Preparation of 2-benzoyl-1-bromo-1-nitroethene

Full text of DOI:10.1023/B:RUJO.0000045911.51240.a1

Russian Journal of Organic Chemistry, Vol. 40, No. 8, 2004, pp. 1219-1220. Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 8, 2004,
pp. 1266-1267.
Original Russian Text Copyright Ó 2004 by Sadikov, Litovchenko, Makarenko, Berestovitskaya.
SHORT
COMMUNICATIONS
Preparation of 2-Benzoyl-1-bromo-1-nitroethene
K.D. Sadikov, K.M. Litovchenko, S.V. Makarenko, and V.M. Berestovitskaya
Herzen Russian State Pedagogical University, St. Petersburg, 191186 Russia
e-mail: kohrgpu@yandex.ru
Received April 20, 2004
Halonitroalkenes belong to an interesting class of
organic compounds with reach synthetic opportunities
[1, 2]. Aspecial attention are worth gem-halonitroethenes
containing an electron-withdrawing substituent in a
vicinal position to the nitro group. For instance, gem-
halonitroethenes with a phosphonate function are highly
active in reactions with nucleophilic reagents [3, 4], in
diene synthesis [5, 6], and can be regarded as convenient
“building blocks” for preparation of substances with
specially designed structure.
Bromonitroethenyl phenyl ketone (III) was isolated as
light-yellow low-melting crystals (yield 63%). Reaction
of bromonitroethenyl phenyl ketone (III) with double
excess of aniline in anhydrous benzene furnishes
nitroenamine IV that may be regarded as resulting from
dehydrohalogenation of the primarily arising addition
product. Nitroenamine IV was also prepared directly
from dibromide II, and a mixed sample of nitroenamines
obtained by both methods melted with no depression of
the melting point.
The structure of compounds II–IV was proved by
IR, 1H NMR, and UV spectroscopy. For instance, in the
IR spectrum of compound III were present absorption
bands corresponding to all functional groups; therewith
the bands of nitrogroup stretching vibrations (nas 1560,
We synthesized the first representative of carbonyl-
containing gem-halonitroethenes, 2-benzoyl-1-bromo-1-
nitroethene. The preparation procedure involves two
stages: bromination of initial 2-benzoyl-1-nitroethene (I)
with subsequent dehydrobromination of addition product
II. Reaction of compound I with a double excess of
bromine in the glacial acetic acid or in carbon
tetrachloride afforded dibromide II, and the best yield
(65%) was obtained at at bromination in carbon
tetrachloride. Compound II is a light-yellow oily fluid.
–1
–1
ns 1320 cm ) appear with the difference Dn 240 cm
characteristic of conjugated nitroalkenes containing a
halogen in the gem-position with respect to the nitro
group [7]. In the 1H NMR spectrum the olefin proton is
located downfield (8.48 ppm.) that corresponds to its cis-
orientation regarding the nitro group [8]. The IR and
electronic spectra of compound IV reveal a high
polarization in its molecule.
Dehydrohalogenation of dibromide II in CCl4 was
effected by triethylamine within 1 h at room temperature.
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1070-4280/04/4008-1219Ó2004 MAIK “Nauka/Interperiodica”

1220
SADIKOV et al.
spectrometer Bruker AC-200 (200 MHz) from solutions
The initial 2-benzoyl-1-nitroethene was prepared by
in deuterochloroform, external reference HMDS.
Electron absorption spectra were obtained on
spectrophotometer SF-121 from solutions in ethanol.
a published procedure [9].
The reaction progress was monitored and homo-
geneity of compounds obtained was checked by TLC on
Sulufol UV-254 plates, eluent hexane–acetone, 3:1,
development in iodine vapor or under UV irradiation.
The study was carried out under financial support of
the Ministry of Education of the Russian Federation
(grant no. E02-5.0-138).
2,3-Dibromo-3-nitro-1-phenylpropan-1-one (II). Rf
–1
0.48. IR spectrum, cm : 1690 (C=O), 1572, 1352 (NO2),
REFERENCES
1
1600 (C=C). H NMR spectrum, d, ppm (J, Hz): 8.05–
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7.56 (5H, C6H5), 6.47–6.40 q (1H, CHBrNO2), 5.85–
5.66 q (1H, CHBrCO). Found, %: C 32.20, 32.26; H 2.58,
2.60; N 4.25, 4.23. C9H7Br2NO3. Calculated, %: C 32.05;
H 2.08; N 4.15.
2-Benzoyl-1-bromo-1-nitroethene (III). Rf 0.58,
mp 25–26°C (from petroleum ether). IR spectrum, cm :
1685 (C=O), 1560, 1320 (NO2), 1600, 1580 (C=C). H
NMR spectrum, d, ppm (J, Hz): 8.48 s (1H, CHNO2),
7.27–7.92 m (5H, C6H5). UV spectrum: lmax, nm (e):
253 (14300). Found, %: C 42.41, 42.43; H 2.03, 2.01;
N 5.51, 5.53. C9H6BrNO3. Calculated, %: C 42.35;
H 1.96; N 5.49.
–1
1
2-Anilino-2-benzoyl-1-nitroethene (IV), mp 125–
6. Berestovitskaya, V.M., Anisimova, N.A., Litvinov, I.A.,
Kuzhaeva, A.A., Gubaidullin, A.T., Berkova, G.A.,
Krivolapov, D.V., and Deiko, L.I., Zh. Obshch. Khim., 2004,
vol. 74, p. 574.
–1
126°C (from heptane). IR spectrum, cm : 1680 (C=O),
–
1595, 1583 (C=C, C=N+), 1370, 1282, 1257, 1190 (NOO
). 1H NMR spectrum, d, ppm (J, Hz): 11.0 (1H, NH),
6.9–7.9 m (5H, C6H5), 6.7 (1H, CHNO2). UV spectrum:
7. Paperno, T.Ya. and Perekalin, V.V., Infrakrasnye spektry
nitrosoedinenii (IR Spectra of Nitro Compounds),
Leningrad, 1974, 185 p.
8. Trukhin, E.V., Makarenko, S.V., and Berestovitskaya, V.M.,
Zh. Org. Khim., 1998, vol. 34, p. 72.
l
max, nm (e): 244 (16700), 362 (14900). Found, %:
C 67.22, 67.25; H 4.68, 4.67; N 10.55, 10.54.
C15H12N2O3. Calculated, %: C 67.16; H 4.47; N 10.44.
IR spectra were registered on spectrophotometer
9. Necmeyanov, A.N., Rybin, L.V., and Rybinskaya, M.I., Izv.
Akad. Nauk SSSR, Ser. Khim., 1962, p. 899.
InfraLUM FT-O2 from chloroform solutions, c 0.1–
1
0.001 mol l-1, H NMR spectra were registered on
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 8 2004