A PROCEDURE FOR PREPARING 4-CYANOFLUOREN-9-ONE
1385
(100), 179 (11), 178 (34), 177 (15), 166 (7), 165 (40),
164 (149), 163 (20), 151 (18).
9,10-Phenanthrenequinone monooxime benzoate
was prepared similarly to 2 from 1 and benzoyl chlo-
ride; yield 60%, mp 172 174 C (butanone), Rf = 0.70.
9,10-Phenanthrenequinone monooxime benzene-
sulfonate 2. To a solution of 22.3 g (0.1 mol) of 1
and 17.66 g (0.1 mol) of benzenesulfonyl chloride in
50 ml of acetone was added, with cooling to 0 5 C,
a solution of 4.8 g (0.12 mol) of NaOH in 50 ml of
water. The mixture was stirred for 10 min and then
diluted with 50 ml of cold water. The precipitate was
separated by vacuum filtration, washed with ice-cold
water, and dried at room temperature. Yield 21 g
(78%); yellow-orange compound, mp 140 141 C
(from methyl ethyl ketone); Rf = 0.58.
Found (%): N 4.32.
C21H13NO3.
Calculated (%): N 4.28.
4-Cyanofluoren-9-one 3. A mixture of 3.63 g
(0.01 mol) of 2 and 30 ml of anhydrous butyl acetate
was refluxed on an oil bath at 100 C for 6 h until
sulfonate 2 was completely consumed (chromato-
graphic monitoring). The solvent was distilled off by
half, the mixture was cooled, and the precipitate
was separated by vacuum filtration and crystallized
from benzene. Yield 1.23 g (60%), mp 238 240 C
(published data: mp 240 C [1]), Rf = 0.43. Mass
spectrum, m/z (I, %): 205 (100) M, 177 (57) (M
CO), 176 (8), 175 (5), 150 (17) (M CO HCN),
149 (5), 127 (4), 124 (3), 89 (10), 75 (16), 74 (9).
Found (%): C 66.27, H 3.41, N 3.92, S 8.54.
C20H13NO4S.
Calculated (%): C 66.11, H 3.58, N 3.85, S 8.81.
Mass spectrum, m/z (I, %): 363 (6) M, 299 (4)
(M SO2), 222 (7) (M PhSO2), 206 (100) (M
PhSO3), 179 (11) (M
PhSO3
HCN), 178 (24)
(M PhSO3 CO), 177 (21), 163 (6), 151 (20),
141 (9), 77 (43).
REFERENCES
9,10-Phenanthrenequinone monooxime propio-
nate was prepared similarly to 2 from 4.46 g
(0.02 mol) of 1 in 40 ml of acetone, 2.8 g (0.03 mol)
of propionyl chloride, and 1.6 g (0.04 mol) of NaOH
in 10 ml of water. Yield 4.45 g (80%), mp 109.5
110 C (acetonitrile), Rf = 0.46.
1. Borsche, W. and Sander, W., Ber., 1914, vol. 47,
pp. 2815 2826.
2. Rapoport, H. and Williams, A.R., J. Am. Chem. Soc.,
1949, vol. 71, pp. 1774 1778.
3. Fuson, R., Reactions of Organic Compounds: A Text-
book for the Advanced Student, New York: Wiley,
1962.
Found (%): C 73.40, H 4.65, N 4.86.
4. Terent’ev, P.B. and Stankiavicius, A.P., Khim. Getero-
tsikl. Soedin., 1988, pp. 1518 1521.
C17H13NO3.
Calculated (%): C 73.11, H 4.69, N 5.02.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 79 No. 8 2006