Synthesis of 1-Nitronaphthalene under Homogeneous Conditions

Yuriy G. Khabarov

, Viacheslav A. Veshnyakov, Ivan A. Snigirev and Ilya I. Pikovskoy

Northern (Arctic) Federal University, Northern Dvina Emb., 17, Archangelsk, Russian Federation

Keywords: 1-nitronaphthalene, naphthalene nitration, nitration, dioxane

Abstract: Various reagents can be used for the nitration of naphthalene ranging from the classical nitrating mixture to

unusual reagent systems. In this study, a simple and effective method of nitration of naphthalene using a

classical nitrating mixture in 1,4-dioxane is presented. The reaction occurs under homogeneous conditions

and GC-MS analysis of the product showed 2 peaks corresponding to 1-nitronaphthalene (96%) and 2-

nitronaphthalene (4%). Melting point, UV and IR spectra of the product (isolated in 96-97% yields)

correspond to 1-nitronaphthalene.

1 INTRODUCTION

Nitration of naphthalene is often the first stage in the

synthesis of such naphthalene derivatives as

naphthylamine (Chen et al., 2016), naphthol and

aminonaphthalenesulfonic acids which are used in

the synthesis of dyes (Booth, 2012).

1-Nitronaphthalene can be synthesized from

naphthalene using a classical nitration mixture

(HNO

) in a yield of 95% (Fierz-David and

Blangey, 1949; Duvalma et al., 1964). In addition,

90% HNO

can be used to carry out the reaction in

acetonitrile with 85% yield (Wright, 1965). Instead

of H

, indium(III) triflate (Yin and Shi, 2006) or

lanthanum(III) nitrobenzenesulfonates (Parac-Vogt

et al., 2004) can be used as catalysts. Nitration of

naphthalene with practically complete conversion

can also be carried out on high silica zeolite in

petroleum ether with 70% HNO

(Bakhvalov and

Ione, 1993). The use of zeolites with the NO

system in acetonitrile leads to moderate yields (52-

80%) (Shi et al., 2013). A moderate yield of 1-

nitronaphthalene (63%) is also obtained with 95%

HNO

and a mixed catalyst on silica gel without the

use of solvents (Shi and Cui, 2003).

Bi(NO

)

, KNO

, (NH

)

Ce(NO

)

and even

NaNO

were added into a suspension of silica gel in

THF for the nitration of naphthalene, while the

yields of 1-nitronaphthalene were 76-88% (Badgujar

et al., 2007). Cerium ammonium nitrate was also

used for nitration of naphthalene with a conversion

ratio of more than 98% in a ionic liquid

(Dleersnyder et al., 2009). 1-Nitronaphthalene is

formed in a yield of 99% when naphthalene is

nitrated with an equimolar mixture of

benzyltriphenylphosphonium nitrate and anhydride

of methanesulfonic acid without the use of solvents

(Hajipour and Ruoho, 2004).

Nitration of naphthalene with acetyl nitrate in a

phosphonium ionic liquid gives a 74% yield (Powell

et al., 2005). Usually, direct nitration of naphthalene

with various reagents leads to the formation of a

mixture of 1- and 2-nitronaphthalenes. However, the

reaction is sufficiently regioselective, the content of

1-nitronaphthalene in products, as a rule, is 90-92%.

Ipso-nitration of naphthalene derivatives makes

it possible to obtain individual isomers. Reaction of

1- and 2-naphthylboronic acids with tert-butyl nitrite

in 1,4-dioxane without catalysts leads to the

preparation of 1- and 2-nitronaphthalenes with

yields of 75% and 76%, respectively (Wu et al.,

2011). A higher yield, 88% for 2-nitronaphthalene,

gives nitration with (CH

)

NNO

and Cu

O as a

catalyst in acetonitrile (Yan et al., 2012).

Mononitrotanaphthalenes in yields of 70-82% are

formed as a result of catalytic ipso-substitution of

bromo- or iodo-derivatives of naphthalene with

KNO

in the presence of copper(II) triflate in DMSO

(Amal Joseph et al., 2012). 1-Nitronaphthalene was

unexpectedly obtained from 5-nitronaphthylamine

by deamination (Srivastava et al., 2011).

The purpose of this research was mononitrtaion

of naphthalene using a classical nitrating mixture

under homogeneous conditions with 1,4-dioxane as

a solvent.

Khabarov, Y., Veshnyakov, V., Snigirev, I. and Pikovskoy, I.

Synthesis of 1-Nitronaphthalene under Homogeneous Conditions.

DOI: 10.5220/0008185800730076

In The Second International Conference on Materials Chemistry and Environmental Protection (MEEP 2018), pages 73-76

ISBN: 978-989-758-360-5

2 EXPERIMENTAL

2.1 Reagents

The following reagent grade commercial chemicals

were used: naphthalene, 65% nitric acid, 96%

sulfuric acid, 1,4-dioxane and 96% ethanol.

2.2 Synthesis of 1-Nitronaphtalene

Naphthalene (0.50 g, 3.9 mmol) was dissolved in

1,4-dioxane in a 50-ml Erlenmeyer flask. The

nitrating mixtures were prepared by mixing

concentrated nitric (0.50-1.00 ml, 7.2-14.3 mmol)

and sulfuric (0.50-1.00 ml) acids with cooling. The

acid mixtures were added to a solution of

naphthalene in dioxane and the reaction mixtures

were heated under reflux with stirring for various

periods of time. Each reaction mixture was

transferred to a test tube, cooled, diluted to 25 ml

with ice-cold distilled water. The resultant

precipitate was isolated by vacuum filtration,

washed with ice-cold water until the washings were

neutral and dried in a vacuum desiccator at room

temperature to produce yellow crystals.

2.3 Analytic Methods

Melting points were determined in open capillaries

on a Stuart SMP30 melting point apparatus. UV-Vis

spectra of products in ethanol solutions were

recorded over the wavelength range of 200-500 nm

with a Shimadzu UV-1650PC spectrophotometer in

1 cm path length quartz cuvettes relative to ethanol.

The IR spectra were recorded over the wavelength

range of 4000-600 cm

-1

on a Shimadzu FTIR-8400S

spectrophotometer equipped with a Pike

Technologies MIRacle single reflection horizontal

ATR accessory with a ZnSe crystal plate.

For GC-MS analysis, a product sample (1 mg)

was dissolved in 20 ml HPLC-grade

dichloromethane, injection volume was 1 µl with

split 5:1. Mass spectra were recorded on a Thermo

Scientific Exactive GC Orbitrap mass spectrometer

coupled to a TRACE 1310 Gas Chromatograph

equipped with TriPlus RSH autosampler.

Chromatographic separation was performed on a

Thermo Scientific Trace GOLD TG5-SilMS

capillary column, 30 m×0.25 mm×0.25 µm. Helium

(99.9999%) was used as a carrier gas with flowrate

1.2 ml/min. The inlet temperature was 280°C. The

following thermostat program was used: initial

temperature 40°C, hold 2 min, ramp 10°C/min to

280°C, hold 5 min. The mass spectrometer operated

in fullscan mode with 60 000 FWHM mass

resolution. Electron ionization (70 eV) was used.

Transfer line and ion source temperatures were 280

and 230°C respectively. The control of the mass

spectrometer, the collection and preprocessing of the

data were performed using Thermo Scientific

Xcalibur software. The obtained mass spectra were

evaluated using the NIST 14 spectral library by the

similarity index (SI).

3 RESULTS AND DISCUSSION

In this study nitration of naphthalene was carried out

in homogeneous conditions. Naphthalene was

dissolved in 1,4-dioxane and remained in solution

when the nitration mixture of various compositions

was added and remained homogeneous when heated.

During the nitration nitrogen dioxide was evolved in

the first 10 min of heating. The product was isolated

from the reaction mixture after cooling and addition

of water. The yields were the same under the

selected synthesis conditions (Table 1).

Table 1: Nitration conditions for naphthalene and product

yields.

Reaction condition

Yield

(%)

Isomer, %

Volume, ml

Time

(min)

nitro

HNO

dioxane

96.4

3.6

–

95.8

4.2

0.75

95.7

4.3

0.5

–

0.5

–

The isolated products were characterized by their

melting point, UV and IR spectra, these results are

the same for all samples and correspond to the

literature data for 1-nitronaphthalene (Talukder and

Kates, 1995; Srivastava et al., 2011). GC-MS

analysis was carried out only on 3 samples. The GC-

MS analysis showed 2 detectable peaks in the gas

chromatographic separation and mass spectra

corresponding to 1-nitronaphthalene (retention time

11.38 min, m/z found: 173.04720, SI 797) and 2-

nitronaphthalene (retention time 11.89 min, m/z

found: 173.04714, SI 699). Calculation of the areas

of chromatographic peaks showed that the content of

1-nitronaphthalene in the samples of products is

MEEP 2018 - The Second International Conference on Materials Chemistry and Environmental Protection

about 96%, i.e. nitration of naphthalene with a

classical nitrating mixture in 1,4-dioxane passes with

good regioselectivity. In general, a high

regioselectivity of naphthalene nitration is typical in

the case of using the classic nitration mixture.

(Ikegami and Hiyama, 1954; Alcorn and Wells,

1965). Another advantage of the nitration is the

availability of reagents and simplicity of performing

the synthesis.

1-Nitronaphtalene: isolated yield 0.65 g (96%),

yellow crystalline solid, mp 52.5-53°C [lit. mp 52°C

(Talukder and Kates, 1995)]. IR, cm

-1

: 2831, 1631,

1600, 1568, 1514, 1458, 1439, 1354, 1344, 1261,

1216, 1200, 1173, 1163, 1148, 1141, 1079, 1030,

1000, 978, 961, 953, 930, 914, 872, 861, 815, 804,

787, 759, 726, 655, 628. EIMS: m/z for [M

] found:

173.04720. Calc. for C

: 173.0471.

4 CONCLUSIONS

Nitration of naphthalene with a nitrating mixture in

1,4-dioxane occurs under homogeneous conditions.

The proposed method for the synthesis of 1-

nitronaphthalene is simple and effective. The yield

of the product reaches 96-97%. Nitration of

naphthalene in 1,4-dioxane has a high

regioselectivity. The content of 1-nitronaphthalene

and 2-nitronaphthalene in the product is 96 and 4%,

respectively.

ACKNOWLEDGEMENTS

The work was performed using the instrumentation

of Core Facility Center “Arktika” of Northern

(Arctic) Federal University (project

RFMEFI59417X0013).

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