Synthesis of 4(6)-amino-6(4)-halo-2,1,3-benzoxadiazoles

Article abstract of DOI:10.1134/S1070428010050179

By reactions of 4-amino-2,6-dihalonitrosobenzenes with sodium azide and 4,6-dihalo-2,1,3-benzoxadiazoles with amines a group of 2,1,3-benzoxadiazole aminoderivatives was prepared. Pleiades Publishing, Ltd., 2010.

Full text of DOI:10.1134/S1070428010050179

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 5, pp. 693−698. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © L.M. Gornostaev, E.A. Bocharova, L.V. Dolgushina, I.Yu. Bagryanskaya, Yu.V. Gatilov, 2010, published in Zhurnal
Organicheskoi Khimii, 2010, Vol. 46, No. 5, pp. 702−706.
Synthesis of 4(6)-Amino-6(4)-halo-2,1,3-benzoxadiazoles
L. M. Gornostaeva, E.A. Bocharovaa, L.V. Dolgushinaa, I.Yu. Bagryanskayab, and Yu.V. Gatilovb
aAstaf’ev Krasnoyarsk State Pedagogical University, Krasnoyarsk, 660049 Russia
e-mail: gornostaev@kspu.ru
bVorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Division, Russian Academy of Sciences, Russia
Received June 27, 2009
Abstract—By reactions of 4-amino-2,6-dihalonitrosobenzenes with sodium azide and 4,6-dihalo-2,1,3-
benzoxadiazoles with amines a group of 2,1,3-benzoxadiazole aminoderivatives was prepared.
DOI: 10.1134/S1070428010050179
into benzofurazan (IVf) required more severe conditions
(DMSO, NaN3, DMSO, 140°C) presumably due to the
noncoplanar location of the azido and nitroso groups.
2,1,3-Benzoxadiazoles (benzofurazans) exhibit
antibacterial, fungicidal, acaricidal, and immunodepressant
action. The presence of amino groups in the carbocycle
and also the luminescent properties of the benzofurazan
provide a possibility of their application as fluorescent
labels in biochemical research [1, 2].
4-[Alkyl(dialkyl)amino]-6-bromo(chloro)-2,1,3-
benzoxadiazoles VIa–VIf we obtained by the amination
of the corresponding 4,6-dihalo-2,1,3-benzoxadiazoles Va
and Vb.
In this connection we investigated the methods of the
synthesis of 2,1,3-benzoxadiazoles containing in the
carbocycle halogen atoms and an amino group.
In the preparation of 6-amino-4-bromo(chloro)-2,1,3-
benzoxadiazoles we employed 4-amino-2,6-dihalo-
nitrosobenzenes IIa–IIe synthesized from dihalonitroso-
arenes Ia and Ib by analogy or in accordance with the
previously obtained results [3].
Scheme 1.
N
Y
O
N
N
O
R1
R2
X
X
X
X
HN
The precursors of aminofurazans IVa–IVf, the
corresponding azides IIIa–IIIf, were not isolated or
detected by chromatography in considerable quantities.
Evidently the cyclization of nitrosoazidoarenes into
furazans proceeded faster than their formation. It should
also be noted that the formation of aminofurazans IVa–
IVe occurred far easier than the conversion of 2,6-
dichloronitrosobenzene into 4-chlorobenzofurazan (NaN3,
DMSO, 100°C) [4] or of 2,4,6-tribromonitroso-benzene
into 4,6-dibromobenzofurazan (NaN3, DMSO, 160°C) [5].
Apparently the cyclization of nitrosoazides IIIa–IIIe is
facilitated owing to the electron-donor effect of the
substituted amino group on the nitroso group involved into
the intramolecular reaction. Yet the conversion of 2-
bromo-4-morpholino-6-isobutylamino-nitrosobenzene (IIf)
R1
R2
Iа, Ib
IIа_IIf
O
N
N
N
O
X
X
N3
NaN3
DMSO
_N2
N
N
R1
R2
R1
R2
IIIа_IIIf
IVа_IVf
R = Me (a), Et (b), Pr (c), Bu (d), C5H11 (e), C6H13 (f);
Hlg = Br, I.
693

GORNOSTAEV et al.
694
Formerly [6] the product of amination of dichloro-
Scheme 2.
furazan Va with dimethylamine was described as 6-di-
1
methylamino derivative, In this event the H NMR
R1
N
R2
O
N
O
N
spectrum and the other physicochemical characteristics
of the compound should be identical to those of substance
IVe which was not the case. Consequently, the nucleo-
philic attack of amines is directed in substrates Va and
Vb not on the position 6, but on the position 4.
N
N
R1
HN
X
R2
DMSO
X
X
Vа, Vb
VIа_VIb
This statement was confirmed by the XRD analysis
of the structure of 6-bromo-4-morpholino-2,1,3-
benzoxadiazole (VIa). The spatial arrangement of the
molecule of compound VIa according to XRD data is
shown in Fig. 1.
I, X = Cl,Y= H (a); X= Br,Y= F (b); II–IV, X = Br: R1, R2 =
(CH2CH2)2O (a), (CH2)4 (b), (CH2)5 (c), R1 = R2 = Me (d);
X = Cl, R1 = R2 = Me (e); X = i-Bu, R1, R2 = (CH2CH2)2O
(f). V, X = Cl (a), Br (b); VI, X = Br: R1, R2 = (CH2CH2)2O
(a), R1 = R2 = Me (b); R1 = H, R2 = i-Bu (c); X = Cl: R1,
R2 = (CH2CH2)2O (d), R1 = R2 = Me (e); R1 = H, R2 = Et (f).
The analysis of the geometry of the structure, of the
rings conformation and of intermolecular interactions was
performed using PLATON program [7]. The skeleton of
the molecule has a common structure. The benzofurazan
fragment is flat (the mean-square deviation of atoms from
Fig. 1. Spatial arrangement of the molecule of compound VIa according to XRD data.
Fig. 2. Packing of molecules VIa in the crystal along a axis.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 5 2010

SYNTHESIS OF 4(6)-AMINO-6(4)-HALO-2,1,3-BENZOXADIAZOLES
695
Scheme 3.
O
O
O
O
N
O
O
N
N
N
N
N
N
N
NH
HN
N
N
Br
N
N
Br
N
N
O
O
IVa
VIIa
VIa
VIIb
O
O
N
N
HN
O
HN
O
N
IVa, VIa
Vb
N
O
VIIc
°
the plane 0.019 A), the morpholine ring is present in the
chair conformation: O13 and N10 deviate from the plane
of the rest four atoms (the mean-square deviation of
EXPERIMENTAL
1H NMR spectra were registered on a spectrometer
°
Bruker DRX-500 (500 MHz), internal reference TMS.
The reaction progress was monitored and the homogeneity
of compounds obtained was checked by TLC on Silufol
UV-254 plated. Melting points were measured on
these atoms from the plane 0.016 A) in the opposite
directions by 0.63 (1) and 0.62 (1) A respectively. The
°
plane of the morpholine ring is turned with respect to the
plane of the benzofurazan fragment by 35.4 (3)°. The
bond distances are close to the average statistical values
[8] and within 3σ coincide with analogous published data
[9] for 4-nitro-7-(piperidin-1-yl)-2,1,3-benzoxadiazole.
The molecules in the crystal due to weak hydrogen
bonds of the type C–H···O (C1–H1A 0.93, H1A···O13 2.40,
..
a Boetius heating block. The XRD experiment was
carried out on a diffractometer Bruker P4 (MoKα-
radiation, graphite monochromator, 2θ/θ-scanning in the
range 2θ < 55°).
4,6-Dichloro-2,1,3-benzoxadiazole (Va) and 4,6-
dibromo-2,1,3-benzoxadiazole (Vb) were obtained by
procedure [10].
2,6-Dibromo-4-(dimethylamino)nitrosobenzene
(IId). To a solution of 2 g (7 mmol) of 2,6-dibromo-4-
fluoronitrosobenzene in 7 ml of DMF at 0–2°C was added
1 ml (7 mmol) of 33% water solution of dimethylamine.
The mixture was stirred for 15–20 min till precipitate
formed, then it was cooled, the orange precipitate was
filtered off, dried, and recrystallized from ethanol. Yield
1.5 g (69%), mp 170–171°C. 1H NMR spectrum (CDCl3),
δ, ppm: 3.13 s (6H, 2CH3), 6.86 s (2H, Harom). Found, %:
C 31.44; H 2.64; N 9.00. C8H8Br2N2O. Calculated, %:
C 31.16; H 2.59; N 9.09.
°
C1···O13 3.33A, angle CHO 176°) are linked into endless
chains along the b crystallographic axis (Fig. 2).
The order of entering amino groups into the ring of
dihalobenzofurazans V was confirmed by the formation
in the repeated amination of compounds IV and VI under
more severe conditions of 4,6-diamino derivatives VII.
These compounds can be obtained directly from
substances V at the amination with a large excess of
amine.
The structure and composition of compounds obtained
were confirmed by physicochemical methods.
All newly synthesized compounds possess luminescent
properties, and some among them are photoactive and
thus interesting for further investigation.
4-(Dimethylamino)-2,6-dichloronitrosobenzene
(IIe). To a solution of 3.56 g (20 mmol) of 2,6-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 5 2010

GORNOSTAEV et al.
696
dichloronitrosobenzene in 45 ml of DMF was added at
0–2°C 4 ml (27 mmol) of 33% water solution of
dimethylamine. The mixture was stirred for 10 h and then
it was maintained at 0–5°C for 70 h more. The separated
red-brown precipitate was filtered off, dried, and
recrystallized from ethanol. Yield 1.64 g (37%), mp 215–
C 39.62; H 3.24; N 16.75. C8H8BrN3O. Calculated, %:
C 39.67; H 3.30; N 17.35.
6-(Dimethylamino)-4-chloro-2,1,3-benzoxa-
diazole (IVe) was obtained from 0.33 g (1.5 mmol) of
2,6-dichloro-4-(dimethylamino)nitrosobenzene and 0.14 g
(2.1 mmol) of sodium azide in 5 ml of DMSO. The product
was precipitated by adding 3–5 ml of water to the warm
solution. Yield 0.29 g (96%), orange powder, mp 151–
1
217°C. H NMR spectrum (DMSO-d6), δ, ppm: 3.18 s
(6H, 2CH3), 6.90 s (2H, Harom). Found, %: C 43.67;
H 3.66; N 12.35. C8H8Cl2N2O. Calculated, %: C 43.83;
H 3.65; N 12.78.
1
153°C. H NMR spectrum (DMSO-d6), δ, ppm: 3.08 s
(6H, 2CH3), 6.42 d (1H, H5, J 2 Hz), 7.74 d (1H, H7,
J 2 Hz). Found, %: C 48.77; H 4.07; N 21.26.
C8H8ClN3O. Calculated, %: C 48.60; H 4.05; N 21.26.
4-(Isobutylamino)-6-morpholino-2,1,3-benzoxa-
diazole (IVf) was obtained from 0.8 g (2 mmol) of
2-bromo-6-isobutylamino-4-morpholinonitrosobenzene
and 0.7 g (10 mmol) of sodium azide in 10 ml of DMSO.
The reagents were stirred at 140°C for 3 min, then the
temperature was decreased to 100°C, and the mixture
was kept for another 10 min. The product was precipitated
by adding 3–5 ml of water to the warm solution. The
reaction product was isolated by column chromatography
on silica gel (eluent benzene). Yield ~30%, orange powder,
mp 136–137°C. 1H NMR spectrum (DMSO-d6), δ, ppm:
0.95 d (6H, 2CH3, J 7 Hz), 1.97–2.04 m (1H, CH),
3.07 t (2H, CH2), 3.26 t (4H, CH2N), 3.73 t (4H, CH2O),
6.04 d (2H, H5, H7, J 8 Hz), 6.08 C (1H, NH). Found, %:
C 61.00; H 7.09; N 19.97. C14H20N4O2. Calculated, %:
C 60.86; H 7.24; N 20.28.
4-Bromo-6-morpholino-2,1,3-benzoxadiazole
(IVa). To a solution of 0.7 g (2 mmol) of 2,6-dibromo-4-
morpholinonitrosobenzene in 7 ml of DMSO was added
0.16 g (2.5 mmol) of sodium azide, the mixture was stirred
at 60–70°C for 40−60 min. On cooling the yellow
precipitate was filtered off, dried, and recrystallized from
ethanol. Yield 0.51 g (89%), mp 180–182°C. 1H NMR
spectrum (DMSO-d6), δ, ppm: 3.33 br.t (4H, CH2N),
3.72 t (4H, CH2O), 6.81 s (1H, H5), 8.02 s (1H, H7).
Found, %: C 42.12; H 3.50; N 14.80. C10H10BrN3O2.
Calculated, %: C 42.25; H 3.52; N 14.79.
Compounds IVb–IVf were similarly obtained.
4-Bromo-6-pyrrolidino-2,1,3-benzoxadiazole
(IVb) was obtained from 0.53 g (1.6 mmol) of 2,6-
dibromo-4-pyrrolidinonitrosobenzene and 0.16 g
(2.5 mmol) of sodium azide in 7 ml of DMSO. Yield 0.37
1
g (87%), orange powder, mp 190–192°C. H NMR
spectrum (DMSO-d6), δ, ppm: 1.96–1.99 m (4H, 2CH2),
3.42 br.t (4H, CH2N), 6.25 d (1H, H5, J 2 Hz), 7.71 d
(1H, H7, J 2 Hz). Found, %: C 43.73; H 3.53; N 15.50.
C10H10BrN3O. Calculated, %: C 44.77; H 3.73; N 15.67.
4-Bromo-6-piperidino-2,1,3-benzoxadiazole
(IVc) was obtained from 0.7 g (2 mmol) of 2,6-dibromo-
4-piperidinonitrosobenzene and 0.15 g (2.3 mmol) of
sodium azide in 7 ml of DMSO.After keeping the mixture
to the warm solution was added 3–5 ml of water till the
precipitate separated. Yield 0.52 g (92%), orange powder,
6-Bromo-4-morpholino-2,1,3-benzoxadiazole
(VIa). Asolution of 1.4 g (5 mmol) of 4,6-dibromo-2,1,3-
benzoxadiazole and 2.5 ml (29 mmol) of morpholine in
15 ml of DMSO was maintained at 20–25°C over 70 h,
afterwards the mixture was poured in water with ice, the
yellow reaction product was filtered off, dried, and
recrystallized from ethanol. Yield 1.33 g (93%), mp 144–
1
145°C. H NMR spectrum (DMSO-d6), δ, ppm: 3.63 t
(4H, CH2N), 3.80 t (4H, CH2O), 6.59 d (1H, H5, J 2 Hz),
7.67 d (1H, H7, J 2 Hz). Found, %: C 42.44; H 3.56;
N 14.10. C10H10BrN3O2. Calculated, %: C 42.25; H 3.52;
N 14.79.
1
mp 86–87°C. H NMR spectrum (DMSO-d6), δ, ppm:
1.60–1.61 m (6H, 3CH2), 3.36–3.37 m (4H, CH2N),
6.73 d (1H, H5, J 2 Hz), 7.98 d (1H, H7, J 2 Hz). Found,
%: C 46.48; H 4.23; N 14.82. C11H12BrN3O. Calculated,
%: C 46.81; H 4.25; N 14.89.
Compounds VIb–VIf were similarly obtained.
6-Bromo-4-(dimethylamino)-2,1,3-benzoxa-
diazole (VIb) was obtained from 2.8 g (10 mmol) of
4,6-dibromo-2,1,3-benzoxadiazole and 10 ml (67 mmol)
of 33% water solution of dimethylamine in 30 ml of
DMSO. Yield 1.7 g (70%), orange powder, mp 61–62°C.
1H NMR spectrum (DMSO-d6), δ, ppm: 3.32 s (6H,
2CH3), 6.30 d (1H, H5, J 2 Hz), 7.42 d (1H, H7, J 1 Hz).
Found, %: C 40.34; H 3.25; N 17.11. C8H8BrN3O.
4-Bromo-6-(dimethylamino)-2,1,3-benzoxa-
diazole (IVd) was obtained from 0.2 g (6 mmol) of 2,6-
dibromo-4-(dimethylamino)nitrosobenzene and 0.08 g
(1.2 mmol) of sodium azide in 5 ml of DMSO.Yield 0.13 g
1
(89%), orange powder, mp 164–166°C. H NMR
spectrum (CDCl3), δ, ppm: 3.07 s (6H, 2CH3), 6.35 d
(1H, H5, J 2 Hz), 7.47 d (1H, H7, J 2 Hz). Found, %:
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 5 2010

SYNTHESIS OF 4(6)-AMINO-6(4)-HALO-2,1,3-BENZOXADIAZOLES
697
(1H, H5, J 2 Hz), 6.07 d (1H, H7, J 2 Hz). Found, %:
C 61.26; H 6.63; N 20.42. C14H18N4O2. Calculated, %:
C 61.31; H 6.57; N 20.43.
Calculated, %: C 39.67; H 3.31; N 17.35.
6-Bromo-4-isobutylamino-2,1,3-benzoxadiazole
(VIc) was obtained from 1.4 g (5 mmol) of 4,6-dibromo-
2,1,3-benzoxadiazole and 5 ml (50 mmol) of isobutylamine
in 20 ml of DMSO. Yield 0.9 g (67%), yellow powder,
4-Morpholino-6-pyrrolidino-2,1,3-benzoxadi-
azole (VIIb) was similarly obtained from 0.57 g (2 mmol)
of 6-bromo-4-morpholino-2,1,3-benzoxadiazole and 1 ml
(12 mmol) of pyrrolidine in 4 ml of DMSO. Yield 0.44 g
1
mp 82–83°C. H NMR spectrum (DMSO-d6), δ, ppm:
0.95 d (6H, 2CH3, J 6 Hz), 1.98–2.02 m (1H, CH), 3.09–
3.12 m (2H, CH2), 6.24 s (1H, H5), 7,27 s (1H, H7),
7.54 br.t (1H, NH). Found, %: C 45.12; H 4.36; N 15.17.
C10H12BrN3O. Calculated, %: C 44.44; H 4.44; N 15.55.
1
(81%), orange powder, mp 163–165°C. H NMR
spectrum (DMSO-d6), δ, ppm: 1.95–1.98 m (4H, 2CH2),
3.40 t (4H, 2CH2), 3.48 t (4H, CH2N), 3.80 t (4H, CH2O),
5.81 d (1H, H5, J 2 Hz), 6.20 d (1H, H7, J 2 Hz). Found,
%: C 61.02; H 6.54; N 19.99. C14H18N4O2. Calculated,
%: C 61.31; H 6.57; N 20.43.
4-Morpholino-6-chloro-2,1,3-benzoxadiazole
(VId) was obtained from 0.5 g (2 mmol) of 4,6-dichloro-
2,1,3-benzoxadiazole and 3 ml (34 mmol) of morpholine
in 10 ml of DMSO. Yield 0.5 g (80%), yellow powder,
mp 135–137°C. 1H NMR spectrum (DMSO-d6), δ, ppm:
3.63 t (4H, CH2N), 3.81 t (4H, CH2O), 6.50 d (1H, H5,
J 2 Hz), 7.53 d (1H, H7, J 2 Hz). Found, %: C 49.88;
H 4.12; N 17.37. C10H10ClN3O2. Calculated, %: C 50.10;
H 4.17; N 17.53.
4,6-Dimorpholino-2,1,3-benzoxadiazole (VIIc). a.
A solution of 0.56 g (2 mmol) of 4,6-dibromo-2,1,3-
benzoxadiazole and 3.5 ml (40 mmol) of morpholine in
7 ml of DMSO was heated at 80–85°C over 80 h,
afterwards the mixture was poured in water with ice, the
yellow reaction product was filtered off, dried, and
recrystallized from a mixture ethanol–benzene, 2 :1.Yield
4-(Dimethylamino)-6-chloro-2,1,3-benzoxa-
diazole (VIe) was obtained from 0.5 g (2 mmol) of 4,6-
dichloro-2,1,3-benzoxadiazole and 2 ml (13 mmol) 33%
water solution of dimethylamine in 10 ml of DMSO. Yield
0.45 g (86%), orange powder, mp 58–59°C. 1H NMR
spectrum (DMSO-d6), δ, ppm: 3.32 s (6H, 2CH3), 6.10 d
(1H, H5, J 2 Hz), 7.22 d (1H, H7, J 2 Hz). Found, %:
C 48.36; H 3.97; N 21.03. C8H8ClN3O. Calculated, %:
C 48.60; H 4.05; N 21.26.
1
0.24 g (41%), mp 208–210°C. H NMR spectrum
(DMSO-d6), δ, ppm: 3.29, 3.49, 3.74, 3.80 t (16H, 8CH2),
6.34 d (1H, H5, J 2 Hz), 6.44 d (1H, H7, J 2 Hz). Found,
%: C 57.87; H 6.06; N 18.95. C14H18N4O3. Calculated,
%: C 57.93; H 6.21; N 19.31.
b. A solution of 0.1 g (0.35 mmol) of 4-bromo-6-
morpholino-2,1,3-benzoxadiazole (or 6-bromo-4-
morpholino-2,1,3-benzoxadiazole) and 0.5 ml (5 mmol)
of morpholine in 3 ml of DMSO was heated at 100–
110°C over 90 h, afterwards the mixture was poured in
water with ice, the yellow reaction product was filtered
6-Chloro-4-ethylamino-2,1,3-benzoxadiazole
(VIf) was obtained from 1.89 g (10 mmol) of 4,6-dichloro-
2,1,3-benzoxadiazole and 10 ml (132 mmol) of 70%
solution of ethylamine in 25 ml of DMSO. The mixture
was kept for 80 h at 20–25°C, then for 3 h at 60–65°C.
Yield 1.3 g (66%), yellow powder, mp 123–125°C.
1H NMR spectrum (DMSO-d6), δ, ppm: 1.25 t (3H,
CH3), 3.28–3.32 m (2H, CH2), 6.10 br.s (1H, H5), 7.10
br.s (1H, H7), 7.50 br.t (1H, NH). Found, %: C 48.25; H
4.00; N 21.51. C8H8ClN3O. Calculated, %: C 48.60; H
4.05; N 21.26.
1
off, and dried. Yield 0.06 g (63%). H NMR spectrum
and the other characteristics were identical to those of
the substance obtained along procedure a.
XRD investigation. A crystalline sample of
compound VI selected for the experiment was of the
size 0.70 × 0.12 × 0.06 mm. The special feature of all
tested seven crystals of this compound was twinning
leading to a unit cell a 7.45, b 10.47, c 28.25 , α 90,
β 97.58, γ 90°. Hence the XRD expeiment was carried
out on a twinned crystal. Then the reflections were
considered taking the twinning into consideration that led
to the change in the dimensions of the unit cell: crystals
6-Morpholino-4-pyrrolidino-2,1,3-benzoxadi-
azole (VIIa). Asolution of 0.2 g (0.7 mmol) of 4-bromo-
6-morpholino-2,1,3-benzoxadiazole and 1 ml (12 mmol)
of pyrrolidine in 4 ml of DMSO was stirred for 80 h at
85–90°C. To the warm solution was added 3–5 ml of
water till the precipitate separated, the mixture was
cooled, the orange precipitate was filtered off and dried.
Yield 0.12 g (63%), mp 149–151°C. 1H NMR spectrum
(DMSO-d6), δ, ppm: 1.98–2.01 m (4H, 2CH2), 3.27 t (4H,
CH2N), 3.64 t (4H, CH2N), 3.73 t (4H, CH2O), 5.87 d
monoclinic, a 15.077 (5), b 10.472 (4), c 7.453 (2)
,
β 111.76 (3)°, V 1092.9 (7) 3, space group Cc, Z 4,
C10H10BrN3O2, dcalc 1.727 g/cm, μ 3.750 mm–1. Intensity
of 1359 reflections were measured. The corrections for
extinction were introduced by empirical method along Psi-
curves (transmission 0.76–0.94). Reflections hk(4n)
were rejected for they were contributed by both twins.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 5 2010

GORNOSTAEV et al.
698
R.B., US Patent 2005282818, 2005; Chem. Abstr, 2006,
vol. 144, p. 51590.
2. Katritzky, A.R., Comp. Heterocycl. Chem., 1984, p. 6,
p. 425.
3. Gornostaev, L.M., Bocharova, E.A., and Geets, N.V., Zh.
Org. Khim., 2006, vol. 42, p. 1310.
4. Boulton,A.J., Ghosh, P.B., and Katritzky,A.R., Tetrahedron
Lett., 1966, vol. 25, p. 2887.
The structure was solved by the direct method applying
SIR2002 software [11] using 940 independent reflections.
The refinement of the structural parameters was
performed by the mean-squares method in the full-matrix
anisotropic approximation along SHELXL-97 program
[12]. The parameters of hydrogen atoms in every
refinement cycle were calculated from the coordinates
of the corresponding carbon atoms (rider model). The
final refinement of the structure was performed for 940
F2 till wR2 0.1196, S 1.06, 145 parameters were refined
(R 0.0440 for 727 F > 4σ). The coordinates of atoms,
anisotropic thermal parameters of nonhydrogen atoms,
and the crystallographic data are deposited into the
Cambridge Crystallographic Data Center [13], no. CCDC
693643, and they are available under the address
www.ccdc.cam.ac.uk/data_request/cif.
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The study was carried out under a financial support
of the Astaf’ev Krasnoyarsk Pedagogical University
(grant no. 12-09-1/NSh).
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