1
34
W. Stadlbauer and M. Fischer
Method B.
Vol. 39
5
H-Indeno[1,2-b]indol-10-one (5).
A solution of 3-azido-2-phenylindan-1-one (4) (2.00 g,
mmol) in ethanol (75 mL) was heated to 60-70 °C until the
evolution of nitrogen had stopped and a clear solution was
formed (about 1 hour). Then the mixture was cooled to room
temperature and the formed precipitate isolated by suction
filtration. The yield was 0.90 g (51%), reddish prisms, mp 331 °C
A suspension of 1,2-dichloro-1-(2-trichloromethyl)phenyl-2-
(2-pyridyl)-ethene-hydrochloride (11) in water (70 mL) and
triethylamine (4 mL) was heated in a sealed tube to 190 °C
(pressure 10-15 bar) and kept at this temperature under stirring
for 3 hours. The yield was 1.48 g (70%), mp, tlc and ir was
identical with the product obtained by method A; ir: 1730 w,
8
-1 1
1
665 s, 1620 s, 1600 m, 1570 s cm ; H nmr: δ 7.16 (t, J = 8 Hz,
(
1
(
ethanol); lit. mp 326 °C [12] ir: 3220 br, 1730 w, 1670 s, 1610 s,
-
1
1
1 H, Ar-H), 7.53-7.56 (m, 4 H, Ar-H), 8.06 (t, J = 8 Hz, 1 H,
Ar-H), 8.30 (s, 1 H, Ar-H), 8.50-8.54 (d, J = 8 Hz, 1 H, Ar-H),
580 w cm ; H nmr: δ 7.10-7.64 (m, 8 H, Ar-H), 10.00
s, broad, 1 H, NH).
1
4.20 (s, 1 H, OH).
Anal. Calcd. for C H NO (219.3): C, 82.18; H, 4.14; N, 6.39.
1
5 9
Found: C, 81.97; H, 4.28; N, 6.28.
3
-(4-Methylphenyl)sulfonyloxy-2-(4-pyridyl)-indan-1-one (10).
A) Sodium salt of 8: A solution of 2-(4-pyridyl)-indane-1,3-
2-Phenyl-3-(triphenylphosphoranylideneamino)-indan-1-one (6).
dione (8) (5.96 g, 26.7 mmol) in dry, hot dioxane (80 mL) was
added to sodium methoxide, prepared from sodium (0.76 g,
A solution of 3-azido-2-phenylindan-1-one (4) (5.00 g,
0 mmol) in toluene (100 mL) was mixed with triphenyl-
phosphane (5.80 g, 22 mmol) and the mixture stirred for
0 hours at room temperature. The solvent was removed under
2
3
3 mmol) and methanol (20 mL). The sodium salt of 8
precipitated and was kept overnight at 4 °C, and then isolated by
suction filtration and dried. The yield was 5.57 g (85%),
light-grey powder.
3
reduced pressure, the red-orange residue heated with hexane
to remove soluble impurities and the solid was isolated by
filtration and dried. The yield was 8.97 g (90%), red-orange
prisms, mp 168-169 °C (toluene/hexane); ir: 1665 s, 1600 w,
B) Tosylation of 8-sodium salt: A mixture of 8-sodium salt
(
5.57 g, 22.7 mmol) and 4-toluenesulfonyl chloride (5.09 g,
-
1
26.7 mmol) in dry acetonitrile (40 mL) was heated under reflux
with strirring for 1 hour. The reaction mixture was poured into
ice/water (350 mL) which gave a yellow precipitate. Purification
was performed using a hot extractor with cyclohexane. After
1
570 w cm .
Anal. Calcd. for C H NOP (481.5): C, 82.31; H, 5.02; N,
3
3 24
2
3
.91. Found C, 82.30; H 5.07; N 2.93.
-Amino-2-phenylindan-1-one (7).
2
4 hours extraction, 20 mg (1%) of 10 was obtained,
A suspension of 2-phenyl-3-(triphenylphosphoranylide-
neamino)-indan-1-one (6) (4.00 g, 8 mmol) in hydrochloric acid
0.5 mol/L, 80 mL) and methanol (5 mL) was heated under reflux
for 1 hour. After cooling to room temperature, triphenyl-
phosphanoxide formed during the reaction was removed by
filtration. The oily residue was triturated several times with
toluene and the formed solid isolated by suction filtration. The
yield was 0.89 g (48%), brownish prisms, mp 264-268 °C
mp 215.5-216 °C (cyclohexane); ir: 1695 m, 1650 s, 1620 s,
1530 cm .
Anal. Calcd. for C21H15NO4S (377.4): C, 66.83; H, 4.01; N,
3.71. Found: C, 66.89; H, 4.39; N, 3.76.
-1
(
1
,2-Dichloro-1-(2-trichloromethyl)phenyl-2-(2-pyridyl)-ethene-
hydrochloride (11).
A mixture of 2-(2-pyridyl)-indane-1,3-dione (9) (8.00 g,
3
5 mmol) and phosphorus pentachloride (3.00 g, 14 mmol) in
phosphoroxychloride (20 mL) was stirred for 3 days at 50-60
C. Then the mixture was poured into ice/water (150 mL) and
(
1
toluene); lit. mp 260-275 °C [9,11]; ir: 3460 w, 3320 w, 3160 br,
-
1 1
640 s, 1610 m, 1580 w cm ; H nmr: δ 7.30-7.90 (m, 9 H,
°
Ar-H), 8.19 (s, 2 H, NH2).
the formed precipitate kept for 2 hours at 0 °C and then
isolated by suction filtration and dried in vacuo. The yield was
2
-(4-Pyridyl)-indane-1,3-dione (8).
5
3
1
7
8
.96 g (39%), brownish solid, mp 189-190 °C (xylene); ir:
100-3000 br, 2780-2300 br, 2110 w, 2040 w, 1645 s, 1620 w,
605 w, 1540 m cm ; H nmr: δ 7.46-7.68 (m, 4 H, Ar-H),
A mixture of phthalic anhydride (1) (20.0 g, 0.14 mol),
-methylpyridine (13.33 mL, 0.14 mol), and fresh melted zinc
chloride (1.80 g, 13 mmol) was heated to 200 °C for 5 hours.
Then, the reaction cake was extracted several times with boiling
water, isolated by suction filtration and dried. The yield was
4
-
1 1
.84-7.94 (q, J = 2 Hz, 1 H, Ar-H), 7.96-8.14 (m, 2 H, Ar-H),
1
3
.82-8.86 (d, J = 7 Hz, 1 H, Ar-H); C nmr (DMSO-d ): δ 83.4
6
(
CCl ), 121.4-122.2 (aryl C), 126.5-127.6 (aryl C),
2
1.1 g (70%), orange prisms, mp 313-316 °C (ethanol/water); lit.
3
-1
129.0-132.1 (aryl C), 133.5 (alkene C-1), 134.9 (alkene C-2),
142.7 (α-pyridyl C), 148.5 (γ-pyridyl C).
mp 325 °C [13]; ir (KBr): 3240 br, 1670 m, 1615 s, 1590 w cm ;
1
H nmr: δ 4.70 (s, 1 H, H-2), 7.20-7.35 (m, 1 H, Ar-H), 7.48-7.53
m, 4 H, Ar-H), 7.79-7.95 (m, 1 H, Ar-H), 8.50-8.60 (m, 2 H,
Ar-H), 13.90 (s, 1 H, OH).
Anal. Calcd. for C H Cl N (403.9): C, 41.63; H, 2.25; N,
(
14
9
6
3
3
.47; Cl, 52.66. Found: C, 41.24; H, 2.34; N, 3.08; Cl, 53.03.
-Chloro-2(-2-pyridyl)-indan-1-one (12).
3
-Hydroxy-2-(2-pyridyl)-indan-1-one (9).
A mixture of 2-(2-pyridyl)-indane-1,3-dione (9) (3.00 g,
3 mmol) and phosphorus pentachloride (1.14 g, 5.4 mmol) in
Method A.
1
A mixture of phthalic anhydride (1) (20.0 g, 0.14 mol),
phosphorus oxychloride (10 mL) was stirred for 30 hours at room
temperature. Then the mixture was poured into ice/water
(100 mL), the formed precipitate kept at 0 °C for 2 hours and then
isolated by suction filtration to give 1.1 g of unreacted starting
material. The filtrate was brought to pH = 4-6, the precipitate
4
-methylpyridine (12.57 g, 0.14 mol), and fresh melted zinc
chloride (1.80 g, 13 mmol) was reacted and worked up as
described for 8. The yield was 14.25 g (47%), orange prisms, mp.
280-284 °C (ethanol/water); lit. mp 292 °C [13].