Reaction of 10-(4-tolylsulfonyloxyimino)phenanthren-9-one with aromatic amines, hydrazines, and hydrazides

Full text of DOI:10.1134/S107042800712024X

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 12, pp. 1876–1877. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © A.P. Stankyavichyus, L.N. Yanushene, V.E. Skiryus, 2007, published in Zhurnal Organicheskoi Khimii, 2007, Vol. 43, No. 12,
pp. 1868–1869.
SHORT
COMMUNICATIONS
Reaction of 10-(4-Tolylsulfonyloxyimino)phenanthren-9-one
with Aromatic Amines, Hydrazines, and Hydrazides
A. P. Stankyavichyusa, L. N. Yanushenea, and V. E. Skiryusb
a Institute of Cardiology, Kaunas Medical University, pr. Sukilelyu 17, Kaunas, 50009 Lithuania
e-mail: laima.janusiene@med.kmu.lt
b Faculty of Pharmaceutics, Kaunas Medical University, Kaunas, Lithuania
Received June 15, 2007
DOI: 10.1134/S107042800712024X
We found previously that aliphatic amines smoothly
react with phenanthrene-9,10-quinone O-(p-tolylsul-
fonyl)oxime (I) on cooling to give 2-(2′-cyanophenyl)-
benzamide in a good yield. However, in the reaction of
I with 4-methylaniline, instead of the expected anilide,
we isolated phenanthrene-9,10-quinone 9-(4-methyl-
phenylhydrazone). The same product was obtained in
good yield by heating compound I with 4-methyl-
phenylhydrazine [1]. In the present communication we
report on the reactions of O-(4-methylphenylsulfonyl)-
oxime I with aromatic amines and arylhydrazines
having various substituents in the aromatic ring. In all
cases no amides were obtained, but the corresponding
hydrazones IIa–IIe were formed. In the reaction with
2,4-dinitroaniline we detected only traces of hydrazone
IIg (by chromatography). These data indicate that the
formation of the –N=N– bond is hindered in reactions
with aromatic amines having electron-withdrawing sub-
stituents and that the effect of the ortho-substituent is
insignificant. By reactions of compound I with arylhy-
drazines we obtained hydrazones IIc, IId, and IIf in
good yields, while the yield of 2,4-dinitrophenylhydra-
zone IIg reached 92%. Benzohydrazide reacted with
oxime ester I to give 43% of benzoylhydrazone III.
10-(4-Tolylsulfonyloxyimino)-9,10-dihydrophe-
nanthren-9-one (I) was synthesized according to the
procedure described in [1].
10-(4-Methoxyphenylhydrazono)-9,10-dihydro-
phenanthren-9-one (IIa). Compound I, 1.13 g
(3 mmol), was added to a solution of 0.68 g (6 mmol)
of 4-methoxyaniline in 5 ml of acetonitrile, and the
mixture was stirred until it became homogeneous, left
to stand for 2 days at room temperature, and heated for
30 min at 80°C. The solution was diluted with 20 ml of
water and stirred, and the precipitate was filtered off,
washed with water, and recrystallized from acetic acid
with addition of charcoal. Yield 0.67 g (68%),
mp 248–249°C [2], Rf 0.64 (benzene–hexane–aceto-
nitrile, 2:2:1).
10-(2-Methoxyphenylhydrazono)-9,10-dihydro-
phenanthren-9-one (IIb). A mixture of 0.758 g
(2 mmol) of compound I and 1 ml of 2-methoxyaniline
in 6 ml of acetonitrile was heated for 3 h under reflux
(water bath). The precipitate was filtered off and
recrystallized from acetic acid. Yield 0.18 g (27%),
mp 252°C, Rf 0.60 (benzene–heptane–ethyl acetate,
4:4:1). Mass spectrum, m/z (Irel, %): 298 (35) [M]+,
270 (9), 206 (47), 193 (32), 178 (100), 165 (86), 92
ArNH2 or ArNHNH2
PhCONHNH2
H
N
H
OTs
N
N
Ar
N
N
COPh
O
O
O
IIa–IIg
I
III
II, Ar = 4-MeOC6H4 (a), 2-MeOC6H4 (b), 2-MeC6H4 (c), 3-MeC6H4 (d), 2-Me-4-O2NC6H3 (e), 4-O2NC6H4 (f), 2,4-(O2N)2C6H3 (g).
1876

REACTION OF 10-(4-TOLYLSULFONYLOXYIMINO)PHENANTHREN-9-ONE
1877
(51), 77 (30). Found, %: C 76.58; H 4.61; N 8.37.
C21H16N2O2. Calculated, %: C 76.83; H 4.88; N 8.52.
10-(4-Nitrophenylhydrazono)-9,10-dihydrophe-
nanthren-9-one (IIf). A mixture of 0.38 g (1 mmol) of
compound I and 0.36 g (2 mmol) of 4-nitrophenyl-
hydrazine in 10 ml of acetonitrile was heated for
20 min under reflux. Yield of hydrazone IIf 0.13 g
(38%), mp 249–250°C (from acetic acid) [3], Rf 0.61
(ethyl acetate–carbon tetrachloride, 3:1).
10-(2-Methylphenylhydrazono)-9,10-dihydro-
phenanthren-9-one (IIc). a. A mixture of 1.13 g
(3 mmol) of compound I and 5 ml of 2-methylaniline
(excess) was kept for 4 days at room temperature.
Yield of IIc 0.31 g (33%), mp 225–226°C (from acetic
acid); published data [2]: mp 222–223°C; Rf 0.36 (ben-
zene–hexane, 3:2).
10-(2,4-Dinitrophenylhydrazono)-9,10-dihydro-
phenanthren-9-one (IIg). A mixture of 0.75 g
(2 mmol) of compound I and 1 g (5 mmol) of 2,4-di-
nitrophenylhydrazine in 10 ml of acetonitrile was
heated for 20 min under reflux. The mixture was
diluted with 20 ml of water and acidified with dilute
hydrochloric acid (1:1) to pH 5.5–6.0, and the precip-
itate was filtered off and recrystallized from acetic acid
with addition of charcoal. Yield 0.72 g (92%), mp 334–
336°C [2], Rf 0.11 (benzene–heptane, 3:2). Mass spec-
trum, m/z (Irel, %): 388 (24) [M]+, 360 (20), 206 (59),
193 (67), 182 (41), 178 (88), 167 (12), 165 (100).
b. A mixture of 0.75 g (2 mmol) of compound I and
0.49 g (4 mmol) of (2-methylphenyl)hydrazine in
10 ml of acetonitrile was heated for 20 min under
reflux. The mixture was cooled, diluted with 20 ml of
water, and acidified with dilute hydrochloric acid (1:1)
to pH 5.5–6.0. The product was recrystallized from
acetic acid. Yield 0.38 g (61%), mp 225–226°C,
Rf 0.36 (benzene–heptane, 3:2).
10-(3-Methylphenylhydrazono)-9,10-dihydro-
phenanthren-9-one (IId). a. Compound IId was syn-
thesized from 1.89 g (5 mmol) of oxime I and 8 ml of
3-methylaniline as described above for hydrazone IIc
(method a). Yield 0.54 g (35%), mp 148–149°C (from
acetic acid), Rf 0.72 (benzene–heptane–ethyl acetate,
4:4:1). Found, %: C 80.46; H 4.89; N 8.65. C21H16N2O.
Calculated, %: C 80.77; H 5.12; N 8.97.
N′-(10-Oxo-9,10-dihydrophenanthren-9-ylidene)-
benzohydrazide (III). A mixture of 0.62 g (6 mmol)
of benzohydrazide and 0.75 g (2 mmol) of compound I
in 10 ml of anhydrous ethanol was heated for 7 h under
reflux. The mixture was diluted with 20 ml of water,
and the precipitate was filtered off and recrystallized
from acetonitrile with addition of charcoal. Yield 0.28 g
(43%), mp 195–196°C [4], Rf 0.47 (ethyl acetate–car-
bon tetrachloride, 1:3).
b. A mixture of 0.75 g (2 mmol) of compound I and
1 ml of (3-methylphenyl)hydrazine in 8 ml of acetic
acid was heated for 5 min under reflux. The mixture
was cooled, and the precipitate was filtered off. Yield
0.45 g (72%), mp 148–149°C (from acetic acid),
Rf 0.72 (benzene–heptane–ethyl acetate, 4:4:1). Mass
spectrum, m/z (Irel, %): 312 (43) [M]+, 234 (6), 206
(43), 193 (37), 178 (80), 165 (100), 106 (89), 91 (18).
The purity of the products was checked by TLC on
Silufol UV-254 plates; spots were detected by treat-
ment with iodine vapor. The mass spectra (electron
impact, 70 eV) were recorded on a Finigan MAT-212
mass spectrometer with direct sample admission into
the ion source.
10-(2-Methyl-4-nitrophenylhydrazono)-9,10-
dihydrophenanthren-9-one (IIe). A mixture of 1.13 g
(3 mmol) of compound I and 0.91 g (6 mmol) of
2-methyl-4-nitroaniline in 10 ml of acetonitrile was
heated for 3 h under reflux. The mixture was diluted
with 20 ml of water and cooled, and the precipitate
was filtered off and recrystallized from acetic acid.
Yield 0.29 g (27%), mp 263–265°C (from acetic acid),
Rf 0.8 (benzene–hexane–acetonitrile, 2:2:1). Mass
spectrum, m/z (Irel, %): 357 (32) [M]+, 329 (12), 206
(53), 193 (37), 178 (80), 165 (100), 151 (67), 136 (18).
Found, %: C 70.33; H 4.04; N 11.89. C21H15N3O3. Cal-
culated, %: C 70.59; H 4.20; N 11.76.
REFERENCES
1. Stankyavichyus, A.P., Yanushene, L.N., Terent’ev, P.B.,
and Vitkyavichyus, K.T., Russ. J. Org. Chem., 2006,
vol. 42, p. 1725.
2. Beilsteins Handbuch der organischen Chemie, 1934,
vol. 16, p. 271.
3. Weygand–Hilgetag Organisch-chemische Experimentier-
kunst, Hilgetag, G. and Martini, A., Eds., Leipzig: Johann
Ambrosius Barth, 1964, 3rd ed.
4. Handbook of Tables for Organic Compound Identifica-
tion, Rappoport, Z., Ed., Cleveland: Chemical Rubber
Co, 1967, 3rd ed.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 12 2007