2-acyl(aroyl)-1,1,3,3-tetracyanopropenides: V. Reaction with hydrazine hydrate

Article abstract of DOI:10.1134/S1070428013050126

Reactions of 2-acyl(aroyl)-1,1,3,3-tetracyanopropenides with hydrazine hydrate followed by neutralization led to the formation of 2-amino-4- [hydrazono(aryl)methyl]-2-oxo-1,2-dihydropyridine-3,5-dicarbonitriles.

Full text of DOI:10.1134/S1070428013050126

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 5, pp. 707−711. © Pleiades Publishing, Ltd., 2013.
Original English Text © Ya.S. Kayukov, S.V. Karpov, M.M. Rizatdinov, I.N. Bardasov, O.V. Ershov, O.E. Nasakin, V.A. Tafeenko, 2013, published in Zhurnal
Organicheskoi Khimii, 2013, Vol. 49, No. 5, pp. 724−728.
2-Acyl(aroyl)-1,1,3,3-tetracyanopropenides: V.*
Reaction with Hydrazine Hydrate
Ya. S. Kayukova, S. V. Karpova, M. M. Rizatdinova, I. N. Bardasova,
O. V. Ershova, O. E. Nasakina, and V. A. Tafeenkob
aI.N. Ul’yanov Chuvash State University, Cheboksary, 428015 Russia
e-mail: kaukovyakov@mail.ru
bLomonosov Moskow State University, Moscow, Russia
Received July 15, 2012
Abstract—Reactions of 2-acyl(aroyl)-1,1,3,3-tetracyanopropenides with hydrazine hydrate followed by
neutralization led to the formation of 2-amino-4-[hydrazono(aryl)methyl]-2-oxo-1,2-dihydropyridine-3,5-
dicarbonitriles.
DOI: 10.1134/S1070428013050126
2-Acyl(aroyl)-1,1,3,3-tetracyanopropenides I [2]
demonstrated their opportunities as promising blocks
for designing highly functionalized heterocyclic com-
pounds. They underlie the domino processes affording
2-halodihydrofurans [2], 2-alkylsulfinyldihydrofurans
[3], 2-halopyridines 4], and furo[3,4-c]pyridines [1].
Besides propenides I are intermediates in the reactions of
tetracyanocyclopropyl ketones with some nucleophiles.
For instance, the reaction of tetracyanocyclopropyl ke-
tones with hydroxide ion and primary amines proceeds
through the intermediate formation of propenides I which
transform subsequently into the derivatives of pyrrolo-
[3,4-c]pyridine [5] and pyrrolo[2,3-b]pyrrole [6]. The
reaction of tetracyanocyclopropyl ketones with hydrazine
hydrate occurred with the retention of the there-membered
ring except for the pivaloyltetracyanocyclopropane that
gave in this reaction substituted pyrrolo[2,3-c]pyridazine
[7]. It was presumed that the intermediate in this reaction
was 2-pivaloyl-1,1,3,3-tetracyanopropenide (Ii). To test
this assumption and to extend this reaction to the other
2-acyl(aroyl)-1,1,3,3-tetracyanopropenides we examined
the reactions of propenides Iа–Ii with hydrazine hydrate.
Propenides Iа–Ii react with hydrazine hydrate in equi-
molar amounts in inert solvents at the room temperature
with a notale self-heating. At the excess of hydrazine
hydrate the reaction is accompanied with tarring hamper-
ing the isolation of the reaction products and decreasing
their yields. In the reaction of propenides Ia, Ih in an-
hydrous dioxane we obtained the corresponding sodium
6-amino-4-[hydrazono(aryl)methyl]-3,5-dicyanopyridin-
2-olates IIа, IIh. Pyridones IIIа, IIIh were obtained by
neutralization of the water solutions of salts IIа, IIh with
sulfuric acid. 2-Amino-4-[hydrazono(aryl)methyl]-2-
oxo-1,2-dihydropyridine-3,5-dicarbonitriles IIIb–IIIg,
IIIi were isolated after the neutralization of the reaction
mixture with sulfuric acid.
H2N
H2N
O
CN
N
CN
N
CN
O Na+
O
NH2NH2
H2SO4
R
CN
Na+
R
R
_Na2SO4
NH
N
NC
CN
NC
NC
NH2
NH2
IIа, IIh
Iа_Ii
IIIа_IIIi
R = Ph (а), 3,4-(MеO)2С6H3 (b), 4-MеOС6H4 (c), 4-BrС6H4 (d), 3-СlС6H4 (e), 3-O2NС6H4 (f), C4H3S (g), 2,5-(MеO)2С6H3 (h), t-Bu(i).
–––––––––––––––
a For communication IV, see [1].
707

KAYUKOV et al.
708
The composition and structure of compounds IIа,
the water atom О4iv and the atom N4i of the nitrile group.
In the polymer chain Na1–O2–Na2–O4–Na1–O2 etc. the
interatomic distance Na1…Na2 is 3.204(2) Å.
1
IIh and IIIа–IIIi were derived from the data of Н,
1
13C, NMR, IR, and mass spectra. Н NMR spectra of
compounds IIIа–IIIi contain singlets of the protons
of the NH group of the pyridine ring (pyridone) in the
region 11.41–11.49 ppm, of the aromatic amino group
(7.59–8.30 ppm), and of the amino group of the hydrazone
fragment (6.25–7.48 ppm). The signals of the aromatic
substituents appear with the characteristic multiplicity
in the usual region. The probable alternative structure
of pyrido[3,4-d]-pyridazines is rejected based on the
13С NMR spectra of compounds IIIh, IIIi, for the spec-
tra contained the carbon atom signals from two cyano
groups. Mass spectra are similar, they contain molecu-
lar ion peaks of relatively high intensity, and also ions
[M – 28]+ and [ArC=N]+. The IR spectra of compounds
IIIа–IIIi contain absorption bands of the hydrazone frag-
ment (1650–1682 cm–1), of the conjugated cyano groups
(2200–2235 cm–1), and also of amino groups (3150–3200
and 3300–3350 cm–1). In the 1Н NMR spectra of salts IIа,
IIh the signals from the pyridine unit NH are absent and
besides the signals of the NH2 groups are shifted upfield.
At least two ways are presumable of the formation of
compounds II from propenides I.
The first route assumes an independent occurrence of
heterocyclization due to the addition of a hydroxide ion to
a cyano group and of the nucleophilic substitution at the
carbonyl group under the action of hydrazine. However
it was shown in [5] no direct addition of the hydroxide
ion to cyano groups of propenides I was observed even
at the action of alkali metal hydroxides. Therefore the
alternative path is more probable where the formation of
the hydrazone fragment and of the pyridine ring are the
stages in the single process. The reaction starts with the
nucleophilic addition of hydrazine to the carbonyl group
affording a tetrahedral intemediate, hydrazinehydrin А.
Then a closure occurs of a furan ring resulting from the
hydroxy group addition to the cyano group with the for-
mation of intermediate B. As has been stated formerly
[8], iminofurans are unstable when containing a labile
hydrogen atom bound to a heteroatom in the β-position
with respect to an oxygen. They cannot be isolated since
they undergo a spontaneous iminolactone-lactame rear-
rangement. In our case due to the opening of the furan ring
the hydrazone fragment and the carboxamide function are
formed, and for the latter the addition to the cyano group
to give a pyridine system is preferable.
The structure of salt IIа was established by XRD anal-
ysis of a single crystal(see the figure). Two independent
sodium atoms are located in the crystallographic plane m
and are linked by bridging atoms of water О1 (in a general
position) and О2 (located in the m plane). The octahedral
surrounding of the atom Na1 is completed by the water
atom О4 and by the atom О3, and of the atom Nа2, also by
i = 0.5 + x, y, 0.5 – z; ii = –0.5 + x, 0.5 – y, 0.5 – z; iii = x, 0.5 – y, z; iv = –0.5 + x, 0.5 – y, 0.5 – z.
Afragment of the crystal structure of IIa molecule showing the spatial arrangement of atoms in the molecule and the way of coordination
of sodium cations (Na1, Na2). Thermal ellipsoids are shown with the 50% probability.
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2-ACYL(AROYL)-1,1,3,3-TETRACYANOPROPENIDES: V.
709
OH
N
O
CN
H
O
CN
O
CN
CN
R
N
Na+
NH2
CN
O
OH
OH
R
R
R
NC
H
N2
4
_
_
H
N2
N
N
N
4
NC
NC
Na+
NC
+
+
H
H
O
N2H5
H2N
O
5
Na+
NH2
2
N
N
+
Na+
_H2O
N2H5
II
I
NH2
N
2
Na+
N
NH
H
4
H2N
HN
NH
CN
OH
H2N
HO
R
H2N
HN
O
N
NC
CN
CN
OH
R
CN
CN
CN
Na+
R
R
NC
+ HN
NC
CN
Na+
NC
NC
CN
Na
B
А
was done using program DIAMOND [10].
EXPERIMENTAL
The crystallographic data are deposited to the
Cambridge Crystallographic Data Center and ccan be
freely obtained at the address CCDC, 12 Union Road,
Cambridge, CB2 1EZ, UK (e-mail: deposit@ccdc.cam.
ac.uk or http://www.ccdc.cam.ac.uk), ССDC 889154.
The monitoring of the reaction progress and checking
the purity of obtained compounds was performed by TLC
on Silufol UV-254 plates (development under UV irradia-
tion, in iodine vapor, and also by thermal decomposition).
IR spectra were recorded on a Fourier spectrophotometer
FSM-1202 from mulls in mineral oil. 1Н and 13C NMR
spectra were registered on a spectrometer Bruker DRX-
500 (500.13 and 125.76 MHz respectively) in DMSO-
d6, internal reference TMS. Mass spectra were taken on
an instrument Simadzu GCMS-QP2010S DI (electron
impact, 70 eV).
Sodium 6-amino-4-[hydrazono(phenyl)methyl]-
3,5-dicyanopyridin-2-olate hydrate (IIа). To a solution
of 0.27 g (1 mmol) of propenide Iа in 2 ml of dioxane
was added 0.05 g (1 mmol) of hydrazine hydrate, the mix-
ture was stirred for 10 min, left overnight, the separated
precipitate was filtered off and washed with dioxane.
Yield 0.165 g (55%), decomp. >150°С. IR spectrum, ν,
cm–1: 3224 (NH2), 2210 (C≡N), 1630 (C=O). 1Н NMR
spectrum, δ, ppm: 6.14 s (2H, NH2), 6.53 br.s (2H, NH2),
7.24 t (1Нarom, J 7.3Hz), 7.32 t (2Harom, 3J 7.4 Hz), 7.39 d
(2Harom, 3J 7.9 Hz). Found, %: C 50.24; H 3.87; N 24.67.
C14H9N6NaO·2H2O. Calculated, %: C 50.00; H 3.90; N
24.99.
XRD study on a crystal of compound IIa obtained by
slow evaporation from the water solution was performed
on a diffractometer StadiVari Pilatus 100K STOE, CuKα
radiation from the generator GeniX3D Cu HF equipped
with a microfocus X-ray tube and multilayer thin-
film ellipsoidal monochromator FOX3D HF Xenocs
(France). Data array, establishing and refining of the
unit cell parameters, the diffraction data processing was
performed with the use of the program package STOE
X-Area. The main crystallographic parameters are as
follows: C14H9N6NaO·2H2O, M 336.29; a 9.8673(2), b
34.8250(9), c 8.8329(2) Å; V 3035.24(12) Å3; dcalc 1.472
g/cm3; space group Pnma, Z 8. The structure was solved
by the direct method applying software SHELXS-97 [9].
The refinement of the positions and thermal parameters of
nonhydrogen atoms was carried out in full-matrix aniso-
tropic approximation. Hydrogen atoms were localized
from the difference Fourier synthesis and freely refined
in an isotropic approximation. The final R-factor for 1619
reflections with I > 2σ(I) is 0.035. Molecular graphics
Sodium 6-amino-4-[hydrazono(2,5-dimethoxy-
phenyl)methyl]-3,5-dicyanopyridine-2-olate hydrate
(IIh) was obtained similarly. Yield 78%. IR spectrum, ν,
cm–1: 3237 (NH2), 2209 (C≡N), 1642 (C=O). 1Н NMR
spectrum, δ, ppm: 3.51 s (3Н, ОCH3), 3.70 s (3Н, ОCH3),
5.97 s (2H, NH2), 6.50 br.s (2H, NH2), 6.82 d.d (1Нarom
,
3J 8.9, J 3.1 Hz), 6.88 d (1Нarom, J 8.9 Hz), 7.04 d
(1Нarom, 4J 3.1 Hz). Found, %: C 48.52; H 4.25; N 21.09.
C16H13N6NaO3·2H2O. Calculated, %: C 48.49; H 4.32;
N 21.20.
4
3
6-Amino-4-[hydrazono(phenyl)methyl]-2-oxo-
1,2-dihydropyridine-3,5-dicarbonitrile (IIIа). а. To
a solution of 1.34 g (5 mmol) of propenide Iа in 8 ml
of acetonitrile was added a solution of 0.25 g (5 mmol)
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 5 2013

KAYUKOV et al.
710
of hydrazine hydrate in 2 ml of acetonitrile, the mixture
was stirred for 1 min and left overnight, then it was
neutralized with 5% H2SO4, the separated precipitate
was filtered off, washed with water, and recrystallized
from the mixture acetonitrile–dioxane, 1:1. Yield 1.13 g
(81%), mp 143–146°С (decomp.). IR spectrum, ν, cm–1:
3387, 3326 (NH2), 2223 (C≡N), 1670 (C=O). 1Н NMR
spectrum, δ, ppm: 7.22 s (2H, NH2), 7.35–7.39 m (2Harom,
ААґВВґ system, 3J 8.6 Hz), 7.52–7.54 m (2Harom, АА'ВВ'
system, 3J 8.6 Hz), 7.70–8.30 s (2H, NH2), 11.7 s (1H,
NH). Mass spectrum, m/z (Irel, %): 358 (34), 356 (30),
184 (18), 182 (20). Found, %: C 46.91; H 2.48; N 23.44.
C14H9BrN6O. Calculated, %: C 47.08; H 2.54; N 23.53.
M 356.00.
2-Amino-4-[(hydrazono)(3-chlorophenyl)methyl]-
2-oxo-1,2-dihydropyridine-3,5-dicarbonitrile (IIId).
Yield 84%, t.decomp. 190–200°С. IR spectrum, ν,
cm–1: 3403, 3338, 3216 (NH2), 2225 (C≡N), 1675 (C=O).
1Н NMR spectrum, δ, ppm: 7.30–7.38 m (3Harom), 7.40 s
(2H, NH2), 7.47 s (1Harom), 7.81 s (2H, NH2), 11.82 s
(1H, NH). Mass spectrum, m/z (Irel, %): 314 (9), 312
(28) [M]+, 286 (13), 284 (37) [M – 28]+, 140 (22), 139
(75), 138 (30), 137 (61), 109 (100). Found, %: C 53.73;
H 2.98; N 26.84. C14H9ClN6O. Calculated, %: C 53.77;
H 2.90; N 26.87. M 312.05.
spectrum, δ, ppm: 7.14 s (2H, NH2), 7.26 t (1Harom
,
,
3
3J 7.4 Hz), 7.34 t (2Harom, J 7.4 Hz), 7.43 d (2Harom
3J 7.8 Hz), 7.78 br.s (2H, NH2), 11.82 (1H, NH). Mass
spectrum, m/z (Irel, %): 278 (100) [M]+, 250 (70) [M –
28]+, 103 (32) [PhC=N]+. Found, %: C 60.40; H 3.65;
N 30.17. C14H10N6O. Calculated, %: C 60.43; H 3.62;
N 30.20. M 278.09.
b. To a solution of 0.3 g (1 mmol) of salt IIа in 3 ml of
water was added 5% H2SO4 till neutral pH, the separated
precipitate was filtered off and worked up as in procedure
а. Yield 0.26 g (93%).
2-Amino-4-[hydrazono(3-nitrophenyl)methyl]-
2-oxo-1,2-dihydropyridine-3,5-dicarbonitrile (IIIf).
Yield 62%, mp 231–232°С (decomp.). IR spectrum, ν,
cm–1: 3398, 3211 (NH2), 2223 (C≡N), 1664 (C=O), 1537,
Compounds IIIb–IIIi were synthesized by proce-
dure а.
2-Amino-4-[(hydrazono)(3,4-dimethoxyphenyl)-
methyl]-2-oxo-1,2-dihydropyridine-3,5-dicarbo-
nitrile (IIIb). Yield 65%, mp 139–140°С (decomp.). IR
spectrum, ν, cm–1: 3320, 3214 (NH2), 2230 (C≡N), 1659
(C=O). 1Н NMR spectrum, δ, ppm: 3.76 s (3H, ОCH3),
3.77 s (3H, ОCH3), 6.67 d.d (1Harom, 3J 8.3, 4J 1.9 Hz),
1
1375 (NO2). Н NMR spectrum, δ, ppm: 7.48 s (2H,
3
NH2), 7.64 t (1H, C6H4, J 8.0 Hz), 7.75 d (1H, C6H4,
3J 8.0 Hz), 8.09 d.d (1H, C6H4, 3J 8.0, 4J 1.9 Hz), 8.10 br.s
(2H, NH2), 8.27 t (1H, C6H4, 4J 1.9 Hz), 11.8 (1H, NH).
Mass spectrum, m/z (Irel, %): 323 (2), 297 (5.5). Found,
%: C 52.18; H 2.86; N 30.09. C14H9N7O3. Calculated,
%: C 52.02; H 2.81; N 30.33. M 323.08.
3
6.87 d (1Harom, J 8.5 Hz), 6.89 s (2H, NH2), 7.28 d
4
(1Harom, J 1.9 Hz), 7.90 br.s (2H, NH2), 12.50–11.50
2-Amino-4-[hydrazono(2-thienyl)methyl]-2-oxo-
1,2-dihydropyridine-3,5-dicarbonitrile (IIIg). Yield
64%, t.decomp. >170°С (decomp). IR spectrum, ν, cm–1:
3400, 3230 (NH2), 2225 (C≡N), 1676 (C=O). 1Н NMR
spectrum, δ, ppm: 6.78 d.d (1H, C4H3S, 3J 3.6, 4J 1.0 Hz),
6.97 d.d (1H, C4H3S, 3J 5.1, 3J 3.6 Hz), 7.08 s (2H, NH2),
7.39 d.d (1H, C4H3S, J 5.1, J 1.0 Hz), 7.80 br.s (2H,
NH2), 11.70 br.s (1H, NH). Mass spectrum, m/z (Irel, %):
284 (8). Found, %: C 50.57; H 2.71; N 29.39. C12H8N6OS.
Calculated, %: C 50.70; H 2.84; N 29.56. M 284.05.
br.s (1H, NH). Mass spectrum, m/z (Irel, %): 338 (4), 307
(1). Found, %: C 56.31; H 4.33; N 24.21. C16H14N6O3.
Calculated, %: C 56.80; H 4.17; N 24.84. M 338.11.
2-Amino-4-[hydrazono(4-methoxyphenyl)methyl]-
2-oxo-1,2-dihydropyridine-3,5-dicarbonitrile (IIIc).
Yield 73%, t.decomp. 130–140°С. IR spectrum, ν,
cm–1: 3340, 3320 (NH2), 2219 (C≡N), 1674 (C=O), 1654
(C=N). 1Н NMR spectrum, δ, ppm: 3.76 s (3H, ОCH3),
6.84 s (2H, NH2), 6.89–6.93 m (2Harom, ААґВВґsystem,
3J 8.9 Hz), 7.35–7.39 m (2Harom, ААґВВґsystem,
3J 8.9 Hz), 7.94 br.s (2H, NH2), 10.80–12.60 br.s (1H,
NH). Mass spectrum, m/z (Irel, %): 308 (9). Found, %:
C 58.33; H 3.71; N 26.93. C15H12N6O2. Calculated, %:
58.44; H 3.92; N 27.26. M 308.10.
3
4
2-Amino-4-[(hydrazono)(2,5-dimethoxyphenyl)-
methyl]-2-oxo-1,2-dihydropyridine-3,5-dicarbo-
nitrile (IIIh) was obtained by procedure b. Yield 97%,
t.decomp. 220–230°С. IR spectrum, ν, cm–1: 3410, 3214
(NH2), 2230 (C≡N), 1670 (C=O). 1Н NMR spectrum, δ,
ppm: 3.54 s (3H, ОCH3), 3.71 s (3H, ОCH3), 6.85 d.d
2-Amino-4-[(4-bromophenyl)(hydrazono)methyl]-
2-oxo-1,2-dihydropyridine-3,5-dicarbonitrile (IIId).
Yield 64%, t.decomp. >185°С. IR spectrum, ν, cm–1:
3387, 3222 (NH2), 2224 (C≡N), 1665 (C=O). 1Н NMR
3
4
3
(1Harom, J 8.9, J 3.1 Hz), 6.92 d (1Harom, J 8.9 Hz),
4
7.12 d (1Harom, J 3.1 Hz), 7.16 s (2H, NH2), 7.59 br.s
(2H, NH2), 11.62 br.s (1H, NH). 13С NMR spectrum, δ,
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2-ACYL(AROYL)-1,1,3,3-TETRACYANOPROPENIDES: V.
711
ppm: 55.19 (CH3), 56.55 (CH3), 73.47 (C3), 87.69 (C5),
112.67 (C6'), 114.25 (C3'), 114.42 (C4'), 114.76 (CN),
115.46 (CN), 126.30 (C1'), 133.11 (C4), 148.75 (C=NNH2),
153.21 (C2'), 155.13 (C5'), 159.50 (C6), 160.25 (C2). Mass
spectrum, m/z (Irel, %): 338 (27) [M]+, 310 (30) [M – 28]+,
124 (93), 109 (100). Found, %: C 56.75; H 4.19; N 24.81.
C16H14N6O3. Calculated, %: C 56.80; H 4.17; N 24.84.
M 338.11.
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2-Amino-4-(1-hydrazono-2,2-dimethylpropyl)-
2-oxo-1,2-dihydropyridine-3,5-dicarbonitrile (IIIi).
Yield 78%, mp 217–218°С. IR spectrum, ν, cm–1:
3395, 3192 (NH2), 2231 (C≡N), 1672 (C=O). 1Н NMR
spectrum, δ, ppm: 1.17 s [9H, C(CH3)3], 6.25 s (2H,
NH2), 7.69 s (2H, NH2), 11.72 br.s (1H, NH). 13C NMR
spectrum, δ, ppm: 29.40, 29.51, 29.55 [С(СH3)3], 33.47
[С(СH3)3], 73.42 (С3), 88.12 (С5), 115.56 (СN), 116.39
(СN), 145.09 (С4), 157.26 (С6), 159.03 (С=NNH2), 160.12
(С2). Mass spectrum, m/z (Irel, %): 258 (1), 88 (19), 58
(41), 57 (45). Found, %: C 55.84; H 5.48; N 32.37.
C12H14N6O. Calculated, %: C 55.80; H 5.46; N 32.54.
M 258.12.
ACKNOWLEDGMENTS
The study was carried out under a financial support
of the Ministry of Education and Science of the Russian
Federation (State contract no. 16.740.11.0335, Federal
targeted program «Scientific and pedagogical staff of
innovative Russia»).
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10.Brandenburg, K., DIAMOND, Release 2.1d Crystal Impact,
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 5 2013