BAICHURIN et al.
68
Signals in the regions δC 80.24–90.71 and 47.97–
cm–1: 1575, 1360 (NO2). 1H NMR spectrum (CD3CN),
52.82 ppm in the proton-decoupled 13C NMR spectra
of V–VIII were assigned to C2 and C3, respectively;
dimethylamino group was characterized by a signal at
δ, ppm: A: 2.89 s [6H, N(CH3)2], 4.96 d (1H, HB,
3
3JAB = 9.38 Hz), 6.35 d (1H, HA, JAB = 9.38 Hz),
6.73 d and 7.23 d (2H each, C6H4), 7.25–7.45 m (5H,
1
C6H5); B: 2.87 s [6H, N(CH3)2], 4.96 d (1H, HB, 3JAB
=
δC 39.55–40.48 ppm. The above assignment of H and
1
13C NMR signals was confirmed by H–13C HMQC
3
9.77 Hz), 6.32 d (1H, HA, JAB = 9.77 Hz), 6.68 d and
7.15 d (2H each, C6H4), 7.25–7.45 m (5H, C6H5).
13C–{1H} NMR spectrum (CD3CN), δC, ppm: A: 39.65
[N(CH3)2], 52.66 (C3), 80.34 (C2); B: 39.65 [N(CH3)2],
52.82 (C3), 80.24 (C2); A + B: 112.68, 123.38, 123.59,
127.70, 128.15, 128.36, 128.61, 129.09, 129.22,
137.42, 137.71, 150.51, 150.68 (Carom, C≡N). Found,
%: N 14.33. C17H17N3O2. Calculated, %: N 14.23.
and 1H–13C HMBC experiments. The HMQC spectrum
of VIII revealed correlations between HA (δ 6.95 ppm)
and C2 (δC 90.71 ppm) and between HB (δ 5.19 ppm)
and C3 which resonated in a stronger field
(δC 51.51 ppm). The HMBC spectrum of VIII con-
tained a cross peak due to coupling of HA (δ 6.95 ppm)
with the carbonyl carbon atom (δC 187.76 ppm).
Our results demonstrate that such highly electron-
deficient compounds as geminal cyano- and acylnitro-
ethenes can be used as convenient nitroalkylating
agents for N,N-dimethylaniline. Arylation products V–
VIII also attract interest from the practical viewpoint
as precursors of potentially biologically active substi-
tuted α-amino acids and α-amino ketones. Compounds
containing a p-(dialkylamino)phenyl fragment are
widely used in medical paractice; examples are
Brilliant Green, lofenal, sarcolysine, dimetpramide,
etc. [12].
b. N,N-Dimethylaniline, 0.182 g (1.5 mmol), was
added to a solution of 0.261 g (1.5 mmol) of com-
pound I in 1.5 ml of acetic acid, and the mixture was
left to stand for 3 days in the dark at room temperature.
The mixture was then treated with a small amount of
ethanol, and the precipitate was filtered off. Yield
0.414 g (94%), A/B ratio 1.07:1, colorless crystals,
mp 120–122°C (from EtOH).
3-(4-Dimethylaminophenyl)-3-(4-methoxy-
phenyl)-2-nitropropanenitrile (VI) was synthesized
as described above for compound V (method b). Yield
0.372 g (76%), A/B ratio ~1:1, colorless crystals,
mp 158–160°C (from EtOH). IR spectrum, ν, cm–1:
EXPERIMENTAL
1
1575, 1360 (NO2). H NMR spectrum (CD3CN), δ,
1
1
1
The H, 13C–{1H}, H–13C HMQC, and H–13C
HMBC NMR spectra were recorded on a Jeol JNM-
ECX400A spectrometer at 399.78 (1H) and
100.53 MHz (13C); the chemical shifts were measured
relative to the residual proton and carbon signals of the
solvent. The IR spectra were obtained on a Shimadzu
IR-Prestige-21 spectrometer with Fourier transform
from solutions in chloroform. The elemental composi-
tions were determined on a EuroVector EA 3000
analyzer (CHN Dual).
ppm: A: 2.89 s [6H, N(CH3)2], 3.73 s (3H, OCH3),
4.89 d (1H, HB, 3JAB = 9.46 Hz), 6.27 d (1H, HA, 3JAB
=
9.46 Hz), 6.72 d and 7.14 d (2H each, Me2NC6H4),
6.88 d, 7.23 d (2H each, MeOC6H4); B: 2.87 s [6H,
3
N(CH3)2], 3.75 s (3H, OCH3), 4.90 d (1H, HB, JAB
=
3
9.46 Hz), 6.26 d (1H, HA, JAB = 9.46 Hz), 6.69 d and
7.33 d (2H each, Me2NC6H4), 6.92 d and 7.25 d (2H
each, MeOC6H4). Found, %: N 12.55. C18H19N3O3.
Calculated, %: N 12.92.
3-(4-Dimethylaminophenyl)-2-nitro-3-(2-thienyl)-
propanenitrile (VII). N,N-Dimethylaniline, 0.363 g
(3 mmol), was added to a solution of 0.270 g
(1.5 mmol) of compound III in 4 ml of methanol, and
the mixture was stirred for 6 h at room temperature
using a magnetic stirrer. The mixture was left over-
night, and the precipitate was filtered off. Yield 0.146 g
(32%), A/B ratio ~1.2:1, light violet crystals, mp 140–
142°C (from MeOH). IR spectrum, ν, cm–1: 1575,
Initial cyanonitroethenes I–III [1–3] and benzoyl-
nitrostyrene IV [4] were prepared according to known
procedures.
3-(4-Dimethylaminophenyl)-2-nitro-3-phenyl-
propanenitrile (V). a. Freshly distilled N,N-dimethyl-
aniline, 0.545 g (4.5 mmol), was added to 0.261 g
(1.5 mmol) of 2-nitro-3-phenylprop-2-enenitrile (I),
and the mixture was heated until it became homo-
geneous and left to stand for 3 days in the dark at room
temperature. The mixture was then treated with a small
amount of ethanol, and the precipitate was filtered off.
Yield 0.330 g (75%), A/B ratio ~1.3:1, colorless crys-
tals, mp 104–106°C (from EtOH). IR spectrum, ν,
1
1360 (NO2). H NMR spectrum (CD3CN), δ, ppm: A:
2.91 s [6H, N(CH3)2], 5.23 d (1H, HB, 3JAB = 7.86 Hz),
6.28 d (1H, HA, 3JAB = 7.86 Hz), 6.72 d and 7.27 d (2H
each, C6H4); 6.99 t, 7.20 d, 7.36 d (3H, C4H3S); B:
2.89 s [6H, N(CH3)2], 5.31 d (1H, HB, 3JAB = 8.01 Hz),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 1 2013