100 MHz, ppm) δ
13
3ꢀHydroxyꢀ13otꢀaminoꢀ13, 17ꢀsecoꢀ1, 3, 5(10)ꢀestratienꢀ17ꢀ
22)
1
2
73.7, 39.1, 36.9, 28.4, 26.8, 26.4, 26.2, 25.8, 25.3, 25.0, 24.7,
oic 13, 17ꢀlactam (6) . To a 20 mL flask was added to estron
(1.5 g, 4.80 mmol, 1.0 eq.), oxime 2a (1.4 g, 5.70 mmol, 1.2 eq.),
CH CN (4.8 mL, 1.0 M) under N at room temperature (≈ 23°C).
+
4.0; MS (ESI, positive) m/z calcd for C H NO [M+H]:
1
2
24
198.19, Found 198.20.
3
2
Then H O (90.8 ꢁL, 5.04 mmol, 1.05 eq.) and TsOH·H O (22.8
Nꢀ(6ꢀtertꢀbutylꢀ1,1ꢀdimethylindanꢀ4ꢀyl)acetamide (3w). White
2
2
1
mg, 0.120 mmol, 2.5 mol%) was added to stirred reaction mixꢀ
tures at room temperature. After 24 h, the reaction mixture was
solid (112.8 mg, 87%). H NMR (CDCl 400 MHz, ppm) δ 7.77
3
,
(
s, 1H), 7.00 (br, 1H), 6.96 (s, 1H), 2.73 (t, J = 7.1 Hz, 2H), 2.17
13
quenched by sat. NaHCO aq. (10 mL) and work up with ethyl
(s, 3H), 1.94 (t, J = 7.1 Hz, 2H), 1.31 (s, 9H), 1.25 (s, 6H);
C
3
acetate (30 mL × 3). The combined organic phase was washed
with brine and dried over Na SO . The collected solution was
NMR (CDCl3, 100 MHz, ppm) δ 168.5, 153.3, 151.0, 133.1,
30.8, 117.3, 115.5, 44.5, 41.2, 34.9, 31.6, 28.7, 27.1, 24.2; MS
1
2
4
+
evaporated under reduced pressure and the remained crude mixꢀ
tures was purified by silica gel column chromatography (hexꢀ
ane/ethyl acetate = 60/40 to 20/80, then ethyl acetate/methanol =
(ESI, positive) m/z calcd for C H NO [M+H]: 260.20, Found
17 26
2
60.20; IR (neat) 2857, 1654, 1478, 1372, 1329, 1299, 1038, 982,
ꢀ
1
870, 777, 651, 555 cm ; Anal. Calcd. For C H NO: C, 9.71; H,
1
7
25
9
1
8/2). The obtained white solid (895 mg) was directly added to a
00 mL flask containing K CO (377 mg, 2.73 mmol, 1.0 eq.) and
7
8.72; N, 5.40; found C, 78.74; H, 9.94; N, 5.38.
7
)
1
2
3
Propionanilide (3x) . White solid (68.6 mg, 92%). H NMR
CDCl3, 400 MHz, ppm) δ 7.52 (d, J = 8.0 Hz, 2H), 7.31 (t, J =
.0 Hz, 2H), 7.26 (br, 1H), 7.10 (t, J = 7.4 Hz, 1H), 2.39 (q, J =
MeOH (33 mL). The reaction mixture was stirred at room temperꢀ
ature for 6 h. After the starting material was consumed, the solꢀ
vent was removed under reduced pressure and the remained solid
(
8
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