Reactions of 1-bromo-1-nitro-3,3,3-trichloropropene with O-and N-nucleophiles

Article abstract of DOI:10.1134/S1070363210120108

Reactions of 1-bromo-1-nitro-3,3,3-trichloropropene with alcohols, benzidine and o-, m-, and p-phenylenediamines was investigated and the reaction conditions were developed. The alkoxylation and amination products and an unusual nitrogen-containing bis-aziridine were obtained; their structures were characterized by the spectral (IR, ¹H, ¹³C NMR, HMQC, and HMBC) methods. Pleiades Publishing, Ltd., 2010.

Full text of DOI:10.1134/S1070363210120108

ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 12, pp. 2460–2465. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © E.V. Stukan’, S.V. Makarenko, G.A. Berkova, V.M. Berestovitskaya, 2010, published in Zhurnal Obshchei Khimii, 2010, Vol. 80,
No. 12, pp. 1998–2003.
Reactions of 1-Bromo-1-nitro-3,3,3-trichloropropene
with O- and N-Nucleophiles
E. V. Stukan’, S. V. Makarenko, G. A. Berkova, and V. M. Berestovitskaya
Herzen Russian State Pedagogical University, nab. r. Moyki 48, St. Petersburg, 191186 Russia
e-mail: kohrgpu@yandex.ru
Received May 6, 2010
Abstract―Reactions of 1-bromo-1-nitro-3,3,3-trichloropropene with alcohols, benzidine and o-, m-, and p-
phenylenediamines was investigated and the reaction conditions were developed. The alkoxylation and
amination products and an unusual nitrogen-containing bis-aziridine were obtained; their structures were
characterized by the spectral (IR, 1Н, 13С NMR, HMQC, and HMBC) methods.
DOI: 10.1134/S1070363210120108
Halonitroalkenes containing highly electrophilic
multiple С=С bond are widely used as reactive
synthons for obtaining organic compounds of various
types, including nitrogen-containing carbo- and hetero-
cycles [1].
fully in methanol solution at room temperature within
1–3 h to give oily or crystalline bis-adducts IV–VII in
63–94% yield.
Structures of adducts II–VII were proved by IR, 1Н
1
and 13С NMR spectroscopy. According to the H and
13C NMR spectra containing two sets of signals,
compounds II, III, VI, and VII are mixtures of two
diastereomers in the ratio a:b = 2:1 (II, III, VII) or
a:b = 3:1 (VI). We assign the upfield signals HA and
HB to isomer a, while the signals shifted slightly
downfield, to isomer b. The molecules of compounds
IV and V that have less symmetry elements than in the
case of compounds VI, VII, can form more stereo-
isomers, which apparently results in the complication
of their spectra. However, the signals of HA, HB, and
NH protons in the spectra of these substances are
grouped in such a way that a clear analogy is seen with
the spectra of diastereomers of compounds VI and VII.
The assignment of signals for the atoms 1H and 13C
in the alkoxylation products II and III was made using
the heteronuclear resonance techniques HMQC (Fig. 1)
and HMBC. In the HMBC spectrum of compound II
the signals of methoxy protons (3.86, 3.78 ppm) of the
two diastereomers form two cross-peaks with the
carbon atoms signals at 88.87 and 91.82 ppm, res-
pectively. In the HMQC spectrum these carbon signals
form cross-peaks with the signals of protons HB
resonating at 4.51 and 4.48 ppm, respectively, con-
firming the correctness of assigning the latter to HB
and the respective carbon peak, to C2.
In this connection the 1-bromo-1-nitro-3,3,3-tri-
chloropropene is of undoubted interest [2]. The
chemistry of this compound was poorly studied up to
now [3], meanwhile the combined presence of nitro-,
trichloromethyl groups, and bromine atom in its
molecule is promising for obtaining potential
biologically active materials on the basis of this nitro-
alkene. Its nitroprecursor, 1,1,1-trichloro-3-nitropro-
pene, is known to possess herbicide and fumigant
activity [4], and its alkoxylation products exhibit
spasmolitic [5] and antimicrobic [6] properties.
We examined a reaction of 1-bromo-1-nitro-3,3,3-
trichloropropene I with some aliphatic alcohols and
aromatic diamines. The alkoxylation reaction of 1-
bromo-1-nitro-3,3,3-trichloropropene I occurs under
the mild conditions at reflux in excess of the
corresponding alcohol over 1.5
h
to form
alkoxyderivatives II, III in high yields (96%), in
contrast to the same reaction of its nitro-precursor
(prolonged reflux in alcohol for 1–4 days [5]). Note
that compound II obtained earlier by another method
(yield 34%) was charactirized only by its boiling point
[6].
The reaction of 1-bromo-1-nitro-3,3,3-trichloro-
propene I with aromatic diamines proceeds success-
2460

REACTIONS OF 1-BROMO-1-NITRO-3,3,3-TRICHLOROPROPENE
HA
2461
HA
Br
Br
NO2
O2N
Br
Cl3C
Cl3C
Br
H2N(C6H4)2NH2
1
2
1
2
1
ROH
HA
NO2
HB
RO
2
H
NO2
N
H
Cl3C
N
H
CCl3
HB
HB
I
VII
II, III
NH2
H2N
CH3COOK, EtOH, Δ
HA
O2N
N
NO2
N
Br
HA
O2N
HA
HA
1
Br
NO2
1
2
2
N
H
CCl3
CCl3
Cl3C
HB
HB
HB
N
H
Cl3C
HB
VIII
IV−VI
R = CH3 (II), C2H5 (III); ortho- (IV), meta- (V), para- (VI).
It is evident from the correlation HMQC spectrum
of 1-bromo-2-methoxy-1- nitro-1,1,1-trichloropropane
II that the signal of the HA proton, which is shifted
downfield from the signal of HB proton in the spectra
of both diastereomers, corresponds to the upfield
carbon signals. The signal of the carbon atom С1 at
80.71 corresponds to the proton HA [δ(HА) 6.47 ppm].
In the spectra of the second diastereomer both the
proton HA (6.19 ppm) and the corresponding to it
carbon atom C1 (75.99 ppm) resonate in the stronger field.
1
In the H NMR spectrum of compound VII the
signals of the protons HA, HB, and NH appear as
doublets at 6.87, 5.41, and 4.52 ppm, respectively
(diastereomer a), and at 6.75, 4.89, and 5.07 ppm
(diastereomer b). The 13С NMR spectrum of this
δC, ppm
60.0
70.0
80.0
90.0
100.0
6.5
6.0
5.5
5.0
4.5
4.0
δ, ppm
Fig. 1. HMQC spectrum of 1-bromo-2-methoxy-1-nitro-1,1,1-trichloropropane II (CDCl3).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 12 2010

2462
STUKAN’ et al.
1
compound also contains two set of signals of the
carbon atoms: at 83.40 (С1), 69.68 (C2), 99.55 ppm
(CCl3) for diastereomer а, and at 75.87 (С1), 73.03
(C2), 99.08 ppm (CCl3) for diastereomer b.
The H and 13С NMR spectra characterize the
obtained bis-aziridine VIII as diastereomerically
uniform compound (Fig. 2). Its vicinal methine protons
give rise in the spectrum to unsplit singlets at 4.26
(HB) and 5.60 ppm (HA), as in the spectra of the earlier
reported 1-aryl-2-nitro-3-trichloromethylaziridines [3]
and 1-nitro-2-trichloromethyloxirane [13]. This fact
shows the transoid arrangement of the protons in both
aziridines, since the value of cis spin–spin coupling
constant in these heterocycles as a rule exceeds 4 Hz
[14]. The correctness of assigning the methine protons
signals of aziridine ring is confirmed by the proximity
of the obtained data and the corresponding
characteristics of the related compounds [3, 15–17].
In the IR spectra of adducts II–VII there are
absorption bands of symmetrical (1350–1355 cm–1) and
asymmetrical (1565–1575 cm–1) vibrations of the
nonconjugated nitro group with the separation of the ns
and νas bands (215–225 cm–1) characteristic of the
compounds with geminal nitro group and halogen
atom [7, 8]. In the IR spectra of compounds II and III
a strong band of С–О bond is observed at 1115–
1125 cm–1 characteristic of ethers. In the spectra of the
diadducts IV–VII the absorption bands of aromatic
rings (1605–1615 cm–1) and amino group (3375–
3420 cm–1) are present.
The signals of the atoms H and 13C in bisaziridine
1
VIII were assigned using the heteronuclear resonance
HMQC (Fig. 3). Thus, in the HMQC spectrum of this
compound there are two cross-peaks corresponding to
the correlations of the signal HB proton (4.26 ppm)
with the signal of the carbon atom С2 (56.42 ppm), and
also of the signal of HA proton (5.60 ppm) with the
signal of the carbon atom С1 (71.93 ppm).
Recent studies showed that the products of
alkylation of aniline and its derivatives with 1-bromo-
1-nitro-3,3,3-trichloropropene I made possible an
approach to aziridines containing nitro- and tri-
chloromethyl groups [3]. It is known that aziridine is a
good alkylating agent, and that a number of its
derivatives manifest the high mutagenic and anticancer
action [9–11].
The UV spectrum of bis-aziridine VIII contains the
intensive absorption band of π→π* transition in the
aromatic rings at λmax 269 nm (ε 20400), and also the
band of low intensity of π→π* transition at 337 nm
(ε 3200).
Aiming to extend the range of application of the
previously developed procedure [3], we attempted to
carry out the synthesis of aziridines by the example of
obtained bisadducts IV–VII.
Thus, 1-bromo-1-nitro-3,3,3-trichloropropene was
found to react effectively with the representatives of
The reflux of compounds V and VI with the
solution of potassium acetate in alcohol was found to
end by the formation of oily substances, whose puri-
fication and identification failed. However, we suc-
ceeded to isolate alkoxy-derivative III by treating
diadduct VI with potassium acetate under the same
conditions. Its formation is probably connected with
the initial deamination of compound VI followed by
alkoxylation of the formed bromonitroalkene I.
CH3COOK, EtOH, Δ
III
VI
[I]
deamination
The reaction of the diadduct VII with potassium
acetate gives rise to crude crystalline bis-aziridine VIII
(71%); after the purification by column chromato-
graphy the yield decreased to 32%. Low yield of
compound VIII can be apparently explained by its
partial decomposition on the silica gel that has been
earlier registered at the workup of other nitroaziridines
[12].
δ, ppm
1
Fig. 2. H NMR spectrum of 4,4'-bis(2-nitro-3-trichloro-
methylaziridin-1-yl)diphenyl VIII (CDCl3).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 12 2010

REACTIONS OF 1-BROMO-1-NITRO-3,3,3-TRICHLOROPROPENE
2463
δC, ppm
δ, ppm
Fig. 3. HMQC spectrum of 4,4'-bis(2-nitro-3-trichloromethylaziridin-1-yl)diphenyl VIII (CDCl3).
aliphatic alcohols and aromatic diamines to give the
products of nucleophilic addition in high yields. On the
basis of the dehydrohalogenation reaction of the
product of amination of 1-bromo-1-nitro-3,3,3-trichloro-
propene with benzidine we realized the synthesis of the
first representative of bisaziridines containing nitro-
and trichloromethyl groups in the heterocycle. The
conclusion was made on the trans-orientation of the
protons HA and HB, and consequently on the trans-
location of nitro and trichloromethyl groups relative to
the plane of aziridine ring.
(l 1 mm, с 8.9×10–6 mol l–1). The mass spectra were
registered on a МХ 1321 mass spectrometer (70 eV,
temperature of ionizing chamber 180°С). The
elemental analysis was performed on a EuroVector EA
3000 analyzer. The reaction progress was monitored
by TLC on Silufol UV-254 plates, detecting with
chromatoscope.
The starting 1-bromo-1-nitro-3,3,3-trichloropropene
I was prepared by the earlier described procedure [2].
1-Bromo-2-methoxy-1-nitro-3,3,3-trichloropropane
(II) (a mixture of diastereomers, a:b = 2:1). A
solution of 4.81 of 1-bromo-1-nitro-3,3,3-trichloro-
propene I in 20 ml of anhydrous methanol was re-
fluxed for 1.5 h to decolorizing. Then the solvent was
removed, and the residue (5.18 g, 96%) was distilled at
a reduced pressure. The fraction boiling at 94–97°С
(3 mm Hg) was collected. Yield 2.86 g (53%),
colorless liquid, nD20 1.5150 {bp 105°С (1.6 mm Hg)
[6]}. IR spectrum, ν, cm–1: 1575, 1355 (NO2), 1125
(C–O), 810 (CCl3). 1H NMR spectrum, δ, ppm:
diastereomer IIa, 3.86 s (3H, OCH3), 4.51 d [1H, HB,
3J(HAHB) 4.17 Hz], 6.47 d [1H, HA, 3J(HAHB) 4.17 Hz];
diastereomer IIb, 3.78 s (3H, OCH3), 4.48 d [1H, HB,
3J(HAHB) 6.71 Hz], 6.19 d [1H, HA, 3J(HAHB)
EXPERIMENTAL
The IR spectra were registered on an InfraLUM
FT-02 spectrophotometer from solutions in chloroform
(II–V, VII, VIII) and mull with mineral oil (VI).
1
The Н and 13C NMR spectra were recorded on a
Jeol JNM-ECX400A instrument at operating fre-
quencies 399.78 (1H) and 100.525 MHz (13С) with
chloroform-d as a solvent. The signals of the residual
protons of the solvent were used as reference.
The UV spectrum was recorded on a Shimadzu
UV-2401PC spectrometer in ethanol using quartz cell
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 12 2010

2464
STUKAN’ et al.
6.71 Hz]. 13C–{1H} NMR spectrum, δC, ppm: dia-
stereomer IIa, 63.71 (OCH3), 97.56 (CCl3), 88.87 (C2),
80.71 (C1); diastereomer IIb, 64.94 (OCH3), 97.56
(CCl3), 91.82 (C2), 75.99 (C1). Found, %: N 4.54.
C4H5BrCl3NO3. Calculated, %: N 4.65.
similarly from 1.17 g of 1-bromo-1-nitro-3,3,3-tri-
chloropropene I and 0.23 g of m-phenylenediamine in
15 ml of methanol. The yellowish green precipitate
was filtered off. Yield 1.31 g (94%) (a mixture of
diastereomers), mp 44–46°С. IR spectrum, ν, cm–1:
1
3420 (NH), 1615, 1520 (Ar), 1575, 1350 (NO2). H
1-Bromo-1-nitro-3,3,3-trichloro-2-ethoxypropane
(III) (a mixture of diastereomers, a:b = 2:1) was
similarly prepared from 0.919 g of 1-bromo-1-nitro-
3,3,3-trichloropropene I and 10 ml of ethanol.
Yellowish transparent liquid (1.015 g, 94%) was
isolated and subjected to chromatography on silica gel.
1-Bromo-1-nitro-3,3,3-trichloro-2-ethoxypropane (III)
was eluted with n-hexane. Yield 0.616 g (57%), Rf
0.60 (hexane–acetone, 5:1). IR spectrum, ν, cm–1:
NMR spectrum, δ, ppm: diastereomer Va, 4.44–4.50 m
(1H, NH), 5.34–5.39 m (1H, HB), 6.84–6.87 m (1H,
HA), 6.26–6.42 m, 7.06–7.16 m (4H, Ar); diastereomer
IVb, 5.02–5.05 m (1H, NH), 4.79–4.86 m (1H, HB),
6.74–6.75 m (1H, HA), 6.26–6.42 m, 7.06–7.16 m (4H,
Ar). Mass spectrum: m/z 646 [M+]. Found, %: C 22.62;
H 2.00; N 8.45. C12H10Br2Cl6N4O4. Calculated, %: C
22.28; H 1.56; N 8.66.
1
1575, 1350 (NO2), 1115 (C–O), 805 (CCl3). H NMR
N,N'-Bis[1-(bromonitromethyl)-2,2,2-trichloro-
ethyl]benzene-1,4-diamine (VI) was prepared
similarly from 1.01 g of 1-bromo-1-nitro-3,3,3-tri-
chloropropene I, 0.2 g of p-phenylenediamine in 15 ml
of methanol. The reaction mixture was kept for 1 h.
The yellow precipitate was filtered off and washed
with methanol. Yield 0.68 g (56%) (diastereomers
mixture, а:b = 3:1), mp 174–175°С (decomp.). After
3 days additional 0.12 g (9%) of compound VI was
isolated from the mother liquor. Overall yield 65%. IR
spectrum, ν, cm–1: 3390 (NH), 1520 (Ar), 1565, 1350
spectrum, δ, ppm: diastereomer IIIa, 1.33 t (3H, CH3),
4.06 q (2H, OCH2), 4.59 d [1H, HB, 3J(HAHB) 4.27 Hz],
6.46 d [1H, HA, 3J(HAHB) 4.27 Hz]; diastereomer IIIb,
1.20 t (3H, CH3), 3.85 m, 4.11 m (2H, OCH2), 4.55 d
[1H, HB, 3J(HAHB) 6.41 Hz], 6.19 d [1H, HA, 3J(HAHB)
6.41 Hz]. 13C–{1H} NMR spectrum, δC: diastereomer
IIIa, 15.04 (CH3), 72.25 (OCH2), 97.80 (CCl3), 87.57
(C2), 81.16 (C1); diastereomer IIIb, 15.17 (CH3), 73.77
(OCH2), 97.80 (CCl3), 90.67 (C2), 76.40 (C1). Mass
spectrum, m/z: 198 [M+ – CCl3], 152 [M+ – CCl3 – NO2].
1
(NO2). H NMR spectrum, δ, ppm: diastereomer VIa,
N,N'-Bis[1-(bromonitromethyl)-2,2,2-trichloro-
ethyl]benzene-1,2-diamine (IV). To a solution of 1.13 g
of 1-bromo-1-nitro-3,3,3-trichloropropene I in 5 ml of
methanol was added a solution of 0.23 g of о-
phenylene diamine in 10 ml of methanol. This mixture
was kept for 3 h, and poured on the crushed ice. The
formed yellowish green precipitate suffered tarring
when ice melted. The aqueous solution of the oil was
extracted with diethyl ether (2 × 25 ml), the extract
was dried with MgSO4. The solvent was removed.
Yield 1.04 g (76%). The dark red oil obtained was
subjected to chromatography on silica gel. The
fractions eluted with n-hexane and carbon tetrachloride
afforded 0.86 g (63%) of dark red oily substance IV
(a mixture of diastereomers), Rf 0.48 (hexane–acetone,
2:1). IR spectrum, ν, cm–1: 3375 (NH), 1605, 1520
(Ar), 1575, 1350 (NO2), 810 (CCl3). 1H NMR
spectrum, δ, ppm: diastereomer IVa, 4.43–4.78 m (1H,
NH), 5.30–5.39 m (1H, HB), 6.91–7.00 m (1H, HA),
6.91–7.00 m (4H, Ar); diastereomer IVb, 4.93–5.15 m
(1H, NH), 4.83–4.93 m (1H, HB), 6.81–6.88 m (1H,
HA), 6.91–7.00 m, 7.05–7.10 m (4H, Ar). Mass
spectrum: m/z 646 [M+].
4.25 d [1H, NH, 3J(NHHB) 10.99], 5.23 d.d [1H, HB, 3J
3
(HAHB) 2.44, 3J(NHHB) 10.99 Hz], 6.85 d [1H, HA, J
(HAHB) 2.44 Hz], 6.71–6.81 m (4H, Ar); diastereomer
VIb, 4.74 d [1H, NH, 3J(NHHB) 3.36 Hz], 4.74 d.d
3
3
[1H, HB, J(HAHB) 2.75, J(NHHB) 3.36 Hz], 6.69 d
3
[1H, HA, J(HAHB) 2.75 Hz], 6.73–6.81 m (4H, Ar).
Mass spectrum: m/z 646 [M+]. Found, %: C 21.83; H
1.99; N 8.18. C12H10Br2Cl6N4O4. Calculated, %: C
22.28; H 1.56; N 8.66.
N,N'-Bis[1-(bromonitromethyl)-2,2,2-trichloro-
ethyl]diphenyl-4,4'-diamine (VII) was prepared
similarly from 0.95 g of 1-bromo-1-nitro-3,3,3-tri-
chloropropene I, 0.32 g benzidine in 15 ml of
methanol. The reaction mixture was kept for 1.5 h and
poured on the crushed ice. The yellowish orange pre-
cipitate was filtered off. Yield 1.12 g (88%) (dia-
stereomers mixture, а:b = 2:1), mp 62–65°С. IR
spectrum, ν, cm–1: 3420 (NH), 1615, 1510 (Ar), 1575,
1
1350 (NO2), 815 (CCl3). H NMR spectrum, δ, ppm:
diastereomer VIIa, 4.52 d [1H, NH, 3J(NHHB) 10.99 Hz],
3
3
5.41 d.d [1H, HB, J(HAHB) 2.14, J(NHHB) 10.99 Hz],
3
6.87 d [1H, HA, J(HAHB) 2.14 Hz], 6.85–6.92 m,
N,N'-Bis[1-(bromonitromethyl)-2,2,2-trichloro-
ethyl]benzene-1,3-diamine (V) was prepared
7.39–7.46 m (4H, Ar); diastereomer VIIb, 5.07 d [1H,
NH, 3J(NHHB) 10.68 Hz], 4.89 d.d [1H, HB, J(HAHB)
3
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 12 2010

REACTIONS OF 1-BROMO-1-NITRO-3,3,3-TRICHLOROPROPENE
2465
3
3
3.05, J(NHHB) 10.68 Hz], 6.75 d [1H, HA, J(HAHB)
3.66 Hz], 6.85–6.92 m, 7.39–7.46 m (4H, Ar). 13C–{1H}
NMR spectrum, δC, ppm: diastereomer VIIa, 69.68
(C2), 83.40 (C1), 99.55 (CCl3), 114.81, 127.75, 133.28,
143.60 (C12H8); diastereomer VIIb, 73.03 (C2), 75.87
(C1), 99.08 (CCl3), 114.53, 127.75, 133.09, 144.56
(C12H8). Mass spectrum: m/z 722 [M+]. Found, %: C
30.45; H 2.46; N 7.58. C18H14Br2Cl6N4O4. Calculated,
%: C 29.91; H 1.95; N 7.75.
REFERENCES
1. Perekalin, V.V., Lipina, E.S., Berestovitskaya, V.M.,
and Efremov, D.A., Nitroalkenes. Conjugated Nitro-
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2. Durden, J.A., Jr., Heywood, D.L., Sousa, A.A., and
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3. Berestovitskaya, V.M., Makarenko, S.V., Bushmari-
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kan’, E.V., Izv. Akad. Nauk, Ser. Khim., 2009, no. 5, p. 998.
4,4'-Bis(2-nitro-3-trichloromethylaziridin-1-yl)-
biphenyl (VIII). To a boiling solution of 1.12 g of
diadduct VII in 15 ml of ethanol was added a hot
solution of 0.23 g of potassium acetate in 15 ml of
ethanol. The reaction mixture was refluxed for 4 h and
poured on the crushed ice. The reddish substance (0.62 g,
71%) was filtered off and subjected to chromatography
on silica gel eluting with n-hexane to give 0.27 g
(32%) of greenish crystals, mp 154–156°С (petroleum
ether). IR spectrum, ν, cm–1: 1610, 1495 (Ar), 1560,
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1
9. Gilchrist, T.L., Heterocyclic Chemistry, London:
1350 (NO2), 815 (CCl3). H NMR spectrum, δ, ppm:
Longman, 1992.
4.26 s (1H, HB), 5.60 s (1H, HA), 7.08 d, 7.51 d (8H,
C12H8). 13C–{1H} NMR spectrum, δC, ppm: 56.42 (C2),
71.93 (C1), 94.42 (CCl3), 118.97, 128.27, 137.20,
141.99 (C12H8). UV spectrum, λmax, nm (ε): 269
(20400), 337 (3200). Mass spectrum: m/z 560 [M+].
Found, %: C 38.58; H 2.98. C18H12Cl6N4O4.
Calculated, %: C 38.53; H 2.16.
10. Soldatenkov, A.T., Kolyadina, N.M., and Shendrik, I.V.,
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Reaction of diadduct VI with potassium acetate.
To a boiling solution of 1.3 g of compound VI in
15 ml of ethanol was added a hot solution of 0.3 g of
potassium acetate in 15 ml of ethanol. The reaction
mixture was refluxed for 4.5 h and poured into the
crushed ice. The emulsion formed was extracted with
chloroform, dried over magnesium sulfate, and
evaporated. The formed dark red viscous substance
(0.74 g) was subjected to chromatography on silica gel
eluting with n-hexane to give 0.25 g (38%) of colorless
oil III as a diastereomers mixture (а:b = 2:1), Rf 0.60
13. Sokolov, N.A., Chernov, Yu.G., and Glazkov, Yu.V.,
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Capriati, V., Luisi, R., and Pilati, T., Tetrahedron, 2004,
vol. 60, p. 1175.
15. Fioravanti, S., Marchetti, F., Pellacani, L., Ranieri, L.,
and Tardella, P.A., Tetrahedron: Asymmetry, 2008,
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bicki, M.M., and Blacque, O., Eur. J. Org. Chem., 1999,
p. 1541.
17. Zibinsky, M., Butkevich, A.N., and Kuznetzov, M.A.,
Tetrahedron Lett., 2008, vol. 49, no. 38, p. 5505.
1
(hexane–acetone, 5:1). The IR and H NMR spectral
data are corresponded to that for 1-bromo-1-nitro-
3,3,3-trichloro-2-ethoxypropane III.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 12 2010