INVESTIGATION OF THE REACTION BETWEEN SODIUM HYDROXIDE
987
δ, ppm: 11.26 s (1H, OH), 7.47–7.21 m (9HAr), 3.54 t
(2H, CH2N, J 6.9 Hz), 2.07 t (2H, CH2CO, J 7.9 Hz),
1.77 q (2H, CH2CH2CH2, J 7.5 Hz). Mass spectrum,
m/z (Irel, %): 280 (3.5) [M]+, 264 (18.9), 263 (100), 249
(8.7), 246 (6.1), 235 (5.6). Found, %: C 72.80; H 5.63;
N 9.89. C17H16N2O2. Calculated, %: C 72.84; H 5.75;
N 9.99.
4.18 t (2H, CH2, J 6.7 Hz), 3.22 t (2H, CH2, J 2.8 Hz),
2.89 t (2H, CH2, J 6.4 Hz), 2.64 q (2H, CH2, J 6.9 Hz),
2.46 q (2H, CH2, J 6.9 Hz). Mass spectrum, m/z (Irel, %):
500 (7.4) [M]+, 396 (22.1), 394 (15.8), 343 (8.8), 341
(8.6), 301 (6.6), 275 (41.3), 274 (88.2), 273 (47.4), 272
(78.8), 105 (75.7). Found, %: C 50.35; H 4.32; N 5.35.
C21H21BrCl2N2O3. Calculated, %: C 50.42; H 4.23;
N 5.60.
1-{2-[(E)-(Hydroxyimino)(phenyl)methyl]-4-
methylphenyl}pyrrolidin-2-one (IVa) was obtained by
treating with NaOH compound IIa. Yield 57%, mp 230–
235°C. IR spectrum, ν, cm–1: 1600 (C=N), 1680 (C=O),
3550 (O–H). UV spectrum, λmax, nm (log ε): 223 (4.25).
1H NMR spectrum, δ, ppm: 11.17 s (1H, OH), 7.33–
7.06 m (8HAr), 3.27 t (2H, CH2N, J 6.9 Hz), 2.35 s (3H,
CH3), 1.95 t (2H, CH2CO, J 7.9 Hz), 1.51 q (2H,
CH2CH2CH2, J 7.4 Hz). Mass spectrum, m/z (Irel, %):
294 (1.8) [M]+, 278 (19.6), 277 (100.0), 249 (5.6), 235
(6.3), 221 (7.8), 209 (3.5). Found, %: C 73.43; H 6.10;
N 9.48. C18H18N2O2. Calculated, %: C 73.45; H 6.16;
N 9.52.
The mother liquor was passed through a column
packed with silica gel using benzene as eluent. Yield of
compound Vb 1.33 g (31%), mp 85–90°C. IR spectrum,
ν, cm–1: 1595 (C=N), 1680 (C=Oamide), 1755 (C=Oester),
3245 (N–H). UV spectrum, λmax, nm (log ε): 243 (4.56),
325 (3.75). 1H NMR spectrum, δ, ppm: 10.80 s (1H,
NH), 8.05–8.46 m (8HAr), 4.33 t (2H, CH2, J 5.6 Hz),
4.24 t (2H, CH2, J 6.5 Hz), 3.27 t (2H, CH2, J 7.3 Hz),
2.90 t (2H, CH2, J 7.2 Hz), 2.67 q (2H, CH2, J 6.2 Hz),
2.52 q (2H, CH2, J 5.9 Hz). Mass spectrum, m/z (Irel, %):
500 (10.9) [M]+, 396 (25.4), 394 (18.9), 343 (4.6), 341
(6.2), 301 (4.1), 275 (41.4), 274 (96.5), 273 (52.0), 272
(85.6), 105 (77.6). Found, %: C 50.25; H 4.40; N 5.45.
C21H21BrClN2O32. Calculated, %: C 50.42; H 4.23;
N 5.60.
1-{4-Bromo-2-[(E)-(hydroxyimino)(phenyl)-
methyl]phenyl}pyrrolidin-2-one (IVb) was obtained by
treating with NaOH compound IIb. Yield 70%, mp 216–
220°C. IR spectrum, ν, cm–1: 1575 (C=N), 1685 (C=O),
3545 (O–H). UV spectrum, λmax., nm (log ε): 240 (4.24).
1H NMR spectrum, δ, ppm: 11.54 s (1H, OH), 7.68–
7.23 m (8HAr), 3.25 t (2H, CH2N, J 6.5 Hz), 1.94 t (2H,
CH2CO, J 7.9 Hz), 1.41 q (2H, CH2CH2CH2, J 7.3 Hz).
Mass spectrum, m/z (Irel, %): 360 (0.5) [M]+, 344 (15.2),
343 (99.6), 342 (15.6), 341 (100), 275 (11.3), 273 (11.8).
Found, %: C 56.79; H 4.19; N 7.82. C17H15BrN2O2.
Calculated, %: C 56.84; H 4.21; N 7.80.
Oximes of 5-substituted 2-aminobenzophenones were
obtained previously [5].
REFERENCES
1. Kulikov, O.V., Pavlovskii, V.I., andAndronati, S.A., Khim.
Geterotsikl. Soedin., 2005, p. 1763.
2. Kulikov, O.V., Andronati, S.A., Pavlovskii, V.I., Maze-
pa, O.V., and Kabanova, T.A., Vestn. ONU, Ser. Khim.,
2000, vol. 5, p. 68.
(E)- and (Z)-N-{4-Bromo-2-[(phenyl)(4-chloro-
butyryloxyimino)methyl]phenyl}-4-chlorobutan-
amides (Vb, VI). To a solution of 5 g (17.2 mmol) of
syn-5-bromo-2-aminobenzophenone oxime in 30 ml of
dioxane was added dropwise at stirring a solution of
4.1 ml (36.1 mmol) 4-chlorobutyryl chloride. After
stirring for 3 h the reaction mixture was poured into water,
the separated precipitate was filtered off, washed with
water on the filter, dried, and recrystallized from benzene.
Yield of compound VI 1.93 g (45%), mp 125–126°C. IR
spectrum, ν, cm–1: 1585 (C=N), 1675 (C=Oamide), 1745
(C=Oester), 3400 (N–H). UV spectrum, λmax, nm (log å):
249 (4.44). 1H NMR spectrum, δ, ppm: 10.34 s (1H,
NH), 8.09–8.41 m (8HAr), 4.31 t (2H, CH2, J 6.7 Hz),
3. Andronati, S.A., Simonov, Yu.A., Pavlovskii, V.I., Kuli-
kov, O.V., Gdanets, M., and Mazepa, A.V., Zh. Obshch.
Khim., 2005, vol. 75, p. 969.
4. Kulikov, O.V. and Mazepa, A.V., Khim. Geterotsikl.
Soedin., 2007, p. 1043.
5. Pavlovskii, V.I., Kulikov, O.V., Karaseva, T.L., Kabano-
va, T.A., Mazepa, A.V., and Andronati, S.A., Ukr. Khim.
Zh., 1998, vol. 64, p. 123.
6. SHELXTL, ver.1, Madison: Bruker AXS Inc., 1998.
7. Sheldrick, G.M., SHELXS-97. Program for the Solution of
..
Crystal Structures, Univ. Gottingen, Germany, 1997.
8. Sheldrick, G.M., SHELXL-97. Program for the Refinement
..
of Crystal Structures, Univ. Gottingen, Germany, 1997.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 7 2008