SYNTHESES OF COMPOUNDS ACTIVE TOWARD GLUTAMATE RECEPTORS: II.
1773
5 portions of diethyl ether. The combined extracts
were washed with a saturated solution of sodium
chloride, dried over calcined sodium sulfate, and
evaporated. Yield 6.2 g (100%).
phine, 0.032 g (0.14 mmol) of benzyltriethylammo-
nium chloride, and 0.19 g (0.14 mmol) of potassium
carbonate. The mixture was heated on a water bath
for 6 h at 90 C with occasional stirring. It was then
passed through a chromatographic column using
chloroform petroleum ether (3:1) as eluent. Yield
3-(m-Bromophenyl)propionic acid (VII).
m-Bromobenzylmalonic acid (VI), 6.2 g (0.022 mol),
was placed in a distillation flask and was heated to
170 C under a residual pressure of 30 mm. Vigorous
evolution of carbon dioxide was observed. When the
decarboxylation was complete, the yellow oily sub-
stance was crystallized from hexane. Yield 4.15 g
1
0.16 g (43%). H NMR spectrum (CDCl3), , ppm:
1.20 t (6H, CH3), 2.59 t (2H, CH2), 3.07 t (2H, CH2),
4.02 m (2H, OCH2), 7.84 d (1H, Harom), 7.68 d (1H,
Harom), 7.63 d (1H, Harom). 31P NMR spectrum
(CHCl3):
17.3 ppm, s.
P
1
(80%), light brown crystals, mp 74 C [8]. H NMR
1-Oxoindan-5-carbonitrile (XI). A solution of
0.5 g (0.0024 mol) of 5-bromoindan-1-one (IX) and
0.52 g (0.0027 mol) of copper(I) cyanide in 1 ml of
DMF was stirred for 6 h on heating under reflux.
A 10% aqueous solution of ammonia, 10 ml, was
added, and the precipitate was filtered off, washed
repeatedly with an ammonia solution on a filter,
spectrum (CDCl3), , ppm: 2.66 t (2H, CH2), 2.95 t
(2H, CH2), 7.12 m (2H, Harom), 7.35 m (2H, Harom).
13C NMR spectrum (CDCl3), C, ppm: 30.10 (CH2),
35.28 (CH2), 122.538 (C5), 126.93 (C6), 129.54 (C1),
130.11 (C2), 131.36 (C4), 142.38 (C3), 179.04 (CO).
3-(m-Bromophenyl)propionyl chloride (VIII).
Thionyl chloride, 0.8 ml (0.011 mol), was added
dropwise to 1.28 g (0.0056 mol) of acid VII. When
the mixture became homogeneous, it was heated until
gaseous products no longer evolved. Excess thionyl
chloride was distilled off under reduced pressure on
heating on a water bath. Dry benzene was added, and
thionyl chloride benzene aseotrope was distilled off
under reduced pressure. Yield 1.36 g (96%); purity
96.04% (GLC).
1
and dried. Yield 0.2 g (55%). H NMR spectrum
(DMSO-d6), , ppm: 2.75 t (2H, CH2), 3.16 t (2H,
CH2), 7.75 d (1H, Harom), 7.85 d (1H, Harom), 8.14 s
(1H, Harom).
5-(1H-Tetrazol-5-yl)indan-1-one (XII). A solu-
tion of 0.2 g (0.0013 mol) of 1-oxoindan-5-carbo-
nitrile, 0.12 g (0.0017 mol) of sodium azide, and 0.1 g
(0.0017 mol) of ammonium chloride in 2.5 ml of
DMF was stirred for 24 h at 120 C. The mixture was
evaporated, the residue was washed with cold water
(2 20 ml) and acidified to pH 2 with hydrochloric
acid, and the solid residue was washed with water
(3 20 ml) and ether (2 15 ml), dried for 2 h at 80 C
in a drying box, and recrystallized from acetone. Yield
5-Bromoindan-1-one (IX). A solution of 1.36 g
(0.0056 mol) of acyl chloride VIII in 10 ml of dry
methylene chloride was added dropwise to a solution
of 0.95 g (0.007 mol) of anhydrous AlCl3 in 3 ml
of dry methylene chloride, cooled to 10 C. The mix-
ture was heated on a water bath for 5 h under reflux,
poured onto ice, and a small amount of concentrated
hydrochloric acid was added (to pH 5). The organic
phase was separated, and the aqueous phase was
extracted with methylene chloride (2 30 ml). The
extracts were combined with the organic phase,
washed in succession with water, a 2% solution of
sodium hydroxide, and water again, dried over cal-
cined sodium sulfate, and evaporated. The residue
was recrystallized from heptane. Yield 0.70 g (60%),
light yellow crystals, mp 126 C (purity 100%; GLC);
0.24 g (92%). 1H NMR spectrum (acetone-d6),
,
ppm: 2.84 t (2H, CH2), 3.00 t (2H, CH2), 7.71 d
(1H, Harom), 7.81 d (1H, Harom), 8.10 s (1H, Harom),
9.23 s (1H, NH).
1-Indanone (XVI). A solution of 21.2 g (0.21 mol)
of chromium(VI) oxide in 80 ml of acetic acid and
35 ml of water was added with stirring to a solution
of 10 g (0.086 mol) of indan in 40 ml of acetic acid
at such a rate that the temperature did not exceed
20 C. The mixture was stirred for 16 h, 180 ml of
water was added, and the mixture was extracted with
ether (3 70 ml). The extract was dried over calcined
sodium sulfate and evaporated, and the residue was
distilled under reduced pressure. A fraction with
bp 120 C (10 mm) was collected. Yield 5.62 g (50%),
mp 42 C; published data [10]: mp 40 42 C [10].
The purity of the product was 100% (GLC).
1
published data [9]: mp 125 127 C. H NMR spec-
trum (CDCl3), , ppm: 2.69 t (2H, CH2); 3.14 t (2H,
CH2), 7.52 d (1H, Harom), 7.63 d (1H, Harom), 7.67 s
(1H, Harom).
5-Diethoxyphosphinoylindan-1-one (X). An am-
pule was charged with 0.3 g (0.0014 mol) of 5-bromo-
indan-1-one, 0.19 g (0.0014 mol) of diethyl hydrogen
General procedure for preparation of hydan-
toins XIII XV, XVII, and XVIII. A solution of
0.13 g (0.0026 mol) of sodium cyanide in 2 ml of
water was added to a solution of 0.73 g (0.0076 mol)
5
phosphite, 0.0063 g (2.8 10 mol) of palladium(II)
5
acetate, 0.015 g (5.6 10 mol) of triphenylphos-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 12 2002