Novel transformation of ethyl cyano(dinitro)acetate in the reactions with diazomethane and diazoethane

Full text of DOI:10.1134/S1070428014060256

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2014, Vol. 50, No. 6, pp. 902–903. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © A.G. Tyrkov, E.A. Yurtaeva, 2014, published in Zhurnal Organicheskoi Khimii, 2014, Vol. 50, No. 6, pp. 914–915.
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Novel Transformation of Ethyl Cyano(dinitro)acetate
in the Reactions with Diazomethane and Diazoethane
A. G. Tyrkova and E. A. Yurtaevab
a Astrakhan State University, pl. Shaumyana 1, Astrakhan, 414000 Russia
e-mail: tyrkov@rambler.ru
b Lepra Research Institute, Ministry of Health Protection of the Russian Federation,
proezd Ostrovskogo 3, Astrakhan, 414057 Russia
Received December 27, 2013
DOI: 10.1134/S1070428014060256
Diazomethane is known to react with ethyl cyano-
(dinitro)acetate according to the 1,3-dipolar cycload-
dition pattern to give isomeric ethyl dinitro(N-methyl-
1,2,3-triazol-4-yl)acetates [1]. We have found that pre-
liminary UV irradiation of a solution of diazomethane
in anhydrous diethyl ether changes the direction of its
reaction with ethyl cyano(dinitro)acetate. The reaction
of preliminarily irradiated diazomethane II with ethyl
cyano(dinitro)acetate (I) led to the formation of a mix-
ture of 2,2-dinitropropanenitrile (IV), ethyl formate
(VI), and dinitroacetonitrile ammonium salt (VII).
Diazoethane (III) behaved similarly under analogous
conditions. The formation of compounds IV and V
may be rationalized by intermediate generation of
carbenes from diazoalkanes II and III [2].
position of the corresponding N-nitroso-N-alkylureas
as described in [4].
Reaction of ethyl cyano(dinitro)acetate (I) with
diazoalkanes II and III (general procedure). A solu-
tion of diazoalkane II or III in anhydrous diethyl ether
(preliminarily passed through an OUFK-01 quartz UV
irradiator, λ 320–275 nm) was added in portions to
a solution of 10 mmol of compound I in 50 mL of
anhydrous diethyl ether, cooled to –5 to 5°C, until ni-
trogen no longer evolved. The mixture was kept for 2 h
at 25°C and subjected to chromatography on silica gel
(Silicagel 100/400 µ). Compounds IV and V were
eluted with benzene, ethyl formate (VI) was eluted
with diethyl ether, and ammonium salt VII was eluted
with acetone.
2,2-Dinitropropanenitrile (IV). Yield 0.357 g
(25%), mp 51–52°C (from hexane). IR spectrum, ν,
O
O2N
cm–1: 2250 (C≡N); 1590, 1310 (NO2). H NMR spec-
O2N
O2N
RCHN2 (II, III)
1
R
OEt
O
trum: δ 2.85 ppm, s (3H, CH3). 13C NMR spectrum, δC,
ppm: 24.1 (CH3), 71.9 (C), 106.6 (C≡N). Mass spec-
trum, m/z (Irel, %): 145 (4) [M]+, 130 (16) [M – CH3]+,
99 (62) [M – NO2]+, 46 (100) [NO2]+, 30 (2) [NO]+.
Found, %: C 24.68; H 1.93; N 28.83. C3H3N3O4. Cal-
culated, %: C 24.83; H 2.07; N 28.97. M 145.07.
–N2
O2N
CN
CN
I
IV, V
NO2
CN
VII
NH4
+
+
O2N
H
OEt
2,2-Dinitrobutanenitrile (V). Yield 0.313 g (20%),
mp 87–88°C (from hexane). IR spectrum, ν, cm–1:
2250 (C≡N); 1590, 1310 (NO2). 1H NMR spectrum, δ,
ppm: 1.32 t (3H, CH3, J = 7.5 Hz), 2.55 q (2H, CH2,
VI
II, IV, R = H; III, V, R = Me.
13
The structure of compounds IV and V was deter-
mined on the basis of their IR, H and C NMR, and
mass spectra, and elemental analyses.
J = 7.5 Hz). C NMR spectrum, δC, ppm: 14.1 (CH3),
1
13
39.5 (CH2), 63.4 (C), 106.3 (C≡N). Mass spectrum,
m/z (Irel, %): 159 (3) [M]+, 130 (15) [M – C2H5]+, 113
(60) [M – NO2]+, 46 (100) [NO2]+, 30 (3) [NO]+.
Found, %: C 30.04; H 3.01; N 26.28. C4H5N3O4. Cal-
culated, %: C 30.19; H 3.14; N 26.42. M 159.10.
Ethyl cyano(dinitro)acetate was synthesized ac-
cording to the procedure reported in [3], and diazo-
alkanes II and III were prepared by alkaline decom-
902

NOVEL TRANSFORMATION OF ETHYL CYANO(DINITRO)ACETATE
903
Ethyl formate (VI). Yield 0.109 g (15%), nD20
1.3598 [5].
=
Infrastructure in Russian Higher Schools” (project
no. 13G.637.31.0038) with the use of scientific equip-
ment provided by the “Biotechnologies for the Design
of Novel Pharmaceuticals” Shared Center.
aci-Dinitroacetonitrile ammonium salt (VII).
Yield 0.146 g (10%), mp 182°C [6].
The IR spectra (4000–400 cm–1) were recorded
from solutions in chloroform on an InfraLUM FT-02
spectrometer. The 1H and 13C NMR spectra were meas-
ured on a Bruker Avance II 300 SF instrument at 300
and 75 MHz, respectively, using DMSO-d6 as solvent
and hexamethyldisiloxane as internal reference. The
mass spectra (electron impact, 70 eV) were obtained
on a Finnigan SSQ-7000 instrument with direct sample
admission into the ion source (vaporizer temperature
90–150°C). The elemental compositions were deter-
mined on a Euro Vector EA-3000 automated CHNS
analyzer. The melting points were determined on
an OptiMelt melting point apparatus. The progress of
reactions and the purity of products were monitored by
TLC on Silufol UV-254 plates using acetone–hexane
(2:3) as eluent; spots were developed by treatment
with iodine vapor.
REFERENCES
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grad, 1990.
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Grundpraktikum, Berlin: Wissenschaften, 1976, 15th edn.
Translated under the title Organikum, Moscow: Mir,
1979, vol. 2, p. 254.
3. Parker, C., Tetrahedron, 1962, vol. 17, p. 109.
4. Becker, H.G.O., et al., Organikum. Organisch-chemisches
Grundpraktikum, Berlin: Wissenschaften, 1964, 3rd ed.
Translated under the title Obshchii praktikum po organi-
cheskoi khimii, Moscow: Mir, 1965, p. 532; James, A.,
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5. Dictionary of Organic Compounds, Heilbron, J. and
Bunbury, H.M., Eds., London: Eyre and Spottswoode,
1953, vol. 2, p. 32.
This study was performed under financial support
by the program “Development of Innovative
6. Parker, C.O., Emmons, W.D., Rolewicz, H.A., and
McCallum, K.S., Tetrahedron, 1962, vol. 17, p. 79.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 6 2014