Catalytic and noncatalytic ammonolysis of polyfluorinated 1,3-dichlorobenzenes

Article abstract of DOI:10.1023/A:1020861831098

Reactions of 1,3-dichlorotetrafluorobenzene and 1,3-dichloro-2,4,6-trifluorobenzene with aqueous ammonia in the presence and in the absence of copper(I) salt lead to fluorine replacement by amino group in the para and ortho positions with respect to the chlorine atom. Ammonolysis of the resulting chloropolyfluoroanilines in the absence of a catalyst involves replacement of fluorine atom in the meta position with respect to the amino group. In the presence of copper(I) salt, catalytic aminodechlorination occurs at the para and ortho positions with respect to the amino group introduced in the first stage.

Full text of DOI:10.1023/A:1020861831098

Russian Journal of Organic Chemistry, Vol. 38, No. 7, 2002, pp. 1023 1029. Translated from Zhurnal Organicheskoi Khimii, Vol. 38, No. 7, 2002,
pp. 1066 1072.
Original Russian Text Copyright
2002 by Selivanova, Pokrovskii, Shteingarts.
Catalytic and Noncatalytic Ammonolysis
of Polyfluorinated 1,3-Dichlorobenzenes*
G. A. Selivanova, L. M. Pokrovskii, and V. D. Shteingarts
Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Division, Russian Academy of Sciences,
pr. Akademika Lavrent’eva 9, Novosibirsk, 630090 Russia
e-mail: shtein@nioch.nsc.ru
Novosibirsk State University, ul. Pirogova 2, Novosibirsk, 630090 Russia
Received March 6, 2002
Abstract Reactions of 1,3-dichlorotetrafluorobenzene and 1,3-dichloro-2,4,6-trifluorobenzene with aqueous
ammonia in the presence and in the absence of copper(I) salt lead to fluorine replacement by amino group
in the para and ortho positions with respect to the chlorine atom. Ammonolysis of the resulting chloropoly-
fluoroanilines in the absence of a catalyst involves replacement of fluorine atom in the meta position with
respect to the amino group. In the presence of copper(I) salt, catalytic aminodechlorination occurs at the para
and ortho positions with respect to the amino group introduced in the first stage.
Reactions of polyhalogenated arenes with ammonia
a catalyst heavier halogen atoms are more labile
and amines provide a general procedure for synthesiz- than fluorine [5]. Such a study is also important from
ing polyfluorinated aromatic amines and diamines
[1 4]. If a substrate contains other halogen atoms in
addition to fluorine, replacement of the latter occurs
[1, 2]. For example, ammonolysis of pentafluorohalo-
benzenes gives rise mainly to the corresponding
4-halotetrafluoroanilines [1, 2]. In the subsequent
ammonolysis, the amino group in the primary sub-
stitution products (polyfluoroanilines) behaves as
a meta-orienting group, leading to formation of the
corresponding meta-phenylenediamines. Treatment of
the viewpoint of extending the scope of application
of fairly readily accessible chloropolyfluorobenzenes
which are concomitant products in the synthesis of
hexafluorobenzene from hexachlorobenzene [6]. With
chloropentafluorobenzene as an example [4] we
previously showed that the first stage of the ammo-
nolysis in the absence of a catalyst and in the presence
of copper(I) chloride is replacement of fluorine atom.
As a result, introduction of amino group into the para
or ortho position with respect to chlorine change the
hexafluorobenzene or pentafluoroaniline with aqueous ratio of rates of concurrent processes in the second
ammonia gives mainly tetrafluoro-1,3-phenylenedi-
amine ( 90%) [3], while from 4-chlorotetrafluoro-
aniline 4-chlorotrifluoro-1,3-phenylenediamine is
obtained [4]. Thus polyfluorinated para- and ortho-
phenylenediamines are almost inaccessible via the
above reaction. This considerably narrows the scope
of application of ammonolysis of polyfluoroarenes as
a route to polyfluorophenylenediamines which are
very promising reagents for fine organic synthesis.
Therefore, it becomes important to study the synthetic
potential of catalytic ammonolysis as applied to
polyfluorohalobenzenes. It is known that in the am-
monolysis of halofluorobenzenes in the presence of
____________
stage of ammonolysis to the reverse, namely in favor
of catalytic replacement of chlorine. Thus a new
procedure for preparation of 2,3,5,6-tetrafluoro-1,4-
phenylenediamine appears. With the above in mind,
a question arises so as to whether the observed effect
is general for the ammonolysis of polyfluorinated
chlorobenzenes and how its application scope can be
extended in order to obtain polyfluorinated phenylene-
diamines.
In the present work we studied the ammonolysis of
1,3-dichlorotetrafluorobenzene (I) and 1,3-dichloro-
2,4,6-trifluorobenzene (II) in the absence of a catalyst
and in the presence of copper(I) salt with the goal of
comparing the results with those obtained previously
while studying the ammonolysis of chloropentafluoro-
benzene [4]. In the first case, the substrate was
*
This study was financially supported by the Ministry of
Education of the Russian Federation (project no. E 00-5.0-90).
1070-4280/02/3807-1023$27.00 2002 MAIK Nauka/Interperiodica

1024
SELIVANOVA et al.
Scheme 1.
a mixture of isomers formed by reaction of hexa-
chlorobenzene with potassium fluoride [6]; according
to the GLC data, it contained 67% of compound I,
20% of 1,2-dichlorotetrafluorobenzene (III), and 10%
of 1,4-dichlorotetrafluorobenzene (IV). The reaction
mixtures and products isolated by column chromatog-
raphy were analyzed by GLC, GC MS, and 19F and
1H NMR. The experimental results are summarized
accessible compound I in aqueous ethanol at 180 C
[8]. In our case, the lower yield of V (50%) is fully
compensated by the use as starting material of
an accessible mixture of dichlorotetrafluorobenzenes.
When the same reaction was carried out at 140 C
(48 h), a 3:1 mixture of 4,6-dichloro-2,5-difluoro-1,3-
phenylenediamine (VII) and 2,4-dichloro-5,6-difluoro-
1,3-phenylenediamine (VIII) was obtained (Scheme 1;
Table 1, run no. 2). Separation of this mixture by
column chromatography gave a fraction containing
previously unknown diamine VII with an impurity
of isomer VIII (ratio 5:1); their elemental composi-
tion and molecular weight was determined by high-
resolution mass spectrometry. The 19F NMR chemical
shifts of compounds VII and VIII are very consistent
with those calculated by the additivity scheme using
the corresponding increments [7] (Table 2). In all
1
in Table 1, and Table 2 contains the 19F and H NMR
parameters of the products.
1,3-dichlorotetrafluorobenzene (I) reacted with
aqueous ammonia at 80 C under pressure (reaction
time 48 h) to give 2,4-dichloro-3,5,6-trifluoroaniline
(V) with a small impurity of 2,6-dichloro-3,4,5-tri-
fluoroaniline (VI) (ratio 12:1; Scheme 1; Table 1,
run no. 1). Amine V was synthesized previously in
80% yield by the action of ammonia on difficultly
Table 1. Noncatalytic and catalytic ammonolysis of 1,3-dichlorotetrafluorobenzene (I) and 1,3-dichloro-2,4,6-trifluoro-
benzene (II) (48 h, 60 ml of 30% aqueous ammonia)
Run
no.
Substrate
(3 g)
Tempera-
ture,
Molar ratio
I(II): CuCl
Product
weight, g
Product composition (mol %, GLC data)
C
1a
2a
I
I
80
140
2.9
2.9
I (6), III (9), IV (5), V (60), VI (5), VII (1), XIX (6)
I (1), V (2), VI (5), VII (53), VIII (16), XIX (12), un-
identified (6)
3a
4a
5b
6b
7b
8b
I
I
II
II
II
II
80
140
100
150
100
150
1: 1
1: 1
2.9
1.9
2.9
2.6
2.5
1.0
I (6), III (10), IV (7), V (55), VI (5), XIX (6)
IX (24), X (23), XI (8), XII (9)
XIII (75), XIV (13), XV (4)
XIII (10), XV (76)
XIII (53), XIV (11), XV (4)
1: 1
1: 1
XVI (46), XVII (18), XVII (9)
a
A mixture containing 67% of I, 20% of its ortho isomer III, and 10% of para isomer IV was used (GLC).
A mixture containing 90% of II was used (GLC).
b
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 7 2002

CATALYTIC AND NONCATALYTIC AMMONOLYSIS
1025
Table 2. NMR spectra of polyfluorinated aromatic amines V XIX (acetone-d6, c = 20%)
19F NMR spectrum, F, ppm (J, Hz)
Comp.
no.
1H NMR spectrum,
, ppm (J, Hz)
experimental
calculateda
V
42.1 (3-F), 22.5 (5-F), 3.3 (6-F), (F o-F 22, 3-F 43.8, 5-F 23.3, 6-F 1.2
F p-F 8, F m-F 1)
26.5 (3-F, 5-F), 10.5b (4-F), (F o-F 22, 3-F, 5-F 23.3, 4-F 0.2
F m-F 1)
5.81 (2H, NH2)
VI
5.65 (2H, NH2)
VII
6.5 (2-F), 40.3 (5-F), (F p-F 9)
4.5 (2-F), 40.0 (5-F), (F p-F 9)
21.6 (5-F), 6.1 (6-F), (F o-F 21)
21.2 (5-F), 6.6 (6-F), (F o-F 21)
24.2 (2-F), 5.8 (5-F), 1.2 (6-F), (F o-F 20, 3-F 23.1, 5-F 3.9, 6-F 1.1
F m-F 9, F p-F 9)
2-F 4.0, 5-F 40.2
2-F 4.0, 5-F 40.2
5-F 21.0, 6-F 7.0
5-F 21.0, 6-F 7.0
5.12 (2H, NH2)
4.00 (4H, 2NH2)
5.25 (2H, NH2)
4.25 (2H, NH2)
4.43 (2H, NH2),
4.68 (2H, NH2)
VIIc
VIII
VIIIc
IX
X
2.0 (2-F), 6.9 (3-F), 25.8 (5-F), (F p-F 10, 2-F 3.2, 3-F 6.3, 5-F 25.8
F o-F 19, F m-F 9, H p-F 2, H o-F 10,
H m-F 8)
6.86 m (Harom), (H p-F 2,
H o-F 10, H m-F 8),
4.58 (2H, NH2), 4.91
(2H, NH2)
XI
45.0 (3-F), 25.0 (5-F), 1.2 (6-F), (F p-F 10, 3-F 46.2, 5-F 27.0, 6-F 6.61 m (Harom), (H o-F
F o-F 19, F m-F 1, H o-F 10.5, H o-F 9.5,
0.9
10.5,
H o-F
9.5,
H m-F 7)
H m-F 7), 5.65 (2H,
NH2)
XIc
44.0 (3-F), 24.6 (5-F), 0.2 (6-F), (F p-F 11, 3-F 46.2, 5-F 27.0, 6-F 6.38 m (Harom), (H o-F 10,
F o-F 20, F m-F 3, H o-F 8.5, H o-F 10,
0.9
H o-F 8.5, H m-F 6.5),
H m-F 6.5)
4.37 (2H, NH2)
XII
2.1 (3-F), 14.2 (4-F), 24.6 (6-F), (F p-F 11, 3-F 3.2, 4-F 14.8, 6-F 6.37 m (Harom), (2H o-F
F o-F 22, F m-F 2, H o-F 10, H m-F 7)
25.8
10, H m-F 7), 3.4 (2H,
NH2), 3.4 (2H, NH2)
6.32 d (Harom), (H o-F 9,
H p-F not determined),
4.31 (2H, NH2)
XIIIc
46.2 (3-F), 49.0 (5-F), (H p-F not determined; 3-F 49.9, 5-F 50.2
H o-F 9)
XIVc
XVc
48.8 (3-F,
5-F), (F m-F
3, H o-F 9)
3-F, 5-F 50.2
5-F 51.7
6.42 t (Harom), (2H o-F 9),
4.71 (2H, NH2)
6.03 d (Harom), (H o-F 11),
4.49 (2H, NH2), 4.06
(2H, NH2)
44.85 (5-F), (H o-F 11)
XVI
31.06 (3-F), 40.19 (5-F), (F m-F 3, H o-F 10)
3-F 32.2, 5-F 40.7
2-F, 6-F 32.2
6.24 m (Harom), 3.71 (2H,
NH2), 3.04 (2H, NH2)
6.17 d.d (Harom), (H o-F
10, H m-H 2), 3.40
(2H, NH2), 3.27 (2H,
NH2)
XVII
31.10 (2-F, 6-F), (F m-F
3, H o-F 10)
XVIII
XIX
46.53 (5-F), (2H o-F 10)
5-F 49.3
5.91 t (Harom), (2H o-F 10,
H m-H 1), 4.05 (4H,
2NH2)
28.1 (2-F), 21.7 (5-F), 6.6 (6-F), (F p-F 8, 2-F 25.4, 5-F 19.3, 6-F 6.2
F o-F 21, F m-F 12)
5.59 (2H, NH2)
a
The increments for calculations by the additivity scheme were taken from [7].
b
In some cases, the difference between the calculated and experimental chemical shifts of the fluorine atom in the meta position
with respect to the amino group can be minimized using other increments (see [4]).
The spectra were recorded in CDCl3.
c
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 7 2002

1026
SELIVANOVA et al.
Scheme 2.
cases the reaction mixtures also contained amines
formed by ammonolysis of isomers of I, which were
present in the initial compound (see above; Table 1).
impossible to choose between structure XI and
isomeric 4-chloro-2,3,5-trifluoroaniline for the product
with m/z 181 ([M]+) present in the reaction mixture
Comparison of the monoamine and diamine ratios
V:VI and VII:VIII indicates that the most part of
diamine VIII is formed from amine V. The ratios
of amines V and VI and diamines VII and VIII, the
first of which considerably exceeds the para:ortho
ratio (3) in the ammonolysis of chloropentafluoroben-
zene [4], suggest that the rate of fluorine replacement
by amino group in the para position with respect to
the chlorine atom is generally higher than the rate
of fluorine replacement in the ortho position. This
conclusion is consistent with the compositions of
products formed by reactions of a mixture of isomeric
dichlorotetrafluorobenzenes with various amines in
dimethylformamide [9].
The reaction of I with aqueous ammonia in the
presence of copper(I) chloride at 80 C (Table 1, run
no. 3) gave a mixture of almost the same compounds
as in the ammonolysis of I in the absence of a catalyst
(Table 1; cf. runs nos. 1 and 3). These results indicate
that copper(I) chloride does not affect the orientation
of monoaminodehalogenation of I; an analogous
pattern was observed in the ammonolysis of chloro-
pentafluorobenzene [4]. However, when the reaction
in the presence of CuCl was carried out at 140 C
(Scheme 2; Table 1, run no. 4), a mixture of 2-chloro-
3,5,6-trifluoro-1,4-phenylenediamine (IX), 2,3,5-tri-
fluoro-1,4-phenylenediamine (X), 2-chloro-3,5,6-tri-
fluoroaniline (XI), and previously described [10]
3,5,6-trifluoro-1,2-phenylenediamine (XII) at a ratio
of 3:3:1:1 was obtained. By column chromatography
we isolated diamine IX (yield 19%), amine XI (yield
12%), and a mixture of phenylenediamines X and XII
(yield 60%).
on the basis of 19F NMR data. The calculated
values ( 0.9, 26.7, and 46.2 ppm for 4-chloro-2,3,5F-
trifluoroaniline; cf.
values given in Table 2 for
F
1
amine XI) are almost similar. However, the H signal
is split with two similar coupling constants which
correspond to fluorine atoms in the ortho positions
(Table 2); the respective couplings are observed for
two fluorine atoms in the 19F NMR spectrum. These
data led us to choose structure XI.
Presumably, diamines IX, X, and XII are formed
via replacement of the corresponding chlorine atoms
in aniline V. This indicates a general character of the
assistance by the amino group in the initially formed
aniline to catalytic aminodechlorination in the para
and ortho position (rather than to aminodefluorination
in the subsequent amination), which was revealed by
us while studying the ammonolysis of chloropenta-
fluorobenzene [4]. Obviously, amine XI and diamines
X and XII result from reduction of amines V and
IX with copper(I) salt or material of reactor walls.
Analogous processes, namely the formation of penta-
fluorobenzene in the reduction of chloropentafluoro-
benzene with copper in water at 300 C [11] and of
2,4,5-trifluoro-1,3-phenylenediamine in the reaction of
the same substrate with aqueous ammonia in a steel
high-pressure reactor at 200 C [4], have been reported.
It remains unclear which process, reduction of V or
its ammonolysis, occurs first.
The reaction of 1,3-dichloro-2,4,6-trifluorobenzene
(II) with aqueous ammonia at 100 C gave 2,6-di-
cloro-3,5-difluoroaniline (XIII) with an admixture of
2,4-dichloro-3,5-difluoroaniline (XIV) (ratio 6:1;
Scheme 3; Table 1, run no. 5). At 150 C, the products
were 2,6-dichloro-5-fluoro-1,3-phenylenediamine
(XV) and amine XIII at a ratio of 7:1 (Scheme 3;
Table 1, run no. 6). In both cases, a fairly large frac-
tion of the major product makes it possible to use the
resulting mixtures in further syntheses without separa-
tion into particular isomers. Compound XV was
isolated in 73% yield by column chromatography.
As noted above, the calculated chemical shifts of
fluorine nuclei in diamines IX, X, and XII agree well
with those observed in the experimental 19F NMR
spectra but differ appreciably from those expected
for isomeric compounds. The fine structure of signals
1
in the 19F and H NMR spectra also corresponds to
the assumed structures (Table 2). By contrast, it was
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 7 2002

CATALYTIC AND NONCATALYTIC AMMONOLYSIS
1027
Scheme 3.
Compounds XIII [12, 13] and XIV [13] were
previously synthesized via a series of transformations,
starting from difficultly accessible 3,5-dichloro-2,4,6-
trifluorobenzonitrile. Another known procedure for
preparation of aniline XIII includes synthesis and
subsequent reduction of the corresponding nitroben-
zene [14]. However, no parameters of amines XIII
and XIV were given in the above publications. Also,
we have found no data on phenylenediamine XV
which is likely to be formed from amine XIII and
from XIV. The experimental 19F NMR chemical shifts
(Table 2) showed a better agreement with those cal-
culated by the additivity scheme for isomeric 4,6-di-
chloro-5-fluoro-1,3-phenylenediamine than for com-
pound XV. However, the former cannot be obtained
from amine XIII.
The predominant formation of amine XIII via
replacement by amino group of the fluorine atom in
the ortho position with respect to both chlorine atoms
contradicts the substitution patterns observed for com-
pound I (see above) and chloropentafluorobenzene [4],
where the para-fluorine atom with respect to chlorine
is replaced preferentially. Presumably, in the ammo-
nolysis of II we have the overall effect of five halogen
atoms, which favors replacement of the middle of
them [15].
chloride at 100 C (Table 1, run no. 7) is analogous to
the mixture formed in the ammonolysis in the absence
of catalyst, other conditions being equal (Table 1, cf.
run nos. 5 and 7). When the reaction was carried out
with copper(I) chloride under more severe conditions
(Scheme 4; Table 1, run no. 8), strong tarring was
observed, and the overall yield of ammonolysis prod-
ucts was as low as 30%. The major products were
those formed via aminodechlorination and hydro-
dechlorination: 3,5-difluoro-1,2-phenylenediamine
(XVI), 2,6-difluoro-1,4-phenylenediamine (XVII),
and 2-chloro-5-fluoro-1,3-phenylenediamine (XVIII)
at a ratio of 5:2:1. All these were isolated by column
chromatography in 23, 7, and 5% yield, respectively.
Diamine XVI can be obtained in four steps from
m-difluorobenzene [16] with an overall yield of 30%,
and diamine XVII is available from 1,3,5-trifluoro-
benzene [17] in six steps with an overall yield of
5 8%. We have found no published data on diamine
XVIII. In the reaction shown in Scheme 4 diamine
XVI may be formed from amine XIII or XIV, and
diamine XVII may originate from amine XIV as
a result of aminodechlorination and hydrodechlorina-
tion. Diamine XVIII is likely to arise from amine
XIII or XIV via replacement by amino group of the
fluorine atom in the meta position with respect to
the existing amino group and subsequent hydrode-
chlorination.
The product mixture obtained in the reaction of II
with aqueous ammonia in the presence of copper(I)
Scheme 4.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 7 2002

1028
SELIVANOVA et al.
Thus, as we found previously with chloropenta-
weights were determined on a Finnigan MAT-8200
high-resolution mass spectrometer.
fluorobenzene [4] as an example, the ammonolysis of
1,3-dichlorotetrafluorobenzene (I) and 1,3-dichloro-
2,4,6-trifluorobenzene (II) under mild conditions in
the presence and in the absence of copper(I) salt
results in replacement of fluorine in the para and
ortho positions with respect to the chlorine atom.
The subsequent ammonolysis of the resulting aniline
in the absence of catalyst involves fluorine replace-
ment in the meta position with respect to the amino
group and formation of dichloro-m-phenylenedi-
amines. In the presence of copper(I) chloride, the
main reaction pathway is not aminodefluorination but
replacement of chlorine in the para and ortho posi-
tions with respect to the amino group (in the case of
compound I). In the case of compound II, the pres-
ence of CuCl favors the latter process in the competi-
tion with aminodefluorination. These reactions
illustrate the general character of the previously
revealed effect [4] of amino group as a substituent
ensuring the possibility for catalysis by copper(I) salt
of para- and orto-aminodechlorination in chlorine-
containing polyfluorinated aromatic substrate.
Mixtures of products were separated by column
chromatography on silica gel (40/100 m).
As substrates we used a mixture containing 67% of
compound I, 20% of III, and 10% of IV and com-
pound II containing 90% of the main substance.
These materials were obtained from the chemical pilot
factory at the Novosibirsk Institute of Organic
Chemistry (Siberian Division, Russian Academy of
Sciences). 30% Aqueous ammonia (d = 0.893 g/cm3)
was prepared by saturation of commercial aqueous
ammonia with gaseous ammonia.
Reactions of polyfluorinated aromatic substrates
with aqueous ammonia (Table 1). A mixture of com-
pound I or II, aqueous ammonia, and copper(I) halide
(if required) was kept for 48 h at a specified tempera-
ture in a rotating steel high-pressure reactor. The
mixture was cooled and extracted with diethyl ether,
the extract was dried over MgSO4, the solvent was
evaporated, and the residue was analyzed and sub-
jected to column chromatography.
Column chromatography of the residue (20 g)
obtained in the reaction of compound I with aqueous
ammonia at 80 C (run no. 1), eluent petroleum ether,
bp 40 70 C, gave (in the order of elution): 4.3 g of
a mixture consisting of compounds I (30%), III
(41%), IV (23%), V (3%), and VI (3%); 7.4 g of
2,4-dichloro-3,5,6-trifluoroaniline (V, 90% of the
main substance; yield 50%. Found, %: C 33.05, 33.22;
H 0.80, 0.89; Cl 33.00, 33.10; F 26.00, 26.35; N 6.60.
C6H2Cl2F3N. Calculated, %: C 33.30; H 0.92;
Cl 32.87; F 26.38; N 6.48) with admixtures of amine
VI and 3,4-dichloro-2,5,6-trifluoroaniline (XIX); 6 g
of a mixture of amines V (81%), VI (2.5%), and XIX
(16%); 1.25 g of a mixture of compounds V (43%),
VI ( 1%), XIX (21%), VII (21%), and VIII (7.7%).
Column chromatography of the residue (0.5 g)
obtained in run no. 2 (eluent methylene chloride) gave
(in the order of elution): 0.06 g of a mixture contain-
ing 49% of amine XIX and 8% of diamine VII;
0.32 g of a mixture containing 82% of 4,6-dichloro-
2,5-difluoro-1,3-phenylenediamine (VII) and 15% of
diamine VIII (mp 136 138 C. Found M+: 211.97207.
C6H4Cl2F2N2. Calculated M: 211.97196); 0.6 g of
a mixture containing 57% of diamine VII and 28% of
an unidentified product.
EXPERIMENTAL
The H and 19F NMR spectra were obtained on
1
Bruker WP-200 and Bruker AM-400 instruments from
20% solutions in acetone-d6 using, respectively, hexa-
methyldisiloxane and hexafluorobenzene as internal
references. The product mixtures were analyzed by
GLC on a Hewlett Packard HP-5890 chromatograph
equipped with a thermal conductivity detector; injector
temperature 200 C, detector temperature 240 C, oven
temperature programming from 40 to 240 C at a rate
of 10 deg/min;, capillary column 15000 0.53 mm,
3
stationary phase 1.5 10 mm HP-5 (methylphenyl-
polysiloxane containing 5% of methylphenyl groups);
carrier gas helium, 5 ml/min. The components were
quantitated using the internal normalization technique.
The products were identified by gas chromatog-
raphy mass spectrometry using a Hewlett Packard
G1081A instrument consisting of an HP-5890
Series II gas chromatograph and an HP-5971 mass-
selective detector; energy of ionizing electrons 70 eV;
oven temperature programming from 50 C (2 min) to
280 C at a rate of 10 deg/min (5 min at the final
temperature); injector temperature 280 C; ion source
temperature 173 C; HP-5 capillary column, 30 m
0.25 mm 0.25 m (5% of diphenyl- and 95% of
dimethylsiloxane); carrier gas helium, flow rate
1 ml/min. The data were acquired in the mass range
from 30 to 650 amu at 1.2 scan/s. The molecular
From the residue (1.6 g) obtained in run no. 4,
using benzene as eluent, we isolated (in the order
of elution): 0.20 g of a mixture containing 70% of
2-chloro-3,5,6-trifluoroaniline (XI) (Found M+:
180.98969. C6H3ClF3N. Calculated M: 180.99061);
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 7 2002

CATALYTIC AND NONCATALYTIC AMMONOLYSIS
1029
0.35 g of a mixture containing 70% of 2-chloro-3,5,6-
trifluoro-1,4-phenylenediamine (IX) [sublimation of
this mixture at 100 C (5 mm) gave a crystalline sub-
stance. Found M+: 196.00137. C6H4ClF3N2. Calcu-
lated M: 196.00151]; 0.53 g of a mixture of isomeric
diamines X (73%) and XII (14%); 0.35 g of a mixture
containing 84% of 2,3,5-trifluoro-1,4-phenylenedi-
amine (X) and 7% of its isomer XII (Found M+:
162.04192. C6H5F3N2. Calculated M: 162.04048).
The residue (1 g) obtained in run no. 5 was recrys-
tallized from petroleum ether (bp 40 70 C) to isolate
0.93 g of 2,6-dichloro-3,5-difluoroaniline (XIII) with
its isomer XIV as an impurity. Found M+: 196.96052.
C6H3Cl2F2N. Calculated M: 196.96106.
Column chromatography of the residue (2.3 g)
obtained in run no. 6 (with methylene chloride as
eluent) gave 1.9 g (yield 73%) of 2,6-dichloro-
5-fluoro-1,3-phenylenediamine (XV) containing 92%
of the main substance. mp 115.5 117 C. Found M+:
193.98235. C6H5Cl2FN2. Calculated M: 193.98138.
4. Selivanova, G.A., Pokrovskii, L.M., and Shtein-
garts, V.D., Russ. J. Org. Chem., 2001, vol. 37,
no. 3, pp. 404 409.
5. Vorozhtsov, N.N., Yakobson, G.G., and Rubi-
na, T.D., Dokl. Akad. Nauk SSSR, 1959, vol. 127,
no. 6, pp. 1225 1227.
6. Vorozhtsov, N.N., Platonov, V.E., and Yakob-
son, G.G., Izv. Akad. Nauk SSSR, Ser. Khim., 1963,
p. 1524; Yakobson, G.G., Platonov, V.E., and
Vorozhtsov, N.N., Jr., Zh. Obshch. Khim., 1965,
vol. 35, no. 7, pp. 1158 1161.
7. Emsley, J.W., Feeney, J., and Sutcliffe, L.H., High-
Resolution Nuclear Magnetic Resonance Spectros-
copy, Oxford: Pergamon, 1966, vol. 2. Translated
under the title Spektroskopiya YaMR vysokogo razre-
sheniya, Moscow: Mir, 1969, vol. 2, p. 220.
8. Fr. Patent no. 1408502, 1965; Chem. Abstr., 1966,
vol. 66, p. 17968g.
9. Ge Wen-Zheng, Wu Bao-Ming, and Huahg Wei-
Yuan, Acta Chim. Sinica, 1985, no. 4, pp. 349 355.
Column chromatography of the residue (0.8 g)
obtained in run no. 8 (using petroleum ether as eluent,
bp 40 70 C) gave (in the order of elution): 0.07 g of
3-chloro-5-fluoro-1,3-phenylenediamine (XVIII),
mp 86 87 C. Found M+: 160.02026. C6H5ClF2N2.
Calculated M: 160.02035; 0.3 g of diamine XVI,
mp 48 50 C (published data [16]: mp 48.5 49.5 C);
0.1 g of 2,6-difluoro-1,4-phenylenediamine (XVII),
mp 84 86 C (published data [17]: mp 91 92 C).
Found M +: 144.05001. C6H6F2N2. Calculated
M: 144.04990.
The authors are grateful to I.V. Zibareva (TsMTS-
STN, Novosibirsk Institute of Organic Chemistry,
Siberian Division, Russian Academy of Sciences) for
her assistance in the access to the STN database
(project no. 00-03-32721).
10. Finger, G.C., Reed, F.H., Burness, D.M., Fort, D.M.,
and Blongh, R.R., J. Am. Chem. Soc., 1951, vol. 73,
no. 1, pp. 145 149.
11. Sokolenko, V.I., L’vova, A.Ya., Tyurin, V.S.,
Platonov, V.E., and Yakobson, G.G., Zh. Org. Khim.,
1970, vol. 6, no. 12, pp. 2496 2498.
12. JPN Patent no. 30-87169, 1991; US Patent
no. 5399767, 1995; Chem. Abstr., 1996, vol. 117,
no. 233583s.
13. JPN Patent no. 60-193960, 1986; Chem. Abstr.,
1986, vol. 104, no. 168199m.
14. Fr. Patent no. 9501575, 1995; WO Patent
no. 9616926, 1996; US Patent no. 5856577, 1996;
Chem. Abstr., 1998, vol. 125, no. 114283z.
15. Yakobson, G.G., Kobrina, L.S., Rubina, T.D., and
Vorozhtsov, N.N., Zh. Obshch. Khim., 1963, vol. 33,
no. 7, pp. 1273 1277; Brooke, G.M., Burdon, J.,
Stacey, M., and Tatlow, J.C., J. Chem. Soc., 1960,
no. 4, pp. 1768 1771; Sintezy ftororganicheskikh so-
edinenii (Syntheses of Organofluorine Compounds),
Knunyants, I.L. and Yakobson, G.G., Eds., Moscow:
Khimiya, 1973, p. 192.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 7 2002