Substituted 1-nitro-2-phenylethenes in reaction with N-phenacyl- and N-acetonylisoquinolinium bromides

Full text of DOI:10.1134/S1070428010090319

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 9, pp. 1427−1429. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © S.B. Nosachev, K.A. Del’netskaya, N.A. Solov’ev, A.G. Tyrkov, 2010, published in Zhurnal Organicheskoi Khimii, 2010, Vol. 46, No. 9,
pp. 1422−1424.
Substituted 1-Nitro-2-phenylethenes in Reaction
with N-Phenacyl- and N-Acetonylisoquinolinium Bromides
S. B. Nosachev, K. A. Del’netskaya, N. A. Solov’ev, and A. G. Tyrkov
Astrakhan State University, Astrakhan, 414000 Russia
e-mail: tyrkov@rambler.ru
Received December 21, 2009
DOI: 10.1134/S1070428010090319
by elemental analysis data. The IR spectra contain strong
absorption bands of the stretching vibrations of the NO2
group at 1555 (νas), 1380 cm–1 (νs), and of C=O group
at 1710 cm–1. In cycloadducts V and VI in contrast to
initial phenylethene I (2225 cm–1) the absorption bands
of the CN group are shifted in the longwave direction
(2250 cm–1) with decrease in the intensity, apparently due
to the stronger steric hindrances in the final products. The
parameters of the 1H NMR spectra are consistent with the
assumed structures and are close to those of model com-
pounds of similar structures from the series of pyrrolidine
and isoquinoline [3, 4]. For instance, the protons of the
pyrrolidine ring appear in the region 4.35–5.67 ppm, and
the signals of protons H5 and H6 of the isoquinoline ring,
at 6.57 and 6.35 ppm respectively (Scheme 1).
The information on reactions of nitrophenylethenes
with azomethine ylides is very limited. It is only known
that 1-nitro-2-phenylethene reacted with N-(2-methyl-
5-methoxycarbonylfur-3-yl)methyl-isoquinolinium
bromide giving a product of 1,3-dipolar cycloaddition,
1-nitro-2-phenyl-3-R-2,3-dihydrobenzo[g]indolizine in
a low yield [1].
In order to test the general character of this reaction
we attempted to extend it to a new type of dipolarophile,
1-nitro-2-phenyl-1-cyano-ethene (I), and its analog,
1-bromo-1-nitro-2-phenylethene (II).
It was established that phenylethenes I and II reacted
with the precursors of azomethine ylides, N-phenacyl-
(III) or N-acetonylisoquinolinium bromides (IV), giv-
ing 1-nitro-2-phenyl-1,2,3,10b-tetrahydropyrrolo[2,1-a]
isoquinolines V–VIII. It is presumable that at treating
the N-onium salts III and IV with sodium hydride in
dry dioxane active azomethine ylides A are generated
[2] which as a result of 1,3-dipolar cycloaddition to mol-
ecules of dipolarophiles I or II are stabilized in the form
of substituted tetrahydropyrroloisoquinolines V–VIII
in 55–62% yield. The structure of compounds was con-
firmed by IR and 1H NMR spectra, and the composition,
The presence of a carbonyl group in the cycloadducts
V–VIII provided a possibility to carry out a heterocycli-
zation involving hydrazine hydrate to obtain previously
unknown substituted 1-nitro-2-phenyl-2,2a,5,5a,6,10b-
hexahydrotriazinoindolizine IX–XII (Scheme 2).
It is presumable that the reaction proceeds through the
formation of intermediate hydrazone derivatives of pyr-
rolidine B which undergo a spontaneous heterocyclization
Scheme 1.
O2N
R
Ph
O
R'
R'
NO2
NaH
_NaBr
R'
+
+
I, II
N+
PhCH
C
N+
N
R
O
_
O
Br_
V_VIII
I, II
A
III, IV
R = CN (I), Br (II); R' = Ph (III), Me (IV); R = CN, R' = Ph (V), Me (VI); R = Br, R' = Ph (VII), Me (VIII).
1427

NOSACHEV et al.
1428
Scheme 2.
O2N
R
Ph
N
O2N
R
Ph
N2H4
EtOH
R'
V_VIII
R'
N
N
N
N
H
H2N
B
IX_XII
R = CN (IX, X), Br (XI, XII); R' = Ph (IX, XI), Me (X, XII).
into compounds IX–XII. The structure of compounds
was established from IR and 1H NMR spectra. In the IR
spectra alongside the absorption bands of groups NO2
and CN (for compounds IX, X) an absorption band of
NH group was also observed at 3350 cm–1, and in the 1H
NMR spectrum this group appeared as a broadened singlet
at 5.98 ppm. The signals of protons H5a and H6 because
of the reduction of this fragment in the isoquinoline
ring give rise to signals in the region 3.85 and 2.70 ppm
respectively.
δ, ppm: 4.43 d (1H, H2), 4.61 s (1H, H10b), 5.67 d (1H,
H3), 6.36 d (1H, H6), 6.57 d (1H, H5), 7.78–7.74 m (10H,
2C6H5), 7.85–7.51 m (4Hisoquin.). Found, %: C 73.94;
H 4.33; N 9.83. C26H19N3O3. Calculated, %: C 74.11;
H 4.51; N 9.98.
3-Acetyl-1-nitro-2-phenyl-1,2,3,10b-tetrahydro-
pyrrolo[2,1-a]isoquinoline-1-carbonitrile (VI).
Yield 62%, mp 105–106°C. IR spectrum, ν, cm–1:
1
2250 (CN), 1555, 1380 (NO2), 1710 (C=O). H NMR
spectrum, δ, ppm: 2.12 s (3H, CH3), 4.37 s (1H, H10b),
4.38 d (1H, H2), 4.94 d (1H, H3), 6.35 d (1H, H6),
6.59 d (1H, H5), 7.75 m (5H, C6H5), 7.84–7.50 m
(4Hisoquin). Found, %: C 70.02; H 4.58; N 11.53.
C21H17N3O3. Calculated, %: C 70.19; H 4.74; N 11.70.
Therefore that reactions described permit the prepa-
ration of a number of difficultly accessible by the other
methods pyrrolizine derivatives of isoquinoline and the
fusion to the principal part of the molecule of the 1,2,4-tri-
azine ring.
3-Benzoyl-1-bromo-1-nitro-2-phenyl-1,2,3,10b-
tetrahydropyrrolo[2,1-a]isoquinoline (VII). Yield 57%,
mp 152°C. IR spectrum, ν, cm–1: 1555, 1380 (NO2), 1710
(C=O). 1H NMR spectrum, δ, ppm: 4.43 d (1H, H2), 4.60 s
(1H, H10b), 5.67 d (1H, H3), 6.36 d (1H, H6), 6.56 d (1H,
H5), 7.76–7.73 m (10H, 2C6H5), 7.85–7.53 m (4Hisoquin).
Found, %: C 63.01; H 3.84; N 5.73. C25H19BrN2O3. Cal-
culated, %: C 63.16; H 4.00; N 5.89.
1-Nitro-2-phenyl-1-cyanoethene was obtained by the
method [5], 1-bromo-1-nitro-2-phenylethene, by the pro-
cedure [6], N-phenacyl- and N-acetonylisoquinolinium
bromides, as described in [7].
Reaction of substituted 1-nitro-2-phenylethenes I,
II with N-phenacyl- (III) or N-acetonylisoquinolinium
bromides (IV). To a solution of 5 mmol of phenylethene
I or II in 80 ml of dry dioxane was added at 0 ± 5°C while
stirring 5 mmol of isoquinolinium bromide III or IV
and 1 min later, 7 mmol of sodium hydride. The reaction
mixture was stirred at room temperature for 3 days, the
precipitate was filtered off, washed with 15 ml of dioxane,
the solvent was evaporated from the combined organic
solution, and the residue was subjected to chromatogra-
phy on a column (250 ×10 mm) packed with the activated
Silicagel 100/400 μ eluting with Trappe solvents. The
eluent for compounds V–VIII was benzene.
3-Acetyl-1-bromo-1-nitro-2-phenyl-1,2,3,10b-
tetrahydropyrrolo[2,1-a]isoquinoline (VIII). Yield
55%, mp 140°C. IR spectrum, ν, cm–1: 1555, 1380
(NO2), 1710 (C=O). 1H NMR spectrum, δ, ppm: 2.13 s
(3H, CH3), 4.35 s (1H, H10b), 4.37 d (1H, H2), 4.95 d
(1H, H3), 6.45 d (1H, H6), 6.60 d (1H, H5), 7.74 m (5H,
C6H5), 7.84–7.52 m (4Hisoquin). Found, %: C 57.96;
H 3.97; N 6.62. C20H17BrN2O3. Calculated, %: C 58.11;
H 4.12; N 6.78.
Reaction of substituted tetrahydropyrroloisoquino-
lines V–VIII with hydrazine hydrate. To a solution
of 2 mmol of compounds V–VIII in 20 ml of ethanol
at cooling to 5°C was added while stirring 2.5 mmol of
hydrazine hydrate in 5 ml of ethanol. The reaction mix-
3-Benzoyl-1-nitro-2-phenyl-1,2,3,10b-tetra-
hydropyrrolo[2,1-a]isoquinoline-1-carbonitrile (V).
Yield 60%, mp 125–126°C. IR spectrum, ν, cm–1: 2250
(CN), 1555, 1380 (NO2), 1710 (C=O). 1H NMR spectrum,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 9 2010

SUBSTITUTED 1-NITRO-2-PHENYLETHENES
1429
ture was stirred at room temperature for 6 h. The reaction
mixture of compounds VI or VIII with hydrazine hydrate
was stirred for 12 h at 40°C. The solvent was evaporated
at reduced pressure, the residue was diluted with 20 ml of
ice water, the water layer was extracted with ethyl ether
(2×20 ml), the extract was dried with MgSO4. The solvent
was evaporated, the residue was subjected to chromatog-
raphy as described above, eluent for compounds IX–XII
was chloroform.
Found, %: C 61.19; H 4.06; N 11.28. C25H21BrN4O2.
Calculated, %: C 61.35; H 4.29; N 11.45.
1 - B ro m o - 3 - m e t h y l - 1 - n i t ro - 2 - p h e n y l -
2,2a,5,5a,6,10b-hexahydro-1H-benzo[g][1,2,4]triazi-
no-[5,4,3-cd]indolizine (XII). Yield 28%, mp 115°C.
IR spectrum, ν, cm–1: 3350 (NH), 1555, 1380 (NO2).
1H NMR spectrum, δ, ppm: 2.13 s (3H, CH3), 2.70 d (2H,
C6H2), 3.85 q (1H, H5a), 4.46 C (1H, H10b), 4.55 d (1H,
H2), 4.83 d (1H, H2a), 5.98 br.s (1H, NH), 7.47 m (5H,
C6H5), 7.74–7.51 m (4Hisoquin.). Calculated, %: C 56.04;
H 4.28; N 12.97. C20H19BrN4O2. Found, %: C 56.21;
H 4.45; N 13.11.
1-Nitro-2,3-diphenyl-2,2a,5,5a,6,10b-hexahydro-
1H-benzo[g][1,2,4]triazino[5,4,3-cd]indolizine-1-
carbonitrile (IX). Yield 41%, mp 168°C. IR spectrum,
ν, cm–1: 3350 (NH), 2250 (CN), 1555, 1380 (NO2).
1H NMR spectrum, δ, ppm: 2.70 d (2H, C6H2), 3.86 q
(1H, H5a), 4.48 s (1H, H10b), 4.57 d (1H, H2), 4.86 d (1H,
H2a), 5.98 br.s (1H, NH), 7.62–7.25 m (10H, 2C6H5),
7.75–7.50 m (4Hisoquin.). Found, %: C 71.56; H 4.64;
N 15.92. C26H21N5O2. Calculated, %: C 71.72; H 4.83;
N 16.09.
IR spectra were recorded on a spectrophotometer
ANDQC-29 from solutions in chloroform, concentration
40 mg/ml, l 0.1 mm. 1H NMR spectra were registered on
a spectrometer Tesla BS-487C (80 MHz) in acetone-d6,
internal reference HMDS. The reaction progress was
monitored and the homogeneity of compounds obtained
was checked by ascending TLC on Silufol UV-254 plates
in the solvent mixture acetone–hexane, 2 : 3, development
in iodine vapor.
3-Methyl-1-nitro-2-phenyl-2,2a,5,5a,6,10b-hexa-
hydro-1H-benzo[g][1,2,4]triazino[5,4,3-cd]indolizine-
1-carbonitrile (X). Yield 30%, mp 110°C. IR spectrum,
ν, cm–1: 3350 (NH), 2250 (CN), 1555, 1380 (NO2).
1H NMR spectrum, δ, ppm: 2.13 s (3H, CH3), 2.70 d
(2H, C6H2), 3.85 q (1H, H5a), 4.47 s (1H, H10b), 4.56 d
(1H, H2), 4.84 d (1H, H2a), 5.97 br.s (1H, NH), 7.45 m
(5H, C6H5), 7.74–7.50 m (4Hisoquin.). Found, %: C 67.38;
H 4.94; N 18.62. C21H19N5O2. Calculated, %: C 67.56;
H 5.09; N 18.77.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 9 2010