Synthesis of 3,4,4′- and 2′,3,4-triaminodiphenyl ethers

Article abstract of DOI:10.1023/B:RUGC.0000007620.98209.c6

Procedures were developed for preparing 3,4,4′- and 2′,3,4-triaminodiphenyl ethers by the reaction of 4-acetylaminophenol with, respectively, 4-nitro- or 2-nitrochlorobenzene, followed by nitration of the resulting 4-acetylamino-4′- or -2′-nitrodiphenyl ether, hydrolysis of the product, 4-acetylamino-3,4′- or -2′,3- dinitrodiphenyl ether, and reduction of 4-amino-3,4′- or -2′-3-dinitrodiphenyl ether.

Full text of DOI:10.1023/B:RUGC.0000007620.98209.c6

Russian Journal of General Chemistry, Vol. 73, No. 7, 2003, pp. 1105 1109. Translated from Zhurnal Obshchei Khimii, Vol. 73, No. 7, 2003,
pp. 1170 1175.
Original Russian Text Copyright
2003 by Pilyugin, Mikhailyuk, Kiseleva, Kuznetsova, Chikisheva, Kosareva.
Synthesis of 3,4,4 - and 2 ,3,4-Triaminodiphenyl Ethers
V. S. Pilyugin, A. N. Mikhailyuk, G. V. Kiseleva,
S. L. Kuznetsova, G. E. Chikisheva, and V. M. Kosareva
Research and Technological Institute of Herbicides and Plant Growth Regulators,
Academy of Sciences of Bashkortostan, Ufa, Bashkortostan, Russia
Received May 4, 2001
Abstract Procedures were developed for preparing 3,4,4 - and 2 ,3,4-triaminodiphenyl ethers by the reac-
tion of 4-acetylaminophenol with, respectively, 4-nitro- or 2-nitrochlorobenzene, followed by nitration of the
resulting 4-acetylamino-4 - or -2 -nitrodiphenyl ether, hydrolysis of the product, 4-acetylamino-3,4 - or -2 ,3-
dinitrodiphenyl ether, and reduction of 4-amino-3,4 - or -2 -3-dinitrodiphenyl ether.
3,4,4 -Triaminodiphenyl ether I and 2 ,3,4-triamino-
diphenyl ether II are used as intermediates in produc-
tion of antihelminth preparations [1, 2]. These com-
pounds are prepared [3] by reaction of alkali metal 2-
or 4-aminophenolate with 2-nitro-5-chloroaniline, fol-
lowed by reduction of the resulting 3,4 - or 2 ,3-di-
amino-4-nitrodiphenyl ether over Raney nickel. The
major disadvantage of this procedure, in our opinion,
is the use of difficultly available 2-nitro-5-chloro-
aniline.
VI with, respectively, sodium 4-nitrophenolate and
2-nitrophenolate in DMSO in the presence of sodium
nitrite [5].
Procedures for preparing 4-acetylamino-4 -nitrodi-
phenyl ether V and 4-acetylamino-2 -nitrodiphenyl
ether X from 4-amino-4 -nitrodiphenyl ether III and
4-amino-2 -nitrodiphenyl ether IV have not been re-
ported; only the synthesis directly from 4-acetylami-
no-4 -nitrodiphenyl ether V was published. Ether V
is prepared by condensation of 4-acetylaminophenol
XI with 4-nitrobromobenzene [13] or 4-nitrofluoro-
benzene [14] in methanol in the presence of NaOH
and copper powder, and also by the reaction of acetyl-
aminophenol XI with nitrochlorobenzene VI in the
presence of alkali or, which is preferable, of potas-
sium carbonate in neutral solvents such as DMF,
o-dichlorobenzene, xylene, or diglyme [15].
Procedures for preparing 4-amino-4 -nitrodiphenyl
ether III, 4-amino-2 -nitrodiphenyl ether IV, and
4-acetylamino-4 -nitrodiphenyl ether V have been
reported. Ethers III and IV are prepared by the reac-
tion of 4-nitrochlorobenzene VI or 2-nitrochloroben-
zene VII with sodium (or potassium) 4-aminopheno-
late in DMSO on heating [4, 5]. Also, ether III is
prepared by heating nitro compound VI and sodium
4-aminophenolate in DMSO in the presence of KOH
[6], in chlorobenzene [7], or in DMSO [8] in the
presence of a phase-transfer catalyst.
Thus, published data suggest that the most conve-
nient route to 4-acetylamino-4 -nitrodiphenyl ether V
is single-step synthesis from acetylaminophenol XI
and nitrochlorobenzene VI [15]. Procedures for pre-
paring 4-amino-4 -nitrodiphenyl ether III and 4-amino-
2 -nitrodiphenyl ether IV from sodium 4-aminopheno-
late and 4-nitrochlorobenzene VI or 2-nitrochloroben-
zene VII [5] also deserve attention.
In another procedure, ethers III and IV are prepared
in two steps by the reaction of sodium p-nitropheno-
late with 4-nitrochlorobenzene VI or 2-nitrochloroben-
zene VII, followed by reduction of the resulting 4,4 -
dinitrodiphenyl ether VIII or 2 ,4-dinitrodiphenyl ether
IX. 4,4 -Dinitrodiphenyl ether VIII is also prepared by
the reaction of potassium nitrophenolate with nitro-
chlorobenzene VI in the presence of activated copper
powder [9]. Dinitrodiphenyl ether VIII is then reduced
with sodium disulfide in acetone [9], with hydrogen
sulfide in ammonia [10], with phenylhydrazine in
p-dichlorobenzene [11], or with iron and concentrated
HCl in methanol [12]. In another procedure, 4,4 -dini-
trodiphenyl ether VIII and 2 ,4-dinitrodiphenyl ether
IX are prepared by the reaction of nitrochlorobenzene
It also seems feasible to prepare triaminodiphenyl
ethers I and II from 4-amino- or 4-acetylaminophenol
and 4-nitrochlorobenzene VI or 2-nitrochlorobenzene
VII by Scheme 1.
We prepared diphenyl ethers V and X according to
[15] from acetylaminophenol XI by its reaction with
VI or VII in DMF in the presence of anhydrous potas-
sium carbonate; the yields were 96 and 93%, respec-
tively. To develop a process for commercial synthesis
of V and X, we optimized the reaction parameters. The
1070-3632/03/7307-1105$25.00 2003 MAIK Nauka/Interperiodica

1106
PILYUGIN et al.
Scheme 1.
ONa
NH2
Cl
AcCl
AcHN
O
+
H2N
O
R = H
NO2
O
NO2
NO2
VI, VII
V, X
[H]
HNO3
NaOH
H2N
AcHN
O2N
O
H2N
O2N
O
NO2
NO2
NO2
H2N
I, II
XII, XIII
XIV, XV
p-NO2 (V, VI, XII, XIV), o-NO2 (X, VII, XIII, XV); p-NH2 (I), o-NH2 (II).
Table 1. Synthesis of 4-acetylamino-2 -nitrodiphenyl ether X
Molar ratio
VII : XI
Weight ratio
VII : DMF
Molar ratio VII : K2CO3
T,
C
Time, h
Yield of X, %a
1.0: 1.0
1.0: 1.0
1.0: 1.0
1.0: 1.0
1.0: 1.03
1.0: 1.20
1.0: 1.20
1.0: 1.20
1.0: 1.20
1: 5.34
1: 5.34
1: 5.34
1: 5.34
1: 4.44
145
8.6
8.2
7.0
13.5
7.0
87 (90)
87 (90)
86 (90)
96 (94)
94 (93)
145
146
149
145
1.0: 0.90
1.0 : 0.1 NaOH
1.0: 1.0
1.0 : 0.4 NaOH
1.0: 1.02
1.0:0.28 NaOH
1.0: 0.33
1.0:0.33 NaOH
1.0: 0.45
1.0:0.28 NaOH
1.0: 0.45
1.0:0.28 NaOH
1.0: 0.45
1.0:0.28 NaOH
1.0: 1.02
1.0: 1.07
1.0: 1.06
1.0: 1.09
1.0: 1.09
1.0: 1.10
1.0: 1.10
1.0: 1.10
1: 4.91
1: 4.91
1: 4.91
1: 4.91
1: 3.69
1: 3.69
1: 4.91
145
145
110
120
110
120
145
10
8.4
16
17
14
12.5
8
93 (96)
94 (93)
76 (88)
79 (88)
75 (91)
84 (92)
93 (93)
1.0:0.28 NaOH
1.0: 1.10
1.0: 1.20
1.0: 1.20
1.0: 1.20
1.0: 1.20
1.0: 1.20
1.0: 1.20
1.0: 1.20
1.0: 1.10
1.0: 1.10
1.0: 1.10
1.0: 1.10
1.0: 1.10
1.0: 1.10
1.0: 1.10
1.0: 1.10
1: 5.34
1: 5.34b
1: 5.34
1: 5.34
1: 5.34
1: 5.34
1: 5.34
1: 5.34
145
81
10
13
93 (95)
50 (75)
95 (94)
95 (94)
81 (92)
94 (94)
43 (96)
81 (92)
145
145
145
150
145
145
9.70
8.20
6.75
10
3.75
6.50
a
b
Yield of the crude product; the main substance content (wt %) is given in parentheses. Acetonitrile was taken instead of DMF.
results concerning synthesis of X are listed in Table 1.
The optimal reaction parameters are as follows: 140
Ether V was prepared similarly, and also by inde-
pendent synthesis: acylation with acetic anhydride of
150 C, 8 10 h,molar ratios XI : VII (1.03 1.10) : 1.00, 4-amino-4 -nitrodiphenyl ether III (prepared according
VII : K2CO3 1.0 : (1.1 1.2), VII : NaOH 1.00 : (0.28
0.31); weight ratio VII : DMF 1.0 : (4.4 5.4).
to [4] in 84% yield) in aprotic organic solvents under
the conditions suggested previously for acylation of
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 7 2003

SYNTHESIS OF 3,4,4 - AND 2 ,3,4-TRIAMINODIPHENYL ETHERS
1107
Table 2. Nitration of 4-acetylamino-2 -nitrodiphenyl ether X (40 45 C)
HNO3
concentration,
wt %
Yield of Main substance
Molar ratio
X: HNO3
Molar ratio
CH3CO2H: HNO3 HNO3 : (CH3CO)2O
Molar ratio
Time, h
crude
content in crude
XIII, %
XIII, wt %
1.0: 3.12
1.0: 3.12
1.0: 3.10
1.0: 3.00
1.0: 3.01
1.0: 2.94
1.0: 2.87
1.0: 2.75
1.0: 2.74
1.0: 2.74
1.0: 2.74
1.0: 2.77
1.0: 2.70
1.0: 2.70
1.0: 2.68
1.0: 2.65
1.0: 2.65
1.0: 2.65
1.0: 2.64
1.0: 2.64
1: 3.11
1: 3.11
1: 2.09
1: 4.94
1: 2.77
1: 4.73
1: 5.13
1: 5.11
1: 5.11
1: 5.11
1: 5.11
1: 5.12
1: 5.13
1: 5.13
1: 2.12
1: 2.12
1: 2.12
1: 2.13
1: 2.12
1: 2.12
1.0: 2.35
1.0: 2.35
1.0: 2.04
1.0: 2.65
1.0: 2.65
1.0: 0.34
1.0: 0.37
1.0: 0.37
1.0: 0.36
1.0: 0.36
1.0: 0.36
1.0: 0.36
1.0: 0.37
1.0: 0.37
1.0: 2.10
1.0: 1.77
1.0: 1.77
1.0: 1.77
1.0: 2.09
1.0: 1.76
57
57
57
57
57
90
90
90
90
90
90
90
90
90
57
57
57
57
57
57
5.0
5.5
7.0
8.0
9.0
3a
1.0
1.5
1.0
1.5
2.0
1.75
1.5
1.5
7.0
4.5
5.5
6.5
7.0
6.5
91.5
91.7
83.9
76.3
75.3
89.9
93.0
94.4
79.3
93.1
94.9
93.3
92.0
92.3
85.4
95.7
95.1
95.3
85.6
85.3
97.0
96.0
91.0
99.0
99.0
99.0
97.0
97.7
98.1
98.6
99.0
98.6
98.0
98.3
99.3
96.1
97.0
98.2
99.5
98.2
a
At 32 C.
4-amino-4 -nitrodiphenyl sulfide [16]. The reaction
occurs readily with a qantitative yield.
Thus, ether X, compared to the related sulfide [16],
undergoes nitration more readily, with the higher yield
and better quality of the reaction product. The process
parameters can be varied in a fairly wide range with-
out noticeable deterioration of the results. The follow-
ing parameters can be recommended as optimal for
nitration of X: 40 45 C, 4.5 6.5 h, HNO3 concentra-
tion 90%; molar ratios X : HNO3 1.0 : (2.7 2.9),
HNO3 : acetic acid 1.0 : (2.1 5.1), HNO3 : acetic
anhydride 1.0 : (0.3 1.7).
4-Acetylamino-3,4 -dinitrodiphenyl ether XII and
4-acetylamino-2 ,3-dinitrodiphenyl ether XIII were
prepared by nitration of ethers V and X, respectively.
When optimizing the nitration conditions, we found
that, under the conditions used previously for nitration
of 4-acetylamino-4 -nitrodiphenyl sulfide [16] with
3
dilute nitric acid ( 1.35 g cm ), the reaction is slow,
and heating causes removal of the acetyl protecting
group.
4-Acetylamino-3,4 -dinitrodiphenyl ether XII was
prepared in a quantitative yield by nitration of V with
When the nitration was performed under more rig-
orous conditions, i.e., with more concentrated HNO3
( 1.5 g cm ) and at higher temperature (50 60 C),
the reaction was noticeably faster and gave virtually
pure dinitrodiphenyl ethers XII and XIII in 94 and
97% yields, respectively. When the nitration is per-
formed at a lower temperature (35 40 C), the mixture
contains a large amount of N-nitro compounds [16],
which rearrange into the C-nitro compounds under
these conditions very slowly.
3
HNO3
(
1.50 g cm ) in chloroform (molar ratio
3
V : HNO3 : chloroform 1 : 3 : 17) in the presence of
acetic anhydride at 50 60 C.
Hydrolysis of XII with 30% aqueous KOH at
100 C [molar ratio XII : KOH 1 : (6 7)] gave 4-ami-
no-3,4 -dinitrodiphenyl ether XIV in 96% yield. In the
course of the reaction, first a solution is formed and
then a solid gradually precipitates. Formation of the
homogeneous solution can probably be explained by
initial formation of the potassium salt with deprotona-
tion of the acetanilide moiety. The precipitating hy-
drolysis product is insoluble in water and aqueous
alkali.
Experiments showed that nitration of X can be per-
formed most readily in a mixture of acetic acid and
acetic anhydride. The results of nitration of ether X
in this medium are given in Table 2.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 7 2003

1108
PILYUGIN et al.
Table 3. Synthesis of 4-amino-2,3 -dinitrodiphenyl ether XV (70 75 C)
Main substance
content in crude
XV, wt %
Weight ratio
XIII : (CH3)2CHOH
Yield of crude
Molar ratio XIII : NaOH
Time, h
XV, %
1.0: 1.96
1.0: 1.81
1.0: 1.81
1.0: 1.81
1.0: 1.81
1.0: 1.81
1.0: 1.81
1.0: 1.81
1.0: 1.81
1.0: 1.81
1.0: 1.81
1.0: 1.81
1.0: 1.81
1.0: 1.81
1.0: 1.81
1.0: 1.81
1.0: 1.81
1.0: 1.66
1.0: 1.66
1.0: 1.50
1.0: 1.50
1.0: 1.35
1: 4.10
1: 4.10
1: 4.10
1: 4.10
1: 4.10
1: 4.10
1: 4.10
1: 4.10
1: 4.10
1: 4.10
1: 4.10
1: 4.10
1: 4.10
1: 4.10
1: 4.10
1: 4.10
1: 4.10
1: 4.10
1: 4.10
1: 4.10
1: 4.10
1: 4.10
1.5
4.0
3.0
2.0
2.0
1.6
1.5
1.5
1.5
1.4
1.0
1.0
2.2a
3.0b
1.4c
2.2d
1.2e
3.0
1.0
4.0
2.0
2.0
83.4
92.7
93.0
93.0
92.6
92.5
93.1
92.6
92.4
88.7
87.7
89.8
81.2
87.2
51.6
86.7
88.0
79.3
71.3
79.0
69.0
81.2
99.1
97.4
98.1
97.5
97.4
97.0
98.4
97.2
97.4
98.5
97.0
97.2
85.8
97.5
92.5
98.7
98.6
98.7
95.3
97.3
97.3
92.5
a
b
c
d
e
At 36 C.
At 45 C.
At 44 C.
At 55 C.
At 65 C.
With the aim to replace KOH by cheaper NaOH
EXPERIMENTAL
and reduce the consumption of alkali, we performed
experiments on deprotection of XIII in 2-propanol.
We found that the most promising procedure for de-
acetylation of XIII is treatment of its solution in
2-propanol with aqueous NaOH. 4-Amino-2 ,3-dini-
trodiphenyl ether XV is thus obtained in 96% yield.
At slower (within 50 min) addition of the NaOH solu-
tion, by-products are formed in smaller amounts.
The crude reaction products were analyzed with an
Altex liquid chromatograph (model 100 pump; model
153 UV detector; model 210 20- l loop dosing unit;
30-, 50-, and 100- l SNR Hamilton syringes; stainless
steel column 0.25 m long, 4.6 mm i.d.).
Analysis of mixtures of VI, VII, and XI, of nitro-
diphenyl ethers V and X, of dinitrodiphenyl ethers
XII XV, and of triaminodiphenyl ethers I and II is
based on HPLC separation on a column packed with
Rsil reversed phase or Ultrasphere ODS in the eluent
system 65% methanol + 35% water with addition of
25 ml of a 10% solution of 18-crown-6 in methanol
per liter of the eluent. The chromatograms were cal-
culated by internal normalization of the peak areas.
The results concerning synthesis of XV are given
in Table 3. The optimal reaction conditions are as
follows: 70 75 C, 1.5 2.5 h, molar ratio XIII : alkali
1.0 : 1.8, weight ratio XIII : 2-propanol 1.0 : 4.1.
The last step of the synthesis of I and II is reduc-
tion of XIV and XV. The reduction was performed
in a refluxing mixture of dioxane with ethylene glycol
or in refluxing 1-butanol with hydrazine hydrate in
the presence of FeCl3 and activated carbon under the
conditions similar to those of reduction of 4-amino-
3,4 -dinitrodiphenyl sulfide [17]; ethers I and II were
obtained in 87 and 84% yields, respectively.
4-Acetylamino-2 -nitrodiphenyl ether
X and
4-acetylamino-4 -nitrodiphenyl ether V. To 1.2 l of
DMF, we added with vigorous stirring 2.24 mol of
4-acetylaminophenol V, 2.04 mol of nitrobenzene VI
or VII, and 2.45 mol of anhydrous potassium car-
bonate. The mixture was heated to 145 150 C and
vigorously stirred at this temperature for 8 10 h. The
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SYNTHESIS OF 3,4,4 - AND 2 ,3,4-TRIAMINODIPHENYL ETHERS
1109
reaction completion was judged from the disappearance
of VI or VII. When residual amounts of VI or VII
remained, the mixture was alkalized with a small
amount of 44% aqueous NaOH and stirred for 1 h.
After complete conversion of VI or VII, the mixture
was placed in a crystallizer with water and cooled to
room temperature; the precipitated ether V or X was
filtered off, washed with 0.5 N alkali and water, and
dried. Ether V: yield 93%, Rf 0.36 (benzene hexane,
3 : 7), mp 153 154 C. Found, %: C 61.78; H 4.45;
N 10.22. C14H12N2O4. Calculated, %: C 61.76; H 4.44;
N 10.29. Ether X: yield 96%, Rf 0.30 (benzene
hexane, 10 : 2), mp 128 129 C. Found, %: C 61.81;
H 4.42; N 10.26. C14H12N2O4. Calculated, %: C 61.76;
H 4.44; N 10.29.
Rf 0.78 (benzene ethanol, 10 : 2), mp 162 163 C.
Found, %: C 52.30; H 3.21; N 15.20. C12H9N3O5.
Calculated, %: C 52.36; H 3.29; N 15.27.
3,4,4 -Triaminodiphenyl ether I and 2 ,3,4-tri-
aminodiphenyl ether II. Nitro ethers XIV and XV
were reduced to amino ethers I and II according to
[17]. Ether I: yield 87%, Rf 0.14 (benzene dioxane,
10 : 1), mp 162 163 C. Found, %: C 66.85; H 6.24;
N 19.44. C12H13N3O. Calculated, %: C 66.95; H
6.09; N 19.52. Ether II: yield 84%, Rf 0.23 (benzene
ethanol, 10 : 2), mp 147 148 C. Found, %: C 66.81;
H 5.91; N 19.53. C12H13N3O. Calculated, %: C
66.95; H 6.09; N 19.52.
REFERENCES
4-Acetylamino-3,4 -dinitrodiphenyl ether XII.
To a suspension of 0.69 mol of V in 950 ml of chloro-
form, we added 66 ml of acetic anhydride and then,
1. FRG Patent 2348104, 1973, Ref. Zh. Khim., 1975,
24O112.
2. Kosareva, V.M., Solonenko, I.G., Mikhailyuk, A.N.,
Sorokina, O.N., Demidov, N.V., and Volkova, G.N.,
USSR Inventor’s Certificate 1140433, 1983, Byull.
Izobret., 1985, no. 6.
3. JPN Patent 47-3333, 1968, Ref. Zh. Khim., 1973,
11N146.
4. Schraman, J., Radlmann, E., Lohwasser, H., and
Nisch, G., Lieb. Ann., 1970, vol. 740, no. 1, p. 169.
5. JPN Patent 55-45635, 1978, Izobret. SSSR Rubezh.,
1981, issue 65, no. 5.
3
dropwise, 90 ml of HNO3 ( 1.5 g cm ) at 45 50 C,
after which the mixture was stirred at this temperature
for 6 h. Then 500 ml of water was added, and the pre-
cipitate was filtered off. Yield 97%, Rf 0.7 (benzene
ethanol, 10 : 2), mp 121 123 C. Found, %: C 52.98;
H 3.46; N 13.30. C14H11N3O6. Calculated, %: C
53.00; H 3.49; N 13.24.
4-Acetylamino-2 ,3-dinitrodiphenyl ether XIII.
To 350 ml of acetic acid, we added with stirring
0.6 mol of X. After that, we added 66 ml of acetic
anhydride and then, dropwise with vigorous stirring
6. FRG Patent 1593871, 1967, Chem. Abstr., 1970,
vol. 72, no. 13, 66617z.
7. FR Patent 2459792, 1979, Ref. Zh. Khim., 1982,
14N171; Izobret. SSSR Rubezh., 1981, issue 55, no. 6.
8. FRG Patent 3033836, 1980, Ref. Zh. Khim., 1983,
11N148; Izobret. SSSR Rubezh., 1982, issue 57,
no. 17.
9. Litvinenko, L.M., Cheshko, R.S., and Gofman, A.D.,
Zh. Obshch. Khim., 1957, vol. 27, p. 756.
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Fac. Chim. Ind. Bologna, 1954, no. 12, p. 114.
11. Berzin’, L.E., Murnietse, D.Ya., Dregeris, Ya.Ya., and
Freimanis, Ya.F., Izv. Akad. Nauk Latv. SSR, Ser.
Khim., 1971, no. 4, p. 460.
12. JPN Patent 57-15740, 1974, Ref. Zh. Khim., 1983,
14O50; Izobret. SSSR Rubezh., 1982, issue 57, no. 20.
13. Stohr, R., Z. Physiol. Chem., 1931, vol. 201, no. 1,
p. 141.
14. Rarick, M.J., Brewster, R.Q., and Dains, F.B., J. Am.
Chem. Soc., 1933 vol. 35 no. 5, p. 1289.
15. Hungarian Patent 170959, 1975, Ref. Zh. Khim., 1980,
17O271.
at 10 15 C over a period of 40 50 min, 77 ml of
3
HNO3
(
1.5 g cm ). The resulting mixture was
stirred for 20 25 min at 20 25 C, heated to 40
45 C, and vigorously stirred at this temperature for
an additional 4 6 h. The reaction progress was moni-
tored by TLC. When no ether X was longer detected,
the mixture was placed in a crystallizer with cold
water, and the precipitate of XIII was filtered off,
thoroughly washed on the filter with water, and dried.
Yield 92%, Rf 0.56 (benzene ethanol, 10 : 2), mp 98
99 C. Found, %: C 53.05; H 3.52; N 13.28. C14H11
N3O6. Calculated, %: C 53.00; H 3.49; N 13.24.
4-Amino-3,4 -dinitrodiphenyl ether XIV and
4-amino-2 ,3-dinitrodiphenyl ether XV. To 600 ml of
2-propanol, we added 0.39 mol of XII or XIII. The
mixture was vigorously stirred at 25 30 C, and a
solution of 0.40 mol of NaOH in 66 ml of water was
gradually added. The resulting mixture was heated to
70 75 C, vigorously stirred at this temperature for
1.5 3 h, and placed in a crystallizer with cold water.
The precipitate was filtered off, washed on the filter
with water, and dried. Ether XIV: yield 96%, Rf 0.53
(benzene ethanol, 10 : 2), mp 179 181 C. Found, %:
C 52.42; H 3.32; N 15.47. C12H9N3O5. Calculated,
%: C 52.36; H 3.29; N 15.27. Ether XV: yield 95%,
16. Pilyugin, V.S., Valitov, R.B., Kuznetsova, S.L., Kise-
leva, G.V., Klimakova, E.V., Vorob’eva, T.P., and
Sapozhnikov, Yu.E., Bashkir. Khim. Zh., 2000, vol. 7,
no. 4, p. 43.
17. Pilyugin, V.S., Kiseleva, G.V., and Valitov, R.B.,
Bashkir. Khim. Zh., 2000, vol. 7, no. 1, p. 25.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 7 2003