Amination of 3,5-dibromo-4-nitrosoanilines and 3-halo-4-nitrosophenols

Article abstract of DOI:10.1134/S1070428010110047

Reactions of 3,5-dibromo-4-nitrosoanilines with arylamines and 3-halo-4-nitroso-phenols with alkyl- and arylamines result in the nucleophilic substitution of the halogen atoms. Pleiades Publishing, Ltd., 2010.

Full text of DOI:10.1134/S1070428010110047

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 11, pp. 1639−1644. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © E.A. Bocharova, L.M. Gornostaev, N.P. Gritsan, T.N. Gurova, 2010, published in Zhurnal Organicheskoi Khimii, 2010, Vol. 46, No. 11,
pp. 1634−1638.
Amination of 3,5-Dibromo-4-nitrosoanilines
and 3-Halo-4-nitrosophenols
E. A. Bocharovaa, L. M. Gornostaeva, N. P. Gritsanb, and T. N. Gurovaa
aAstaf’ev Krasnoyarsk State Pedagogical University, Krasnoyarsk, 660049 Russia
e-mail: gornostaev@kspu.ru
bInstitute of Chemical Kinetics and Burning, Siberian Division, Russian Academy of Sciences, Novosibirsk, Russia
Received June 27, 2009
Abstract—Reactions of 3,5-dibromo-4-nitrosoanilines with arylamines and 3-halo-4-nitroso-phenols with alkyl-
and arylamines result in the nucleophilic substitution of the halogen atoms.
DOI: 10.1134/S1070428010110047
We showed formerly [1] that in reactions of 2,6-di-
halonitrosoarenes with secondary amines the nitroso
group remained intact but a halogen and (or) hydrogen
atom in the para-position to the nitroso group suffered
a nucleophilic substitution with an amino group.
The initial 3,5-dibromo-4-nitrosoanilines IIa–IIc
prepared from 1,3-dibromo-2-nitroso-5-fluorobenzene
(I) by procedure [1] were brought into the reaction with
arylamines leading to the nucleophilic substitution of one
of the bromine atoms. We obtained by this reaction previ-
ously unknown 2-nitroso derivatives of the substituted
diphenylamine IIIa–IIIc. The alternative way involving
the condensation with the formation of azo compounds
did not occur (Scheme 1).
In this connection it seemed purposeful to study the
reactions with various amines of aromatic C-nitroso
compounds containing in the aromatic ring alongside the
nitroso group also amino, hydroxy groups and halogen
atoms. The nucleophilic substitution of halogens would
provide a possibility to synthesize compounds inavail-
able in another way.
In general compounds II proved to be less active
than compound I. Also by an example of the reaction
of compound I with morpholine and p-toluidine the
higher reactivity of morpholine in fluorine substitution
was established that was also confirmed by kinetic data:
the rate constant of reaction with morpholine equaled
In this study we investigated the reactions of 3,5-di-
bromo-4-nitrosoanilines with primary aromatic amines,
and also the amination of 3-halo-4-nitrosophenols.
Scheme 1.
N
O
H
Br
N
X
N
N
N
O
O
N
Br
Br
Br
Br
R1
R2
H2N
DMF
X
R1R2NH
IIIa_IIIc
Br
R1
F
R1
R2
N
N N
Br
X
I
IIa_IIc
R2
II, R1,R2 = (CH2CH2)2O (a); R1 = R2 = Me (b); R1 = H, R2 = C6H4=4-Me (c); III, R1,R2 = (CH2CH2)2O, X = H (a), Me
(b); R1 = R2 = Me, X = H (c).
1639

BOCHAROVA et al.
1640
11.5 l mol–1s–1, and with p-toluidine, 0.0175 mol–1s–1.
concentrations (5 × 10–4 mol–1l–1) of 4-chloro- and
4-bromonitrosobenzenes, for in the preparative concen-
trations the para-substituted nitrosobenzenes underwent
in the sulfuric acid the cyclization into the corresponding
2,6-disubstituted phenazine N-oxides [6]. Evidently the
bromine atoms in compound I are screening the nitroso
group impeding the like cyclization.
1,3-Dibromo2-nitroso-5-fluorobenzene (I) under the
treatment with excess aniline at 50–60°C suffered nucleo-
philic substitution of both fluorine and bromine atoms.
N
O
N
O
H
Br
N Ph
Br
Br
PhNH2
The amination of halonitrosophenols IVa–IVc in wa-
ter or aqueous ethanol at 25–30°C with aliphatic, aromatic
and alicyclic amines proceeded through the nucleophilic
substitution of halogen, and the reactions involving the
nitroso, hydroxy, carbonyl, and oxime groups character-
istic of nitrosophenols (quinone oximes), did not occur
(Scheme 2).
HN Ph
F
IIId
I
This reaction path followed by 1,3-dibromo-2-nitroso-
5-fluorobenzene (I) and 3,5-dibromo-4-nitroso-anilines
II with amines stimulated the interest in the study of the
amination of 3-halo-4-nitrosophenols.
The structure and composition of compounds obtained
were confirmed by physicochemical methods. The analy-
sis of the electron absorption sprctra of compounds V
shows that only compounds Vg–Vi with the absorption
at 670–675 nm exist in the tautomeric nitroso form. In
compounds Va–Vf the quinone oxime form prevails.
Nitrosophenols IVa–IVc were obtained by nitrosation
of the corresponding halophenols with nitrosylsulfuric
acid in the acetic acid medium [3], 2,6-dibromo-4-
nitrosophenol (IVe) was prepared by bromination of
p-nitrosophenol [4], 3,5-dibromo-4-nitrosophenol (IVd)
formed from reagent I as a result of keeping in sulfuric
acid.
It is characteristic that in the amination of 2,5-dichlo-
ro-4-nitrosophenol (IVc) only one chlorine atom is sub-
stituted located in the ortho-position to the nitroso group.
The substitution of just this chlorine atom is confirmed by
the fact that the isomer of compound IVd, 2,6-dibromo-
4-nitrosophenol (IVe) does not react with amines under
mild conditions, and in more severe conditions (DMF,
90–100°C) formed a mixture of substances.
N
O
N
O
Br
Br
Br
Br
92%H2SO4
F
In order to understand the reactivity of compounds
obtained and, in particular, the difference in the chemistry
of isomeric halonitrosoarenes IVd and IVe, we performed
the quantum-chemical calculations of the properties of
these compounds by the density functional theory in the
version of the hybrid method B3LYP/6-31G(d) [7] apply-
ing the program GAUSSIAN03 [8]. The influence of the
solvent (water) was taken into account by the polarized
continuum model (PCM) [9] in the version included into
the program GAUSSIAN03.
OH
I
N OH
Br
Br
O
IVc
Formerly [5] the halogen substitution by water in
the concn. H2SO4 was observed only in the spectral
The nitrosophenols are known to exist in a tautomeric
Scheme 2.
R1
R2
N OH
N
O
N
N OH
R1
R2
O
R1
R2
HN
Y
Z
X
Y
Z
X
Y
Z
N
Y
Z
N
IVа_IVd
O
OH
Vа_Vi
OH
OH
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 11 2010

AMINATION OF 3,5-DIBROMO-4-NITROSOANILINES AND 3-HALO-4-NITROSOPHENOLS
1641
_
_
0.23
equilibrium with the quinone oximes. The position of the
tautomeric equilibrium depends both on the structure of
the nitrosophenol and on the solvent [10]. The introduc-
tion of substituents can affect the tautomeric equilibrium
position. In turn, the reactivity of the nitrosophenols and
quinone oxime toward nucleophiles is different. Therefore
we first estimated the thermodynamics of the tautomerism
of compounds IVd and IVe.
0.05
OH
N
N
O
Br
Br
Br
Br
0.07
0.09
0.07
0.09
_
_
_
_
0.22
0.21
0.21
0.22
OH
N
O
N
IVd
_
_
0.05
0.23
OH
_
O
_
_
_
The calculations show that in water solutions of com-
pounds IVa–IVd the nitroso form prevails. For instance,
in compound IVd the free energy (ΔG) of the nitroso
form is lower by 1.5 kcal mol–1. In turn, for isomer IVe
in water the quinone oxime form is significantly lower by
the energy (ΔG –3.9 kcal mol–1).Actually, the calculation
results are confirmed by the electron absorption spectra.
In the electronic spectra of solutions in dioxane of com-
pounds IVa–IVd the characteristic for the nitroso form
absorption bands n –>π* were registered at 750–780 nm.
This band is absent from the spectrum of compound IVe.
0.15
0.15
0.007
0.15
0.15
0.03
0.03
0.007
Br
Br
Br
Br
OH
O
IVe
Charges on atoms in the nitrosophenol and quinine oxime
forms of compounds IVd and IVe calculated by the method
B3LYP/6-31G(d).
reactions with nucleophiles.
Similar conclusions follow from the analysis of
the boundary electron density. The contribution of the
pz-orbitals localized on the carbon atoms linked to the
bromine atoms into the lowest unoccupied molecular
orbital (LUMO) is considerably higher in the nitroso and
quinine oxime forms of IVd than in the quinine oxime
form IVe. The contribution of these orbitals into LUMO
of nitroso form IVe is negligible.
It is possible to understand the direction of the nu-
cleophilic substitution in compounds IVa–IVd and the
essentially different properties of halonitrosoarene IVe
(isomeric to IVd) analyzing the distribution of the charge
and boundary electron density in these compounds [11].
All simple correlations with various reactivity indices
are underlain by the “non-intersection rule” [11]. It is
assumed that for similar compounds the energy ratio in
tentative points on the reaction coordinate, also in the
initial stage of the reaction, equals the ratio of the reac-
tion barriers. At the same time it is possible to use the
perturbation theory in the initial stage of the reaction.
Under the conditions of the validity of the perturbation
theory the energy of the interaction may be represented
as a sum of several contributions, one of which is the
Coulomb interaction of the positively charged atom of
the reaction center of the electrophile and of the negative,
of the nucleophile.
Thus the experimental data obtained in this study are
easily understood by the use of simple concepts of the
indices of reactivity.
EXPERIMENTAL
1H NMR spectra were registered on a spectrometer
Bruker DRX-500 (500 MHz), internal reference TMS.
The monitoring of the reaction progress and checking of
the homogeneity of compounds obtained was performed
by TLC on Silufol UV-254 plates. The melting points
were measured on a Boёtius heating microblock. The
electron absorption spectra in the range 550–800 nm
were recorded on a spectrophotometer Evolution 300 in
dioxane, measured layer thickness 1 cm, concentration
1 × 10–2 mol l–1. The thermogram of compound Vd was
obtained on an instrument NETZSCH STA 409 PC/P.
As seen from the figure, in both tautomers of
3,5-dibromo-4-nitrosophenol (IVd) a negative charge is
observed on the nitrogen atom and a considerable posi-
tive charge on the carbon atoms (0.07 and 0.09) linked
to bromine atoms. The substitution reaction occurs just
at these carbon atoms.
In 2,6-dibromo-4-nitrosophenol (IVe) the positive
charge on the carbon atoms linked to bromine atoms is
essentially decreased in the nitroso form and virtually
zero in the quinine oxime form that prevails in the water
solution. Therefore compound IVe is less active in the
Nitrosophenols IVa–IVc, IVe were synthesized by
known procedures [3, 4].
The spetrophotometric investigation of the kinetics
of formation of 3,5-dibromo-4-nitrosoanilines IIa, IIc
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 11 2010

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

AMINATION OF 3,5-DIBROMO-4-NITROSOANILINES AND 3-HALO-4-NITROSOPHENOLS
1643
Compounds Vb–Vi were obtained similarly.
3-Bromo-5-morpholino-4-nitrosophenol (Vf) was
obtained from 2 ml (22 mmol) of morpholine in 15 ml of
water and 1 g (3.5 mmol) of 3,5-dibromo-4-nitrosophenol
at 30°C over 4 h. Yield 1 g (98%), red crystals, mp 165–
167°C (EtOH). 1H NMR spectrum (DMSO-d6), δ, ppm:
3.62 t (4H, CH2N), 3.77 m (4H, CH2O), 5.61 s (1H, H6),
7.73 br.s (1H, H2), 12.00–14.00 br.s (1H, OH). Found, %:
C 42.08; H 3.72; N 9.62. C10H11BrN2O3. Calculated, %:
C 41.81; H 3.83; N 9.75.
4-Nitroso-3-piperidinophenol (Vb) was obtained
from 1 ml (10 mmol) of piperidine in 4 ml of water and
0.31 g (2 mmol) of 4-nitroso-3-chlorophenol at 25°C
over 9 h. Yield 0.17 g (41%), red crystals, mp 161–163°C
1
(EtOH–H2O). H NMR spectrum (DMSO-d6), δ, ppm:
1.59 s (6H, 3CH2), 3.32 br.s (14H, 2CH2), 5.56 s (1H,
H2), 6.15 d.d (1H, H6, J 10, 2 Hz), 7.53 br.s (1H, H5),
13,10 s (1H, OH). Found, %: C 64.20; H 6.72; N 13.66.
C11H14N2O2. Calculated, %: C 64.07; H 6.79; N 13.59.
3-Benzylamino-5-bromo-4-nitrosophenol (Vg)
was obtained from 0.4 ml (3 mmol) of benzylamine in
4 ml of water and 0.2 g (0.7 mmol) of 3,5-dibromo-4-
nitrosophenol at 50°C over 8 h. Yield 0.13 g (60%), red
4-Nitroso-3-(4-phenylpiperazin-1-yl)phenol (Vc)
was obtained from 1.62 ml (10 mmol) of 4-phenyl-
piperazine in 5 ml of water and 0.31 g (2 mmol) of
4-nitroso-3-chlorophenol at 25°C over 6 h. The precipitate
was separated by adding to the reaction mixture 18%
hydrochloric acid till pH 6. The brown precipitate was
filtered off, dried, and recrystallized from ethanol. Yield
0.54 g (98%), brown crystals, mp 184–186°C (EtOH).
1H NMR spectrum (DMSO-d6), δ, ppm: 3.27 br.t, 3.50 br.t
(8H, 4CH2), 5.65 s (1H, H2), 6.19 d (1H, H6, J 10 Hz),
7.56 d (1H, H5, J 8 Hz), 6.80 t, 6.95 d (8 Hz), 7.23 t (5H,
5CH), 12.00–14.00 br.s (1H, OH). Found, %: C 66.45;
H 5.92; N 14.28. C16H17N3O2. Calculated, %: C 67.84;
H 6.01; N 14.84.
1
crystals, mp 178–180°C (EtOH). H NMR spectrum
(DMSO-d6), δ, ppm: 4.45 d (2H, CH2, J 2 Hz), 5.95 s (1H,
H2), 6.80 s (1H, H6), 7.29 d (J 6 Hz), 7.36 t (5H, 5CH),
10.00–13.00 br.s (1H, NH, 1H, OH). Found, %: C 50.53;
H 3.60; N 8.37. C13H11BrN2O2. Calculated, %: C 50.81;
H 3.58; N 9.12.
3-Bromo-4-nitroso-5-(4-toluidino)phenol (Vh)
was obtained from 0.52 g (5 mmol) of p-toluidine in 7
ml of aqueous ethanol (1:1) and 0.46 g (1.6 mmol) of
3,5-dibromo-4-nitrosophenol at 25°C over 2 h. Yield
1
0.44 g (88%), red crystals, mp 207–209°C (EtOH). H
NMR spectrum (DMSO-d6), δ, ppm: 2.33 s (3H, CH3),
6.14 s (1H, H6), 6.88 d (1H, H2, J 2 Hz), 7.20 d, 7.27 d
(4H, 4CH, J 8 Hz), 12.00–13.00 br.s (1H, NH, 1H, OH).
4-Nitroso-3-(pyrrolidin-1-yl)phenol (Vd) was ob-
tained from 1 ml (12 mmol) of pyrrolidine in 10 ml of
water and 1 g (5 mmol) of 3-bromo-4-nitrosophenol at
25°C over 7 h. Yield 0.43 g (45%), red crystals, mp 205–
207°C (EtOH). 1H NMR spectrum (DMSO-d6), δ, ppm:
1.90 br.s, 3.50 br.s (8H, 4CH2), 5.24 s (1H, H2), 6.13 d
(1H, H6, J 10 Hz), 7.47 br.s (1H, H5), 12.00–13.00 br.s
(1H, OH). Compound Vd was obtained as a crystal
hydrate (C10H12N2O2·H2O) as proved by the elemental
analysis. Found, %: C 57.05; H 6.74; N 13.17. The ther-
mogram of the substance showed that at 87°C the mass
loss was 8.5% corresponding to the elimination of one
water molecule.After heating the sample to 100°C the el-
emental analysis data correspond to the dehydrated form.
Found, %: C 61.69; H 6.22; N 14.31. C10H12N2O2·H2O.
Calculated, %: C 57.14; H 6.67; N 13.33.
Found, %: C 50.79; H 3.75; N 9.50. C13
Calculated, %: C 50.81; H 3.58; N 9.12.
H11BrN2O2.
3-Bromo-5-isobutylamino-4-nitrosophenol (Vi) was
obtained from 0.45 ml (4.5 mmol) of isobutylamine in
18 ml of water and 0.5 g (1.75 mmol) of 3,5-dibromo-
4-nitrosophenol at 35°C over 4.5 h. Yield 0.22 g (46%),
1
orange crystals, mp 158–160°C. H NMR spectrum
(DMSO-d6), δ, ppm: 0.93 t (6H, 2CH3), 1.86–1.89 m
(1H, CH), 3.05 t (2H, CH2), 6.07 br.s (1H, H6), 6.81 br.s
(1H, H2), 10.00–13.00 br.s (1H, OH, 1H, NH). Found,
%: C 44.04; H 4.77; N 10.55. C10H14BrN2O2. Calculated,
%: C 43.79; H 5.11; N 10.21.
4-Nitroso-5-(pyrrolidin-1-yl)-2-chlorophenol
(Ve) was obtained from 0.5 ml (6 mmol) of pyrrolidine
in 6 ml of water and 0.5 g (2 mmol) of 4-nitroso-2,5-
dichlorophenol at 25°C over 2.5 h. Yield 0.45 g (78%)
red crystals, mp 208–210°C (EtOH). 1H NMR spectrum
(DMSO-d6), δ, ppm: 1.90 m, 3.46 m (8H, 4CH2), 5.38 s
(1H, H6), 7.67 s (1H, H3), 13.50 s (1H, OH). Found, %:
C 52.61; H 5.42; N 11.16. C10H11ClN2O2. Calculated, %:
C 52.98; H 4.85; N 12.36.
ACKNOWLEDGMENTS
The study was carried out under a financial support
of Astaf’ev Krasnoyarsk State Pedagogical University
(grant 12-09-1/NSh).
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