β-Acetyl-β-nitrostyrenes: Structure and use for synthesis of heteryl-containing structures

Article abstract of DOI:10.1134/S1070363208090120

¹H, IR, and electronic absorption spectroscopy and X-ray diffraction analysis were used to establish that 1-acetyl-1-nitro-2-phenyl-and 2-(p-methoxyphenyl)ethenes have Z configuration, and their 2-(p-N, Ndimethylaminophenyl)-substituted analog exists in chloroform-d ³ as a mixture of Z and E isomers. The reactions of gem-acetylnitroethenes with N-methylpyrrole were shown to involve alkylation at the C²-reaction center of the heterocycle. The reactions of these nitroalkenes with hydrazine form pyrazoles and azines, with acetylhydrazine, the corresponding hydrazones (via transalkenylation), and with sodium azide, acetylsubstituted 1,2,3-triazoles.

Full text of DOI:10.1134/S1070363208090120

ISSN 1070-3632, Russian Journal of General Chemistry, 2008, Vol. 78, No. 9, pp. 1711–1718. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © N.I. Aboskalova, N.N. Smirnova, О.N. Kataeva, R.I. Baichurin, A. V. Fel’gendler, G.A. Berkova, V.M. Berestovitskaya, 2008,
published in Zhurnal Obshchei Khimii, 2008, Vol. 78, No. 9, pp. 1479–1488.
β-Acetyl-β-Nitrostyrenes: Structure and Use for Synthesis
of Heteryl-containing Structures
N. I. Aboskalovaa, N. N. Smirnovaa, О. N. Kataevab, R. I. Baichurina,
A. V. Fel’gendlera, G. A. Berkovaa, and V. M. Berestovitskayaa
a Gertsen Russian State Pedagogical University,
nab. r. Moiki 48, St. Petersburg, 191186 Russia
e-mail: kohrgpu@yandex.ru
bArbuzov Institute of Organic and Physical Chemistry, Kazan Research Center,
Russian Academy of Sciences, Kazan, Tatarstan, Russia
Received March 18, 2008
Abstract―1Н, IR, and electronic absorption spectroscopy and X-ray diffraction analysis were used to establish
that 1-acetyl-1-nitro-2-phenyl- and 2-(p-methoxyphenyl)ethenes have Z configuration, and their 2-(p-N,N-
dimethylaminophenyl)-substituted analog exists in chloroform-d3 as a mixture of Z and E isomers. The
reactions of gem-acetylnitroethenes with N-methylpyrrole were shown to involve alkylation at the С2-reaction
center of the heterocycle. The reactions of these nitroalkenes with hydrazine form pyrazoles and azines, with
acetylhydrazine, the corresponding hydrazones (via transalkenylation), and with sodium azide, acetyl-
substituted 1,2,3-triazoles.
DOI: 10.1134/S1070363208090120
Geminally activated nitroethenes containing a
carbonyl group as the second electron-acceptor
function are preparatively available and highly reactive
compounds [1, 2]. The enhanced interest in the
chemistry of such polyfunctional electron-deficient
compounds is due to the possibility of inclusion in
their molecules of biologically active blocks (e. g.,
indole [3]), and also to the possibility of designing on
their basis heterocyclic structures with potentially
useful properties (e. g., pyrimidine derivatives [4-7],
etc.). Moreover, a combination of two competing
centers, an activated multiple bond and a carbonyl
group, in gem-acetylnitrostyrenes makes them very
suitable models for studying of regioselectivity
problems in reactions with nucleophiles.
I-III was the value of the chemical shift of the olefin
proton: When the nitro group is cis to НА, the signal of
the latter should be shifted downfield from the
corresponding signal of the trans isomer, due to the
deshielding effect of the nitro group [8].
1
The Н NMR spectra of β-acetyl-β-nitrostyrene I
and its analog II in CDCl3 solution (Table 1) provide
evidence for stereohomogeneity of these compounds;
the olefin protons resonate at 7.46 and 7.32 ppm,
1
respectively. In the Н NMR spectra of model (Е)-β-
nitrostyrenes measured in the same conditions, the
olefin НА proton signals are registered at 7.87 and 7.94
ppm. The fact that the НА signals of compounds I and
II are shifter upfield from those of Е-β-nitrostyrenes
suggests that introduction in the latter of one more
electron-acceptor substituent (acetyl group) produces a
configurational change and attests that compounds I
and II exist in CDCl3 in the Z form.
1
A joint analysis of Н NMR, UV and IR spectral
data for β-acetyl-β-nitrostyrenes I-III with the use of
corresponding arylnitroethenes as models made it
possible to reveal the structural features of these
compounds and establish, in particular, their
configuration.
1
The Н NMR spectrum of β-acetyl-β-nitrostyrene
(III) in CDCl3, unlike those of compounds I and II,
contains a double set of signals, implying that III
exists as a mixture of isomers. There are signals of
olefin protons in spectrum at 7.30 (Z form) and
7.90 ppm (Е form); the Z/Е ratio is ≈ 3:1.
1Н NMR spectroscopy gave valuable information
on the steric structure of gem-acetylnitroethenes. A
principal criterion for the configuration of compounds
1711

1712
ABOSKALOVA et al.
Table 1. 1Н NMR, IR, and electric absorption data for β-acetyl-β-nitrostyrenes I–III
Electronic
1Н NMR spectra (CDCl3),
δ, ppm (J, Hz)
absorption spectra IR spectra (CHCl3), ν, cm–1
(EtOH)а
Compound
R
H
C=C,
CH3O
λmax
,
ε,
NO2
HA
CH3
2.45
Ar
C=O (С=С,
C=N+)
[(CH3)2N]
nm l mol–1 cm–1 (NOO–)
n-RC6H4
NO2
Z
7.46
–
7.46
290
17000
1535,
1555,
1380
1550,
1350
1540,
1360
1700 1630,
1680 1650
I
HA
COCH3
CH3O
Z
Zc
Еc
Е
7.32
7.30
7.90
2.42
2.38
2.50
3.86
[3.05]
[3.10]
–
6.92, 328
7.43
6.65, 410b
23000
32000
1700 1610
1690 1600
II
(CH3)2N
IIIa
IIIb
7.24
6.65,
7.36
n-RC H
H
H
7.87 (НА) 7.60 (НВ)
(3JAB 14)
7.38
309
17200
21000
1530,
1343
–
–
1640
6
4
B
CH3O
Е
7.94 (НА) 7.51 (НВ)
(3JAB 14)
3.91
6.95, 355
7.52
(1320,
1300,
1258)
(1320,
1298,
1267)
(1627,
1600)
NO
H
2
A
(CH3)2N
Е
7.90 (НА) 7.42 (НВ) [3.10]
(3JAB 14)
6.64, 437
7.40
28700
–
(1600)
Long-wave absorption bands (λmax > 280 nm) are given. b In the spectrum in CHCl3, a long-wave absorption band (λmax 414 nm, ε 28000)
with a shoulder at 460 nm. c The Z/E ratio for compounds IIIa and IIIb is 3:1.
a
The electronic absorption data do not contradict the
I exists as an equilibrium mixture of the s-cis and s-
suggested configurations of the compounds under
consideration (Table 1). Thus, the spectra (in ethanol)
of b-acetyl-β-nitrostyrenes II and III show long-wave
absorption bands characteristic of nitrostyrenes
containing electron-donor substituents at the opposite
end (with respect to NO2) of the conjugated system.
Acetyl substitution in Е-β-nitrostyrenes induces a
hypsochromic shift of long-wave absorption bands
compared to the corresponding unsubstituted analogs
[9]. Thus, the band of Е-p-methoxy-β-nitrostyrene is at
λmax 355 nm (ε 21000), and the band of its acetyl
analog, at λmax 328 nm (ε 23000).
trans conformers.
O
H
H
O
C6H5
s-cis
NO2
C6H5
NO2
s-trans
The IR spectra of (Z)-β-acetyl-β-nitrostyrenes II
and III that contain electron-donor substituents in the
para position of the benzene ring differ significantly
from the spectra of the corresponding model E-β-
nitrostyrenes, which contain absorption bands of an
ionized nitro group [9, 10]. In the spectra of II and III
we observe absorption bands of a covalently bound
nitro group (Table 1). Compounds II and III, like E-β-
nitrostyrenes, have polarized molecules, and their
polarization is much contributed by effective conjuga-
tion involving the carbonyl group.
The IR spectra gave further information on the
structure of compounds I–III (Table 1). The
absorption bands characteristic of a conjugated
covalently bound nitro group are observed in the IR
spectrum of the simplest β-acetyl-β-nitrostyrene (I).
Noteworthy is splitting of the absorption bands
belonging to stretching vibrations of the nitro group
(νas 1555, 1535 cm−1), double bond (νС=С 1650, 1630 сm−1)
[Δν ≈ 20 сm−1], and carbonyl group also (νС=О 1700,
1680 сm−1). These observation suggests that compound
Hence, analysis of the spectral characteristics of β-
acetyl-β-nitrostyrenes I–III led us to conclude that
these compounds prefer the Z form.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 9 2008

β-ACETYL-β-NITROSTYRENES
Table 2. Bond lengths (d, Å) in molecule II
1713
One of the β-acetyl-β-nitrostyrenes, 4-(4-metho-
xyphenyl)-3-nitrobut-3-en-2-оne (II), was studied by
X-ray diffraction to show that it is a Z isomer in
crystal. Its geometry is presented in Fig.1. The
principal structural parameters of molecule II (bond
lengths and valence and torsion angles) are given in
Tables 2–4.
Bond
d
Bond
d
C1–C2
C1–C8
C2–N3
C2–C6
N3–O4
N3–O5
C6–O7
C6–С16
1.337 (2)
1.459 (2)
1.476 (2)
1.481 (2)
1.220 (1)
1.221 (2)
1.216 (2)
1.497 (2)
C8–C13
C8–C9
1.400 (2)
1.402 (2)
1.378 (2)
1.391 (2)
1.364 (2)
1.391 (2)
1.385 (2)
1.433 (2)
C9–C10
C10–C11
C11–O14
C11–C12
C12–C13
O14–C15
The presented data suggest that molecule II in
crystal is virtually planar, except that the nitro group is
orthogonal to the molecular plane (С1С2N3O4 torsion
angle 94.58°), which excludes conjugation of the nitro
group with the aromatic π-system and multiple bond.
Correspondingly, the C2–N3 bond length that equals
1.476(2) Å in β-acetyl-β-nitrostyrene (II) is slightly
larger than in mononitrostyrene (1.451 Å). It is
important that the above bond length is close to that in
1-(ethoxycarbonyl)-1-nitro-2-(p-nitrophenyl)ethene
(1.472(3) Å [11]), where the nitro group, too, deviates
from the multiple-bond plane.
Table 3. Valence angles (ω, deg) in molecule II
Bond angle
ω
Bond angle
ω
C2C1C8
C1C2N3
C1C2C6
N3C2C6
O4N3O5
O4N3C2
O5N3C2
O7C6C2
O7C6C16
C2C6C16
C13C8C9
131.3 (1)
121.1 (1)
128.2 (1)
110.6 (1)
124.4 (1)
118.0 (1)
117.6 (1)
119.2 (1)
121.9 (1)
119.0 (1)
117.4 (1)
C13C8C1
125.8 (1)
116.9 (1)
121.4 (1)
120.1 (1)
116.0 (1)
124.1 (1)
119.8 (1)
119.5 (1)
121.8 (1)
117.2 (1)
C9C8C1
C10C9C8
C9C10C11
O14C11C10
O14C11C12
C10C11C12
C13C12C11
C12C13C8
C11O14C15
According to [12], 1-acetyl-1-nitro-2-(2-thienyl)
ethane which is structurally similar to compound II,
too, has Z configuration in crystal, and the dihedral
angle between the nitro group and ring planes is 93.3°.
We earlier showed that aromatic gem-
acylnitroethenes actively react with СН-acids to form
Michael adducts (ethyl and acetylaminoethyl malo-
nates), transalkenylation products (malonodinitrile,
ethyl cyanoacetate), substituted dihydrofurans and
hexahydrobenzofurans (acetylacetone, dihydroresor-
cinol, dimedone) [1, 2]; with indole and its derivatives,
С-adducts were obtained [3].
Table 4. Torsion angles (τ, deg) in molecule II
Torsion angle
τ
Torsion angle
τ
C8C1C2N3
C8C1C2C6
C1C2N3O4
C6C2N3O4
C1C2N3O5
C6C2N3O5
C1C2C6O7
N3C2C6O7
C1C2C6C16
N3C2C6C16
C2C1C8C13
C2C1C8C9
–0.03
–179.11
94.58
C13C8C9C10
C1C8C9C10
1.84
177.68
–0.18
C8C9C10C11
C9C10C11O14
C9C10C11С12
O14C11C12C13
C10C11C12C13
C11C12C13C8
C9C8C13C12
C1C8C13C12
C10C11O14C15
C12C11O14C15
–86.20
–86.47
92.76
179.17
–1.45
To proceed with research into the chemistry of
nitroalkenes, we reacted β-acetyl-β-nitrostyrenes I–III
–179.33
1.34
179.47
0.31
0.39
–0.22
–1.95
–179.37
–8.83
177.52
–178.01
2.64
C10
C9
O14
170.64
C16
C11
C8
C1
C2
with N-methylpyrrole, N,N-binucleophiles (hydrazine,
acetylhydrazine), and sodium azide.
C6
O7
C15
C12
C13
Nitroethylation of pyrrole was shown to proceed in
the absence of any catalytic agents and solvents and
results in formation of alkylation products IV and V;
this reaction is known as “substitutive addition” [13].
N3
O5
O4
It should be pointed out that reactions of pyrrole
with β-nitrostyrenes and their analogs are reportedly
Molecular geometry of 4-(4-methoxyphenyl)-3-nitrobut-3-
en-2-one (II).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 9 2008

1714
ABOSKALOVA et al.
O
Ar
C
CH3
N
Ar
NO2
NO2
CHA
NaN3
CH3
N
N
Ar = C6H5, 4-H3COC6H5
Ar = C6H5,
4-H3COC6H4
COCH3
CHB
N
N
C
CH3
H
Ar
CH3
O
XII, XIII
I_III
IV, V
H2NNHCOCH3
H2NNH2
Ar = C6H5,
4-H3COC6H4
4-(CH3)2NC6H4
Ar = C6H5,
4-H3COC6H4
Ar = 4-(CH3)2NC6H4
Ar
Ar
O
N
N
Ar
C
CH3
HN
CH3
N
NH
N
Ar
IX_XI
VI, VII
VIII
Ar = C6H5 (I, IV, VI, IX, XII); 4-H3CO–C6H4 (II, V, VII, X, XIII); 4-(CH3)2N–C6H4 (III, VIII, XI).
very laborious to perform, occur for a long time, and
often require catalysts (ZnI2, I2, etc.) [14, 15].
reactions of β-acetyl-β-nitrostyrenes I and II with
hydrazine result in direct isolation (even after 30–
40 min) of heterocyclization products: substituted
pyrazoles VI (61%) and VII (57%).
The structure of pyrrolylnitrobutanones IV and V is
proved by spectral data (Table 5). Their IR spectra
show strong stretching vibration bands of
unconjugated nitro (1560, 1360 сm−1) and carbonyl
(1740 сm−1) groups. The 1Н NMR spectra of IV and V
in chloroform contain double sets of signals, implying
that the compounds are present as mixtures of
diastereomers in 2 : 1 and 4 : 1 ratios, respectively
(Table 5).
Probably, the reaction of β-acetyl-β-nitrostyrenes I
and II with hydrazine initially forms adducts by the
C=C bond, as is the case with heterocyclic
nitroeneketones [20]. The isolation of substituted
pyrazoles V and VI suggests that the initially formed
monoadducts are susceptible to further intramolecular
nucleophilic addition of the NH2 group to carbonyl,
forming pyrazoline derivatives which undergo
spontaneous elimination of HNO2 to give stable
pyrazole systems. Obviously, PTSA activates the
carbonyl group at the stage of cyclization of linear
adducts.
The reactions studied demonstrate the use of β-
acetyl-β-nitrostyrenes as nitroketoalkylating agents for
pyrrole (С2).
According to published data, reactions of such N,N-
binucleophiles as hydrazine and its derivatives with
unsaturated ketones are a suitable method for
preparing pyrazolidones [16], 2-pyrazolines [16, 17]
and pyrazoles [18]. We found that gem-
acetylnitroethenes I-III react with hydrazine (рKв 5.5
[19]) in ethanol at a small excess of N,N-binucleophile
at room temperature in the absence of a catalyst; the
products are formed in low yield and they are difficult
to isolate. Significantly better results were obtained
with a sixfold excess of hydrazine in the presence of р-
toluenesulfonic acid (PTSA). In these conditions, the
Evidence for the suggested structure of VI comes
from the fact that its melting point is close to that of
the earlier described sample synthesized by others
methods [21, 22].
The structures of pyrazoles VI and VII were
1
proved by Н NMR and IR spectroscopy. Thus the IR
spectrum of substituted pyrazole VII contains no
absorption bands of the carbonyl and nitro groups. The
pyrazole NH stretching vibration band is observed at
1
3435 сm−1. In the Н NMR spectrum of compound
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 9 2008

β-ACETYL-β-NITROSTYRENES
1715
Table 5. Yields, melting points, and spectral data of pyrrolylbutanones IV and Va
IR spectra (СНCl3), ν, cm–1
1Н NMR spectra (СDCl3), δ, ppm (J, Hz)
Yield,
%
mp,
Comp. no.
°С
NO2
C=O
НА
НВ
СН3 (N–CH3) [O–CH3]
2.29 s
Pyr (Ar)
5.86 d
4.99 d
6.09, 6.20, 6.52
(7.27 m)
IVa
3JАВ 11.77 Hz
(3.49 s)
1560
1360
44
68–70
1740
5.87 d
5.00 d
1.86 s
6.05, 6.20, 6.52
(7.27 m)
3JАВ 11.03 Hz
(3.40 s)
IVb
Va
5.79 d
4.86 d
4.94 d
2.28 s
5.95, 6.04, 6.51
(6.80–7.30 m)
3JАВ 11.77 Hz
(3.46 s) [3.80 s]
1560
1360
28
88–90
1740
5.83 d
1.88 s
5.73, 6.16, 6.51
(6.80–7.30 m)
3JАВ 11.03 Hz
(3.38 s) [3.74 s]
Vb
a
Compounds IV and V were isolated as mixtures of diastereomers a and b in 1:2 and ≈3:1 respectively; isomer a gives upfield НА
and НВ proton signals and isomer b gives downfield НА and НВ proton signals.
VII, the signals of pyrazole ring protons fall into the
resonance region of benzene ring protons at 6.85–
7.60 ppm. The singlets at 2.50 and 3.85 ppm belong to
the СН3 and ОСН3 groups, respectively.
first stage, do not heterocyclize (as in the case of hyd-
razine) but are cleaved, releasing the acetylnitromethyl
anion and transforming into N-acetylhydrazones. This
is likely to be due to the reduced basicity, steric
inaccessibility of the second nucleophilic center of
acetylhydrazine, high stability of the leaving finc-
tionalized carbanion, and formation of energetically
advantageous conjugated systems.
No pyrazole formation is not observed in the
hydrazine reaction with β-acetyl-β-nitrostyrene III
containing an N,N-dimethylamino group in the рara
position of the aromatic ring. In this case, 4-
(dimethylamino)benzaldehyde azine (VII) was isolated
in high yield (96%). The structure of azine VIII was
proved by its independent synthesis from the
corresponding aldehyde and hydrazine. Probably, the
reaction of compound III with hydrazine involves an
AdN reaction (2 mol of nitroeneketone with 1 mol of
hydrazine) providing a bis-adduct which undergoes
cleavage with elimination of the acetylnitromethyl
anion and formation of 4-(dimethylamino)benzal-
dehyde azine. The energetic advantage of the
conjugated system in the latter product is likely to be a
key factor responsible for this reaction direction; just
this transformation was observed in the reaction of 1-
acyl-2-(1-methylindol-3-yl)-1-nitroethenes with hyd-
razine [20].
The structure of N-acetylhydrazones IX-XI is
1
additionally proved by IR and Н NMR spectroscopy.
Thus the IR spectrum of benzaldehyde N-acetyl-
hydrazone IX show C=O and С=N absorption bands at
1680 and 1615 сm−1. The broad absorption band in the
range 3100–3300 cm−1 corresponds to stretching
vibrations of NH-associated secondary amide group.
1
The Н NMR spectrum of compound IX contains
olefin and aromatic ring proton signals at 7.26–
7.85 ppm. The singlet at 2.34 ppm corresponds to СН3
protons, and the NH proton resonates at 10.03 ppm.
The reactions of β-acetyl-β-nitrostyrenes I and II
with sodium azide proceed in DMF under com-
paratively mild conditions (room temperature, 2.5 h,
nitroeneketone:sodium azide 1:2) and forms aryl-
substituted 4-acetyl-1,2,3-triazoles XII and XIII in 94
and 91% yields, respectively. It likely that the process
formally follows the 1,3-dipolar cycloaddition scheme,
like reactions of others functionally substituted
nitroethenes with NaN3 [24–28].
gem-Acetylnitroethenes I–III, too, react with
acetylhydrazine (рKВ 10.76 [23]) in fairly mild
conditions (reaction time 1 h, solvent ethanol–benzene,
room temperature) and gives rise to aromatic aldehyde
N-acetylhydrazones IX–XI in yields of up to 87%. The
products were identified by measuring of the melting
points of their mixed samples with model samples
specially synthesized from aromatic aldehydes and
acetylhydrazine. Probably, the adducts of acetyl-
hydrazine by the multiple С=С bond, formed at the
It should be noted that compounds XII and XIII
were earlier prepared in a different way, e.g. by the
reaction of sodium azide with gem-sulfonyl-substituted
unsaturated ketones, but only under more rigid
conditions and in lower yields (64–70%) [29].
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 9 2008

1716
ABOSKALOVA et al.
Thus, we showed that β-acetyl-β-nitrostyrenes react
4-(1-Methylpyrrol-2-yl)-3-nitro-4-phenylbutan-
2-one (IV). N-Methylpyrrole, 0.133 ml, was added to
0.143 g of 3-nitro-4-phenylbut-3-en-2-one (I). The
reaction mixture was heated to the melting point under
continuous stirring, allowed to stand for 4 days in a
dark place, treated with ethanol, and the precipitate
was filtered off. Yield 0.09 g (44%), crystals (mixture
of diastereomers in a 1:2 ratio), mp 68–70°С (from
ethanol). Found, %: С 66.00; 66.02; Н 5.41; 5.44.
C15H16N2O3. Calculated, %: С 66.18; Н 5.88.
with N-methylpyrrole, hydrazine, and sodium azide to
form nitroketenes containing an active pharmacophoric
pyrrole structure, as well as substituted pyrazoles and
1,2,3-triazoles. These reactions can be used for
preparative synthesis of the above heteryl-containing
systems which are potentially biologically active
compounds. We can mention here haemoglobin,
chlorophyll, vitamin B12, proline, and many medicinals
(atropin, cocaine, pyrrolenitrin, etc.) containing the
pyrrole ring in their molecules. Carbonyl-containing
pyrazole derivatives, such as pyrazolones, are widely
used as antipyretic, anesthetic, and anti-inflammatory
drugs (antipyrine, amidopyrine, analgine, butadiene,
etc.). Certain 1,2,3-triazoles posses antifungal, anti-
microbial, and antiviral properties. For example, 5-(4-
bromophenyl)- and 5-(4-nitrophenyl)-4-nitro-1,2,3-
triazoles exhibit turbecularstatic and antifungal effects
[25].
4-(4-Methoxyphenyl)-4-(1-methylpyrrol-2-yl)-3-
nitrobytan-2-one (V). N-methylpyrrole, 1.8 ml, was
added to 0.442 g of 4-(4-methoxyphenyl)-3-nitrobut-3-
en-2-one (II). The mixture allowed to stand at room
temperature in a dark place. After 3 days, ethyl acetate
and water (4:1) were added, and the layers were
separated in a separatory funnel. The organic layer was
washed with two portions of saturated sodium chloride
and dried over magnesium sulfate for 1 day. The
solvent was evaporated in a Petri dish, and the residue
was treated with ethanol. Yield 0.16 g (28%), crystals
(mixture of diastereomers in a 1:4 ratio), mp 88–90°С
(from ethanol). Found, %: N 9.55; 9.48. C16H18N2O4.
Calculated, %: N 9.27.
EXPERIMENTAL
The IR spectra were registered on an Infralum FT-
02 instrument (CDCl3, KBr). The UV spectra were
recorded on a Specord M-40 spectrophotometer in
3(5)-Мethyl-5(3)-phenylpyrazole (VI). To a
suspension of 0.288 g of 3-nitro-4-phenylbut-3-en-2-
one (I) in 2 ml of ethanol, 0.44 ml of 98% hydrazine
hydrate solution and 0.07 g of p-toluenesulfonic acid
were added. The reaction mixture was stirred at room
temperature for 40 min, poured into water with ice,
and cooled in a refrigerator for 3 h. The precipitate was
filtered off and dried. Yield 0.145 g (61.2%), white
crystals, mp 124-126˚С (from 50% methanol);
published data [30a]: mp 127˚С (from benzine).
1
ethanol. The Н NMR spectra were measured on a
Bruker AC-200 (200 МHz) spectrometer (CDCl3-d1,
CD3CN-d3) against external HMDS with an accuracy
of 0.5 Hz.
Compounds I–III were prepared by the procedures
described in [1].
X-ray diffraction analysis of compound II.
Crystals II: C11H11NO4, monoclinic, space group Р21/с.
Unit cell parameters at –75°С: a 7.418(1), b 11.134
(1), c 13.613(1) Å, b 104.37(1)°, V 1089.2(2) Å3, Z 4,
dcalc 1.349 g сm–3. The unit cell parameters and
intensities of 23198 reflections, of which 2680 were
unique (Rint 0.026] were measured on a Nonius
KappaCCD automatic diffractometer (λMoKα, graphite
monochromator, θ ≤ 28.39°) at –75°С using COLLECT
(Nonius B.V., 1998), Dirax/lsq (Duisenberg &
Schreurs, 1989—2000), and EvalCCD (Duisenberg &
Schreurs, 1990–2000) programs. Empirical absorption
corrections were applied. The structure was decoded
by a direct method using SHELXS-97 and refined
using SHELXL-97 (G.M. Sheldrick, Universität
Göttingen, 1997). The final divergence factors were R
0.040 and RW 0.105, on 2187 unique reflections with
F2 ≥ 2σ.
3(5)-Мethyl-5(3)-(4-methoxyphenyl)pyrazole
(VII). To a suspension of 0.332 g of 4-(4-me-
thoxyphenyl)-3-nitrobut-3-en-2-one (II) in 2 ml of
ethanol, 0.44 ml of 98% hydrazine hydrate solution
and 0.07 g of p-tolunesulfonic acid were added. The
reaction mixture was stirred at room temperature for
40 min and then poured into water with ice. The
precipitate was filtered off and dried. Yield 0.162 g
(57.4%), white crystals, mp 130–132°С (from 50%
methanol). Found, %: N 14.60; 14.68. C11H12N2O.
Calculated, %: N 14.89.
4-(N,N-Dimethylamino)benzaldehyde azine (VIII)
was prepared similarly from 0.351 g of 4-(4-N,N-
dimethylaminophenyl)-3-nitrobut-3-en-2-one
(III).
Yield 0.214 g (96%), orange crystals, mp 240–242°С
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β-ACETYL-β-NITROSTYRENES
1717
4. Remennikov, G.Ya., Shavran, S.S., Boldyrev, I.V.,
Kurilenko, L.K., Klebanov, B.М., and Kukhar’, V.G.,
Khim.-Pharm. Zh., 1991, vol. 25, no. 3, p. 35.
5. Remennikov, G.Ya., Boldyrev, I.V., Kapran, N.А., and
Kurilenko, L.K., Khim. Geterotsikl. Soedin., 1993, no. 3,
p. 388.
(from carbon tetrachloride). A mixture with the sample
obtained from 4-N,N-dimethylaminobenzaldehyde and
hydrazine does not give melting point depression;
published data [30b]: mp 250–253°С. Found, %: N
19.27; 19.20. C18H22N4. Calculated, %: N 19.05.
Benzaldehyde N-acetylhydrazone (IX). To a sus-
pension of 0.191 g of 3-nitro-4-phenyl-but-3-en-2-one
(I) in 2 ml of benzene, a solution of 0.148 g of
acetylhydrazine in 3 ml of ethanol was added. The
reaction mixture was stirred at room temperature for 1 h
and then poured into a Petri dish. The precipitate that
formed after evaporation of the solvent was washed
with benzene and filtered off. Yield 0.075 g (46%),
colorless crystals, mp 126–128°С (from carbon
tetrachloride). A mixture with the sample obtained by
independent synthesis from benzaldehyde and
acetylhydrazine gave no melting point depression.
6. Remennikov, G.Ya., Boldyrev, I.V., Kravchenko, S.А.,
and Pirozhenko, V.V., Khim. Geterotsikl. Soedin., 1993,
no. 9, p. 1290.
7. Remennikov, G.Ya., Boldyrev, I.V., Kravchenko, S.А.,
and Pirozhenko, V.V., Khim. Geterotsikl. Soedin., 1993,
no. 10, p. 1398.
8. Trukhin, Е.V., Makarenko, S.V., and Berestovitskaya, V.М.,
Zh. Org. Khim., 1998, vol. 34. no. 1, p. 72.
9. Peprno, Т.Ya., Perekalin, V.V., and Sopova, А.S., Zh.
Prikl. Spektrosk., 1973, vol. 19, no. 4, p. 649.
10. Peprno, Т.Ya. and Perekalin, V.V., Infrakrasnye spektry
nitrosoyedinenii (Infrared Spectra of Nitro Compounds),
Leningrad: Len. Gos. Ped. Inst. im. А.I. Gertsena, 1974,
p. 185.
11. Wallis, J.D., and Watkin, D.J., Acta Crystallogr., Sect.
B, 1982, vol. 38, part 7, p. 2057.
4-Methoxybenzaldehyde N-acetylhydrazone (X)
was prepared similarly from 4-(4-methoxyphenyl)-3-
nitrobut-3-en-2-one (II). Yield 67%.
12. Panfilova, L.V., Antipin, M.Yu., Churkin, Yu.D., and
Struchkov, Yu.T., Khim. Geterotsikl. Soedin., 1979, no. 9,
p. 1201.
4-(N,N-Dimethylamino)benzaldehyde N-acetyl-
hydrazone (XI) was prepared similarly from 4-(4-
N,N-dimethylaminophenyl)-3-nitrobut-3-en-2-one (III).
Yield 87%.
13. Yuryev, Yu.K., Zefirov, N.S., and Shteinman, А.А.,
Zh. Obshch. Khim., 1963, vol. 33, no. 4, p. 1150.
4-Аcetyl-5-phenyl-1,2,3-triazole (XII). A mixture
of 0.191 g of 3-nitro-4-phenylbut-3-en-2-one (I) and
0.13 g of sodium azide in 7 ml of DMF was stirred at
room temperature for 2.5 h and then poured in crushed
ice and acidified with 10% HCl to pH ~ 1. A day after,
the precipitate was filtered off and dried. Yield 0.176 g
(94%), colorless crystals, mp 111–112°С (from
benzene); published data [29]: 112°С [29]. Found, %:
N 22.53; 22.50. C10H9N3O. Calculated, %: N 22.46.
14. Cambell, M.M., Cosford, N. Zongli li, and Sains-
bury, M., Tetrahedron, 1987, vol. 43, no. 6, p. 1117.
15. Lin, С., Hsu, J., Sastry, M.N.V., Fang, H., Tu, Z., Liu, J.,
and Ching-Fa, Y., Tetrahedron, 2005, vol. 61, no. 49,
p. 11751.
16. Nenaydenko, V.G., Sanin, А.V., and Balenkova, Е.S.,
Zh. Org. Khim., 1995, vol. 31, no. 5, p. 786.
17. Long, L.M. and Troutman, H.D., J. Am. Chem. Soc.,
1949, vol. 71, no. 7, p. 2469.
18. El-Rayyes, N.R., Novakeemian, G.H., and Ham-
moud, H.S., J. Chem. Eng. Data, 1984, vol. 29, no. 2,
p. 225.
4-Аcetyl-5-(4-methoxyphenyl)-1,2,3-triazole (XIII)
was prepared similarly from II. Yield 91%, mp 98–99°С
(from benzene); published data [29]: 102°С. Found, %:
N 19.41; 19.38. C11H11N3O2. Calculated, %: N 19.30.
19. Mathieu, J. and Panico, R., Mécanismes Réactionnels
en Chimie, Paris: Hermann, 1972. Translated under the
title Printsypy organicheskogo sinteza, Leningrad:
Khimiya, 1962, p. 591.
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