NEW ONE-STEP PROCEDURE FOR THE SYNTHESIS OF 6H-CHROMENO-...
81
1
1
25.0, 125.2, 126.2, 127.5, 129.0, 130.1, 131.4, 131.6,
5.01 d (1H, J = 2.9 Hz), 6.56 s (1H), 6.58 d (1H, J =
8.7 Hz), 7.05 d (1H, J = 9.5 Hz), 7.36 t (1H, J =
8.0 Hz), 7.47 d.d (1H, J = 8.7, 1.4 Hz), 7.52–7.58 m
(2H), 7.74 d (1H, J = 9.6 Hz), 7.80 d (1H, J = 6.0 Hz),
36.0, 146.8, 148.0, 151.7. Mass spectrum, m/z
+
(
I , %): 247 (76) M , 246 (100), 232 (12), 217 (11),
rel
2
03 (8), 124 (17), 118 (10), 96 (13), 77 (4), 63 (7), 39
1
3
(
8). Found, %: C 74.62; H 4.97; N 4.52. C H NO.
8.07 d (1H, J = 8.0 Hz), 11.5 br.s (1H). C NMR spec-
trum (DMSO-d ), δ , ppm: 28.6, 28.7, 44.7, 65.6,
1
7
13
Calculated, %: C 74.75; H 4.92; N 4.59. M 247.30.
-Allyloxynaphthalene-1-carbaldehyde (V) was
synthesized as described above for aldehyde II. Yield
0%, mp 77–78°C (from hexane) [12].
1-Nitro-8a,9,14,14a-tetrahydro-8H-benzo[5,6]-
chromeno[4,3-b]quinoline (VIa). A mixture of 0.65 g
4.72 mmol) of p-nitroaniline (Ia), 1.00 g (4.72 mmol)
of aldehyde V, and 0.73 g (5.17 mmol) of BF ·Et O in
6
C
113.3, 115.6, 115.8, 118.2, 119.4, 123.1, 123.8, 127.5,
2
1
1
28.9, 129.3, 129.8, 130.1, 131.8, 133.4, 146.9, 151.9,
+
68.3. Mass spectrum, m/z (I , %): 331 (48) M , 330
rel
8
(
1
23), 187 (12), 182 (20), 181 (100), 174 (23), 166 (15),
52 (15), 115 (21), 77 (11). Found, %: C 76.11;
H 5.18; N 4.23. C H NO . Calculated, %: C 76.14;
1
2
1
17
3
(
H 5.21; N 4.23. M 331.37.
1-Methyl-8a,9,14,14a-tetrahydro-8H-benzo-
5,6]chromeno[4,3-b]quinoline (VId) was synthe-
sized as described above for compound VIa. mp 143–
3
2
1
1
5 ml of acetonitrile was heated for 35 h under reflux.
[
The mixture was evaporated on a rotary evaporator, the
residue was dissolved in 30 ml of methylene chloride,
the solution was washed with a saturated solution of
1
1
45°C (from hexane). H NMR spectrum (CDCl ), δ,
3
ppm: 2.17 s (3H), 2.45 m (1H), 2.63 d (1H, J =
6.7 Hz), 3.27 d.d (1H, J = 16.7, 6.5 Hz), 4.02–4.14 m
(2H), 4.89 d (1H, J = 2.9 Hz), 5.29 s (1H), 6.42 d
1H, J = 8.0 Hz), 6.66 d (1H, J = 8.0 Hz), 6.71 s (1H),
.04 d (1H, J = 9.5 Hz), 7.33 t (1H, J = 7.3 Hz), 7.52 t
1H, J = 7.6 Hz), 7.71 d (1H, J = 8.7 Hz), 7.78 d (1H,
NaHCO and water and evaporated, and the residue
3
1
was recrystallized from propan-2-ol. mp 235–237°C.
1
H NMR spectrum (CDCl ), δ, ppm: 2.7 m (1H),
3
(
7
2.86 d.d (1H, J = 17.1, 1.5 Hz), 3.38 d.d (1H, J = 16.7,
5.8 Hz), 3.95 t (1H, J = 12.0 Hz), 4.21 d.d (1H, J =
10.9, 3.6 Hz), 4.93 s (1H), 5.12 d (1H, J = 3.6 Hz),
6.36 d (1H, J = 6.5 Hz), 7.13 d (1H, J = 8.7 Hz), 7.43 t
(
13
J = 8.0 Hz), 8.06 d (1H, J = 8.0 Hz). C NMR spec-
trum (CDCl ), δ , ppm: 20.5, 28.0, 28.9, 44.2, 65.3,
3
C
(
(
(
1H, J = 7.6 Hz), 7.6 d.t (1H, J = 7.6, 1.5 Hz), 7.78 d
1H, J = 8.7 Hz), 7.86 d (1H, J = 8.0 Hz), 7.93 d.d
1H, J = 8.7, 2.2 Hz), 8.00 d (1H, J = 8.0 Hz), 8.01 s
114.0, 115.8, 116.7, 118.8, 122.5, 123.1, 124.5, 126.8,
1
27.5, 128.3, 128.8, 129.2, 129.5, 132.8, 140.0, 151.4.
+
Mass spectrum, m/z (I , %): 301 (99) M , 303 (23),
1
3
rel
(
1H). C NMR spectrum (CDCl ), δ , ppm: 27.2,
3 C
3
(
00 (51), 194 (31), 182 (23), 181 (100), 158 (23), 150
25), 144 (40), 120 (24). Found, %: C 83.86; H 6.37;
N 4.65. C H NO. Calculated, %: C 83.76; H 6.46;
2
1
1
7.3, 44.0, 64.5, 112.6, 114.1, 116.4, 118.8, 122.5,
23.7, 124.2, 125.8, 127.3, 128.6, 128.8, 130.1, 132.6,
2
1
19
35.8, 149.1, 151.33. Mass spectrum, m/z (I , %): 332
rel
N 4.60. M 301.39.
1-Chloro-8a,9,14,14a-tetrahydro-8H-benzo-
5,6]chromeno[4,3-b]quinoline (VIe) was synthesized
+
(
(
51) M , 302 (24), 285 (20), 186 (22), 182 (46), 181
100), 175 (25), 152 (26), 148 (30), 147 (31). Found,
1
[
%
: C 72.96; H 4.87; N 7.96. C H NO. Calculated, %:
17 13
in a similar way. mp 180–182°C (from propan-2-ol).
C 72.29; H 4.82; N 8.43. M 332.36.
a,9,14,14a-Tetrahydro-8H-benzo[5,6]chromeno-
4,3-b]quinoline-11-carboxylic acid (VIb). A mixture
of 0.65 g (4.72 mmol) of p-aminobenzoic acid (Ib),
.00 g (4.72 mmol) of aldehyde V, and 0.73 g
5.17 mmol) of BF ·Et O in 15 ml of acetonitrile was
1
H NMR spectrum (CDCl ), δ, ppm: 2.45 m (1H),
3
8
2
6
.69 d (1H, J = 16.9 Hz), 3.29 d.d (1H, J = 17.1,
.5 Hz), 4.01 d.d (1H, J = 12.0, 10.2 Hz), 4.14 d.d (1H,
[
J = 10.9, 3.6 Hz), 4.91 d (1H, J = 2.9 Hz), 5.93 s (1H),
.57 d (1H, J = 8.7 Hz), 6.82 d.d (1H, J = 8.7, 2.2 Hz),
1
(
6
3
2
6.91 d (1H, J = 1.5 Hz), 7.06 d (1H, J = 8.7 Hz), 7.35 t
(1H, J = 7.6), 7.54 t (1H, J = 7.6 Hz), 7.73 d (1H, J =
8.7 Hz), 7.8 d (1H, J = 8.0 Hz), 8.06 d (1H, J =
heated for 35 h under reflux. The mixture was evap-
orated on a rotary evaporator, the residue was dissolv-
ed in 50 ml of 5% aqueous sodium hydroxide, the
solution was filtered, the filtrate was carefully acidified
until a solid material no longer separated, and the
precipitate was filtered off and washed on a filter with
1
3
8.0 Hz). C NMR spectrum (CDCl ), δ , ppm: 28.4,
3
C
28.9, 45.0, 65.8, 115.0, 115.2, 119.3, 119.5, 121.7,
121.9, 124.0, 127.6, 127.7, 129.3, 129.4, 130.3, 132.8,
+
140.5, 152.0. Mass spectrum, m/z (I , %): 323 (18) M
rel
1
37
+ 35
water. mp 280–282°C (from propan-2-ol). H NMR
spectrum (DMSO-d ), δ, ppm: 2.55 m (1H), 2.78 d
( Cl), 321 (52) M ( Cl), 322 (16), 320 (22), 182 (20),
181 (100), 165 (21), 164 (20), 152 (21), 127 (14).
Found, %: C 74.64; H 5.02; N 4.35. C H ClNO. Cal-
6
(
3
1H, J = 18.0 Hz), 3.32 d.d (1H, J = 15.0, 6.0 Hz),
.96 t (1H, J = 12.0 Hz), 4.17 d.d (1H, J = 9.0, 3.0 Hz),
2
0
16
culated, %: C 74.65; H 5.09; N 4.20. M 321.81.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 1 2007