The Journal of Organic Chemistry
Article
3
H), 7.27−7.25 (m, 1H), 6.75 (d, J = 8.4 Hz, 1H), 5.28 (s, 1H), 3.66
Methyl 2-(6-Pentyl-5,6-dihydrophenanthridin-6-yl)acetate (3x).
(
s, 3H), 2.85 (d, J = 15.2 Hz, 1H), 2.48 (d, J = 15.2 Hz, 1H), 1.73 (s,
Eluent: petroleum ether/ethyl acetate (20:1). Yellowish solid (59.2
H). 13C{ H} NMR (CDCl , 100 MHz): δ 171.9, 145.7, 138.7, 129.5,
1
1
3
1
1
mg, 61%), mp 60.5−61.2 °C. H NMR (CDCl , 600 MHz): δ 7.76
3
3
3
1
28.3, 128.0, 126.0 (q, J = 3.4 Hz), 124.9 (q, J = 268.0 Hz),
23.6, 122.8, 120.9 (d, J = 33.0 Hz), 120.6, 120.5 (d, J = 4.8
(dd, J = 7.8 Hz, J = 0.6 Hz, 1H), 7.66 (dd, J = 7.8 Hz, J = 1.2 Hz,
C‑F
C‑F
1 2 1 2
2
3
C‑F
C‑F
1H), 7.29 (td, J = 7.8 Hz, J = 1.2 Hz, 1H), 7.23 (td, J = 7.2 Hz, J =
1 2 1 2
1
9
Hz), 115.6, 54.6, 51.6, 44.0, 26.0. F NMR (CDCl , 376 MHz): δ
−
3
1.2 Hz, 1H), 7.16 (dd, J = 7.8 Hz, J = 1.2 Hz, 1H), 7.10 (td, J = 7.8
3
1
2
1
+
61.3 (s). HRMS (ESI) m/z: [M + H] Calcd for C H F NO
Hz, J = 1.2 Hz, 1H), 6.79 (td, J = 7.8 Hz, J = 1.2 Hz, 1H), 6.69 (dd,
2 1 2
J = 7.8 Hz, J = 1.2 Hz, 1H), 4.78 (s, 1H), 3.62 (s, 3H), 2.87 (d, J =
1 2
1
8
17
3
2
1
1
7
1
1
5.0 Hz, 1H), 2.49 (d, J = 15.0 Hz, 1H), 2.11−2.06 (m, 1H), 1.89−
.84 (m, 1H), 1.51−1.47 (m, 1H), 1.31−1.26 (m, 5H), 0.84 (t, J =
1
3
1
.2 Hz, 3H). C{ H} NMR (CDCl , 150 MHz): δ 172.1, 143.2,
3
36.6, 131.5, 129.2, 127.5, 127.2, 124.4, 123.1, 122.7, 120.2, 118.7,
15.6, 58.0, 51.5, 44.3, 37.9, 32.3, 24.0, 22.6, 14.1. HRMS (ESI) m/z:
+
2
1
Methyl 2-(3,6-Dimethyl-5,6-dihydrophenanthridin-6-yl)acetate
3u). Eluent: petroleum ether/ethyl acetate (20:1). Yellowish syrup
(
1
(
53.2 mg, 63%). H NMR (CDCl , 400 MHz): δ 7.71 (d, J = 8.0 Hz,
3
1
2
3
3
1
1
H), 7.58 (d, J = 8.0 Hz, 1H), 7.32−7.28 (m, 1H), 7.25−7.23 (m,
H), 6.67 (d, J = 8.0 Hz, 1H), 6.56 (s, 1H), 4.89 (br s, 1H), 3.64 (s,
H), 2.87 (d, J = 15.2 Hz, 1H), 2.40 (d, J = 15.2 Hz, 1H), 2.29 (s,
13
1
H), 1.71 (s, 3H). C{ H} NMR (CDCl , 100 MHz): δ 172.2,
Methyl 2-(6-Phenethyl-5,6-dihydrophenanthridin-6-yl)acetate
(3y). Eluent: petroleum ether/ethyl acetate (20:1). Yellowish syrup
3
43.0, 139.3, 138.5, 130.9, 127.6, 127.1, 123.4, 123.2, 122.5, 120.4,
+
1
18.7, 116.5, 54.6, 51.5, 43.3, 25.7, 21.4. HRMS (ESI) m/z: [M + H]
(75.1 mg, 70%). H NMR (CDCl
3
, 400 MHz): δ 7.80 (d, J = 7.6 Hz,
1H), 7.68 (d, J = 7.2 Hz, 1H), 7.35−7.24 (m, 5H), 7.17−7.10 (m,
18
20
2
4
H), 6.83−6.79 (m, 1H), 6.72 (d, J = 8.0 Hz, 1H), 4.93 (s, 1H), 3.59
(
(
(
s, 3H), 2.93 (d, J = 15.2 Hz, 1H), 2.88−2.80 (m, 1H), 2.64−2.56
m, 1H), 2.51 (d, J = 15.2 Hz, 1H), 2.45−2.37 (m, 1H), 2.26−2.18
1
3
1
m, 1H). C{ H} NMR (CDCl , 100 MHz): δ 172.0, 143.2, 142.4,
3
1
1
36.1, 131.7, 129.3, 128.5, 128.4, 127.8, 127.4, 125.9, 124.4, 123.2,
22.8, 120.1, 118.9, 115.7, 58.1, 51.6, 44.4, 39.9, 30.9. HRMS (ESI)
+
Methyl 2-(3-Chloro-6-methyl-5,6-dihydrophenanthridin-6-yl)-
acetate (3v). Eluent: petroleum ether/ethyl acetate (20:1). Yellowish
1
syrup (41.6 mg, 46%). H NMR (CDCl , 400 MHz): δ 7.70 (d, J =
3
7
.6 Hz, 1H), 7.60 (d, J = 8.4 Hz, 1H), 7.35−7.24 (m, 3H), 6.80 (dd,
J = 8.4 Hz, J = 2.0 Hz, 1H), 6.73 (d, J = 2.0 Hz, 1H), 5.03 (s, 1H),
1
2
3
1
1
1
.67 (s, 3H), 2.85 (d, J = 15.6 Hz, 1H), 2.44 (d, J = 15.2 Hz, 1H),
.71 (s, 3H). 13C{ H} NMR (CDCl , 100 MHz): δ 171.9, 144.1,
1
3
Methyl 2-(6-(2-Phenoxyethyl)-5,6-dihydrophenanthridin-6-yl)-
38.6, 134.5, 129.9, 127.80, 127.78, 124.4, 123.5, 122.6, 119.7, 119.3,
+
acetate (3z). Eluent: petroleum ether/ethyl acetate (20:1). Yellowish
15.5, 54.6, 51.6, 43.5, 25.7. HRMS (ESI) m/z: [M + H] Calcd for
1
syrup (76.2 mg, 68%). H NMR (CDCl , 400 MHz): δ 7.86 (d, J =
3
17
17
2
7
1
(
.6 Hz, 1H), 7.76 (dd, J = 7.6 Hz, J = 0.8 Hz, 1H), 7.42−7.38 (m,
1
2
H), 7.35−7.27 (m, 4H), 7.20 (td, J = 7.8 Hz, J = 1.2 Hz, 1H), 6.97
1
2
t, J = 7.2 Hz, 1H), 6.92−6.86 (m, 3H), 6.80 (dd, J = 8.0 Hz, J = 0.8
1
2
Hz, 1H), 5.25 (br s, 1H), 4.26−4.21 (m, 1H), 4.04−3.98 (m, 1H),
3
2
.72 (s, 3H), 3.00 (d, J = 15.6 Hz, 1H), 2.80 (d, J = 15.6 Hz, 1H),
1
3
1
.75−2.67 (m, 1H), 2.55−2.48 (m, 1H). C{ H} NMR (CDCl , 100
3
MHz): δ 172.0, 158.7, 142.8, 135.8, 131.3, 129.5, 129.4, 127.9, 127.4,
1
4
24.1, 123.3, 123.0, 120.7, 120.3, 119.2, 115.9, 114.4, 64.3, 56.9, 51.7,
Methyl 2-(6-Butyl-5,6-dihydrophenanthridin-6-yl)acetate (3w).
+
3.7, 36.6. HRMS (ESI) m/z: [M + H] Calcd for C H NO
Eluent: petroleum ether/ethyl acetate (20:1). Yellowish solid (52.9
24 24
3
1
mg, 57%), mp 85.7−86.3 °C. H NMR (CDCl , 600 MHz): δ 7.77−
3
7
.56 (m, 1H), 7.66 (dd, J = 7.8 Hz, J = 1.2 Hz, 1H), 7.30 (td, J =
1
2
1
7
.8 Hz, J = 1.2 Hz, 1H), 7.24 (td, J = 7.2 Hz, J = 1.2 Hz, 1H), 7.17
2
1
2
(
dd, J = 7.8 Hz, J = 1.2 Hz, 1H), 7.11 (td, J = 7.8 Hz, J = 1.2 Hz,
1 2 1 2
1
0
2
1
H), 6.79 (td, J = 7.2 Hz, J = 0.6 Hz, 1H), 6.69 (dd, J = 7.8 Hz, J =
1 2 1 2
.6 Hz, 1H), 4.79 (s, 1H), 3.62 (s, 3H), 2.88 (d, J = 15.0 Hz, 1H),
.50 (d, J = 15.0 Hz, 1H), 2.12−2.07 (m, 1H), 1.90−1.84 (m, 1H),
.50−1.45 (m, 1H), 1.33−1.24 (m, 3H), 0.86 (t, J = 7.2 Hz, 3H).
13
1
Ethyl 2-(6-Methyl-5,6-dihydrophenanthridin-6-yl)acetate (3aa).
C{ H} NMR (CDCl , 150 MHz): δ 172.1, 143.2, 136.6, 131.5,
3
Eluent: petroleum ether/ethyl acetate (20:1). Yellowish syrup (56.6
1
5
29.2, 127.5, 127.1, 124.4, 123.1, 122.6, 120.2, 118.7, 115.6, 58.0,
1.5, 44.3, 37.7, 26.5, 23.1, 14.1. HRMS (ESI) m/z: [M + H] Calcd
1
+
mg, 67%). H NMR (CDCl
3
, 600 MHz): δ 7.75 (d, J = 7.8 Hz, 1H),
7
7
4
=
.70 (d, J = 7.8 Hz, 1H), 7.34−7.32 (m, 1H), 7.27−7.25 (m, 2H),
20
24
2
.15−7.13 (m, 1H), 6.86 (t, J = 7.8 Hz, 1H), 6.74 (d, J = 7.8 Hz, 1H),
.96 (s, 1H), 4.13−4.09 (m, 2H), 2.86 (d, J = 15.0 Hz, 1H), 2.41 (d, J
1
3
1
15.0 Hz, 1H), 1.73 (s, 3H), 1.24 (t, J = 7.2 Hz, 3H). C{ H} NMR
(
CDCl , 150 MHz): δ 171.7, 143.1, 139.0, 130.8, 129.1, 127.6, 127.5,
3
1
23.5, 123.3, 122.8, 121.3, 119.3, 116.0, 60.5, 54.6, 43.6, 25.7, 14.2.
+
HRMS (ESI) m/z: [M + H] Calcd for C H NO 282.1489; Found
1
8
20
2
282.1486.
5
813
J. Org. Chem. 2021, 86, 5805−5819