BOCHAROVA et al.
1642
was carried out in the temperature-controlled block of
the spectrophotometer Evolution 300 at 29°C in DMSO
using quartz cells 1 cm thick at the concentration of
initial compound I 0.5 × 10–4 mol l–1. Morpholine and
p-toluidine were taken in exess at the concentration
10–3 mol l–1. The accumulation of compounds IIa, IIc
was measured at their longwave absorption maxima
431 and 432 nm respectively. The rate constants of
pseudofirst order were calculated by usual method
from the results of two runs for every sample that were
averaged: kapp 115 × 10–4 (IIa), kapp 0.175 × 10–4 s–1 (IIc).
C 54.25; H 4.78; N 11.17.
1-Anilino-3-bromo-5-(N,N-dimethylamino)-2-
nitrosobenzene (IIIc). To a solution of 1 g (3 mmol) of
1,3-dibromo-5-(N,N-dimethylamino)-2-nitrosobenzene
in 10 ml of DMF was added at 25°C 1 ml (11 mmol) of
aniline, the mixture was stirred at 60–70°C for 80–90 min.
To the warm solution water was added dropwise. On
cooling the brown precipitate was filtered off, dried, and
recrystallized from DMF. Yield 0.62 g (60%), mp 171–
172°C. 1H NMR spectrum (CDCl3), δ, ppm: 3.04 s (6H,
2CH3), 5.91 d (1H, H6, J 2 Hz), 6.86 d (1H, H4, J 2 Hz),
7.21 t, 7.36 t (5H, 5CH), 13.51 s (1H, NH). Found, %:
C 52.63; H 4.44; N 13.02. C14H14BrN3O. Calculated, %:
C 52.50; H 4.37; N 13.12.
1,3-Dibromo-5-(4-methylphenyl)-2-nitrosobenzene
(IIc). To a solution of 0.28 g (1 mmol) of reagent I in
5 ml of DMSO was added at 29°C 0.21 g (2 mmol) of
4-methylphenylamine, the mixture was stirred at the
same temperature for 10–15 min. The reaction mixture
was poured into water with ice. The brown precipitate
was filtered off, dried, and recrystallized from ethanol.
Yield 0.37 g (81%), mp 137–139°C. 1H NMR spectrum
(CDCl3), δ, ppm: 2.37 s (3H, CH3), 6.42 s (1H, NH),
7.07 s (2H, H4,6), 7.11 d, 7.24 d (4H, 4CH). Found, %:
C 42.52; H 2.89; N 7.05. C13H10Br2N2O. Calculated, %:
C 42.16; H 2.70; N 7.56.
1,3-Dianilino-5-bromo-4-nitrosobenzene (IIId).
To a solution of 0.28 g (1 mmol) of 1,3-dibromo-5-mor-
pholino-2-nitrosobenzene in 10 ml of DMF was added at
25°C 1 ml (11 mmol) of aniline, the mixture was stirred at
50–60°C for 40–50 min. The separated brown precipitate
was filtered off, dried, and recrystallized from ethanol.
Yield 2.66 g (68%), mp 219–221°C. 1H NMR spectrum
(CDCl3), δ, ppm: 6.27 d (1H, H2, J 2 Hz), 6.41 s (1H,
NH), 6.88 d (1H, H6, J 2 Hz), 7.12–7.36 m (10H, 10CH),
13.49 s (1H, NH). Found, %: C 58.93; H 3.96; N 11.39.
C18H14BrN2O. Calculated, %: C 58.69; H 3.80; N 11.41.
1-Anilino-3-bromo-5-morpholino-2-nitrosoben-
zene (IIIa). To a solution of 1.14 g (3 mmol) of 1,3-di-
bromo-5-morpholino-2-nitrosobenzene in 10 ml of DMF
was added at 20–25°C 1.4 ml (15 mmol) of aniline, the
mixture was stirred at 60–70°C for 80–90 min. To the
warm solution water was added dropwise. On cooling
the brown precipitate was filtered off, dried, and recrys-
tallized from DMF. Yield 1.03 g (88%), mp 197–199°C.
1H NMR spectrum (CDCl3), δ, ppm: 3.33 t (4H, CH2N),
3.74 t (4H, CH2O), 6.05 d (1H, H6, J 2 Hz), 6.92 d (1H,
H4, J 2 Hz), 7.21 t, 7.37 t (5H, 5CH), 13.44 s (1H, NH).
Found, %: C 53.31; H 4.39; N 11.79. C16H16BrN3O2.
Calculated, %: C 53.03; H 4.41; N 11.60.
3,5-Dibromo-4-nitrosophenol (IVd). Into 150 ml of
92% sulfuric acid was added by small portions at 0–5°C
6 g (21 mmol) of 1,3-dibromo-5-DMF-2-nitrosobenzene.
The stirring was continued at the same temperature for 72
h. The solution was poured into water with ice, the yellow-
brown precipitate was filtered off, washed with water,
dried, and recrystallized from a mixture toluene–dioxane,
5 : 1. Yield 5.8 g (97%), mp 136–138°C. UV spectrum,
λmax, (ε): 782 (28). Found, %: C 26.38; H 1.08; N 4.84.
C6H3Br2NO2. Calculated, %: C 25.62; H 1.06; N 4.98.
3-Morpholino-4-nitrosophenol (Va). To a solution
of 2 ml (22 mmol) of morpholine in 15 ml of water was
added at 25°C 1 g (5 mmol) of 3-bromo-4-nitrosophenol,
and the mixture was stirred at 30°C for 8 h. The pre-
cipitate was separated by adding to the reaction mixture
18% hydrochloric acid till pH 6.The dark red precipitate
was filtered off, dried, and recrystallized from ethanol.
Yield 0.85 g (82%), mp 147–149°C. 1H NMR spectrum
(CDCl3), δ, ppm: 3.31 t (4H, CH2N), 3.77 t (4H, CH2O),
5.64 d (1H, H2, J 2 Hz), 6.24 d.d (1H, H6, J 8, 2 Hz),
7.61 d (1H, H5, J 10 Hz), 11.48 s (1H, OH). Found, %:
C 57.37; H 5.77; N 13.45. C10H12N2O3. Calculated, %:
C 57.69; H 5.77; N 13.46.
1-Bromo-3-(4-methylphenyl)-5-morpholino-2-
nitrosobenzene (IIIb). To a solution of 0.5 g (1.4 mmol)
of 1,3-dibromo-5-morpholino-2-nitrosobenzene in 5
ml of DMF was added at 20–25°C 0.8 g (7.5 mmol) of
4-methylaniline, the mixture was stirred at 60–70°C for
80–90 min. To the warm solution water was added drop-
wise. On cooling the brown precipitate was filtered off,
dried, and recrystallized from DMF. Yield 0.5 g (92%),
1
mp 205–207°C. H NMR spectrum (CDCl3), δ, ppm:
2.34 s (3H, CH3), 3.33 t (4H, CH2N), 3.74 t (4H, CH2O),
6.02 d (1H, H4, J 2 Hz), 6.92 d (1H, H6, J 2 Hz), 7.08 d,
7.17 d (4H, 4CH, J 8 Hz), 13.42 s (1H, NH). Found, %:
C 54.24; H 5.12; N 11.16. C17H18BrN3O2. Calculated, %:
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 11 2010