Alkoxylation of 4-chloronitrobenzene with aliphatic alcohols and glycols in the presence of NaOH

Article abstract of DOI:10.1134/S1070427212080162

The reaction of 4-chloronitrobenzene with aliphatic C_1-n-C ₄ alcohols and with mono-, di-, and triethylene glycols in the presence of NaOH in liquid ammonia at 15-50°C was studied.

Full text of DOI:10.1134/S1070427212080162

ISSN 1070-4272, Russian Journal of Applied Chemistry, 2012, Vol. 85, No. 8, pp. 1232−1238. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © E.V. Malykhin, V.D. Shteingarts, 2012, published in Zhurnal Prikladnoi Khimii, 2012, Vol. 85, No. 8, pp. 1295−1302.
ORGANIC SYNTHESIS
AND INDUSTRIAL ORGANIC CHEMISTRY
Alkoxylation of 4-Chloronitrobenzene with Aliphatic
Alcohols and Glycols in the Presence of NaOH
E. V. Malykhin and V. D. Shteingarts
Vorozhtsov Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
e-mail: malykhin@nioch.nsc.ru
Received January 24, 2011
Abstract—The reaction of 4-chloronitrobenzene with aliphatic C1–n–C4 alcohols and with mono-, di-, and tri-
ethylene glycols in the presence of NaOH in liquid ammonia at 15–50°C was studied.
DOI: 10.1134/S1070427212080162
Alkoxylation of nitrohaloarenes yields alkyl nitro-
phenyl ethers, which are base intermediates for the syn-
thesis of valuable compounds: dyes [2], pharmaceuticals
[3], components for color photography [4], and other
materials [5–7]. In alcoholic media, the target process is
accompanied by side reactions of nitro group reduction
with the formation of aniline derivatives, azobenzenes,
and azoxybenzenes [8]. The relative contribution of the
transformation pathways largely depends on the volume
of the alkyl group in the alcoholate and alcohol and, to
a lesser extent, on the mutual location of the halogen
atom and nitro group in the aromatic ring, on the ra-
tio and concentrations of the reactants, on the reaction
temperature, and on the presence in the reaction mix-
ture of molecular oxygen, water, and agents compen-
sating the nucleophile counterion [9, 10]. For example,
to prevent reduction of nitro compounds, methoxy- and
ethoxylation of nitrochlorobenzenes is performed in the
presence of molecular oxygen [11–14] and of transition
metal oxides [15–17] and salts [18, 19], and the oxida-
tion of alkali is suppressed by introducing alkali metal
sulfites [20] or urea [21]. With an increase in the volume
of the alkyl radical to n-С3,4, the nitro group reduction
becomes prevalent [9, 10]. Apparently, for this reason,
С3,4-alkyl ethers of nitrophenols are prepared by the re-
action of alkali metal or silver nitrophenolate with the
corresponding alkyl halide, mainly with bromide or io-
dide [22].
Bis-4-nitrophenyl ethers of mono-, di-, and trieth-
ylene glycols are used as intermediates in syntheses of
the diamine component for polyimides [23–25], rubber
antiozonants [26], and drugs [27–31]. It is known that
these ethers are formed by fluorine replacement in 4-flu-
oronitrobenzene under the action of glycols and potas-
sium carbonate in the medium of the nitro compound in
~70% yield [32]. In reactions of 4-chloronitrobenzene
with ethylene glycol in the presence of excess KОН and
KI in DMF at 140°С [33, 34] or of NaOH and a qua-
ternary ammonium salt in water at 90°C [35], the yield
of the corresponding ethylene glycol diether does not
exceed 30%. In practice, these diethers, like alkyl ni-
trophenyl ethers, are prepared by nucleophilic substitu-
tion of the halogen atom at the aliphatic carbon atom (of
bromine in 1,2-dibromoethane or in 2,2'-dibromodiethyl
ether [27, 30, 36–38], of chlorine in 1,2-dichloroethane
or 2,2'-dichlorodiethyl ether [39, 40]) under the action
of alkali metal 4-nitrophenolate [27, 30, 36–38, 40] or
of 4-nitrophenol in the presence of potassium carbonate
[39] or of potassium tert-butylate [28] in ethylene glycol
[36], diethylene glycol [27, 38], or aprotic bipolar sol-
vents (DMF [39, 40], DMSO [28], dimethylacetamide,
N-methylpyrrolidone [40]) at 150°С.
It should be emphasized that smooth alkoxydeha-
1232

ALKOXYLATION OF 4-CHLORONITROBENZENE
1233
logenation of nitroarenes under the action of alkali
metal alcoholates or of alcohol in the presence of alkali
is accomplished by performing fluorine replacement in
aqueous/alcoholic media [32] and of other halogens in
aprotic bipolar media [39, 40]. However, large-scale use
of fluorinated substrates is restricted by their relatively
difficult availability, and the use of aprotic bipolar sol-
vents involves problems with the target product isola-
tion and solvent regeneration.
the stoichiometric ratio (Table 1, run nos. 2, 3), or with
the same excess of alcohol II relative to compound I
and NaOH, taken in the stoichiometric ratio (Table 1,
run nos. 4, 5), the conversion of the starting compound
increases to 10–17%. When the amounts of both reagents
are increased simultaneously (Table 1, run nos. 6–8), the
yield increases to 30–50%. If, in addition, the reaction
time is made longer (Table 1, run nos. 9–11 and 8, 12,
13), the conversion of I can be increased to 65%. To
determine the optimal ratio I : II : NaOH, we analyzed
how the conversion of I depends on the amounts of
NaOH (Table 1, run nos. 4, 6, 10, and 14) and alcohol
II (Table 1, run nos. 2, 6, 15, and 16–19). The results
we obtained show that the optimal ratio ensuring the
highest yield of IX is I : II : NaOH = 1 : (2–3) : 1. It is
not improbable that this reactant ratio ensures the best
balance between the sodium methylate concentration
and its activity as nucleophile in the ammonia–alcohol–
water system. The product yield does not noticeably
change when the reactants are taken in a larger excess
relative to the substrate. It should also be noted that
compound I reacts with alcohol II and NaOH at –33°С
in liquid ammonia more slowly than with sodium
methylate prepared in situ from sodium amide [41],
which can be accounted for by the lower activity of the
methylate ion in the first case because of its solvation
with water.
As shown in [41], in liquid ammonia at–33 to –40°С
4-chloronitrobenzene reacts with С1–3 alcoholates
prepared in situ from the corresponding alcohols
and sodium amide to form methyl, ethyl (in 6–10 h),
n-propyl, and isopropyl (in 24 h) ethers of 4-nitrophenol
with 85–90% conversion of the starting compound.
Hence, with liquid ammonia as medium for preparing
the alcoholate and performing the reaction, the reagent
activity is enhanced owing to minimization of the water
content and weak solvation of the anionic nucleophile.
However, the most important feature of the process
is high selectivity: Practically no products of nitro
group reduction are formed. On the whole, high rates
of SNAr reactions involving charged nucleophiles in
liquid ammonia, compared to those in aprotic bipolar
media [42], and the ease of product isolation and solvent
regeneration cause practical interest in processes based
on such reactions. In particular, it is appropriate to study
in detail the alkoxylation of chloronitroarenes in liquid
ammonia. The process would be considerably simplified
by eliminating the step of preliminary preparation of the
alcoholate by hydrolysis of sodium amide.
To attain higher conversion of I, the reactions
were performed at 10–15°С in a steel autoclave. To
demonstrate the process feasibility, we used alkali flakes
(see Experimental) without additional pulverization. We
found that, at the ratio I : II : NaOH = 1 : 3 : 1, compound
I quantitatively transformed into ether IX in 5 and
12 h at the substrate : ammonia weight ratio of 1 : 16
(Table 2, run no. 2) and 1 : 1.8 (Table 2, run no. 3). With
alcohol III, compound I reacts more slowly (Table 2,
In this study we examined the feasibility, efficiency,
and selectivity of alkoxydechlorination of 4-chloro-
nitrobenzene (I) under the action of aliphatic alcohols
[methanol (II), ethanol (III), n-propanol (IV), n-butanol
(V)] and glycols [ethylene glycol (VI), diethylene gly-
col (VII), triethylene glycol (VIII)] in the presence of
commercial NaOH in liquid ammonia at temperatures
from –33 to 50°С.
Scheme 1.
The reaction of I with alcohol II and pulverized
NaOH in liquid ammonia at –33°С yield 4-nitroanisole
(IX) (Scheme 1) in the yield depending on the I : II :
NaOH ratio, which was varied from 1 : 1 : 1 to 1 : 30
: 10 and 1 : 10 : 30 at the process time of 2–25 h. For
example, in the reaction of equimolar amounts of the
reactants for 5.5 h (Table 1, run no. 1), only 4–6% of
I transforms into ether IX. With a 3–9-fold amount of
NaOH relative to compound I and alcohol II, taken in
R = CH3 (II, IX), C2H5 (III, X), n-C3H7 (IV, XI), or
n-C4H9 (V, XII).
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 85 No. 8 2012

1234
MALYKHIN, SHTEINGARTS
Table 1. Reaction of I (1.57 g) with alcohol II (0.4–4.0 g) and
NaOH (0.4–12 g) in liquid ammonia (150 ml) at –33°С
run nos. 1, 2 and 4, 5), but in 17–24 h the transformation
into p-nitrophenetole is almost quantitative (Table 2, run
nos. 6 and 7).
Run
no.
I : II : NaOH
molar ratio
Time τ, h
I : IX ratio
To find conditions for commercial use of the process,
we examined the effect of temperature on the result of
the reaction of I with II. We found that, with an increase
in temperature to 30 and then to 50°С, higher conversion
of I is attained already in 5 h (Table 3). However, in this
case, in contrast to the reactions at –33 and 10–15°С,
we detected products corresponding to the reduction of
the nitro group in the starting compound I (Table 3, run
nos. 1 and 2, 3 and 4), but have not detected anisole
derivatives with the nitrogen-containing functional
group different from the nitro group. In addition, at the
alcohol : alkali ratio close to stoichiometric, the products
of the reduction of I or of replacement of the halogen
atom by the hydroxy group are formed in 3–10 times
larger amount than at the 3 : 1 ratio (Table 3, run nos. 1
and 3, 2 and 4). These facts can be accounted for, first,
by an increase in the equilibrium concentration of alkali
responsible for the formation of 4-nitrophenol and,
second, by stronger increase in the rate of side processes
with temperature, compared to the rate of formation of
the target product. Thus, to minimize the amount of by-
products, it is necessary to take the alcohol in excess
relative to alkali and to perform the reaction at 10–20°С.
1
2
1 : 1 : 1
1 : 1 : 3
5.5
5.5
5.5
5.5
5.5
5.5
5.5
5.5
2.0
5.5
25
95 : 5
90 : 10
89 : 11
83 : 17
89 : 11
67 : 33
56 : 44
48 : 52
94 : 6
3
1 : 1 : 9
4
1 : 3 : 1
5
1 : 9 : 1
6
1 : 3 : 3
7
1 : 5 : 15
1 : 10 : 30
1 : 3 : 9
8
9
10
11
12
13
14
15
16
17
18
19
1 : 3 : 9
77 : 23
35 : 65
80 : 20
47 : 53
83 : 17
64 : 36
49 : 51
57 : 47
55 : 45
75 : 25
1 : 3 : 9
1 : 10 : 30
1 : 10 : 30
1 : 3 : 27
1 : 4.5 : 3
1 : 6 : 3
2.0
8.0
5.5
5.5
5.5
5.5
5.5
5.5
To make the process suitable for technology, it
is necessary to provide not only for isolation and
purification of the target products to remove NaCl,
organic by-products, and excess alcohol, but also for
regeneration and reuse of the alcohol and ammonia.
Another important item is elimination of the operation
of alkali pulverization. We found that these goals can
1 : 9 : 3
1 : 12 : 3
1 : 27 : 3
Table 2. Reaction of I with alcohol II or III and NaOH in liquid ammonia (300–350 ml, 10°С)
Reactant amounts, g
alcohol
I : alcohol :
NaOH molar
ratio
Mixture
composition, %
(GLC data)
Run
no.
Time τ, h
Product yield, g
I
NaOH
1
2
3
4
5
6
7
15.7
15.7
100
II 4.0
II 9.6
5
5
1 : 1.2 : 1.2
1 : 3.0 : 1.2
1 : 3.0 : 1.2
1 : 1.2 : 1.2
1 : 3.0 : 1.2
1 : 3.0 : 1.2
1 : 3.0 : 1.2
24
5
IX 14.7–15.0
IX 14.0–14.4
IX 103.5
X 14.1
IX >93, (I) 2–5
IX >99, (I) 0–0.6
IX
II 62.4
III 5.6
III 13.6
III 13.6
III 88.0
30
5
12
24
5
15.7
15.7
15.7
100
X 72.5, (I) 23.2
X 84, (I) 11
X 97.4, (I) 0–2.4
X 99.4
5
X 13.5
5
17
24
X 14.6
30
X 99.0
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 85 No. 8 2012

ALKOXYLATION OF 4-CHLORONITROBENZENE
1235
Table 3. Influence of reaction temperature on the composition of products formed in reaction of I (100 g) with alcohol II
(31–73 ml) in liquid ammonia (300 ml, I : NH3 = 1 : 18, 2 h)
Product yield, % (GLC data)
I : alcohol :
NaOH molar Т, °С
Run
no.
4,4'-dichloro-
azoxybenzene
4,4'-dichloro-
azobenzene
IX
I
4-nitrophenol
4-chloroaniline
ratio
1
2
3
4
1 : 1.2 : 1.2
1 : 1.2 : 1.2
1 : 3 : 1.2
1 : 3 : 1.2
28
50
28
50
79–81 8–12
84–86 0.5–1.5
90–94 4.5–8.5
0.5–0.6
2.0–2.5
0.5–0.6
0.7–1.0
5–6
0.3–0.4
1.5–3
2–3
7–8.5
1.0–1.2
1.3–1.7
3.4–3.8
–
–
<0.2
<0.2
94–95
1–2
be accomplished by successively performing the
following operations: (a) condensation of the major
fraction of ammonia distilled off from the reaction
mixture; (b) heating of the remaining mixture of the
products with water; (c) distillation of aqueous alcohol
from the aqueous-organic mixture, followed by the
alcohol recovery by rectification; (d) separation of the
hot aqueous-organic residue after distillation of aqueous
alcohol to the organic and aqueous layers. In Table 4,
we give the quality characteristics and yields for ethers
IX and X obtained using the above procedures with
commercial alkali flakes (run nos. 1, 3), and also for
the regenerated alcohol and ammonia (run nos. 2, 4).
It should be emphasized that these data refer to crude
products, not subjected to additional purification.
Using the optimal ratio alcohol : alkali = 3 : 1 and the
developed procedure, we prepared 4-nitro-n-propoxy-
and -n-butoxybenzenes (ХI and XII, respectively) in
high yields (Table 4, run nos. 5, 6).
the process conditions are given in Table 5.
We found that the starting compound I is practically
fully consumed within 10–15 h at Т ~50°С. The
content of the initially formed glycol mononitrophenyl
ethers in the reaction products is low, and that of the
target products XII–XIV is high, suggesting higher
nucleophilic activity of salts of glycol mononitrophenyl
ethers, compared to the salts of the starting glycols.
At the same time, 4-nitrophenol is formed in higher
yield relative to the desired diethers (up to ~10% in
the reaction with glycol VIII) than in the reaction with
alcohols. The results can probably be accounted for by
ratios of the equilibrium concentrations of alkali, glycol
alcoholates, and glycol monoether alcoholates and of
the solubilities of their salts and neutral compounds
present in the reaction mixture [43].
Thus, liquid ammonia at moderate temperatures
(15–50°С) is highly efficient as solvent for alkoxyde-
chlorination of 4-chloronitrobenzene by the action of
aliphatic alcohols and glycols in the presence of NaOH.
The use of this solvent allows the yield of compounds
with the reduced nitro group (chlorinated amino, azo,
azoxy compounds), significant in the reactions per-
formed in alcohols, to be minimized. The mono- and
bis-4-nitrophenyl ethers obtained are high-quality prod-
ucts suitable for further use without additional purifi-
cation. These chemical and technological advantages
Acceptable time of the synthesis of alkyl nitrophenyl
ethers and high quality of the products gave grounds
to examine the synthesis of bis-p-nitrophenyl ethers of
glycols by the similar procedure (Scheme 2).
Dataontheyieldsofmono-,di-,andtriethyleneglycol
bis-4-nitrophenyl ethers XII–XIV formed by reactions
of compound I with glycols VI–VIII, respectively, and
Scheme 2.
n = 1 (VI), (XIII); 2 (VII), (XIV); 3 (VIII), (XV).
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 85 No. 8 2012

1236
MALYKHIN, SHTEINGARTS
Table 4. Reaction of I with alcohols II–V and NaOH flakes at 10–20°С
Reactant amounts, g
Run
Product yield, g
(%)
Purity, % (GLC
data)
τ, h
no.
I
alcohol
II 45.0
NaOH
21.0
21.0
15.8
15.8
10.5
15.7
NH3(g)
123
1
2
3
4
5
6
70.0
70.0
52.5
52.5
35.0
52.5
12
12
15
15
10
10
IX 65.0 (95.6)
IX 66.3 (97.5)
X 54.2 (97.4)
X 53.8 (96.6)
IX 39.5 (98.2)
XII 54.8 (84.3)
99.8
99.8
99.3
99.4
96.8
99
a
b
II 22+23
III 46.9
31+92
102
a
b
III 24.5+22.4
IV 40.0
25+77
70
V 73.6
110
a Regenerated alcohol.
b Regenerated ammonia.
Table 5. Reaction of I (12.6 g) with diols VI–VIII and NaOH in liquid ammonia (150 ml)
Reactant amounts, g
Product yield, g (%)
Run
no.
τ, h
Т, °С
4-nitro-
4-nitro-
diol
NaOH
diether
monoether
I
aniline
phenol
0.6 (0.2)
2.8
1
2
3
4
5
VI 2.48
VI 2.48
VII 4.24
VII 4.24
VIII 6.0
8.0
4.0
4.0
4.0
4.0
15
15
10
10
15
15
50
15
65
15
XIII 77.4 (9.4)
XIII 88.0 (10.7)
XIV 85.7 (11.9)
XIV 87.5 (12.1)
XV 90.0 (12.5)
1.4 (0.4)
4.0
0.6 (0.2)
18.2 (2.5)
0.4
–
–
1.3
3.6
6.4
1.1
–
1.1
0.6
–
2.3
0.7
10
of the process performed in liquid ammonia as solvent
make this process promising for commercial synthesis
of alkyl nitrophenyl ethers by alkoxydechlorination of
chloronitroarenes. This process can become an alterna-
tive to processes based on the same reactions performed
in alcohols or on nucleophilic substitution of the halo-
gen atom at the carbon atom under the action of nitro-
phenolate ions.
μm layer of НР 5 stationary phase (5% diphenyl-/95%
dimethylsiloxane). The carrier gas was He, flow rate
1 ml min–1. The column was kept for 2 min at 50°С, then
heated at a rate of 10 deg min–1 to 280°С, and kept at the
final temperature for 5 min. The vaporizer temperature
was 280°С, and the ion source temperature, 173°С. The
mass spectra were scanned in the range 30–550 amu at
a rate of 1.2 scan s–1. The mixture compositions were
determined by GLC (internal normalization) with an HP
5890 device (thermal conductivity detector). In these
experiments, we used a quartz capillary column 30 m
long, 0.22 mm i.d., coated with HP 5 stationary phase
(layer thickness 2.6 μm). The carrier gas was He, flow
rate 1 ml min–1. The column was kept for 2 min at 90°С,
then heated at a rate of 10 deg min–1 to 330°С, and finally
kept at 330°С. The vaporizer and detector temperatures
were 300 and 320°С, respectively. The melting points of
samples were determined with a Temp-2 device in the
automatic mode.
EXPERIMENTAL
1
The Н NMR spectra were recorded with a Bruker
АС-200 device using as internal reference the signal
of residual protons in acetone-d6. The IR spectra
were measured with a Bruker Vector-22 device using
samples pelletized with calcined KBr. The GLC–MS
identification of the components was performed with an
HP G1081A complex consisting of an HP 5890 Series II
chromatograph and an HP 5971 mass-selective detector.
The ionizing electron energy was 70 eV. We used a
column 30 m long, 0.25 mm i.d., coated with a 0.25-
We used commercial chemicals without pretreatment:
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ALKOXYLATION OF 4-CHLORONITROBENZENE
1237
technical-grade liquid ammonia (gradeA, supreme, or I);
4-nitrochlorobenzene, grade II; methanol; ethanol; pure
grade ethylene glycol, n-propanol, n-butanol, diethylene
glycol, and triethylene glycol; technical-grade sodium
hydroxide (TR OKP 213211 grade) was pulverized
in a porcelain mortar in a dry box or used without
pretreatment (TKh brand, grade I, flakes); potable water;
gaseous nitrogen; pharmacopoeial grade diethyl ether;
chemically pure grade benzene; concentrated sulfuric
acid; ammonium chloride. Methyl tert-butyl ether was
purified by fractional distillation (99%, GLC, internal
normalization); pure grade magnesium sulfate was
calcined at 400°С and stored in a sealed vessel.
To identify the by-products and determine their
amount, we performed extraction from the aqueous
layer with methyl tert-butyl or diethyl ether (3 ×
30 ml). The combined extracts were dried over calcined
magnesium sulfate, filtered, and evaporated. Chlorinated
aromatic compounds, 4-nitroaniline, and unchanged
4-chloronitrobenzene were quantitatively determined
in the dry residue by GLC (calibration using artificially
prepared mixtures). The aqueous solution was cooled to
0°С and acidified with 10% sulfuric acid to pH ~2–3,
after which the solid product containing 4-nitrophenol
was isolated by extraction with diethyl ether (3 × 30 ml).
By this general procedure [44], we prepared
4-nitroanisole (IX, mp 49–53°C; published data: mp
54°С [45]), 4-nitrophenetole (X, mp 53–56°C; published
data: mp 60°С [45]), 4-nitro-n-propoxybenzene (XI,
bp 163–165°C/20 mm Hg; published data: bp 285–
287°C [46], 135–137°C/8 mm Hg [41]), and 4-nitro-n-
butoxybenzene (ХII, mp 30–33°C; published data: mp
32–33°С [47].
Alkoxylation of I with alcohol II or III and NaOH
in an open vessel at –33°С (general procedure). An
elongated round-bottomed glass flask placed in a Dewar
vessel for temperature control and equipped with
a power-driven stirrer, a thermometer, and a gas removal
tube was charged in a stream of dry nitrogen gas with
pulverized NaOH and with 200 ml of liquid ammonia.
After that, we added with stirring the alcohol (dropwise)
and then compound I (in small portions). The mixture
was stirred for the required time, with monitoring the
level of ammonia in the flask and adding ammonia, when
necessary, to maintain the initial volume. After the end
of the reaction period, ammonium chloride was added in
a 3–5-fold amount relative to the alkali, the cooling was
ceased, and the ammonia was allowed to evaporate. The
residue was processed as described below.
1
The Н NMR and IR spectra of ethers IX–XI are
identical to those given in [48].
In preparation of glycol bis-4-nitrophenyl ethers, the
reaction mixture was transferred onto a porous glass
filter, with thoroughly washing off the mixture from
autoclave walls with hot water (3 × 30 ml), washed on
the filter with hot water (5 × 20 ml), squeezed, and dried
in air to constant weight. The solid mass was washed
on the filter in succession with benzene (2 × 20 ml) and
diethyl ether (2 × 20 ml) and dried to constant weight to
obtain diethers XIII–XV.
Alkoxylation of I with aliphatic alcohols or glycols
in the presence of NaOH in an autoclave at 15–50°С
(general procedure). A 200–500-ml stainless steel
autoclave (Vishnevskii’s vessel) equipped with a blade
stirrer was charged with 4-nitrochlorobenzene, alcohol
or glycol, and NaOH flakes. The vessel was sealed,
stirring was switched on, and 100–175 ml of ammonia
was introduced into the autoclave from a thick-walled
volumetric glass vessel equipped with a counterpressure
unit. The mixture was stirred for 5–15 h at 15 or 50–
65°C. The ammonia was distilled off from the reaction
mixture into a Dewar vessel cooled to –50°С.
For exhaustive determination of the reaction
products, we performed extraction of wash waters.
For this purpose, we combined the ether and benzene
extracts obtained when washing the desired solid product
and extracted wash waters with them. The extract was
dried over calcined magnesium sulfate, the solvents
were evaporated, and the solid residue was analyzed
as described above for alkyl 4-nitrophenyl ethers. Then
the wash waters were cooled to 0°С, acidified with 10%
sulfuric acid to pH ~2–3, and extracted with diethyl
ether (3 × 30 ml). The extract was dried over calcined
magnesium sulfate and evaporated to dryness to obtain a
mixture of 4-nitrophenol and glycol 4-nitrophenyl ether,
which were identified and quantitatively determined by
gas chromatography–mass spectrometry.
In the synthesis of alkyl 4-nitrophenyl ethers, 110 g
of water was added to the residue in the autoclave, the
autoclave was sealed, and a mixture of alcohol and water
was distilled off at vapor temperatures of up to 98°С. The
hot (70–80°С) bottom residue was filtered off on a heated
pressure filter through a layer of coarse calico on belting.
4-Nitrophenyl ether was isolated from the filtrate after its
phase separation in a heated separating funnel.
Bythisgeneralprocedure, weprepared1,2-bis(4-nitro-
phenoxy)ethane (XIII, mp 149.5–150°C; published data:
mp 147°С [37], 148–149°С [27–31]), bis-2-(4-nitrophe-
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1238
MALYKHIN, SHTEINGARTS
noxy)ethylether{XIV,mp156.8–158.0°C(fromethanol);
publisheddata:mp155–156°С[27–31],154–157°С[38]},
and 1,2-bis[2-(4-nitrophenoxy)ethoxy]ethane (XV, mp
95–98°C; published data: mp 96–97°С [27–31]). Found,
%: С 55.05, Н 5.03, N 7.02. C18H20N2O8. Calculat-
ed, %: С 55.10, Н 5.09, N 7.10. 1Н NMR spectrum
(δ, ppm): 3.9 m (12Н, –OCH2CH2O–), 7.6 q (8Н, Сar–Н).
IR spectrum (ν, cm–1): 1350 and 1530 (NO2).
19. JPN Patent 3970 ('52).
20. German Patent 10561.
21. JPN Patent 74126634.
22. UK Patent 585940.
23. Strong, C.E., Endrey, A.L., Abramo, S.V., et al., J. Polym.
Sci., Part A, 1965, vol. 3, no. 4, pp. 1373–1390.
24. Weiner, B. and Zilka, A., J. Macromol. Sci. Chem., Part
A, 1980, vol. 14, no. 3, pp. 379–388.
25. Honore, R., Deleens, G., and Mareshal, E., Eur. Polym.
J., 1980, vol. 16, no. 9, pp. 909–916.
26. German Patent 2850995.
CONCLUSIONS
27. German Patent 2143570.
28. Ashley, J.N., Collins, R.F., Davis, M., and Sirett, N.E.,
J. Chem. Soc., 1958, pp. 3298–3313.
29. US Patent 3862227.
30. King, J.A., J. Am. Chem. Soc., 1944, vol. 66, no. 12,
pp. 2076–2080.
31. Gireva, R.N., Mal’tseva, N.F., Trappel’, L.N., et al.,
Khim.-Farm. Zh., 1972, vol. 6, no. 5, pp. 5–7.
32. Field, W.A., Ramalingam, В., and Harri, F.W., J. Polym.
Sci., Polym. Chem. Ed., 1983, vol. 21, no. 2, pp. 319–328.
33. Koton, M.M., Zhukova, T.I., Florinskii, F.S., et al., Zh.
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(1) The chlorine atom in 4-nitrochlorobenzene is effi-
ciently replaced under the combined action of alkyl alco-
hols (C1–4) or diols (mono-, di-, triethylene glycols) and
NaOH in liquid ammonia at relatively low temperatures
(15–50°С) to form the corresponding alkyl 4-nitrophenyl
mono- and diethers of high quality in high yields.
(2) In contrast to the processes in alcoholic media,
alkoxydechlorination of 4-nitrochlorobenzene in liquid
ammoniaattemperaturesbelow30°Сisnotaccompanied
by side reactions of the nitro group reduction in the
starting compound and products.
34. Adrova, N.A., Koton, M.M., and Dubnova, A.M.,
Vysokomol. Soedin., Ser. B, 1968, vol. 10, no. 5, pp. 354–
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