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Synthesis of 2,4-dinitrophenol

Article in Russian Journal of Applied Chemistry · October 2012

DOI: 10.1134/S1070427212100163

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Yu. G. Khabarov Dmitry Lakhmanov

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ISSN 1070-4272, Russian Journal of Applied Chemistry, 2012, Vol. 85, No. 10, pp. 1577−1580. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © Yu.G. Khabarov, D.E. Lakhmanov, D.S. Kosyakov, N.V. Ul’yanovskii, 2012, published in Zhurnal Prikladnoi Khimii, 2012, Vol. 85,
No. 10, pp. 1644−1647.

ORGANIC SYNTHESIS
AND INDUSTRIAL ORGANIC CHEMISTRY

Synthesis of 2,4-Dinitrophenol

Yu. G. Khabarov, D. E. Lakhmanov, D. S. Kosyakov, and N. V. Ul’yanovskii

Lomonosov Northern (Arctic) Federal University, Arkhangelsk, Russia

e-mail: khabarov.yu@mail.ru

Received May 10, 2012

Abstract—New highly selective method is suggested for synthesis of 2,4-dinitrophenol by nitration of phenol
with nitric acid in an aqueous-alcoholic medium at the boiling point of the reaction mixture. The yield of 2,4-di-
nitrophenol is as high as 80%.
DOI: 10.1134/S1070427212100163

2,4-Dinitrophenol is an important product of organic By the nitration reaction, 2,4-dinitrophenol can

synthesis used as means of corrosion protection of metals be synthesized using the classical nitrating mixture
[1], styrene polymerization inhibitor [2], antiseptic for [14]. The reaction product is dark red oil. After the
wood impregnation [3], and raw material for synthesis reaction product is purified with bone coal, the yield of
of aromatic amino and nitro derivatives [4–6], dyes [7], 2,4-dinitrophenol is 65%.
and chemicals for agriculture [8, 9].
A method has been suggested for synthesis of mono-
The main method for obtaining 2,4-dinitrophenol is and dinitrophenol, in which sodium nitrite, oxalic
by nitration of benzene, phenol, or mononitrophenol; acid, and wet silicon dioxide are used. The reaction is
it is also synthesized by alkaline hydrolysis of performed in methylene chloride [15].
2,4-dinitrochlorobenzene.
Nitration of phenol with liquid N2O4 yields
2,4-Dinitrophenol is produced from benzene via
2,4-dinitrophenol [16]. The expenditure of N2O4
oxidative nitration with nitric acid in the presence of
is 4–6 mL g–1 phenol. It is recommended to purify
mercury(II) hydroxide and a minor addition of sodium
2,4-dinitrophenol by heating its alcoholic solution with
nitrite. The yield of the product is 56.8% [10].
bone coal. The yield of 2,4-dinitrophenol is 76%.
Another method for oxidative nitration of benzene
consists in bubbling of air or nitrose gases through 2,4-Dinitrophenol is formed from sodium
a nitric acid solution of mercury(II) nitrate, heated to nitromalonic aldehyde monohydrate and 1-nitro-2-
above 40°C. 2,4-Dinitrophenol with a melting point of propanone via cyclodehydration in an alkaline medium
about 105°C has been produced by this technique [11]. at room temperature in the course of 18 h. A purification
A synthesis of 2,4-dinitrophenol has been described by column chromatography (SiO2; CH2Cl2) yielded
in which nitrosophenol is produced from phenol and 440 mg of pale yellow 2,4-dinitrophenol from 2 g of
then is subjected to oxidative nitration with nitric sodium nitromalonic aldehyde monohydrate and 1.18 g
acid at 90°C in the course of 1.5 h [12]. The yield of of 1-nitro-2-propanone [17].
2,4-dinitrophenol is 79%. Thus, a large number of multistage labor-
2,4-Dinitrophenol is produced from 2,4-dinitrochloro- consuming methods have been developed for synthesis
benzene by the reaction of nucleophilic substitution of 2,4-dinitrophenol. The goal of our study was to
[13]. The reaction is performed in an alkaline medium at develop a new high-selectivity method for synthesis
a temperature of 95–97°C in the course of 3.5 h. of 2,4-dinitrophenol, based on the reaction of phenol

1577
1578 KHABAROV et al.

nitration with nitric acid in an aqueous-alcoholic acetonitrile in a 0.5% aqueous solution of HCOOH
medium. served as eluent. The flow rate was 0.4 mL min–1. The
HPLC data indicate that the preparation is an impurity-
EXPERIMENTAL free individual substance.
The melting point (104.8°C) was determined with
We used for synthesis freshly distilled crystalline a DSC Q2000 differential scanning calorimeter (TA
phenol, concentrated nitric acid of chemically pure grade Instruments, United States).
(concentration 65%), and rectified ethanol (ethanol The elemental composition was determined with
content 95.3%). a EuroEA-3000 CHNS-analyzer (EuroVector, Italy).
2,4-Dinitrophenol. A 2.5-g portion of phenol and Found (%): C 39.3 ± 1.1, H 2.13 ± 0.06, N 17.1 ± 0.5.
an aqueous-ethanolic solution of nitric acid, prepared Calculated (%): C 39.13, H 2.17, N 15.2.
from 12.5 mL of concentrated nitric acid and 50 mL of The elemental composition of the synthesized
ethanol, was mixed in a round-bottomed flask. 2,4-dinitrophenol coincides with that theoretically
The reaction mixture was heated in an installation predicted.
with a reflux for 0.5–2 h. Then, approximately 50 mL An electronic absorption spectrum of 2,4-dinitro-
of a liquid was obtained by vacuum distillation. The phenol in a 2 M NH4OH solution was recorded in the
residue was transferred to a cup. The product crystallized spectral range 200–500 nm with a Shimadzu UV1650
as yellow crystals. The crystals were washed with cold PC spectrophotometer (Fig. 1). Results of three
water and dried in a vacuum-desiccator. parallel measurements were used to calculate the molar
It was found that the yield of the product little depends extinction coefficients at wavelengths corresponding
on the reaction duration. It was 4.8, 4.8, 4.7, and 4.8 g to absorption peaks (see table). These data pint to
at reaction durations of 0.5, 1, 1.5, and 2 h, respectively, a good reproducibility of the electronic spectra, and
which is close to the theoretical value (4.89 g). the calculated extinction coefficients coincide with the
To be purified, 2,4-dinitrophenol was dissolved values reported in [18].
in a hot 1 M solution of NaOH and 16% activated An IR spectrum was recorded with a Vertex IR
carbon was added. In 5–10 min, the activated carbon Fourier spectrometer (Bruker, Germany) by the method
was separated by filtration. The filtrate was cooled of attenuated total internal reflection method (diamond
and acidified with hydrochloric acid to pH 2–3. The ATIR crystal, resolution 4 cm–1). The IR spectrum of
precipitated light yellow crystals were separated from the synthesized 2,4-dinitrophenol (Fig. 2, spectrum 1)
the solution by vacuum-filtration and dried. The yield coincides with spectrum 2 from the General library
upon the purification was 80% relative to the mass of the database of IR spectra.
product taken for recrystallization. Chromato-mass-spectrometric studies were
A chromatographic analysis by reverse-phase HPLC performed on an LCMS-2020 liquid chromato-mass-
was made on a Zorbax Eclipse Plus C18 150 × 3 mm, spectrometer (Shimadzu, Japan). The mass-detector
3.5 μm (Agilent, United States). A 40% solution of operated in the negative APCI (atmospheric pressure

Molar extinction coefficients of 2,4-dinitrophenol

Extinction coefficient, M–1 cm–1

Standard Variation
λ, nm
deviation coefficient
ε1 ε2 ε3 εav ε [18]

220 12.7 12.4 12.4 12.5 – 0.2 1.3

256 7.2 7.1 7.0 7.1 7 0.1 1.9

360 12.6 12.5 12.0 12.4 13 0.3 2.7

395 10.6 10.4 10.1 10.4 10 0.3 2.5

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 85 No. 10 2012

 SYNTHESIS OF 2,4-DINITROPHENOL 1579

I, rel. units
Fig. 3. Mass spectrum of 2,4-dinitrophenol. (I) Intensity and
(m/z) mass-to-charge ratio.

CONCLUSIONS
λ, nm
A new selective method for synthesis of 2,4-dini-
Fig. 1. Electronic spectrum of 2,4-dinitrophenol in a 2 M
solution of ammonia. 2,4-Dinitrophenol concentration trophenol in high yield was developed. The method is
0.065 mM. (D) Optical density and (λ) wavelength. based on nitration of phenol with nitric acid in an aque-
ous-alcoholic medium.

T ACKNOWLEDGMENTS

The study was carried out at the Center for Collective

Use, Research Association Arktika [Lomonosov
Northern (Arctic) Federal University] under the finan-
cial support from the Ministry of Education and Science
of the Russian Federation.

REFERENCES

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Fig. 2. IR spectra of 2,4-dinitrophenol. (T) Transmission
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RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 85 No. 10 2012

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