ISSN 1070-4272, Russian Journal of Applied Chemistry, 2015, Vol. 88, No. 11, pp. 1783−1787. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © Yu.G. Khabarov, D.E. Lakhmanov, D.S. Kosyakov, N.V. Ul’yanovskii, V.A. Veshnyakov, O.A. Nekrasova, 2015, published in Zhurnal
Prikladnoi Khimii, 2015, Vol. 88, No. 11, pp. 1568−1572.
ORGANIC SYNTHESIS AND INDUSTRIAL
Nitration of Phenol in 1,4-Dioxane
Yu. G. Khabarov, D. E. Lakhmanov, D. S. Kosyakov, N. V. Ul’yanovskii,
V. A. Veshnyakov, and O. A. Nekrasova
Lomonosov Northern (Arctic) Federal University, nab. Severnoi Dviny 17, Arkhangel’sk, 163002 Russia
Received December 9, 2014
Abstract—The nitration of phenol with excess nitric acid in aqueous dioxane, in contrast to the nitration in aque-
ous ethanol, yields exclusively 2,4-dintrophenol, whereas at equimolar ratio of phenol and nitric acid the major
reaction products are mononitrophenols (99%), among which the p-isomer prevails.
2,4-Dinitrophenol (DNP) is an important product of
organic synthesis, a synthetic precursor of various organic
compounds, including sulfurous dyes , herbicides,
pesticides, and fungicides . DNP inhibits the metal
corrosion  and styrene polymerization ; antiseptic
properties of DNP are used in preparing formulations
for wood impregnation ; DNP stimulates the plant
growth, inﬂ uences the oxidative phosphorylation in
cells , and exhibits catalytic properties .
Numerous nitration procedures have been developed
for the DNP synthesis: nitration with the classical
nitrating mixture, with liquid N
, oxidative nitration
of benzene with nitric acid or with air in the presence
of mercury(II) hydroxide and a small amount of nitrite.
Nitrosophenol and 2,4-dinitrochlorobenzene can also
be used as starting compounds for preparing DNP.
A procedure using sodium nitrite, oxalic acid, and
wet silicon dioxide has been developed for preparing
mono- and dinitrophenol; the reaction is performed in
methylene chloride . From nitropropanedial hydrate
and 1-nitro-2-propanol, DNP is synthesized in alkaline
medium at room temperature within 18 h .
1,4-Dioxane is a speciﬁ c and versatile solvent widely
used in chemistry and biochemistry [10–18]. It was
interesting to study the nitration of phenol with nitric
acid in 1,4-dioxane.
The following chemicals were used in the study:
freshly distilled phenol (boiling point 182°С), 63% nitric
acid (chemically pure grade), 1,4-dioxane (chemically
pure grade), and ethanol (rectiﬁ ed, 96%).
To perform the phenol nitration, a 50-mL glass ﬂ ask
equipped with a reﬂ ux condenser was charged with 1 g
of phenol and with the required volume of the reagent,
which was prepared by mixing the required volume of
concentrated nitric acid with 20 mL of 1,4-dioxane or
ethanol. The volumes of nitric acid were 0.8, 1.2, and
5 mL, which corresponds to the phenol : nitric acid
molar ratio of 1 : 1, 1 : 1.5, and 1 : 6.2, respectively.
To determine the reaction mixture composition,
2-mL samples of the liquid were taken 10, 20, 30, and
60 min after the start of the reaction. The samples were
quickly cooled in an ice bath, after which 10 mL of
water and 2 mL of chloroform were added. The resulting
mixture was thoroughly shaken, and the lower layer was
taken after the phase separation. The extract was ﬁ ltered
through a membrane ﬁ lter with the pore diameter of
0.2 μm and was injected into a chromatographic column
without further pretreatment.
Analysis by chromatography–mass spectrometry
was performed with an LCMS-8030 HPLC/MS–MS
system (Shimadzu, Japan) equipped with two LC-30