A procedure for preparing 4-cyanofluoren-9-one

Article abstract of DOI:10.1134/S1070427206080362

A procedure was developed for preparing 4-cyanofluoren-9-one by intramolecular cyclization of 9,10-phenanthrenequinone monooxime benzenesulfonate.

Full text of DOI:10.1134/S1070427206080362

ISSN 1070-4272, Russian Journal of Applied Chemistry, 2006, Vol. 79, No. 8, pp. 1384 1385.
Original Russian Text A.P. Stankevicius, L.N. Janusiene, P.B. Terent’ev, M.S. Saprogoniene, 2006, published in Zhurnal Prikladnoi Khimii,
2006, Vol. 79, No. 8, pp. 1397 1398.
Pleiades Publishing, Inc., 2006.
BRIEF
COMMUNICATIONS
A Procedure for Preparing 4-Cyanofluoren-9-one
A. P. Stankevicius, L. N. Janusiene, P. B. Terent’ev, and M. S. Saprogoniene
Institute of Cardiology, Kaunas Medical University, Kaunas, Lithuania
Lomonosov Moscow State University, Moscow, Russia
Received June 19, 2006
Abstract A procedure was developed for preparing 4-cyanofluoren-9-one by intramolecular cyclization of
9,10-phenanthrenequinone monooxime benzenesulfonate.
DOI: 10.1134/S1070427206080362
Fluorenones, mainly 2- and 4-substituted, are wide-
ly used in electrophotography [1] and as drugs [2].
In particular, Grintsev et al. studied a series of fluore-
nones [3] and synthesized a novel antiviral agent, Flo-
renal [4]. It is widely used in medical practice against
herpesis and adenoviruses. However, the lack of facile
routes to 4-substituted fluorenones hinders the devel-
opment of this novel group of antiviral agents.
[2]. Experiments on the Beckmann rearrangement of
the second kind of 9,10-phenanthrenequinone mono-
oxime 1 have shown that suspensions of this com-
pound in ether under the action of PCl5 give 4-cyano-
fluoren-9-one 3 in a low yield [3]. Proceeding with
studies of o-quinone monooxime sulfonates, we found
that 9,10-phenanthrenequinone monooxime benzene-
sulfonate 2, when melted ( 215 C) or crystallized
from ethyl acetate, forms traces of a new substance
with mp 238 240 C (dec.), whose mass spectrum was
consistent with the structure of 4-cyanofluoren-9-one.
Prolonged refluxing of 2 in ethyl acetate or (which
is better) in butyl acetate always gives fluorenone 3
in a good yield:
Fluorenones are usually prepared from 2-arylben-
zoic acids by the Friedel Crafts reaction or its modifi-
cations [1]. Even 2 -cyanodiphenyl-2-carboxylic acid
in thionyl chloride forms, along with the corre-
sponding acid chloride, also 4-cyanofluoren-9-one
SO2Ph
O
OH
N
N
O
O
O
AcOBu, T, C
PhSO2Cl, NaOH
CN
3
2
1
An attempt to perform the reaction with 9,10-phen-
anthrenequinone monooxime propionate or benzoate
resulted in the recyclization.
MAT-1303 and MAT-212 devices (Varian-MAT) at
ionizing electron energies of 50 and 70 eV, respec-
tively, with direct sample input. The elemental com-
position of the major ions was determined with
an MAE-212 device at high resolution (M/ M =
10000).
EXPERIMENTAL
The purity of the compounds was checked by TLC
on Silufol UV-254 plates, solvent system tetrachloro-
methane ethyl acetate, 3 : 1; the spots were developed
with iodine vapor. The mass spectra were recorded on
9,10-Phenanthrenequinone monooxime 1 was
prepared by the procedure described in [4]; mp 157 C.
Mass spectrum, m/z (I, %): 223 (96), 207 (20), 206
1384

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