Notes
J . Org. Chem., Vol. 62, No. 5, 1997 1531
potassium hydroxide. After ca. 15 min, a white solid mass
formed that was allowed to stand an additional 0.5 h. The
mixture was treated with 95% ethanol (15 mL), stirred for ca. 3
h, and filtered, and the solid was washed with 95% ethanol (5
mL). Crystallization from acetic acid gave 5.14 g (78%) of
of 7, mp 220-221 °C. The TLC, MS, and 1H-NMR data were
the same as those for 7 obtained in procedure C.
To a stirred mixture of sodium hydride (60% in mineral oil,
0.40 g, 0.01 mol of NaH) in anhydrous DMF (15 mL) under N
2
was added in one portion a solution of 1 (2.203 g, 0.01 mol) in
DMF (25 mL). The mixture was heated to 60 °C for 2 h, allowed
to cool to room temperature, and then poured into water (150
mL). A pale yellow solid was filtered off, washed with water
(50 mL), and crystallized from acetic acid to give 0.500 g (23%)
of 7, mp 224-226 °C. The TLC, MS, and 1H-NMR data were
the same as those for 7 obtained in procedure C.
F . P ota ssiu m Ca r bon a te. A mixture of 1 (2.20 g, 0.01 mol)
and anhydrous potassium carbonate (2.07 g, 0.015 mol) in
2
anhydrous DMF (75 mL) under N was stirred and refluxed for
2 h. The mixture was allowed to cool to room temperature,
poured into water (150 mL), treated with 37% hydrochloric acid
(3.0 mL, 0.04 mol of HCl), and then stirred at room temperature
for ca. 1 h. The solid was filtered off and crystallized from acetic
acid to give 1.20 g (58%) of 7, mp 226-227 °C. The TLC, MS,
and 1H-NMR data were the same as those for 7 obtained in
procedure C.
2
1
-(phenylmethylene)-2,3-dihydro-1H-inden-1-one (1): mp 109-
5
1
10 °C (lit. mp 109-111 °C); R
f
0.56 (CHCl
3
); H NMR (CDCl
3
)
δ 4.10 (s, 2H), 7.35-7.74 (m, 9H), 7.94 (d, J ) 7.0 Hz, 1H); 3C
1
NMR (CDCl
30.74, 133.95, 134.65, 138.1, 141.5, 194.5.
B. P ota ssiu m Ca r bon a te. A solution of benzaldehyde (1.06
3
) δ 32.47, 124.46, 126.19, 127.70, 128.95, 129.69,
1
g, 0.01 mol), 2,3-dihydro-1H-inden-1-one (1.23 g, 0.01 mol), and
anhydrous potassium carbonate in 100% ethanol (25 mL) was
stirred vigorously at room temperature for ca. 48 h. The light
red mixture was treated with 37% hydrochloric acid (2 mL,
0
.0242 mol), and a white solid was formed. The solid was
filtered, washed with water (5 mL), and crystallized from acetic
acid to give 1.85 g (84%) of 1, mp 108-109 °C, TLC R 0.54
). The H-NMR and MS data were identical with those
f
1
(CHCl
3
of 1 obtained from potassium hydroxide.
When the above reaction was repeated using 10 drops of
saturated potassium carbonate in 95% ethanol or 50% ethanol,
no reaction, as determined by TLC and MS, occurred after
stirring at room temperature for ca. 48 h.
Mon ooxim e 8 of 7. The procedure given below is essentially
that of Witschard and Griffin.3
A solution of 7 (1.00 g, 0.0023 mol), hydroxylamine hydro-
chloride (1.00 g, 0.014 mol), and potassium hydroxide (4.0 g,
Rea ction of 2-(P h en ylm eth ylen e)-2,3-d ih yd r o-1H-in d en -
0
.071 mol) in 95% ethanol was stirred and refluxed for 2 h. The
1
-on e (1) w ith Va r iou s Ba ses. C. Ben zyltr ip h en ylp h os-
hot mixture was filtered to remove insoluble material (0.578 g,
MS 115), and the filtrate was acidified with 10% hydrochloric
acid (36.5 mL). The resultant solid was filtered off and crystal-
p h on iu m Ch lor id e a n d Sod iu m Eth oxid e. The procedure
described below is that reported by Witschard and Griffin.3
To a freshly prepared solution of 0.25 M ethanolic sodium
ethoxide (100 mL anhydrous ethanol, 0.57 g, 0.025 mol sodium)
under N were added, each in one portion, 1 (5.50 g, 0.025 mol)
2
and benzyltriphenylphosphonium chloride (9.72 g, 0.025 mol).
The orange slurry was stirred at room temperature for 2 h and
then treated dropwise with 48% hydrobromic acid (10.4 mL, 0.05
mol, HBr) followed by water (100 mL). After being stirred for
ca. 0.5 h, the mixture was extracted with chloroform (100 mL)
and separated. The chloroform layer was dried (anhydrous
6
lized from acetic acid and dried in vacuo at 100 °C to give 0.703
f 3
g (67%) of 8, the 8-oxime of 7: mp > 250 °C; R 0.52, 0.61 (CHCl /
+
-1
2 5
C H OH, 95:5); MS 456 (MH , 100); IR (KBr) cm 3398 (OH),
1
1
1
716 (CdO), 1604 (CdN); H NMR (DMSO-d
7.0 Hz, 2H H-3′), 3.68 and 3.82 (d, J ) 10.6 Hz, 0.25- and 0.75H,
H-1), 3.62 (d, J ) 10.7 Hz, 1H, H-3), 4.25 and 4.38 (dd, J ) 10.6,
6
) δ 3.05 (AB, J )
8
6
0
1
3
5
1
1
1
1
.7 Hz, 0.75- and 0.25H, H-8a), 4.65 (dd, J ) 10.6, 8.7 Hz, H-3a),
.83-7.35 (m, 16H), 7.46 and 7.49 (d, J ) 7.0 Hz, 0.25- and
.75H, H-7′), 7.65 and 8.46 (d, J ) 7.0 Hz, 0.25- and 0.75H, H-7),
4
MgSO ) and filtered, and the filtrate was concentrated in vacuo
1.21 (br, 1H, OH); 13C NMR (DMSO-d
) δ 29.26 and 29.64 (C-
6
to give a viscous light orange oil (17.3 g) that upon treatment
with 95% ethanol gave a white solid. Crystallization from acetic
acid gave 3.85 g (70%) 1,3-diphenyl-3a,8a-dihydrospiro[cyclo-
′), 46.08 and 46.18 (C-3a), 47.31 and 48.54 (C-8a), 57.49 and
9.77 (C-1), 61.45 and 61.61 (C-3), 67.75 and 68.40 (C-2), 120.98,
22.41, 123.78, 125.49, 125.60, 125.67, 126.30, 126.55, 126.68,
26.77, 126.83, 127.16, 127.38, 127.49, 127.66, 127.82, 127.91,
28.11, 128.28, 129.05, 129.38, 130.46, 132.51, 134.33, 133.43,
35.67, 136.39, 136.51, 136.72, 136.98, 138.63, 148.05 and 149.49
penta[a]indene-2,2′(1H,3′H)-indene]-1′,8(3H)-dione (7), mp 222-
3
2
24 °C (lit. mp 228-233 °C); R
f
0.22 (CHCl
3
); MS (CI) 458 (100,
) δ 3.10
+
+
1
M + NH
(
(
4
4
), 441 (2.3, MH ), 136 (33.4); H NMR (CDCl
3
q, J ) 17.0 Hz, 2H, H-3′), 3.85 (d, J ) 10.1 Hz, 1H, H-3), 4.00
(
CdNOH, 25:75 ratio), 152.60, 158.21 and 159.73 (C-3b, 75:25
ratio), 208.22 and 208.29 (CdO, 75:25 ratio).
Anal. Calcd for C32 C, 84.37; H, 5.53; N, 3.07.
Found: C, 84.30; H, 5.58; N, 2.99.
dd, J ) 10.5, 8.7 Hz, 1H, H-8a), 4.15 (d, J ) 10.6 Hz, 1H, H-1),
.60 (dd, J ) 10.4, 8.7 Hz, 1H, H-3a), 6.91-7.80 (m, 18H); 13
C
H
2
25NO :
NMR (DMSO-d) δ 30.50 (C-3′), 46.70 (C-3a), 53.60 (C-8a), 54.80
(
C-1), 59.80 (C-3), 70.00 (C-2), 122.72, 123.81, 125.01, 125.94,
1
1
2
1
26.87, 127.17, 127.23, 127.98, 128.05, 128.23, 128.31, 135.01,
35.15, 135.38, 136.17, 136.39, 136.99, 137.69, 152.64, 155.79,
05.92 and 207.86 (C-1′ and C-8); UV (95% EtOH) nm 207.4 (67,
-1
29), 248.6 (24,779), 295.6 (4,854); IR (CHCl
3
) cm 1703 (CdO).
Anal. Calcd for C32
H, 5.44.
24 2
H O : C, 87.25; H, 5.49. Found: C, 87.27;
D. Sod iu m Eth oxid e. To a freshly prepared solution of 0.25
M ethanolic sodium ethoxide (40 mL of anhydrous ethanol, 0.23
g, 0.01 mol Na) under N was added 1 (2.20 g, 0.01 mol) in one
2
portion. The orange mixture was stirred at room temperature
for 2 h, treated dropwise with 48% hydrobromic acid (5 mL, 0.024
mol HBr), poured into water (50 mL), and then stirred at room
temperature for ca. 0.5 h. The pale yellow solid was filtered off
and crystallized from acetic acid to give 0.246 g (11%) of 7, mp
2
31-232 °C. The TLC, MS, and 1H-NMR data were the same
as those for 7 obtained in procedure E.
Ack n ow led gm en t. The authors are grateful to Mrs.
Bertha Owens for mass spectra and Eric Roos for
elemental analysis.
E. Sod iu m Hyd r id e. The procedure described below is that
reported by Witschard and Griffin.
To a stirred mixture of sodium hydride (60% in mineral oil,
3
0
.40 g, 0.01 mol NaH) and anhydrous ethylene glycol dimethyl
Su p p or tin g In for m a tion Ava ila ble: PCMODEL of 7 (1
page). This material is contained in libraries on microfiche,
immediately follows this article in the microfilm version of the
journal, and can be ordered from the ACS; see any current
masthead page for ordering information.
ether (glyme, 25 mL) under N was added dropwise at room
2
temperature a solution of 1 (2.204 g, 0.01 mol) in glyme (25 mL)
over ca. 0.5 h. The mixture was refluxed for ca. 20 h, cooled to
room temperature, treated dropwise with water (5 mL), and then
poured into water (250 mL) and stirred at room temperature
for ca. 3 h. The light tan solid was filtered off and crystallized
from 95% ethanol/methylene chloride (9:1) to give 0.912 g (41%)
J O960649F
(
6) When the compound was allowed to dry at room temperature, it
(5) Hassner, A.; Cromwell, N. H. J . Org. Chem. 1958, 80, 893.
retained 0.7 mol of acetic acid/mol of compound.