Reactions of 2′-oxo-1′,2′-dihydrospiro[cyclopropane-1, 3′-indole]-2,2,3,3-tetracarbonitriles with nucleophiles

Article abstract of DOI:10.1134/S1070428011030110

2′-Oxo-1′,2′-dihydrospiro[cyclopropane-1,3′-indole] -2,2,3,3-tetracarbonitriles reacted with oxygencentered nucleophiles to form addition products at the cyano groups with conservation of the three-membered ring. Reactions of the title compounds with alcohols required the presence of base catalyst, and the products, 2-amino-4,4-dialkoxy-2′-oxo-1′, 2′-dihydrospiro[3-azabicyclo[3.1.0]hex-2-ene-6,3′-indole]-1, 5-dicarbonitriles, were converted into the corresponding 2-imino-2′,4- dioxospiro[3-azabicyclo[3.1.0]hexane-6,3′-indole]-1,5-dicarbonitriles and 2,2′,4-trioxospiro[3-azabicyclo[3.1.0]hexane-6,3′-indole]-1, 5-dicarbonitriles by the action of acetic and sulfuric acids, respectively. The reactions with ketone oximes occurred in the absence of a catalyst, yielding 2-amino-4,4-bis(alkylideneaminooxy)-2′-oxo-1′,2′- dihydrospiro[3-azabicyclo[3.1.0]hex-2-ene-6,3′-indole]-1, 5-dicarbonitriles. The reactions with thiols, aliphatic amines, and anilines were accompanied by opening of the three-membered ring. In the reactions with triphenylphosphine and thiols 2-(2-oxo-2,3-dihydro-1H-indol-3-ylidene) malononitrile was obtained, while morpholine and N,N-dimethylaniline gave rise, respectively, to 3,3-diaryl-and 3,3-dimorpholino-1H-indol-2(3H)-ones and tri- and dicyanoethylene derivatives.

Full text of DOI:10.1134/S1070428011030110

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 3, pp. 392–401. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © Ya.S. Kayukov, O.V. Kayukova, E.S. Kalyagina, I.N. Bardasov, O.V. Ershov, O.E. Nasakin, V.A. Tafeenko, 2011, published in
Zhurnal Organicheskoi Khimii, 2011, Vol. 47, No. 3, pp. 400–408.
Reactions of 2′-Oxo-1′,2′-dihydrospiro[cyclopropane-1,3′-indole]-
2,2,3,3-tetracarbonitriles with Nucleophiles
Ya. S. Kayukova, O. V. Kayukovaa, E. S. Kalyaginaa, I. N. Bardasova, O. V. Ershova,
O. E. Nasakina, and V. A. Tafeenkob
a I.N. Ul’yanov Chuvash State University, Moskovskii pr. 15, Cheboksary, 428015 Russia
e-mail: kaukovyakov@mail.ru
b Faculty of Chemistry, Moscow State University, Vorob’evy gory 1, Moscow, 119992 Russia
Received March 25, 2010
Abstract—2′-Oxo-1′,2′-dihydrospiro[cyclopropane-1,3′-indole]-2,2,3,3-tetracarbonitriles reacted with oxygen-
centered nucleophiles to form addition products at the cyano groups with conservation of the three-membered
ring. Reactions of the title compounds with alcohols required the presence of base catalyst, and the products,
2-amino-4,4-dialkoxy-2′-oxo-1′,2′-dihydrospiro[3-azabicyclo[3.1.0]hex-2-ene-6,3′-indole]-1,5-dicarbonitriles,
were converted into the corresponding 2-imino-2′,4-dioxospiro[3-azabicyclo[3.1.0]hexane-6,3′-indole]-1,5-
dicarbonitriles and 2,2′,4-trioxospiro[3-azabicyclo[3.1.0]hexane-6,3′-indole]-1,5-dicarbonitriles by the action of
acetic and sulfuric acids, respectively. The reactions with ketone oximes occurred in the absence of a catalyst,
yielding 2-amino-4,4-bis(alkylideneaminooxy)-2′-oxo-1′,2′-dihydrospiro[3-azabicyclo[3.1.0]hex-2-ene-6,3′-
indole]-1,5-dicarbonitriles. The reactions with thiols, aliphatic amines, and anilines were accompanied by
opening of the three-membered ring. In the reactions with triphenylphosphine and thiols 2-(2-oxo-2,3-dihydro-
1H-indol-3-ylidene)malononitrile was obtained, while morpholine and N,N-dimethylaniline gave rise, respec-
tively, to 3,3-diaryl- and 3,3-dimorpholino-1H-indol-2(3H)-ones and tri- and dicyanoethylene derivatives.
DOI: 10.1134/S1070428011030110
Cyclopropane derivatives having five or six elec-
tron-withdrawing substituents are characterized by low
electron density on the three-membered ring, i.e., they
are electron-deficient cyclopropanes. These compounds
exhibit high reactivity toward various nucleophilic
reagents, and the direction and depth of such trans-
formations strongly depend on the nature of both nu-
cleophile and substituents in the cyclopropane ring [1].
We previously synthesized spiro-fused indole deriva-
tives Ia–If (Scheme 1) [2] in which the heterocyclic
fragment acts as an electron-withdrawing (carbamoyl)
substituent in addition to four cyano groups. Therefore,
compounds Ia–If may be regarded as electron-defi-
cient cyclopropanes. In the present article we report
the results of our study on reactions of cyclopropanes
Ia–If with nucleophilic reagents.
three-membered ring. The result depends on both
cyclopropane structure and amount of nucleophilic
reagent. Reactions of diacetyltetracyanocyclopropane
with alcohols can follow both pathways; in the pres-
ence of excess substrate 3-azabicyclo[3.1.0]hexane
derivative is formed, while dihydrofuran derivative is
obtained in the presence of excess alkoxide [3].
Phthaloyltetracyanocyclopropane reacts only accord-
ing to the second pathway leading to dihydrofurans [4].
The reactions of cyclopropanes Ia–If with alcohols
and ketone oximes followed the first pathway. In the
case of alcohols, the process starts after addition of
base catalyst (the corresponding alkoxide or triethyl-
amine) and leads to the formation of 2-amino-4,4-di-
alkoxy-2′-oxo-1′,2′-dihydrospiro[3-azabicyclo[3.1.0]-
hex-2-ene-6,3′-indole]-1,5-dicarbonitriles IIa–IIh
(Scheme 1). The reactions with ketone oximes required
no catalyst, and the products were 2-amino-4,4-bis(al-
kylideneaminoxy)-2′-oxo-1′,2′-dihydrospiro[3-azabi-
cyclo[3.1.0]hex-2-ene-6,3′-indole]-1,5-dicarbonitriles
IIi–IIm. Compounds II can be regarded as amide
acetals; by heating in acetic acid they were readily
Electron-deficient cyclopropanes can react with
oxygen-centered nucleophiles along two pathways.
The first of these involves initial nucleophile addition
to the cyano or acyl group with conservation of the
three-membered ring and subsequent heterocycliza-
tion. The second pathway is carbanion cleavage of the
392

REACTIONS OF 2′-OXO-1′,2′-DIHYDROSPIRO[CYCLOPROPANE-1,3′-INDOLE]-...
393
Scheme 1.
HN
HN
CN
N
CN
OR3
OR3
CN
CN
NC
NC
NC
R3OH, base
R1
R1
R1
CN
O
CN
O
O
N
N
N
R2
R2
R2
Ia–If
H
HN
H2N
NC
OR3
OR3
OR3
OR3
CN
N
N
NC
R3OH
R1
R1
CN
O
O
N
N
R2
IIa–IIm
R2
I, R1 = R2 = H (a); R1 = Me, R2 = H (b); R1 = H, R2 = Me (c); R1 = H, R2 = MeCO (d); R1 = H, R2 = EtOC(O)CH2 (e); R1 = H,
R2 = PhCH2 (f); II, R1 = R2 = H, R3 = Me (a); R1 = H, R2 = R3 = Me (b); R1 = H, R2 = PhCH2, R3 = Me (c); R1 = H, R2 = MeCO, R3 =
Me (d); R1 = H, R2 = EtOC(O)CH2, R3 = Me (e); R1 = R2 = H, R3 = Et (f); R1 = H, R2 = PhCH2, R3 = Et (g); R1 = H, R2 = Me, R3 =
Et (h); R1 = R2 = H, R3 = Me2C=N (i); R1 = H, R2 = Me, R3 = Me2C=N (j); R1 = H, R2 = PhCH2, R3 = Me2C=N (k); R1 = Me, R2 = H,
R3 = (CH2)5C=N (l); R1 = R2 = H, R3 = (CH2)5C=N (m).
converted into the corresponding 2-imino-2′,4-dioxo-
spiro[3-azabicyclo[3.1.0]hexane-6,3′-indole]-1,5-dicar-
bonitriles IIIa–IIIc (Scheme 2).
consistent with the assumed structure. Compounds II
and III could give rise to amino–imino tautomerism
(Schemes 1, 2). Protons in the amino group at the pyr-
role ring in II gave two signals in the region δ 7.0–
8.5 ppm, the difference between the chemical shift
being 0.5 ppm, and the corresponding signals of com-
pound III were two singlets at δ 9.4 and 10.1 ppm.
Therefore, we presumed that compounds II have
aminodihydropyrrole structure and that iminopyrroli-
Heating of IIa–IIc in dilute sulfuric acid was ac-
companied by more profound hydrolysis with forma-
tion of 2,2′,4-trioxospiro[3-azabicyclo[3.1.0]hexane-
6,3′-indole]-1,5-dicarbonitriles IVa–IVc (Scheme 3).
The structure of compounds IIa–IIm, IIIa–IIIc,
and IVa–IVc was determined on the basis of their IR,
1H NMR, and mass spectra. The IR spectra contained
absorption bands belonging to stretching vibrations of
non-conjugated cyano groups at 2260–2265 cm–1 and
carbonyl groups in the region 1652–1729 cm–1. In the
1H NMR spectra of these compounds we observed
signals from protons in the indole fragment and hydro-
carbon groups R1, R2, and R3, whose position was
1
dine tautomer of III is more stable. The H NMR data
led us to conclude that the addition of oxygen-centered
nucleophiles to the tetracyanoethyl fragment is regio-
selective. The stereochemistry of the addition was
1
determined on the basis of the H–1H NOESY spec-
trum of compound IVb; it showed that the pyrrole ring
is formed at the side corresponding to the carbonyl
group in the indole fragment.
Scheme 2.
H
O
O
N
N
NH
NH2
NC
NC
AcOH
IIa–IIc
CN
O
CN
O
N
N
R
R
IIIa–IIIc
R = H (a), Me (b), PhCH2 (c).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 3 2011

KAYUKOV et al.
ing products in the above reaction; on the other hand,
394
Scheme 3.
phosphorane D is a known compound which was not
detected in the reaction mixture by thin-layer chroma-
tography. Moreover, phosphorane D added to the reac-
tion mixture during the process remained unchanged.
These findings may be regarded as evidences in sup-
port of the first rather than second pathway.
H
O
N
O
NC
H2SO4
IIa–IIc
CN
O
N
R
There are no published data on reactions of sulfur-
centered nucleophiles with electron-deficient cyclopro-
panes. We found that compounds I react with butane-
thiol and ethyl 2-sulfanylacetate in an inert solvent in
the absence of catalyst to produce dicyanomethylidene
derivatives V. Presumably, the mechanism of this
transformation is analogous to that inherent to the reac-
tion with triphenylphosphine. The reaction direction
did not change in the presence of base catalyst (organic
base or the corresponding thiolate).
IVa–IVc
R = H (a), Me (b), PhCH2 (c).
It is known that electron-deficient cyclopropanes
readily react with phosphines to give different prod-
ucts, depending on the substituent nature [1]. Cyclo-
propane derivative Ia reacted with triphenylphosphine
in such solvents as isopropyl alcohol, acetonitrile, and
dioxane to afford dicyanomethylidene-substituted in-
dole V (Scheme 4), i.e., compounds I in the reaction
with triphenylphosphine behave similarly to phthaloyl-
tetracyanocyclopropane [5].
Polycyanocyclopropanes are known to readily react
with anilines via opening of the three-membered ring
with formation of tricyanovinyl derivatives [1]. We
examined the reaction of compound Ia with N,N-di-
methylaniline and revealed simultaneous formation of
two products which were isolated as individual sub-
stances due to their different solubilities in acetonitrile.
When the reaction was carried out in acetonitrile,
3,3-bis(4-dimethylaminophenyl)-1H-indol-2(3H)-one
(VII) crystallized first from the reaction mixture
(Scheme 5). After removal of the solvent, we isolated
2-(4-dimethylaminophenyl)ethylene-1,1,2-tricarboni-
trile (IX). The structure of compound VII was deter-
mined by X-ray analysis (Fig. 1).
We presumed two possible transformation path-
ways in the observed decyanomethylation reaction,
which differ by the site of initial addition of triphenyl-
phosphine. According to the first pathway, addition of
triphenylphosphine molecule to one of the cyano
groups gives intermediate A (Scheme 4) which under-
goes rearrangement with opening of the cyclopropane
ring; the subsequent elimination of phosphorus-con-
taining species B yields the final product. The second
pathway implies initial nucleophilic opening of the
three-membered ring by the action of triphenylphos-
phine, formation of four-membered intermediate C,
and elimination of triphenyl-λ5-phosphanylidenemalo-
nonitrile (D). We failed to isolate phosphorus-contain-
Our experiments showed that cyclopropanes I vig-
orously react with amines and ammonia to produce
a violet reaction mixture. However, we failed to isolate
Scheme 4.
N
CN
CN
NC
NC
PPh3
NC
·
CN
O
PPh3
N
–[NCC
≡
CN=PPh3]
O
B
NC
N
H
N
H
CN
O
PPh3
A
Ia
CN
NC
N
CN
NC
NC
H
NC
V
CN
NC
PPh3
PPh3
O
–[Ph3P=C(CN)2]
O
D
N
N
H
H
C
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 3 2011

REACTIONS OF 2′-OXO-1′,2′-DIHYDROSPIRO[CYCLOPROPANE-1,3′-INDOLE]-...
395
Scheme 5.
NC
NMe2
NMe2
NC
NC
NC
NC
H
CN
VI
C6H4NMe2-4
C6H4NMe2-4
Ia
+
+
O
O
N
N
VI
H
H
NC
CN
E
F
Me2N
NMe2
VI
NC
CN
+
E
O
CN
N
H
CN
VII
NMe2
VIII
G
–HCN
CN
Me2N
CN
NC
CN
NC
IX
CN
VI, Ia
F
+
CN
O
Me2N
N
H
E
G
Scheme 6.
CN
N
NC
NC
O
NC
NC
H
O
O
O
NC
X
N
Ia
+
+
N
O
O
N
H
N
N
NC
CN
H
H
X
O
NC
NC
H
O
O
N
X
N
N
+
VIII
O
O
N
N
H
H
XI
O
NC
NC
H
O
NC CN
N
Ia, X
N
+
CN
N
O
O
CN
N
NC
CN
H
NC
N
CN
NC CN
N
X
CN
N
–2HCN
O
CN
O
O
XII
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 3 2011

KAYUKOV et al.
is analogous to the reaction of I with anilines with the
396
C23
N2
difference that the corresponding tricyanovinyl deriva-
tive reacts further with the second morpholine mole-
cule (Scheme 6).
C24
C15
C25
C20
C14
C13
The structure of compounds XI and XII was also
determined by X-ray analysis (Figs. 2, 3). Molecules
XII in crystal are linked through numerous C–H···O
and C–H···N hydrogen bonds, whereas crystal pack-
ing of compounds VII and XI is largely determined by
the presence of amide fragment. Head-to-tail N–H···O
hydrogen bonding in the crystalline structure of VII
gives rise to chains oriented along the b crystallo-
graphic axid, and analogous interaction in the crystal-
line structure of compound XI leads to formation of
centrosymmetric dimers.
C16
N3
C26
C21
C22
C3
C19
C17
C5
C12
C11
C18
O1
C10
C9
C2
N1
C6
C7
C8
EXPERIMENTAL
Fig. 1. Structure of the molecule of 3,3-bis(4-dimethyl-
aminophenyl)-1H-indol-2(3H)-one (VII) according to the
X-ray diffraction data.
The progress of reactions and the purity of products
were monitored by TLC on Silufol UV-254 plates;
spots were visualized by UV irradiation, treatment
with iodine vapor, or thermal decomposition. The IR
spectra were recorded from samples dispersed in
mineral oil on an FSM-1202 spectrometer with Fourier
individual compounds from the reaction mixture. Un-
like other amines, morpholine reacted with cyclopro-
pane derivative Ia to give a white solid which was
a mixture of previously reported 3,3-dimorpholino-1H-
indol-2(3H)-one (XI) and 2-(dimorpholinomethyli-
dene)malononitrile (XII). A probable reaction scheme
1
transform. The H NMR spectra were measured on
a Bruker DRX-500 spectrometer at 500.13 MHz using
DMSO-d6 as solvent and tetramethylsilane as internal
reference. The mass spectra (electron impact, 70 eV)
were obtained on a Finnigan MAT INCOS 50 instru-
ment. X-Ray analysis was performed using an Enraf–
Nonius CAD-4 four-circle automatic diffractometer
(CuKα irradiation for single crystals of VII and XI,
MoKα irradiation for XII, graphite monochromator,
ω-scanning). The structures were solved by the direct
method using SHELXS-97 software package. The
positions and thermal parameters of non-hydrogen
atoms were refined in full-matrix anisotropic approxi-
mation. Hydrogen atoms in structures XI and XII were
localized by Fourier difference syntheses, and their
positions were refined in isotropic approximation. The
positions of hydrogen atoms in structure VII were cal-
culated and were refined according to the riding
model. The crystallographic data for compounds VII,
XI, and XII were deposited to the Cambridge Crystal-
lographic Data Centre (entry nos. CCDC 762 427,
CCDC 763334, and CCDC 763333, respectively) and
are available at CCDC, 12 Union Road, Cambridge,
CB2 1EZ, UK (fax: +44-1233-336033; e-mail:
deposit@ccdc.cam.ac.uk; http://www.ccdc.cam.ac.uk).
C7
C6
C8
C9
N1
C5
C10
C2
C18
O2
C11
C3
N2
C17
C12
N3
O4
C15
C14
C16
O3
C13
2-Amino-4,4-dimethoxy-2′-oxospiro[3-azabi-
cyclo[3.1.0]hex-2-ene-6,3′-indole]-1,5-dicarbonitrile
Fig. 2. Structure of the molecule of 3,3-dimorpholino-1H-in-
dol-2(3H)-one (XI) according to the X-ray diffraction data.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 3 2011

REACTIONS OF 2′-OXO-1′,2′-DIHYDROSPIRO[CYCLOPROPANE-1,3′-INDOLE]-...
397
N2
N2i
(IIa). a. One drop of a solution of sodium methoxide
C7
C7i
in methanol was added to a suspension of 0.259 g
(0.001 mol) of compound Ia in 3 ml of methanol, and
the mixture was stirred for 5 min. The mixture slightly
warmed up and became homogeneous, and a white
solid separated. The mixture was kept for 2 h at 5°C,
and the precipitate was filtered off, washed with cold
methanol, recrystallized, and dried in a vacuum desic-
cator. Yield 0.171 g (53%), decomposition point 165°C
(from MeOH–MeCN, 10:1). IR spectrum, ν, cm–1:
C2
C1
C3
C4i
C4
C3i
N1
N1i
O1i
O1
1
3350 (NH), 2248 (C≡N), 1710 (C=O), 1678. H NMR
C5i
C6i
spectrum, δ, ppm: 3.15 s (3H, OCH3), 3.33 s (3H,
3
C6
C5
OCH3), 6.96 t (1H, C6H4, J = 7.2 Hz), 7.00 d (1H,
C6H4, 3J = 8.0 Hz), 7.34 s (1H, NH), 7.36 t (1H, C6H4,
3
3J = 8.0 Hz), 7.42 d (1H, C6H4, J = 8.6 Hz), 7.81 s
(1H, NH), 11.35 s (1H, NH, indole). Mass spectrum,
m/z (Irel, %): 323 (7) [M]+, 306 (1) [M – 17]+, 291 (10),
249 (11), 234 (10), 90 (43), 45 (100). Found, %:
C 54.25; H 2.14; N 27.49. C16H13N5O3. Calculated, %:
C 59.44; H 4.05; N 21.66. M 323.31.
Fig. 3. Structure of the molecule of 2-(dimorpholinomethyli-
dene)malononitrile (XII) according to the X-ray diffraction
data.
1′-Acetyl-2-amino-4,4-dimethoxy-2′-oxospiro-
[3-azabicyclo[3.1.0]hex-2-ene-6,3′-indole]-1,5-dicar-
bonitrile (IId). Yield 63%, decomposition point 146–
148°C. IR spectrum, ν, cm–1: 3368 (NH), 2250 (C≡N),
b. Compound IIa was synthesized in a similar way
using a drop of triethylamine (instead of sodium meth-
oxide) as catalyst. Yield 0.174 g (54%).
1
1725, 1712 (C=O), 1680. H NMR spectrum, δ, ppm:
Compounds IIb–IIe were synthesized as described
above for IIa (method a) from the corresponding
cyclopropane derivatives I.
2.65 s (3H, COCH3), 3.22 s (3H, OCH3), 3.37 s (3H,
3
OCH3), 7.18 s (1H, NH), 7.20 t (1H, C6H4, J =
3
8.2 Hz), 7.50 t (1H, C6H4, J = 8.2 Hz), 7.60 d (1H,
C6H4, 3J = 8.4 Hz), 7.90 s (1H, NH), 8.25 d (1H, C6H4,
3J = 8.4 Hz). Mass spectrum, m/z (Irel, %): 365 (20)
[M]+, 346 (11), 334 (12), 323 (20), 292 (19), 249 (10),
234 (25), 155 (30), 115 (20), 90 (60), 43 (100). Found,
%: C 59.21; H 4.18; N 19.14. C18H15N5O4. Calculated,
%: C 59.18; H 4.14; N 19.17. M 365.34.
2-Amino-4,4-dimethoxy-1′-methyl-2′-oxospiro-
[3-azabicyclo[3.1.0]hex-2-ene-6,3′-indole]-1,5-dicar-
bonitrile (IIb). Yield 72%, decomposition point 190–
195°C. IR spectrum, ν, cm–1: 3350 (NH), 2248 (C≡N),
1
1710 (C=O), 1678. H NMR spectrum, δ, ppm: 3.15 s
(3H, NCH3), 3.25 s (3H, OCH3), 3.35 s (3H, OCH3),
3
3
7.05 t (1H, C6H4, J = 8.0 Hz), 7.20 d (1H, C6H4, J =
8.4 Hz), 7.30 s (1H, NH), 7.42 m (2H, C6H4), 7.85 s
(1H, NH), Mass spectrum: m/z 337 (Irel = 2%) [M]+.
Found, %: C 60.58; H 4.52; N 20.70. C17H15N5O3. Cal-
culated, %: C 60.53; H 4.48; N 20.76. M 337.33.
Ethyl 2-(2-amino-1,5-dicyano-4,4-dimethoxy-2′-
oxospiro[3-azabicyclo[3.1.0]hex-2-ene-6,3′-indol]-
1′-yl)acetate (IIe). Yield 51%, decomposition point
190–193°C. IR spectrum, ν, cm–1: 3360 (NH), 2252
(C≡N), 1727, 1710 (C=O). 1H NMR spectrum, δ, ppm:
3
1.23 t (3H, CH2CH3, J = 7.0 Hz), 3.15 s (3H, OCH3),
2-Amino-1′-benzyl-4,4-dimethoxy-2′-oxospiro-
[3-azabicyclo[3.1.0]hex-2-ene-6,3′-indole]-1,5-dicar-
bonitrile (IIc). Yield 56%, decomposition point 235–
240°C. IR spectrum, ν, cm–1: 3370 (NH), 2247 (C≡N),
3.37 s (3H, OCH3), 4.17 m (2H, NCH2), 4.75 m (2H,
3
OCH2), 7.07 t (1H, C6H4, J = 7.6 Hz), 7.20 d (1H,
3
3
C6H4, J = 7.8 Hz), 7.45 t (1H, C6H4, J = 7.6 Hz),
7.48 d (1H, C6H4, 3J = 7.6 Hz), 7.55 s (1H, NH), 7.95 s
(1H, NH). Mass spectrum: m/z 409 (Irel = 1%) [M]+.
Found, %: C 58.71; H 4.69; N 17.13. C20H19N5O5. Cal-
culated, %: C 58.68; H 4.68; N 17.11. M 409.40.
1
1711 (C=O), 1678. H NMR spectrum, δ, ppm: 3.17 s
(3H, OCH3), 3.37 s (3H, OCH3), 5.07 d and 5.12 d
(1H each, CH2Ph, 2J = 15.7 Hz), 7.10 t (1H, C6H4, 3J =
3
8.1 Hz), 7.15 d (1H, C6H4, J = 8.2 Hz), 7.35 m (1H,
C6H4), 7.38–7.40 m (5H, C6H5), 7.45 s (1H, NH),
7.45 d (1H, C6H4, 3J = 8.4 Hz), 7.80 s (1H, NH). Mass
spectrum, m/z (Irel, %): 413 (1) [M]+, 91 (100) [C7H7]+.
Found, %: C 66.84; H 4.68; N 16.85. C23H19N5O3. Cal-
culated, %: C 66.82; H 4.63; N 16.94. M 413.43.
2-Amino-4,4-diethoxy-2′-oxospiro[3-azabicyclo-
[3.1.0]hex-2-ene-6,3′-indole]-1,5-dicarbonitrile (IIf).
a. One drop of a solution of sodium ethoxide in
ethanol was added to a suspension of 0.259 g
(0.001 mol) of compound Ia in 3 ml of ethanol, and
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 3 2011

KAYUKOV et al.
398
the mixture was stirred for 5 min. The mixture slightly
warmed up and became homogeneous, and a white
solid separated. The mixture was kept for 2 h at 5°C,
and the precipitate was filtered off, washed with cold
ethanol, recrystallized, and dried in a vacuum desic-
cator. Yield 0.179 g (51%), decomposition point 149–
152°C (from EtOH–MeCN, 10:1). IR spectrum, ν,
cm–1: 3060 (CH, cyclopropane), 2260 (C≡N), 1720
Mass spectrum: m/z 365 (Irel = 1%) [M]+. Found, %:
C 62.37; H 5.28; N 19.11. C19H19N5O3. Calculated, %:
C 62.46; H 5.24; N 19.17. M 365.39.
2-Amino-2′-oxo-4,4-bis(propan-2-ylideneamino-
oxy)spiro[3-azabicyclo[3.1.0]hex-2-ene-6,3′-indole]-
1,5-dicarbonitrile (IIi). Acetone oxime, 0.219 g
(0.003 mol), was added to a solution of 0.259 g
(0.001 mol) of compound Ia in 3 ml of acetonitrile, the
resulting solution was kept for 2 days at room tempera-
ture, and the precipitate was filtered off, washed with
cold acetonitrile, recrystallized, and dried in a vacuum
desiccator. Yield 0.259 g (64%), decomposition point
204–203°C (from MeCN). IR spectrum, ν, cm–1: 3430
(NH), 2250 (C≡N), 1730 (C=O). 1H NMR spectrum, δ,
ppm: 1.46 s (3H, CH3), 1.62 s (3H, CH3), 1.90 s (3H,
CH3), 1.92 s (3H, CH3), 6.80 m (2H, C6H4), 7.33 t.d
1
(C=O). H NMR spectrum, δ, ppm: 0.80 t (3H,
3
3
CH2CH3, J = 7.0 Hz), 1.22 t (3H, CH2CH3, J =
7.0 Hz), 3.60–3.70 m (3H, OCH2), 3.75–3.82 m (1H,
OCH2), 6.95–7.05 m (2H, C6H4), 7.35 s (1H, NH),
3
3
7.37 t (1H, C6H4, J = 7.7 Hz), 7.42 d (1H, C6H4, J =
7.8 Hz), 7.80 s (1H, NH), 11.35 s (1H, NH, indole).
Mass spectrum, m/z (Irel, %): 351 (12) [M]+, 322 (5)
[M – 29]+, 306 (17), 277 (22), 250 (30), 235 (100), 207
(38), 179 (23), 152 (32), 45 (55). Found, %: C 61.54;
H 4.91; N 19.89. C18H17N5O3. Calculated, %: C 61.53;
H 4.88; N 19.93. M 351.36.
3
4
(1H, C6H4, J = 7.7, J = 1.2 Hz), 7.48 s (1H, NH),
3
7.55 d (1H, C6H4, J = 7.8 Hz), 7.73 s (1H, NH),
11.25 s (1H, NH, indole). Mass spectrum, m/z (Irel, %):
336 (2) [M – 69]+, 213 (1), 118 (23), 73 (71), 58 (75),
39 (100). Found, %: C 59.29; H 4.76; N 21.12.
C20H19N7O3. Calculated, %: C 59.25; H 4.72; N 21.18.
M 405.41.
b. Compound IIf was synthesized in a similar way
using a drop of triethylamine (instead of sodium meth-
oxide) as catalyst. Yield 0.168 g (48%).
2-Amino-1′-benzyl-4,4-diethoxy-2′-oxospiro-
[3-azabicyclo[3.1.0]hex-2-ene-6,3′-indole]-1,5-dicar-
bonitrile (IIg) was synthesized as described above for
IIf (method b) using cyclopropane If as starting com-
pound. Yield 57%, mp 180–184°C (decomp.). IR spec-
trum, ν, cm–1: 3360, 3110 (NH), 2245 (C≡N), 1711
Compounds IIj and IIk were synthesized in a simi-
lar way from the corresponding cyclopropane deriva-
tives I.
2-Amino-1′-methyl-2′-oxo-4,4-bis(propan-2-
ylideneaminooxy)spiro[3-azabicyclo[3.1.0]hex-2-
ene-6,3′-indole]-1,5-dicarbonitrile (IIj). Yield 68%,
decomposition point 210–212°C (from MeCN). IR
spectrum, ν, cm–1: 3440, 3368 (NH2), 2250 (C≡N),
1703 (C=O), 1680 (C=N). 1H NMR spectrum, δ, ppm:
1.48 s (3H, CH3), 1.63 s (3H, CH3), 1.89 s (3H, CH3),
1.91 s (3H, CH3), 2.66 s (3H, NCH3), 7.21 m (2H, NH,
1
(C=O). H NMR spectrum, δ, ppm: 0.80 t (3H,
3
3
CH2CH3, J = 7.0 Hz), 1.25 t (3H, CH2CH3, J =
7.1 Hz), 3.35–3.45 m (1H, OCH2), 3.65–3.70 m (3H,
2
OCH2), 5.04 d and 5.12 d (1H each, CH2Ph, J =
3
15.8 Hz), 7.05 t (1H, C6H4, J = 7.8 Hz), 7.16 d (1H,
3
C6H4, J = 7.8 Hz), 7.32 m (1H, C6H4), 7.38–7.42 m
(6H, C6H5, NH), 7.50 d (1H, C6H4, 3J = 8.2 Hz), 7.85 s
(1H, NH). Mass spectrum, m/z (Irel, %): 441 (1) [M]+,
91 (100) [C7H7]+. Found, %: C 68.07; H 5.28; N 15.81.
C25H23N5O3. Calculated, %: C 68.01; H 5.25; N 15.86.
M 441.48.
3
C6H4), 7.48 t (1H, C6H4, J = 8.6 Hz), 7.71 d (1H,
C6H4, 3J = 7.1 Hz), 7.83 s (1H, NH), 8.23 d (1H, C6H4,
3J = 8.1 Hz), Mass spectrum: m/z 419 (Irel = 1%) [M]+.
Found, %: C 60.19; H 5.12; N 23.32. C21H21N7O3. Cal-
culated, %: C 60.13; H 5.05; N 23.38. M 419.44.
2-Amino-4,4-diethoxy-1′-methyl-2′-oxospiro-
[3-azabicyclo[3.1.0]hex-2-ene-6,3′-indole]-1,5-dicar-
bonitrile (IIh) was synthesized as described above for
IIf (method b) using cyclopropane Ic as starting com-
pound. Yield 61%, mp 189–191°C (decomp.). IR spec-
trum, ν, cm–1: 3342, 3122 (NH2), 2250 (C≡N), 1709
2-Amino-1′-benzyl-2′-oxo-4,4-bis(propan-2-
ylideneaminooxy)spiro[3-azabicyclo[3.1.0]hex-2-
ene-6,3′-indole]-1,5-dicarbonitrile (IIk). Yield 53%,
decomposition point 216–218°C (from acetonitrile). IR
spectrum, ν, cm–1: 3438, 3350 (NH2), 2252 (C≡N),
1700 (C=O), 1680 (C=N). 1H NMR spectrum, δ, ppm:
1.39 s (3H, CH3), 1.52 s (3H, CH3), 1.90–1.93 m
1
(C=O). H NMR spectrum, δ, ppm: 0.80 t (3H,
3
3
2
CH2CH3, J = 7.0 Hz), 1.22 t (3H, CH2CH3, J =
(6H, CH3), 4.99 d and 5.13 d (1H each, CH2Ph, J =
3
7.1 Hz), 3.31 s (3H, NCH3), 3.35–3.45 m (1H, OCH2),
15.9 Hz), 7.02 t (1H, C6H4, J = 7.7 Hz), 7.07 d (1H,
3
3
3.65–3.70 m (3H, OCH2), 7.05 t (1H, C6H4, J =
C6H4, J = 7.7 Hz), 7.25–7.35 m (6H, C6H5, C6H4),
3
3
7.7 Hz), 7.21 d (1H, C6H4, J = 7.8 Hz), 7.28 s (1H,
7.40 s (1H, NH2), 7.60 d (1H, C6H4, J = 7.9 Hz),
NH2), 7.45–7.50 m (2H, C6H4), 7.81 s (1H, NH2).
7.83 s (1H, NH). Mass spectrum, m/z (Irel, %): 481 (1)
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REACTIONS OF 2′-OXO-1′,2′-DIHYDROSPIRO[CYCLOPROPANE-1,3′-INDOLE]-...
399
[M]+, 91 (100) [C7H7]+. Found, %: C 65.41; H 5.12;
N 19.72. C27H25N7O3. Calculated, %: C 65.44; H 5.09;
N 19.79. M 495.53.
10.08 s (1H, NH), 11.48 s (1H, NH, indole). Found, %:
C 60.69; H 2.66; N 25.22. C14H7N5O2. Calculated,
%: C 60.65; H 2.54; N 25.26.
2-Amino-4,4-bis(cyclohexylideneaminooxy)-
5′-methyl-2′-oxospiro[3-azabicyclo[3.1.0]hex-2-ene-
6,3′-indole]-1,5-dicarbonitrile (IIl) was synthesized
as described above for compound IIi from cyclopro-
pane Ib and cyclohexanone oxime. Yield 61%, decom-
position point 185–190°C (from MeCN). IR spectrum,
ν, cm–1: 3440–3380 (NH2), 2250 (C≡N), 1710 (C=O),
1682 (C=N). 1H NMR spectrum, δ, ppm: 0.45 m (1H),
0.85 m (1H), 1.30 m (2H), 1.40 m (1H), 1.60 m (6H),
1.70 m (1H), 1.80 m (1H), 1.95 m (2H), 2.30 m (3H),
2.35 m (1H), 2.60 m (1H) [(CH2)5]; 2.21 s (3H, CH3),
6.86 d (1H, C6H3, 3J = 7.6 Hz), 7.12 d (1H, C6H3, 3J =
7.6 Hz), 7.47 s (2H, NH, C6H3), 7.80 s (1H, NH),
11.12 s (1H, NH, indole). Mass spectrum, m/z (Irel, %):
412 (1) [M – 87]+, 209 (12), 177 (9), 113 (100). Found,
%: C 64.95; H 5.92; N 19.58. C27H29N7O3. Calculated,
%: C 64.91; H 5.85; N 19.63. M 499.56.
Compounds IIIb and IIIc were synthesized in
a similar way.
1′-Benzyl-2-imino-2′,4-dioxospiro[3-azabicyclo-
[3.1.0]hexane-6,3′-indole]-1,5-dicarbonitrile (IIIb).
Yield 58%, decomposition point 170–175°C (from
MeCN). IR spectrum, ν, cm–1: 3651, 3596 (NH), 2254
1
(C≡N), 1733, 1710 (C=O), 1696 (C=N). H NMR
spectrum, δ, ppm: 5.00 d and 5.09 d (1H each, CH2Ph,
3
2J = 15.8 Hz), 7.07 t (1H, C6H4, J = 7.7 Hz), 7.18 d
3
3
(1H, C6H4, J = 7.9 Hz), 7.22 d (1H, C6H4, J =
7.5 Hz), 7.28–7.33 m (1H, C6H5), 7.37–7.41 m (4H,
C6H5), 7.43 t.d (1H, C6H4, 4J = 0.9, 3J = 7.8 Hz), 9.48 s
(1H, NH), 10.12 s (1H, NH). Found, %: C 54.29;
H 2.12; N 27.52. C21H13N5O2. Calculated, %: C 54.36;
H 2.37; N 27.46.
2-Imino-1′-methyl-2′,4-dioxospiro[3-azabicyclo-
[3.1.0]hexane-6,3′-indole]-1,5-dicarbonitrile (IIIc).
Yield 46%, decomposition point 165–168°C (from
MeCN). IR spectrum, ν, cm–1: 3645, 3582 (NH), 2255
2-Amino-4,4-bis(cyclohexylideneaminooxy)-2′-
oxospiro[3-azabicyclo[3.1.0]hex-2-ene-6,3′-indole]-
1,5-dicarbonitrile (IIm) was synthesized as described
above for compound IIh from cyclopropane Ia and
cyclohexanone oxime. Yield 46%, decomposition point
185–187°C (from MeCN). IR spectrum, ν, cm–1:
3440–3370 (NH2), 2250 (C≡N), 1708 (C=O), 1680
1
(C≡N), 1728, 1710, 1700 (C=O), (C=N). H NMR
spectrum, δ, ppm: 3.31 s (3H, CH3), 7.09 t (1H, C6H4,
3
3J = 7.7 Hz), 7.20 d (1H, C6H4, J = 7.7 Hz), 7.25 t
(1H, C6H4, 3J = 7.9 Hz), 7.52 t.d (1H, C6H4, 4J = 1.0,
3J = 7.7 Hz), 9.43 s (1H, NH), 10.09 s (1H, NH).
Found, %: C 61.92; H 3.18; N 10.92. C15H9N5O2. Cal-
culated, %: C 61.85; H 3.11; N 10.99.
1
(C=N). H NMR spectrum, δ, ppm: 0.51 m (1H),
0.90 m (1H), 1.30 (3H), 1.55–1.70 m (7H), 1.80–
2.00 m (3H), 2.20 m (3H), 2.35 m (1H), 2.55 m (1H)
3
2,2′,4-Trioxospiro[3-azabicyclo[3.1.0]hexane-
6,3′-indole]-1,5-dicarbonitrile (IVa). A suspension of
0.323 g (0.001 mol) of compound IIa in 3 ml of 10%
sulfuric acid was stirred at 60°C until the initial com-
pound disappeared completely (according to the TLC
data). The mixture was cooled to room temperature,
and the precipitate was filtered off, washed with cold
acetonitrile, recrystallized, and dried in a vacuum
desiccator. Yield 0.142 g (51%), decomposition point
181–183°C (from MeCN). IR spectrum, ν, cm–1: 3340
(NH), 2255 (C≡N), 1723, 1716, 1708 (C=O). 1H NMR
[(CH2)5]; 6.95 m (2H, C6H4), 7.35 t (1H, C6H4, J =
3
8.2 Hz), 7.40 s (1H, NH), 7.51 d (1H, C6H4, J =
8.0 Hz), 7.75 s (1H, NH), 11.13 s (1H, NH, indole).
Mass spectrum, m/z (Irel, %): 343 (1) 177 (5), 113 (15),
53 (100). Found, %: C 64.29; H 5.62; N 20.12.
C26H27N7O3. Calculated, %: C 64.32; H 5.60; N 20.19.
M 485.54.
2-Imino-2′,4-dioxospiro[3-azabicyclo[3.1.0]hex-
ane-6,3′-indole]-1,5-dicarbonitrile (IIIa). A suspen-
sion of 0.323 g (0.001 mol) of compound IIa in 3 ml
of glacial acetic acid was heated under stirring.
Initially compound IIa dissolved, and then a solid sep-
arated. The mixture was cooled to room temperature,
and the precipitate was filtered off, washed with cold
acetonitrile, recrystallized, and dried in a vacuum
desiccator. Yield 0.147 g (53%), decomposition point
185–187°C (from acetonitrile). IR spectrum, ν, cm–1:
3651, 3442, 3360 (NH), 2252 (C≡N), 1731, 1700,
1685 (C=O), (C=N). 1H NMR spectrum, δ, ppm: 6.98–
3
spectrum, δ, ppm: 7.09 d (1H, C6H4, J = 7.8 Hz),
3
3
7.18 t (1H, C6H4, J = 7.6 Hz), 7.24 d (1H, C6H4, J =
7.9 Hz), 7.52 t (1H, C6H4, 3J = 7.8 Hz), 13.00 br.s (1H,
NH). Found, %: C 60.49; H 2.21; N 20.19. C14H6N4O3.
Calculated, %: C 60.44; H 2.17; N 20.14.
Compounds IVb and IVc were synthesized in
a similar way.
1′-Methyl-2,2′,4-trioxospiro[3-azabicyclo[3.1.0]-
hexane-6,3′-indole]-1,5-dicarbonitrile (IVb). Yield
72%, decomposition point 197–199°C (from MeCN).
3
7.09 m (2H, C6H4), 7.35 d (1H, C6H4, J = 8.0 Hz),
3
7.42 t (1H, C6H4, J = 7.8 Hz), 9.47 s (1H, NH),
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KAYUKOV et al.
400
IR spectrum, ν, cm–1: 3370 (NH), 2260 (C≡N), 1720,
3,3-Bis(4-dimethylaminophenyl)-1H-indol-
2(3H)-one (VII). N,N-Dimethylaniline, 2.5 ml, was
added to a solution of 2.6 g (0.01 mol) of compound Ia
in 30 ml of acetonitrile. The mixture initially turned
dark, and then a colorless solid separated. The precip-
itate was filtered off, washed with acetonitrile, and
dried in air. Yield 0.32 g (86%), mp 249–251°C
(decomp.); published data [7]: mp 249–251°C
(decomp.).
1
1715, 1700 (C=O). H NMR spectrum, δ, ppm: 7.08–
3
7.16 m (2H, C6H43), 7.27 d (1H, C6H4, J = 8.2 Hz),
7.55 t (1H, C6H4, J = 8.0 Hz), 12.98 br.s (1H, NH).
Found, %: C 61.67; H 2.79; N 19.14. C15H8N4O3. Cal-
culated, %: C 61.65; H 2.76; N 19.17.
1′-Benzyl-2,2′,4-trioxospiro[3-azabicyclo[3.1.0]-
hexane-6,3′-indole]-1,5-dicarbonitrile (IVc). Yield
53%, decomposition point 200–205°C (from MeCN).
IR spectrum, ν, cm–1: 3360 (NH), 2251 (C≡N), 1725,
1718, 1705 (C=O). 1H NMR spectrum, δ, ppm: 5.03 m
(2H, CH2), 7.08–7.16 m (3H, C6H5, C6H4), 7.30–
7.45 m (6H, C6H5, C6H4), 13.00 s (1H, NH). Found, %:
C 68.49; H 3.32; N 15.17. C21H12N4O3. Calculated, %:
C 68.48; H 3.28; N 15.21.
2-(2-Oxo-2,3-dihydro-1H-indol-3-ylidene)malono-
nitrile (V). a. Triphenylphosphine, 0.27 g (0.001 mol),
was added to a solution of 0.26 g (0.001 mol) of com-
pound Ia in 3 ml of acetonitrile, and the mixture was
stirred for 15 min. The mixture initially darkened, and
a dark red crystalline product separated. The precip-
itate was filtered off, washed with propan-2-ol, and
dried in air. Yield 0.14 g (72%), mp 238–240°C
(decomp.).
b. Compound Ia, 0.26 g (0.001 mol), was dissolved
in 3 ml of ethyl 2-sulfanylacetate, and the mixture was
kept for 24 h. The dark red precipitate was filtered off,
washed with propan-2-ol, and dried in air. Yield 0.13 g
(65%), mp 239–240°C (decomp.).
c. A solution of 0.26 g (0.001 mol) of compound Ia
in 3 ml of butane-1-thiol was kept for 24 h. The dark
red precipitate was filtered off, washed with propan-2-
ol, and dried in air. Yield 0.12 g (61%), mp 238–240°C
(decomp.).
X-Ray diffraction data for compound VII. Color-
less transparent prisms, monoclinic crystal system;
C22H16N6O; M 380.41; unit cell parameters (at 293 K):
a = 12.4196(13), b = 8.8971(10), c = 19.2044(18) Å;
β = 106.46(1)°; V = 2035.07(40) Å3; dcalc = 1.242 g/cm3;
space group P121/c1; Z = 4. Final divergence factor
R = 0.071.
2-(4-Dimethylaminophenyl)ethylene-1,1,2-tricar-
bonitrile (IX). N,N-Dimethylaniline, 2.5 ml, was
added to a solution of 2.6 g (0.01 mol) of compound Ia
in 30 ml of acetonitrile. The mixture initially turned
dark, and then a colorless solid separated. The precip-
itate was filtered off, the filtrate was evaporated under
reduced pressure (water-jet pump), the residue was
ground with a mixture of acetic acid with water (1:1),
and the black precipitate was filtered off, recrystallized
from acetic acid, and dried in air. Yield 0.36 g (32%),
dark violet needles, mp 170–171°C; published data
[8]: mp 170–171°C.
3,3-Dimorpholino-1H-indol-2(3H)-one (XI) and
2-(dimorpholinomethylidene)malononitrile (XII).
Compound Ia, 2.6 g (0.01 mol), was dispersed in
30 ml of acetonitrile, 2.5 ml of morpholine was added,
and exothermic reaction started. After 2 min, abundant
white solid was filtered off and subjected to fractional
recrystallization from acetonitrile to isolate compound
XI as colorless crystals. Yield 1.88 g (62%), mp 120°C
(decomp.); published data [9]: mp 120°C (decomp.).
Evaporation of the mother liquor gave compound XII
as a white crystalline solid. Yield 0.15 g (12%),
mp 277–279°C; published data [10]: mp 277.5–
278.9°C.
d. Compound (Ia), 0.26 g (0.001 mol), was dis-
solved in 3 ml of butane-1-thiol, a solution of sodium
butane-1-thiolate in butan-1-ol was added, and the
mixture was kept for 24 h. The dark red precipitate
was filtered off, washed with propan-2-ol, and dried in
air. Yield 0.1 g (52%), mp 238–240°C (decomp.).
e. A mixture of 1.5 g (0.01 mol) of 1H-indole-2,3-
dione and 0.7 g (0.01 mol) of malononitrile in aceto-
nitrile in the presence of piperidinium acetate was
heated for 2 h under reflux. The dark red precipitate
was filtered off, washed with propan-2-ol, and dried in
air. Yield 1.66 g (85%), mp 238–240°C (decomp.);
published data [6]: mp 235°C. A sample of V synthe-
sized according to method e was used as reference for
TLC identification and determination of melting points
of mixtures with samples obtained as described in a–d.
X-Ray diffraction data for compound XI. Color-
less transparent prisms, monoclinic crystal system;
C16H21N3O3; M 303.36; unit cell parameters (at
293 K): a = 14.908(7), b = 8.890(1), c = 22.879(1) Å;
β = 97.71(1)°; V = 3004.79(150) Å3; dcalc = 1.341 g/cm3;
space group C12/c1; Z = 8. Final divergence factor
R = 0.090.
X-Ray diffraction data for compound XII. Color-
less transparent prisms, monoclinic crystal system;
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REACTIONS OF 2′-OXO-1′,2′-DIHYDROSPIRO[CYCLOPROPANE-1,3′-INDOLE]-...
401
3. Yashkanova, O.V., Nasakin, O.E., Urman, Ya.G.,
Khrustalev, V.N., Nesterov, V.N., Antipin, M.Yu.,
Lukin, P.M., and Vershinin, E.V., Russ. J. Org. Chem.,
1997, vol. 33, p. 484.
4. Yashkanova, O.V., Nasakin, O.E., Urman, Ya.G.,
Khrustalev, V.N., Nesterov, V.N., Antipin, M.Yu., and
Lukin, P.M., Russ. J. Org. Chem., 1997, vol. 33, p. 475.
5. Lukin, P.M., Kayukova, O.V., Khrustalev, V.N., Neste-
rov, V.N., and Antipin, M.Yu., Russ. J. Org. Chem.,
1999, vol. 35, p. 1693.
6. Walter, W., Chem. Ber., 1902, vol. 35, p. 1320.
7. Bergman, J. and Eklund, N., Tetrahedron, 1980, vol. 36,
p. 1445.
C12H16N4O2; M 248.28; unit cell parameters (at 293 K):
a = 15.731(2), b = 8.148(2), c = 9.582(2) Å; β =
100.13(2)°; V = 1209.0(4) Å3; dcalc = 1.364 g/cm3;
space group C2/c; Z = 8. Final divergence factor
R = 0.0587.
The authors thank the Nanotechnology Collective
Use Center of the Chuvash Republic for performing IR
and mass spectral studies. This work was performed in
the framework of a federal special-purpose program
(state contract no. 16.740.11.0160).
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