Preparation of 4-nitrostyrene

Article abstract of DOI:10.1134/S1070363213100101

The interaction of D,L-1-(4-nitrophenyl)ethanol with SOCl₂ and P₄O₁₀ has been studied. In the reaction of D,L-1-(4-nitrophenyl)ethanol with SOCl₂ a mixture of 1-(4-nitrophenyl)-1-chloroethane, 1,1′-bis-(4-nitrop

Full text of DOI:10.1134/S1070363213100101

ISSN 1070-3632, Russian Journal of General Chemistry, 2013, Vol. 83, No. 10, pp. 1859–1863. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © A.L. Shultsev, 2013, published in Zhurnal Obshchei Khimii, 2013, Vol. 83, No. 10, pp. 1649–1653.
Preparation of 4-Nitrostyrene
A. L. Shultsev
Institute of Macromolecular Compounds, Russian Academy of Sciences,
Bol’shoi pr. Vasil’evskogo ostrova 31, St. Petersburg, 199004 Russia
e-mail: shultsev@list.ru
Received March 12, 2013
Abstract—The interaction of D,L-1-(4-nitrophenyl)ethanol with SOCl
reaction of D,L-1-(4-nitrophenyl)ethanol with SOCl a mixture of 1-(4-nitrophenyl)-1-chloroethane, 1,1'-bis-(4-
nitrophenyl)diethyl ether, and 4-nitrostyrene (yield 21%) has been formed. The direction of reaction of D,L-1-
4-nitrophenyl)ethanol with Р 10 in toluene has been affected significantly by the order of reagents addition
and the solution concentration. 4-Nitrostyrene has been obtained in the only case: the addition of Р
2 4
and Р О10 has been studied. In the
2
(
4
О
4
О10 to a
diluted solution of D,L-1-(4-nitrophenyl)ethanol and subsequent refluxing. Also the procedure of 4-nitrostyrene
preparation via the cleavage of 2-(4-nitrophenyl)ethyl nitrate with alkoxy anion in the alcoholic solution has
been upgraded.
DOI: 10.1134/S1070363213100101
Nowadays several methods of 4-nitrostyrene pre-
paration are known, for instance, decarboxylation of 4-
nitrocinnamic acid in the presence of quinoline and
copper powder at 160–165°C [1, 2] dehydrohalogena-
tion of β-(4-nitrophenyl)ethyl bromide in the presence
of triethanolamine [3], and the interaction of 2-(4-
nitrophenyl)ethyl nitrate with alkaline reagents [5, 6].
However, the latter method has remained imperfect,
being time-, energy-, and materials-consuming and
giving only a crude product that requires purification.
Other procedures to prepare 4-nitrostyrene have not
been described so far. Therefore, development of new
synthetic pathways to this compound as well as im-
provement of the existing procedures is an important task.
This work aimed at a study of D,L-1-(4-nitro-
phenyl)ethanol interaction with thionyl chloride and
phosphorus(V) oxide and at an upgrading of the known
method of 4-nitrostyrene preparation via the treatment
of 2-(4-nitrophenyl)ethyl nitrate with alkoxy anion.
The starting 4-nitroacetophenone was reduced in
ethanol or methanol, avoiding heating above 30°С;
O
OH
NaBH4
CH3
CH3
O N
O N
2
2
I
II
Cl
O N
2
CH3
SOCl2
CH3
CH2
O
+
+
O N
O N
2
2
CH3
NO2
III
IV
V
P4O
10
CH2
O N
2
1
859

1
860
SHULTSEV
1
that gave nitroalcohol II in 93.8–100% yield without
amine impurities. Further treatment of II with SOCl2
gave a mixture of products III–V, the corresponding
chloro derivative being the major one. After elimina-
tion of most part of minor 1,1'-bis-(4-nitrophenyl)-
From the Н NMR spectrum (see the Figure), the
major component of the products mixture was 4-
nitrostyrene. To the СН = protons corresponds the
doublet of doublets at δ = 5.536–5.564 ppm, the
vicinal proton at the double bond appeared as quartet
at δ of 6.904–6.948 ppm., whereas the aromatic
protons at the 2, 6 and 3, 5 appeared at doublets at
2
diethyl ether, we obtained a mixture containing about
1
2
1% of 4-nitrostyrene ( Н NMR).
7
8
.79, 7.81 ppm (J = 8.83 Hz) and 8.23, 8.25 ppm (J =
.73 Hz), respectively.
In [4] 3-nitrostyrene was obtained with low yield
via dehydration of 1-(3-nitrophenyl)ethanol with phos-
phorus(V) oxide in benzene solution. The amount of
consumed Р О and the reaction duration were not
When the reagents were mixed without solvent,
their interaction was faster, in particular, after a short
induction period the exothermic decomposition of the
reaction products occurred. If a certain amount of
solvent with high boiling point was added to the
mixture prior to the start of the uncontrolled reaction, it
allowed for efficient heat exchange, and the process
was fast but safe. Within 15–20 min of such reaction a
mixture of products was obtained, however, containing
only minor amount of 4-nitrostyrene. Its subsequent
treatment with phosphorus(V) oxide under reflux
during 5.5 h gave a solid complex compound, decom-
position of it with water gave a mixture lacking 4-
nitrostyrene.
4
10
reported; the described procedures implied a set of
technology cycles. In this work, the dehydration of p-
isomer of nitroalcohol II was performed in toluene
solution, thus the reaction temperature could be
increased, whereas the reaction duration was
shortened. In the case of Р О addition to the diluted
4
10
solution of 1-(4-nitrophenyl)ethanol and subsequent
refluxing the dehydration became the major reaction
pathway. After isolation of organic part and steam
discillation of major part of starting nitroalcohol with
admixture of 4-nitrostyrene, a mixture of products was
obtained containing 60–70 mol % of 4-nitrostyrene.
For the reaction to proceed smoothly, the solvent
should be anhydrous.
As was discussed above, the method of 4-
nitrostyrene production via nucleophilic cleavage of 2-
δ, ppm
1
Н NMR spectrum of the residue after volatile compounds after steam discillation.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 10 2013

PREPARATION OF 4-NITROSTYRENE
1861
(
4-nitrophenyl)ethyl nitrate [6] was not perfect. The
NMR spectra [δ, ppm: 8.031 (CDO) DMF-d ; 7.283
7
drawbacks of the method were as follows. The hetero-
geneous nature of the process slowed it down, ad-
ditionally the reaction should be performed at 10–12°C
СDCl ] were registered using Bruker AVANCE II 400
spectrometer [ H (400.1 MHz), С (100.6 MHz)].
3
1
13
Preparation of D,L-1-(4-nitrophenyl)ethanol. In
a 500 ml 2-neck flask equiped with a condenser a
solution of 7.45 g (0.0451 mol) of 4-nitroacetophenone
in 100 ml of methanol was prepared; then 2.0 g
(
under cooling). The unreasonably slow addition of
EtONa solution (during 1.5 h) and the long stirring
after EtONa introduction (45 min) led to the total
reaction time of 2 h 15 min. Furthermore, the decom-
position of excessive EtONa in the reaction mixture
(
0.0529 mol) of NaBH was added to it at 20–30°С
4
during 45 min, in small portions, at stirring. After 1 h,
after the gas evolution stopped, the obtained mixtire
was evaporated at a rotary evaporator to half of the
was performed by treatment with СН СООН, the latter
3
being added to the anhydrous mixture till pH 6; that
resulted in the presence of acetic acid and sodium
acetate in the crude product. Note that the salt could
not be removed by filtration since it is dissolved and
remained in the product after solvent evaporation.
Then, the described procedure did not imply the
removal of the residual amounts of the side product
NaNО3 after removal of its major part, that
additionally decreased the yield. The losses were no
less than 7.9–17% of the potential yield. Finally, the
target product isolation by drying from the anhydrous
mass led to considerable losses of 4-nitrostyrene and
was time- and material-consuming.
initial volume, and then 50 ml of Н О was added
2
(temporary opacification was observed). The clear solu-
tion was extracted with chloroform (70 and 2×30 ml)
and then with 20 ml of benzene. The solvent was
evacuated from the combined extracts with rotary
evaporator. Yield 7.07 g (93.8%), colored liquid.
D,L-1-(4-Nitrophenyl)ethanol was purified by
discillation at 137.5–138°С (1–1.5 mm Hg). The pro-
1
duct was a clear green-yellow fluid. Н NMR spec-
trum, δ, ppm: 1.44 d (3Н, СН
(1Н, СН, J 6.5 Hz), 5.58 d (1Н, ОН, J 4.3 Hz), 7.72 d
, J 6.5 Hz), 4.97–5.03 m
3
(
2Н, 2,6-Ar, J 8.9 Hz), 8.25 d (2Н, 3,5-Ar, J 8.8 Hz).
EtONa
1
3
CH2
С NMR spectrum, δ , ppm: 26.40 (СН ), 69.18 (СН),
С
3
_NaNO3
124.37 (3,5-Аr), 127.58 (2,6-Аr), 147.72 (4-Аr),
156.65 (1-Аr).
ONO2
O N
O N
2
2
VI
Treatment of D,L-1-(4-nitrophenyl)ethanol with
thionyl chloride. 3.28 g (0.0276 mol) of SOCl was
2
Thus, the discussed method could only give
technical product, vacuum discillation of which gave
the target compound in 81% yield.
added to 3.87 g (0.0232 mol) of D,L-1-(4-nitrophenyl)-
ethanol. After the initial vigorous reaction slowed
down, the reaction mixture was heated at 70–85°С till
gas evolution almost stopped, then 1.64 g (0.0138 mol)
After having significantly changed the procedure,
1
we were able to prepare pure ( Н NMR) 4-nitrostyrene
of SOCl was added, the gas evolution stopped at this
2
from 2-(4-nitrophenyl)ethyl nitrate. The yield of 4-nitro-
styrene reached 100% and the yield of sifficiently pure
by-product, alkali metal nitrate, was of 97.9–100%; the
process duration was reduced to a minimum.
point, and the mixture became dark. The volatile
components were removed in a vacuum, 4.44 g of dark
liquid (partially crystallizing at cooling) was obtained.
To thus obtained suspension, 25 ml of acetone was
added, the precipitate was filtered off, washed with
acetone, and dried in air. 0.06 g of 1,1'-bis-(4-
nitrophenyl)diethyl ether was thus obtained. Then, the
solvent was evaporated from the filtrate in a vacuum at
heating, 4.0 g of colored liquid was obtained. After its
keeping at –21°С, the precipitate was formed, it was
filtered off, washed several times with acetone, and
dried in air; 0.01 g of 1,1'-bis-(4-nitrophenyl)diethyl
ether was thus obtained. Acetone was then evaporated
from the filtrate at heating in ar vacuum, from the
obtained colored liquid the precipitate of 1,1'-bis-(4-
nitrophenyl)diethyl ether was formed after keeping at
EXPERIMENTAL
The following chemicals were used: 4-nitroaceto-
phenone (99.6%, mp 80°С), NaBH4 (glanules,
chemically pure grade or B grade according to TU 1-
9
4
2-162-90), СНСl (chemically pure grade, TU 6-09-
263-76). 2-(4-Nitrophenyl)ethyl nitrate was prepared
3
as described in [7]. Diethyl ether was purified. Acetone
was distilled, the fraction with bp of 56.3°С (760 mm
Hg) was used. Anhydrous toluene was obtained by
refluxing over Na, then it was treated with Р О prior
4
10
to use.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 10 2013

1
862
SHULTSEV
2
3°С. The precipitate was filtered off, washed with
added to the liquid, and the mixture was refluxed
during 5.5 h. The colorless solution was decanted from
dark precipitate, and the obtained solid complex was
decomposed with water. The so obtained emulsion was
extracted with toluene, the solutions were combined
and treated as described above. After removal of the
volatile compounds, 23.58 g of non-crystallizible
brown liquid was obtained, it contained traces of 4-
nitrostyrene.
small amount of acetone, and dried (0.04 g). The
combined yield of 1,1'-bis-(4-nitrophenyl)diethyl ether
was 0.11 g (3.7%), white crystalline compound,
soluble in СНСl , sparingly soluble in (СН ) СО and
DMF, and insoluble in Н О. Found, %: С 59.34; Н
5
5
3
3 2
2
.26; N 8.63. С Н N O . Calculated, %: С 60.75; Н
16 16 2 5
1
.10; N 8.86. Н NMR spectrum (CDCl ), δ, ppm: 1.44
3
d (6Н, CH , J 6.5 Hz), 4.35 q (2Н, СН, J 6.5 Hz), 7.48
3
d (4Н, 2,6-Ar, J 8.5 Hz), 8.26 d (4Н, 3,5-Ar, J 8.8 Hz).
1
3
С NMR spectrum (СDСl ), δ , ppm: 24.47 (СН ),
b. A mixture of 23.64 g (0.1416 mol) of D,L-1-(4-
3
С
3
7
4.86 (СН), 124.05 (3,5-Аr), 126.90 (2,6-Аr), 147.60
nitrophenyl)ethanol, 500 ml of anhydrous toluene, and
1
3
(
4-Аr), 151.107 (1-Аr). С NMR spectrum (DMF-d ),
40.0 g (0.1409 mol) of Р О10 was refluxed during
4
7
δ , ppm: 24.09 (СН ), 74.95 (СН), 124.05 (3,5-Аr),
25 min, then the heating was stopped, and the solution
was decanted. The precipitate was washed with 50 ml
of anhydrous toluene, the extract was combined with
the solution, and 60.0 g (0.2113 mol) of Р О was
С
3
1
27.63 (2,6-Аr), 147.63 (4-Аr), 152.35 (1-Аr).
The filtrate was vacuum-evaporated. 3.26 g of
4
10
liquid was obtained of the following molar composi-
added; at that point the yellowish color changed to
orange-browm. The mixture was then refluxed during
1.5 h. The formed precipitate was decomposed by
water; the solution was extracted with 55 ml of
chloroform, then with 20 ml of benzene, and finally
with 75 ml of chloroform. After the reaction was
finished, the toluene solution was decanted, the
precipitate was twice extracted with 100 ml of boiling
toluene. All the extracts and organic solutions were
combined, and the solvent was evaporated in a vacuum.
The liquid residue was steam distilled; thus, 1 l of the
distillate was obtained, then it was extracted with
diethyl ether. After ether was evaporated in a vacuum,
2.17 g of D,L-1-(4-nitrophenyl)ethanol was obtained
with admixture of 4-nitrostyrene. The distillation
residue was extracted with diethyl ether, the extract
1
1
tion ( Н NMR): 21.0 (V), 72.8 (III), 6.2 (IV). Н NMR
spectrum (СDСl ), δ, ppm: 1.87 d [3Н, СН (III), J 6.9
3
3
Hz], 5.15 q [1Н, СН, (III) J 6.8 Hz], 7.61 d [2Н, 2,6-
Ar (III), J 8.6 Hz], 8.22 d [2Н, 3,5-Ar (III), J 8.9 Hz],
5
.52 d. d (1Н, cis-H, J 10.9 Hz), 5.95 d. d (1Н, trans-
H, J 17.6 Hz), 6.80 q (1Н, vic-H, J 10.9 hz), 7.55 d
2H, 2,6-Ar (V), J 8.6 Hz], 8.19 d [2H, 3,5-Ar (V),
J 8.9 Hz].
[
Treatment of D,L-1-(4-nitrophenyl)ethanol with
Р О . a. 50.0 g (0.1761 mol) of Р О was added to
4
10
4
10
2
1.53 g (0.1289 mol) of D,L-1-(4-nitrophenyl)ehtanol,
the compounds were mixed, and 50 ml of anhydrous
toluene was added. The obtained dense mass was
crushed, 30 ml of anhydrous toluene was then added,
and the mixture was vigorously stirred. After 5 min
from the reaction start, the mixture was refluxed
during 10 min at stirring, and then maintained during 6
min. Then, the mixture was heated up to boiling,
cooled down, and decanted. The solid residue in the
flask was twice extracted with 40 ml of toluene. The
extracts were combined, and the solvent was eva-
porated in a vacuum. The solid residue was
decomposed with water, the obtained emulsion was
extracted with toluene, and the solvent was evaporated
in a vacuum. The liquid residues were combined, water
was added, and toluene admixture was distilled off
with water. The residue was extracted with diethyl
ether, the extract was dried over Na SO , and ether
was dried over CaCl , and the solvent was evaporated
2
in a vacuum. 23.32 g of dark-orange liquid was
obtained, crystallizing under cooling. 4-Nitrostyrene
was isolated from it via fractional distillation in a
vacuum. Yield 15.27 g (64.6%).
Preparation of 4-nitrostyrene from 2-(4-nitro-
phenyl)ethyl nitrate [8]. Solution of EtONa was
prepared from 1.15 g of Na and 45 ml of anhydrous
ethanol. That solution was added dropwise under
stirring at 22–25°С to a solution of 10.608 g (0.050 mol)
of 2-(4-nitrophenyl)ethyl nitrate in 160 ml of an-
hydrous ethanol. 4/5 of the EtONa solution was added
within 20 minutes, the rest was added in portions; after
addition of a portion, pH went up to 8; each next
portion was added when pH was back at 7. After
addition of all EtONa, the mixture was kept for 0.5 h at
2
4
was evaporated in a vacuum. 24.18 g of brown liquid
was obtained, not crystallizible at –21°С; it contained
admixture of 4-nitrostyrene. 200 ml of anhydrous
toluene and 80 g (0.2817 mol) of Р О were then
4
10
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 10 2013

PREPARATION OF 4-NITROSTYRENE
cooling, and then its pH (8–8.5) was adjusted to 6 by
1863
REFERENCES
adding concentrated HCl dropwise. The precipitate
was filtered off, washed with ethanol, and dried in air.
1
. Wiley, R.H. and Smith, N.R., J. Am. Chem. Soc., 1950,
vol. 72, p. 5198.
. Kolesnikov, G.S., Sintez vinilovykh proizvodnykh
aromaticheskikh i geterotsiklicheskikh soedinenii (Pre-
paration of Vinyl Derivatives of Aromatic and Hetero-
cyclic Compounds), Moscow: Akad. Nauk SSSR, 1960.
2
Thus 3.83 g of NaNO was obtained. Ethanol was
3
evacuated from the filtrate at rotary evaporator. The
residue (orange liquid containing inorganic precipitate)
was dissolved in diethyl ether, NaNO was filtered off,
3. Koton, M.M., Mitin, Yu.V., and Florinskii, F.S., Zh.
Org. Khim., 1955, vol. 25, p. 1469.
3
the precipitate was washed with diethyl ether and
combined with the major part after drying. Ether was
evacuated from the filtrate at rotary evaporator at 50°С,
and then by keeping at the residual pressure of 3 mm
Hg. Yield 7.45 g (100%) of 4-nitrostyrene in the form
4
. Marvel, С.S., Overberger, C.G., Allen, R.E., and
Saunders, J.H., J. Am. Chem. Soc., 1946, vol. 68, p. 736.
. Kochergin, P.M. and Blinova, L.S., USSR Inventor’s
Certificate no. 371220, 1959.
5
6. Kochergin, P.M., Blinova, L.S., Karpov, G.A.,
Mikhailova, I.S., Aleksandrova, E.V., and Korol, O.V.,
Pharm. Chem. J., 1999, vol. 33, no. 1, p. 41.
1
of yellow liquid crystallizing at cooling. H NMR
spectrum, δ, ppm: 5.57 d. d (1Н, cis-H, J 10.9 Hz),
7
. Shul’tsev, A.L., Russ. J. Gen. Chem., 2011, vol. 81,
no. 11, p. 2300.
. Shul’tsev, A.L. and Panarin, E.F., RF Patent no. 2432351,
2010.
6
.16 d. d (1Н, trans-H, J 17.7 Hz), 6.95 q (1Н, vic-H,
J 10.9 Hz), 7.83 d (2H, 2,6-Ar, J 8.8 Hz), 8.26 d (2H,
,5-Ar, J 8.9 Hz).
8
3
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 10 2013