Reaction of tetracyanocyclopropyl ketones with hydrazine hydrate

Article abstract of DOI:10.1134/S1070428011050113

The reaction of 2,2,3,3-tetracyanocyclopropyl ketones with hydrazine involved the addition at the carbonyl and cyano groups and resulted in the formation of previously unknown polycyclic systems whose common feature was the presence in the structure of a

Full text of DOI:10.1134/S1070428011050113

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 5, pp. 722−727. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © Ya.S. Kayukov, I.N. Bardasov, O.V. Kayukova, O.V. Ershov, O.E. Nasakin, A.V. Eremkin, V.A. Tafeenko, 2011, published in Zhurnal
Organicheskoi Khimii, 2011, Vol. 47, No. 5, pp. 717−722.
Reaction of Tetracyanocyclopropyl Ketones
with Hydrazine Hydrate
Ya. S. Kayukova, I. N. Bardasova, O. V. Kayukovaa, O. V. Ershova,
O. E. Nasakina, A. V. Eremkina, and V. A. Tafeenkob
aI.N. Ul’yanov Chuvash State University, Cheboksary, 428015 Russia
e-mail: kaukovyakov@mail.ru
bLomonosov Moscow State University, Moscow, Russia
Received July 3, 2010
Abstract—The reaction of 2,2,3,3-tetracyanocyclopropyl ketones with hydrazine involved the addition at the
carbonyl and cyano groups and resulted in the formation of previously unknown polycyclic systems whose common
feature was the presence in the structure of a pyridazine ring. In the general case 3-substituted 6-amino-8-oxo-4,5,7-
tрtriazatricyclo[4.3.0.02.9]-non-3-ene-1,9-dicarbonitriles were obtained. The reaction with 3-pivaloylcyclopropane-
1,1,2,2-tetracarbonitrile took another route with the opening of the three-membered ring and the formation of
3-amino-7a-tert-butyl-6-oxo-5,6,7,7a-tetrahydro-4aH-pyrrolo[2,3-c]pyridazine-4,5-dicarbonitrile.
DOI: 10.1134/S1070428011050113
The most important methods of heterocycles prepara-
tion containing nitrogen–nitrogen bonds are founded on
the reactions of hydrazine with bielectrophilic reagents
(1,3- for the synthesis of pyrazole derivatives and 1,4-
for pyridazine) [1–3]. The promising for these syntheses
bielectrophilic substances are 2,2,3,3-tetracyanocyclopro-
pyl ketones [4, 5] containing five electron-withdrawing
groups of various types. These compounds are highly
reactive toward nucleophiles [6–8] and can be brought
into reactions both like 1,3-bielectrophiles involving
the geminal groups and like 1,4-bielectrophiles involv-
ing the vicinal groups. Bringing them into the reaction
with hydrazine may open the way to preparation of new
nitrogen polyfunctional heterocyclic systems as prove
the publications on the hydrazine reaction with tet-
raacetylcyclopropane [9] and on phenylhydrazine with
tetracyanocyclopropanes [10]. In both cases the nucleo-
philic attack is directed on the geminal substituents in
the cyclopropane ring followed by its recyclization into
pyrazole derivatives.
transformations were discovered. The main pathway
characteristic of aryl, heteryl, and alkyl derivatives led
to the formation of 3-substituted 6-amino-8-oxo-4,5,7-
triazatricyclo[4.3.0.02.9]non-3-ene-1,9-dicarbonitriles
IIа–IIg (Scheme 1). Into the reaction a carbonyl and two
cyano groups are involved retaining the three-membered
Scheme 1.
H
NH2
N
N
NH
R
O
O
CN
CN
CN
H
R
NH2NH2 H2O
CN
IIа_IIg
CH3
CN
CN
Iа_Ih
H
N
NH2
CN
H3C
H3C
N
HN
H
H
CN
O
III
Here the results are reported on the investigation of
the reaction of tetracyanocyclopropyl ketones Iа–Ih
with hydrazine hydrate. Two possible directions of
R = Ph (a), 4-BrС6Н4 (b), 4-MeOС6Н4 (c), 3,4-(MeO)2С6Н3
(d), 3-NO2С6Н4 (e), thien-2-yl (f), Me (g), (СH3)3C (h).
722

REACTION OF TETRACYANOCYCLOPROPYL KETONES
723
ring intact. The alternative reaction pathway was observed
N
NH
CN
NH2
for tert-butyl cyclopropyl ketone Ih: The three-membered
ring suffered opening, and the process resulted in the
formation of diastereomers of 3-amino-7a-tert-butyl-6-
oxo-5,6,7,7a-tetrahydro-4aH-pyrrolo[2,3-c]pyridazine-
4,5-dicarbonitrile (III).
NH
H
The data of mass spectra and elemental analysis of
compounds IIа–IIg show that in the course of the reac-
tion one hydrazine molecule has added. The peaks of
molecular ions in the mass spectra are of low intensity.
The fragmentation proceeds similarly with the splitting
of cations [NH=C=O]+, m/z 43, and (or) [NH2=C=O]+,
m/z 44, having the strongest peaks, and also with the
elimination of the nitrogen molecule, therefore in the
mass spectra of all compounds IIа–IIg a moderately in-
tense peak is present [M – 71]+. According to the 1H and
13С spectra of compounds IIа–IIg the cyclopropane ring
is not affected by the reaction. It is proved by the signal
of the protons of the cyclopropane ring (4.0–4.5 ppm) in
the 1H NMR spectra and of signals of the carbon atoms
of the three-membered ring (27.84–29.29 ppm) in the
13С NMR spectra. Besides in the 1H NMR spectra a sig-
nal present at 3.47–3.50 ppm belongs to the protons of
a nonconjugated amino group. The assumed assignment
of the signals in the 13С NMR spectra of compounds IIa
and IIc is presented in the table [11].
CN
O
Fig. 1. Correlations of the cyclopropane proton with carbon
atoms according to the НMВС NMR spectrum of compound IIa.
N
NH
NH2
NH
H
CN
CN
O
Fig. 2. Correlation of NH and ortho-protons of phenyl ring
with carbon atoms according to the НMВС NMR spectrum of
compound IIa.
Data of 13С NMR spectra of compounds IIa and IIc
H31C5
10
11
11
10
N
NH
N
NH
NH2
NH2
NH
The final structure was suggested proceeding from
the 2D HMBC and NOESY spectra of compound IIa. In
the HMBC spectrum on the line of the chemical shift of
the proton of the cyclopropane ring (4.23 ppm) nine cor-
relation peaks were observed (Fig. 1): at the coordinates
of atoms С4, С5, and С6 of the cyclopropane ring (27.84,
29.29, 28.55 ppm), С7 and С8 of cyano groups (114.04,
113.69 ppm), С2, С3 of pyrrole (79.28, 162.63 ppm) and
С1 of pyridazine ring (138.30 ppm), at the coordinates of
the atom С9 of the benzene ring (135.37 ppm).
2
O12
2
9
1
1
9
12
6
6
8
CN
5
5
NH
14
8
14
13
13
H
H
CN
3
3
NC4
4
O
NC
IIа
O
IIc 7
7
Chemical shifts, δ, ppm
Number of
carbon
IIa
IIc
atom
С3
С1
С9
162.63
138.30
135.37
162.55
138.50
128.08
The chemical shift of the proton at the nitrogen
of pyrrole (8.64 ppm) correlates with the shifts of all
carbon atoms of the pyrrole ring: С2 (79.28 ppm), С3
(162.63 ppm), С4 (27.84 ppm), С6 (28.55 ppm). On the
line of the chemical shift of the proton at the nitrogen of
the pyridazine ring (8.29 ppm) three correlation peaks
appear: at the coordinates of atoms С1 (138.30 ppm), С2
(79.28 ppm), С6 (28.55 ppm). The shift of the protons
of amino group (3.47 ppm) correlates with the shifts of
atoms С2 (79.28 ppm) and С6 (28.55 ppm) (Fig. 2).
С10, С11, С12, 129.08, 128.79, 124.08 160.13, 125.63,
С7, С8
С2
114.04, 113.69
79.28
114.04, 113.69
79.31
С5
29.29
29.24
С6
28.55
28.84
С4
27.84
27.93
Besides in the HMBC spectrum correlation peaks
were observed at coordinates of chemical shifts of carbon
С15
55.38
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 5 2011

KAYUKOV et al.
724
isomerism is due to the different position of the tert-butyl
substituent. IR spectra of compounds IIа–IIg and III are
in agreement with the assumed structures.
As was previously established the cyclopropane ring
of compounds Iа–Ih suffered opening under the treat-
ment with various bases, in particular, with acetate ion
(pKВ 9.3). Hydrazine (pKВ 6.2) is a stronger base and also
should effect the opening of the three-membered ring of
cyclopropanes Iа–Ih. However, as seen from the structure
of compounds IIа–IIg the majority of initial compounds
Iа–Ig do not demonstrate the CH-acid properties in the
reaction with hydrazine and consequently the cyclopro-
pane ring is not opened. It evidently occurs in this way
because the competing addition to the carbonyl group
prevails followed by the cyclization with the cyano group
and the formation of pyridazine derivative B (Scheme 2).
The assumption of the primary addition to the cyano
group does not explain the regioselectivity of the addi-
tion to cyano group in the cis-position with respect to the
carbonyl. Moreover, when the reaction occurs only at the
cyano groups (with ketone oximes), the attack of the nu-
cleophile is in contrast directed to the nitrile group in the
trans-position to the carbonyl [7]. Water elimination may
occur as well as from intermediate А and from B, but in
any case with the assistance of the cyano group which is
thus converted into the carboxamide group. The reaction
is completed by the addition of the amide group to the
amidine fragment of intermediate D. Similar conversions
are usual for the polycyano substances where the hydroxy
and nitrile groupd are spatially close. It results as a rule
in the formation of 2-iminofurane fragment and when
therewith the oxygen atom of the furan ring is adjacent to
the atom bearing the proton-containing nitrogen hetero-
atom (as in intermediate C) always further recyclization
occurs into a pyrrole ring [12-15]. Yet if this recyclization
is initiated by a reagent of basic character, in some cases
decyclization is observed and the subsequent cyclization
at the vicinal cyano group [16, 17], namely, the process
is analogous to the path we suggested for the conversion
Fig. 3. Molecular structure of (4аS*,5S*,7aR*)-3-amino-
7a-tert-butyl-6-oxo-5,6,7,7a-tetrahydro-4aH-pyrrolo[2,3-c]-
pyridazine-4,5-dicarbonitrile (III) according to XRD analysis.
atoms and protons of the benzene ring. The most informa-
tive among them for establishing the final structure was
the correlation peak on the line of the chemical shifts of
the ortho-protons of the benzene ring (8.64 ppm) and
atom С1 (138.30 ppm). The NOESY spectrum contained
the correlation peaks at the coordinates of the chemical
shifts of the protons at the nitrogen toms of the pyrrole
and pyridazine ring and of amino group, and also of the
protons of the benzene ring.
1
According to Н NMR spectrum the product of the
reaction of cyclopropane Ih with hydrazine is not an in-
dividual compound but a mixture of two diastereomers in
the retio 1:4. The tert-butyl group gives rise to a singlet at
0.90 ppm and all other signals are doubled. The structure
of one diastereomer was established by XRD method
(Fig. 3). The hydrogen atoms of the pyrrole ring appear
as doublets with the coupling constant J 9.7 Hz for both
diastereomers indicating that in both cases the protons are
in the trans-position with respect to each other, and the
Scheme 2.
NH2
N
N
NH2
CN
N
NH2
CN
NH
OH
2 NC
HN
HN
O
N
NH2NH2
HN
R
Iа_Ig
CN
CN
IIа_Ig
CN
CN
R
R
R
NH2
OH
CN
NC
NC
NC
O
NH
B
C
D
А
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 5 2011

REACTION OF TETRACYANOCYCLOPROPYL KETONES
725
Scheme 3.
NH2
N
NH2
CN
O
CN
HN
CN
HN
NH2NH2
NH2NH2
CN
Ih
_
CN
_NH2NH3
+
_
OH
OH
NC
_
NC
CN
NC
CN
CN
E
F
NH2
N
NH2
CN
N
NH2
CN
N
HN
O
N
HN
NH2NH3+
_NH2NH2
CN
III
HN
O
HN
O
H
_
_
_
CN
G
CN
CN
HN
H
of intermediate C into final compound II.
synthesized was monitored by TLC on Silufol UV-254
plates, detection of spots by UV irradiation, iodine va-
por, or thermal degradation. IR spectra were recorded on
a Fourier spectrophotometer FSM-1202 from mulls in
mineral oil. 1Н and 13С NMR spectra were registered on
a spectrometer Bruker DRX-500 at operating frequencies
500.13 and 125 MHz, solvent DMSO-d6. Mass spectra
were taken on an instrument Finnigan MАT INCOS 50
(electron impact, 70 eV). Elemental analysis was carried
out on an analyzer Laboratorni Pristroje, Praha. The pa-
rameters of the unit cell of molecule III and the intensity
of the reflections for the XRD analysis were measured
on a diffractometer Enraf-Nonius CAD-4. The structure
was solved by the direct method using program pack-
age SHELX [18]. The positions and thermal parameters
of nonhydrogen atoms were refined in the anisotropic
approximation, of the hydrogen atoms, in the isotropic
approximation. The molecular graphic was performed
applying the DIAMOND program [19]. Crystallographic
The formation of bicyclic intermediates and final
compound II prevents the occurrence of the electrocyclic
opening of the cyclopropane ring.
In cyclopropane Ih the tert-butyl substituent due
to the steric hindrance prevents the approach of the
nucleophile to the carbonyl group, and thus the reac-
tion proceeds by the competing route starting with the
deprotonation followed by the electrocyclic opening of
the ring (Scheme 3). At the formation of intermediate
anion E the initial steric hindrances are partially removed
thus providing the possibility for the reaction between
the carbonyl group and hydrazine with the formation of
intermediate F. Further in th course of successive series of
heterocyclization arises intermediate G. The subsequent
1,5-sigmatropic shift of the proton may occur both in the
cis- and trans-position with respect to the tert-butyl group
leading to the formation of diastereomeric intermediates
H whose protonation gives final compound III.
Compound III can exist as three diastereomers
(Fig. 4), and the formation in the reaction of only two
may be due to the configurational stability of the proton
in the place of joining the pyrrole and pyridazine ring;
evidently, the proton conserves the position it acquired
in the 1,5-prototropic shift. The hydrogen atom at the
cyano group is on the contrary labile and in the course
of the reversible deprotonation gets the most feasible
trans-position.
CN
CN
CN
H
CN
H
H
H2N
H2N
H
O
O
N
N
N
N
N
N
H
H
CN
CN
H
H2N
H
O
N
N
N
H
EXPERIMENTAL
Fig. 4. Diastereomes of compound III.
The reaction completeness and purity of compounds
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 5 2011

KAYUKOV et al.
726
data of compound III are deposited into the Cambridge
Crystallographic Data Center (ССDC deposition no.
767063) and may be obtained free at CCDC, 12 Union
Road, Cambridge, CB2 1EZ, UK (e-mail: deposit@ccdc.
cam.ac.uk, http://www.ccdc.cam.ac.uk).
(IId). Yield 2.77 g (82%), mp 190–191°С (decomp.)
(acetonitrile). IR spectrum, δ, cm–1: 3422 (NH), 3417
(NH), 3356, 3345 (NH2), 3024 (СН, cyclopropane), 2259
(C≡N), 1737 (С=О), 1711 (С=N). 1Н NMR spectrum, δ,
ppm: 3.49 s (2Н, NH2), 3.77 s (3Н, ОСН3), 3.80 s (3Н,
ОСН3), 4.26 s (1Н, CH), 7.06 d (1Н, С6Н3, 3J 8.5 Hz),
7.13 d.d (1Н, С6Н3, 3J 8.4, 4J 2.0 Hz), 7.29 d (1Н, С6Н3,
4J 2.0 Hz), 8.07 s (1Н, NH), 8.61 s (1Н, NH). Mass spec-
trum: m/z 339 [M + Н]+, 163 [(СН3O)2С6Н4C=N]+. Found,
%: C 56.83; H 4.15; N 24.80. C16H14N6O3. Calculated,
%: C 56.80; H 4.17; N 24.84. M 338.11
6-Amino-8-oxo-3-phenyl-4,5,7-triazatricyc-
lo[4.3.0.02.9]non-3-ene-1,9-dicarbonitrile (IIа). In
10 ml of acetonitrile was dissolved 2.46 g (0.01 mol) of
cyclopropane Ia, and to the solution was added at stirring
0.50 g of 99% water solution of hydrazine hydrate. The
precipitate formed in 15 min was filtered off, washed with
acetonitrile and water, and recrystallized from acetonitrile.
Yield 2.03 g (73%), mp 196–197°С (decomp.). IR spec-
trum, ν, cm–1: 3437 (NH), 3378 (NH), 3307, 3286 (NH2),
3028 (С–Н), 2257 (C≡N), 1744 (С=О), 1706 (С=N).
1Н NMR spectrum, δ, ppm: 3.47 s (2Н, NH2), 4.23 s (1Н,
6-Amino-3-(3-nitrophenyl)-8-oxo-4,5,7-triaza-
tricyclo[4.3.0.02.9]non-3-ene-1,9-dicarbonitrile
(IIe). Yield 2.49 g (77%), mp 192–193°С (decomp.)
(ацеtонtрил). IR spectrum, δ, cm–1: 3437 (NH), 3404
(NH), 3346, 3327 (NH2), 3029 (СН, cyclopropane), 2254
3
1
C–H), 7.67 d (2Н, С6Н5, J 7.3 Hz), 7.47 t (2Н, С6Н5,
(C≡N), 1727 (С=О), 1712 (С=N). Н NMR spectrum,
3J 7.8 Hz), 7.40 t (1Н, С6Н5, 3J 7.2 Hz), 8.29 s (1Н, NH),
8.64 s (1Н, NH). Mass spectrum: m/z 278. Found, %:
C 60.37; H 3.64; N 30.15. C14H10N6O. Calculated, %:
C 60.43; H 3.62; N 30.20. M 278.09
δ, ppm: 3.57 s (2Н, NH2), 4.42 s (1Н, CH), 7.78 t (1Н,
3-NO2С6Н4, 3J 8.0 Hz), 8.06 d (1Н, 3-NO2С6Н4, 3J 8.0 Hz),
8.24 d.d (1Н, 3-NO2С6Н4, 3J 8.3, 4J 2.1 Hz), 8.46 s (1Н,
3-NO2С6Н4), 8.74 s (1Н, NH), 8.77 s (1Н, NH). Mass
spectrum: m/z 223. Found, %: C 51.93; H 2.69; N 30.28.
C14H9N7O3. Calculated, %: C 52.02; H 2.81; N 30.30.
M 323.08
Compounds IIb–IIg were obtained similarly.
6-Amino-3-(4-bromophenyl)-8-oxo-4,5,7-tri-
azatricyclo[4.3.0.02.9]non-3-ene-1,9-dicarbonitrile
(IIb). Yield 2.78 g (78%), mp 127–128°С (decomp.)
(acetonitrile). IR spectrum, δ, cm–1: 3414 (NH), 3377
(NH), 3325, 3311 (NH2), 3024 (СН, cyclopropane),
2254 (C≡N), 1747 (С=О), 1709 (С=N). 1Н NMR spec-
trum, δ, ppm: 3.50 s (2Н, NH2), 4.22 s (1Н, CH), 7.58 d
6-Amino-8-oxo-3-(2-thienyl)-4,5,7-triazatricyc-
lo[4.3.0.02.9]non-3-ene-1,9-dicarbonitrile (IIf). Yield
1.99 g (70%), mp 149–150°С (decomp.) (acetoni-
trile). IR spectrum, δ, cm–1: 3439 (NH), 3360 (NH),
3310, 3304 (NH2), 3027 (СН, cyclopropane), 2253
1
3
(C≡N), 1726 (С=О), 1709 (С=N). Н NMR spectrum,
(2Н, 4-BrС6Н4, J 8.8 Hz), 7.66 d (2Н, 4-BrС6Н4,
3J 8.8 Hz), 8.45 с (1Н, NH), 8.68 с (1Н, NH). Mass
spectrum: m/z 358, 356. Found, %: C 47.00; H 2.61;
N 23.52. C14H9BrN6O. Calculated, %: C 47.08; H 2.54;
N 23.53. M 356.00.
δ, ppm: 3.48 s (2Н, NH2), 4.32 s (1Н, CH), 7.12 d.d
3
4
(1Н, С4Н3S, J 5.1, J 3.7 Hz), 7.34 d.d (1Н, С4Н3S,
3J 3.7, 4J 1.1 Hz), 7.54 d.d (1Н, С4Н3S, 3J 5.1, 4J 1.2 Hz),
8.18 s (1Н, NH), 8.68 s (1Н, NH). Mass spectrum: m/z
284. Found, %: C 50.65; H 2.86; N 29.56. C12H8N6OS.
Calculated, %: C 50.70; H 2.84; N 29.56. M 284.05
6-Amino-3-(4-methoxyphenyl)-8-oxo-4,5,7-triaza-
tricyclo[4.3.0.02.9]non-3-ene-1,9-dicarbonitrile (IIc).
Yield 2.13 g (69%), mp 194–195°С (decomp.) (aceto-
nitrile). IR spectrum, δ, cm–1: 3380 (NH), 3323, 3313
(NH2), 3028 (СН, cyclopropane), 2258 (C≡N), 1743
(С=О), 1706 (С=N). 1Н NMR spectrum, δ, ppm: 3.44 s
(2Н, NH2), 3.79 s (3Н, СH3O), 4.20 s (1Н, CH), 7.03 d
(2Н, 4-CH3OС6Н4, 3J 8.9 Hz), 7.59 d (2Н, 4-CH3OС6Н4,
3J 8.9 Hz), 8.03 s (1Н, NH), 8.59 s (1Н, NH). Mass
spectrum: m/z 308. Found, %: C 58.34; H 3.91; N 27.29.
C15H12N6O2. Calculated, %: C 58.44; H 3.92; N 27.26.
M 308.10.
6-Amino-3-methyl-8-oxo-4,5,7-triazatricyc-
lo[4.3.0.02.9]non-3-ene-1,9-dicarbonitrile (IIg). Yield
1.40 g (65%), mp 218–219°С (decomp.) (acetonitrile).
IR spectrum, ν, cm–1: 3440 (NH), 3418 (NH), 3353, 3342
(NH2), 3024 (СН, cyclopropane), 2251 (C≡N), 1730
(С=О), 1710 (С=N). 1Н NMR spectrum, δ, ppm: 1.96 s
(3Н, СН3), 3.40 s (2Н, NH2), 3.56 s (1Н, СН), 7.41 s (1Н,
NH), 8.50 s (1Н, NH). Mass spectrum: m/z 216. Found,
%: C 50.05; H 3.76; N 38.89. C9H8N6O. Calculated, %:
C 50.00; H 3.73; N 38.87. M 216.08.
3-Amino-7a-tert-butyl-6-oxo-5,6,7,7a-tetrahydro-
4aH-pyrrolo[2,3-c]pyridazine-4,5-dicarbonitrile (III),
6-Amino-3-(3,4-dimethoxyphenyl)-8-oxo-4,5,7-
triazatricyclo[4.3.0.02.9]non-3-ene-1,9-dicarbonitrile
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 5 2011

REACTION OF TETRACYANOCYCLOPROPYL KETONES
Ollis, W.D., Eds., Oxford: Pergamon, 1979, vol. 5.
727
diastereomers mixture. In 10 ml of acetonitrile was dis-
solved 2.26 g (0.01 mol) of cyclopropane Ih, and into
the solution was added at stirring 0.50 g of 99% water
solution of hydrazine hydrate.After 24 h the solvent was
evaporated, the residue was diluted with 20 ml of water.
The solid compound was ground, filtered off, washed
with water and 2-propanol, and recrystallized from
a mixture dioxane−2-propanol, 1:1. Yield 1.52 g (59%),
mp 236–237°С (decomp.). IR spectrum, ν, cm–1: 3441
(NH), 3338, 3250 (NH2), 2256 (C≡N), 2197 (C≡N),
4. Bardasov, I.N., Kayukova, O.V., Kayukov, Ya.S.,
Ershov, O.V., and Nasakin, O.E., Zh. Org. Khim., 2007,
vol. 43, p. 1254.
5. Bardasov, I.N., Kayukova, O.V., Kayukov, Ya.S.,
Ershov, O.V., and Nasakin, O.E., Belikov, M.Yu., Zh. Org.
Khim., 2007, vol. 43, p. 1568.
6. Bardasov, I.N., Kayukova, O.V., Kayukov, Ya.S.,
Ershov, O.V., and Nasakin, O.E. Zh. Prikl. Khim., 2009,
vol. 45, 1332.
7. Bardasov, I.N., Kayukova, O.V., Kayukov, Ya.S.,
Ershov, O.V., Nasakin, O.E., and Tafeenko, V.A., Zh. Org.
Khim., 2009, vol. 45, p. 1340.
1
1717 (С=О). Н NMR spectrum, δ, ppm: 0.90 s [9Н,
С(СН3)3], 3.36 d [3.48 d] (1Н, СН, 3J 9.7 [3J 9.7] Hz),
3
4.20 d [4.26 d], (1Н, СН, J 9.7 [3J 9.7] Hz), 7.93 s
8. Bardasov, I.N., Kayukova, O.V., Kayukov, Ya.S.,
Ershov, O.V., Belikov, M.Yu., and Nasakin, O.E., Khim.
Geterotsikl. Soedin., 2009, vol. 9, p. 1297.
[8.06 s] (2Н, NH2), 10.01 s [10.15 s] (1Н, NH). Found,
%: С 55.86; Н 5.57; N 32.41. C12H14N6O. Calculated,
%: C 55.80; H 5.46; N 32.54.
9. Celli, A.M., Lampariello, L.R., Chimichi, S., Nesi, R., and
Scotton, M., Gazz. Chim. Ital., 1983, vol. 113, p. 427.
10. Takahashi, M., Orihara, T., Sasaki, T., Yamatera, T.,
Yamazaki, K., andYoshida,A., Heterocycles, 1986, vol. 24,
p. 2857.
11. Pretsch, E., Buhlmann, P., and Affolter, C., Structure
Determination of Organic Compounds, Springer-Verlag,
2000.
Crystallographic parameters of compound III
:
а 8.3223(9), b 8.6959(5), c 10.6443(6) A, α 71.605(5),
β 72.104(8), γ 72.104(8)°, V 643.96(9) A3, Z 2. Overall
number of reflections 2566. Number of reflections with
I > 2σ(I) 2064. Number of refined parameters 229. Factor
of uncertainty R 0.0433.
ACKNOWLEDGMENTS
12. Ershov, O.V., Lipin, K.V., Eremkin, A.V., Kayukov, Ya.S.,
and Nasakin, O.E., Zh. Org. Khim., 2009, vol. 45, p. 479.
13. Sheverdov, V.P., Ershov, O.V., Nasakin, O.E.,
Chernushkin, A.N., Tafeenko, V.A., and Firgang, S.I.,
Tetrahedron, 2001, vol. 57, p. 5815.
14. Nasakin, O.E., Sheverdov, V.P., Ershov, O.V., Moiseeva, I.V.,
Lyshchikov, A.N., Khrustalev, V.N., and Antipin, M.Ju.,
Mendeleev Commun., 1997, vol. 3, p. 112.
The study was carried out under the financial sup-
port of the Russian Foundation for Basic Research
(grant no. 10-03-97013 r-povolzhe-а) and of Ministry of
Education and Science of the Russian Federation (State
contract no. 16.740.11.0335 of the Federal targeted
program «Scientific and scientific-pedagogical staff of
innovation Russia»).
15. Ershov, O.V., Sheverdov, V.P., Nasakin, O.E., and
Tafeenko, V.A., Zh. Org. Khim., 2001, vol. 37, p. 1732.
16. Ershov, O.V., Sheverdov, V.P., Nasakin, O.E., Efimov, R.N.,
and Tafeenko, V.A., Zh. Org. Khim., 2001, vol. 37, p. 1578.
17. Sheverdov, V.P., Ershov, O.V., Efimov, R.N., Nasakin, O.E,
Firgang, S.I., and Tafeenko, V.A., Zh. Obshch. Khim., 2004,
vol. 74, p. 811.
REFERENCES
1. Heterocyclic Compounds, Elderfield, R.C., Ed., NewYork:
Wiley, 1957, vol. 5, p. 44.
2. Heterocyclic Compounds, Elderfield, R.C., Ed., NewYork:
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3. Comprehensive Organic Chemistry, Barton, D. and,
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 5 2011