Synthesis of a new organic anion by reaction of 4-aryl(hetaryl)-4- oxobutane-1,1,2,2-tetracarbonitriles with ammonia

Full text of DOI:10.1134/S1070428010040299

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 4, pp. 597–598. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © M.Yu. Belikov, O.V. Ershov, A.V. Eremkin, Ya.S. Kayukov, O.E. Nasakin, 2010, published in Zhurnal Organicheskoi Khimii, 2010,
Vol. 46, No. 4, pp. 604–605.
SHORT
COMMUNICATIONS
Synthesis of a New Organic Anion by Reaction of 4-Aryl(hetaryl)-
4-oxobutane-1,1,2,2-tetracarbonitriles with Ammonia
M. Yu. Belikov, O. V. Ershov, A. V. Eremkin, Ya. S. Kayukov, and O. E. Nasakin
I.N. Ul’yanov Chuvash State University, Moskovskii pr. 15, Cheboksary, 428015 Russia
e-mail: belikovmil@mail.ru
Received July 7, 2009
DOI: 10.1134/S1070428010040299
4-Oxoalkane-1,1,2,2-tetracarbonitriles are known to
react with concentrated aqueous ammonia to produce
compounds of two types. Adducts of tetracyanoethyl-
ene and cyclic ketones (such as cyclopentanone and
cyclohexanone) give rise to 2,7-diazabicyclic com-
pounds [1], whereas from aliphatic tetracyanoethylated
ketones isonicotinic acid derivatives are formed [2].
a new organic anion. Intermediate formation of ammo-
nium salts IIa–IIc is confirmed by their transformation
into initial ketones Ia–Ic by the action of dilute hydro-
chloric acid immediately after isolation. Some struc-
tural similarity of salts IIIa–IIIc to betaines described
in [5] may be noted. The latter were synthesized from
tetracyanoethylene and pyridinium ylides.
The structure of compounds IIIa–IIIc was con-
firmed by their IR, H NMR, and mass spectra and
elemental analyses. The synthesis of salts III is an ex-
ample of new reaction pathway of 4-oxoalkane-
1,1,2,2-tetracarbonitriles with ammonia.
There are no published data on reactions of aqueous
ammonia with tetracyanoalkanones derived from
methyl aryl(hetaryl) ketones. When such reactions
were carried out under the conditions reported in
[1, 2], strong tarring occurred, and no individual prod-
ucts were isolated. By varying the conditions of this
reaction we succeeded in obtaining ammonium 4-aryl-
1,1,2,2-tetracyano-4-oxobutan-1-ides IIa–IIc by mix-
ing ketones Ia–Ic with a freshly prepared solution of
ammonia in ethyl acetate at reduced temperature.
1
Ammonium 1,1,2-tricyano-4-(4-methoxyphenyl)-
4-oxobut-2-en-1-ide (IIIa). 4-(4-Methoxyphenyl)-4-
oxobutane-1,1,2,2-tetracarbonitrile (Ia), 0.139 g
(0.5 mmol), was added to 2 ml of a freshly prepared
solution of ammonia in ethyl acetate, cooled to –10°C,
and the mixture was vigorously stirred until it became
homogeneous. After several minutes, a solid separated
and was filtered off, washed with cold ethyl acetate,
and kept for 5–7 days on exposure to air. Yield 0.115 g
(86%), mp 84–85°C. IR spectrum, ν, cm–1: 2230, 2199
Structures analogous to IIa–IIc but having singly
charged metal cations were reported in [3, 4]. Com-
pounds IIa–IIc turned out to be unstable in the solid
state: on exposure to air they lost hydrogen cyanide
with formation of ammonium 4-aryl-1,1,2-tricyano-4-
oxobut-2-en-1-ides IIIa–IIIc that are derivatives of
1
(C≡N); 1667 (C=O). H NMR spectrum, δ, ppm:
3.81 s (3H, OCH3), 6.51 s (1H, CH), 7.01 d (2H,
Harom), 7.07 br.s (4H, NH4), 7.79 d (2H, Harom). Mass
spectrum: m/z 251 (Irel 49%) [M – NH3]+. Found, %:
C 62.51; H 4.77; N 20.95. C14H12N4O2. Calculated, %:
C 62.68; H 4.51; N 20.88.
O
O
NC
NC
CN
CN
NH3, EtOAc
CN
CN
NH4
R
R
CN
CN
Ia–Ic
IIa–IIc
Compounds IIIb and IIIc were synthesized in
a similar way.
O
CN
CN
NH4
Ammonium 1,1,2-tricyano-4-oxo-4-(2-thienyl)-
but-2-en-1-ide (IIIb). Yield 0.096 g (79%), mp 85–
87°C. IR spectrum, ν, cm–1: 2221, 2196 (C≡N); 1672
R
–HCN
CN
1
IIIa–IIIc
(C=O). H NMR spectrum, δ, ppm: 6.41 s (1H, CH),
R = 4-MeOC6H4 (a), 2-thienyl (b), 3,4-(MeO)2C6H3 (c).
7.16 d.d (1H, Harom), 7.19 br.s (4H, NH4), 7.65 d.d (1H,
597

BELIKOV et al.
598
Harom), 7.82 d.d (1H, Harom), Mass spectrum: m/z 227
(Irel 35%) [M – NH3]+. Found, %: C 53.97; H 3.37;
N 22.99. C11H8N4OS. Calculated, %: C 54.09; H 3.30;
N 22.94.
measured on a Bruker DRX-500 spectrometer at
500.13 MHz using DMSO-d6 as solvent and tetra-
methylsilane as internal reference. The mass spectra
(electron impact, 70 eV) were obtained on a Finnigan
MAT Incos 50 instrument.
Ammonium 1,1,2-tricyano-4-(3,4-dimethoxy-
phenyl)-4-oxobut-2-en-1-ide (IIIc). Yield 0.121 g
(81%), mp 108–109°C. IR spectrum, ν, cm–1: 2235,
2197 (C≡N); 1664 (C=O). 1H NMR spectrum, δ, ppm:
3.80 s (3H, OCH3), 3.82 s (3H, OCH3), 6.52 s (1H,
CH), 7.03 d (1H, Harom), 7.08 br.s (4H, NH4), 7.40 d
(1H, Harom), 7.42 d.d (1H, Harom). Mass spectrum: m/z
281 (Irel 41%) [M – NH3]+. Found, %: C 60.32; H 4.79;
N 18.85. C15H14N4O3. Calculated, %: C 60.40; H 4.73;
N 18.78.
REFERENCES
1. Nasakin, O.E., Sheverdov, V.P., Ershov, O.V., Moisee-
va, I.V., Lyshchikov, A.N., Khrustalev, V.N., and Anti-
pin, M.Yu., Mendeleev Commun., 1997, vol. 7, p. 112.
2. Nasakin, O.E., Sheverdov, V.P., Moiseeva, I.V., Lyshchi-
kov, A.N., Ershov, O.V., and Nesterov, V.N., Tetrahedron
Lett., 1997, vol. 38, p. 4455.
3. Nikolaev, E.G., Cand. Sci. (Chem.) Dissertation,
The progress of reactions and the purity of products
were monitored by TLC on Silufol UV-254 plates;
spots were visualized under UV light, by treatment
with iodine vapor, or by heating. The IR spectra were
recorded on an FSM-1202 spectrometer from samples
Moscow, 1985.
4. Carlucci, L., Ciani, G., Proserpio, D.M., and Sironi, A.,
Angew. Chem., Int. Ed. Engl., 1996, vol. 35, p. 1088.
5. Shestopalov, A.M., Sharanin, Yu.A., Aitov, I.A., Neste-
rov, V.N., Struchkov, Yu.T., and Litvinov, V.P., Khim.
Geterotsikl. Soedin., 1991, vol. 27, p. 1087.
1
dispersed in mineral oil. The H NMR spectra were
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 4 2010