Phthalocyanines and related compounds: XLVIII. Stepwise nucleophilic substitution in tetrachlorophthalonitrile: Synthesis of polysubstituted phthalonitriles

Article abstract of DOI:10.1134/S1070363208090247

Chlorine-containing products of incomplete nucleophilic substitution in tetrachlorophthalonitrile were subjected to further reaction with nucleophiles. The nature of the nucleophiles and the order of their introduction into stepwise nucleophilic substitut

Full text of DOI:10.1134/S1070363208090247

ISSN 1070-3632, Russian Journal of General Chemistry, 2008, Vol. 78, No. 9, pp. 1794–1801. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © K.A. Volkov, V.M. Negrimovskii, G.V. Avramenko, E.A. Luk’yanets, 2008, published in Zhurnal Obshchei Khimii, 2008, Vol. 78,
No. 9, pp. 1564–1571.
Phthalocyanines and Related Compounds:
XLVIII.1 Stepwise Nucleophilic Substitution
in Tetrachlorophthalonitrile:
Synthesis of Polysubstituted Phthalonitriles
K. A. Volkova, V. M. Negrimovskiia, G. V. Avramenkob, and E. A. Luk’yanetsa
a Scientific Research Institute of Organic Intermediates and Dyes,
ul. Bol’shaya Sadovaya 1/4, Moscow, 123995 Russia
e-mail: rmeluk@niopik.ru
b Mendeleev Russian University of Chemical Technology, Moscow, Russia
Received May 15, 2008
Abstract―Chlorine-containing products of incomplete nucleophilic substitution in tetrachlorophthalonitrile
were subjected to further reaction with nucleophiles. The nature of the nucleophiles and the order of their
introduction into stepwise nucleophilic substitution in tetrachlorophthalonitrile were shown to be of principal
importance for selective synthesis on this basis of phthalonitrile derivatives with various substituents.
DOI: 10.1134/S1070363208090247
The overwhelming majority of presently known
substituted phthalocyanines is represented by various
tetra- and octa-substituted phthalocyanines generally
obtained by tetramerization of respective mono- and
disubstituted phthalonitriles [2]. The latter were
commonly synthesized by nucleophilic substitution of
halogen atoms or nitro groups in phthalonitrile
precursors, that include widely known commercially
synthesis of substituted phthalonitriles. It was
subjected to O- [21–23], C- and N-substitution in
reactions with the sterically hindered 2,6-di-tert-
butylphenol and 3,5-di-tert-butyl-4-hydroxyaniline,
respectively [24].
Unlike complete substitution products [7, 9–14, 19,
21], the products of partial substitution contain
substituents of two types: remaining halogen atom(s)
and other one [7, 13, 20–24], two [7, 13, 21, 22] or
three identical groups [18, 21] which are the fragments
of the nucleophile. Theoretically, acting on a
tetrahalophthalonitrile consecutively by different
nucleophiles one can obtain phthalonitriles even with
four different substituents. However, in practice, this
synthetic possibility was realized only partially. The
examples include consecutive disubstitution to prepare
3,6-difluoro-5-phenoxy-4-phenylsulfanylphthalonitrile
[16], trisubstitution to prepare 4,5-bis(2-chloro-
phenylsulfanyl)-3-(2,6-dimethylphenoxy)-6-fluorophtha-
lonitrile [18] and several tris(aryloxy)chloro(fluoro)
phthalonitriles with different aryloxy groups [22], and
tetrasubstitution to prepare bis(aryloxy)bis(alkoxy)
phthalonitriles [22].
available 3- and 4-nitrophthalonitriles
dichloro- [4], 3,5-dinitro- [5],
nitrophthalonitriles [6] and some others.
[3], 4,5-
4-bromo-5-
Phthalocyanines containing in their macrocycle
sixteen substituents are much less known, because the
development of studies in this direction is hindered by
the limited accessibility of respective tetrasubstituted
phthalonitriles. The latter are represented mainly by
tetrafluoro- and tetrachlorophthalonitriles and by some
products of halogen substitution in the tetrahalides.
First of all, this relates to tetrafluorophthalonitrile that
was introduced into nucleophilic substitution with O-
(alcohols, phenols) [7–16], S- (thiols) [7, 15–18], N-
(amines) [7, 13, 19], C- (malonic ester) [20], and P-
nucleophiles (diethylphosphine) [7].
Tetrachloro-
phthalonitrile was rarely used as a precursor for the
The last example is represented by one publication
only, where halogen-free tetrasubstituted phthalo-
1
For communication XLVII, see [1].
1794

PHTHALOCYANINES AND RELATED COMPOUNDS: XLVIII.
1795
nitriles with more than one sort of substituents were
obtained by substitution in tetrafluorophthalonitrile.
Several such phthalonitriles were obtained by other
methods: 4,5-Bis(phenylsulfanyl)-3,6-dialkoxyphthalo-
nitriles were prepared from 2,3-dichloroо-5,6-dicyano-
1,4-benzoquinone by its reduction followed by alkyla-
tion [25], and dialkyldialkoxyphthalonitriles were
prepared by the Rosemund–Brown reaction from
corresponding substituted o-dibromobenzenes [26–30].
pounds from tetrachlorophthalonitrile under the action
of the first nucleophile. Now we involved some of
them, namely, 3,6-dichloro-4,5-bis(pyridin-3-yloxy)-
(I) [32], 3,6-dichloro-4,5-bis(phenylsulfanyl)- (II)
[31], 3,5,6-trichloro-4-phenylamino- (III), and 4,5-bis-
(alkylamino)-3,6-dichlorophthalonitriles (IV) [1] in
further reactions with nucleophiles.
Initially we attempted to replace the chlorine atoms
in phthalonitrile I by sulfanyl groups to obtain new
symmetrical dinitriles with two different substituents
(aryloxy and sulfanyl), but the reactions with two or
four mol of a thiol (thiophenol, butanethiol) at room
temperature in the presence of an equimolar amount of
triethylamine as a base afforded, instead of the
expected product of substitution of two chlorine
atoms, a mixture of three other phthalonitriles (Scheme 1,
Tables 1, 2).
For enhancing the synthetic potential of
tetrachlorophthalonitrile and proceeding with our
studies on the regularities of chlorine substitution in
this compound under the action of various
nucleophiles [1, 31, 32], we involved tetrachloro-
phthalonitrile into consequtive reactions with two
different nucleophiles.
In previous works we determined conditions for the
synthesis of a series of chlorine-containing com-
Scheme 1.
Cl
SR
SR
RS
CN
CN
PyO
RS
CN
CN
RS
RS
CN
CN
+
+
RS
Cl
SR
SR
SR
PyO
PyO
CN
CN
RSH
VII
V
VI
Et3N, DMF, 20оС
SR
Cl
PyO
PyO
CN
CN
I
SR
R = Ph (Va–VIIa), Bu (Vb–VIIb). Py = pyridine-3-yl.
The products included tetrasulfanyl-substituted
dinitriles VII indentical to those we obtained and
characterized earlier [31]. Two other products were
trisulfanyl-substituted phthalonitriles V and VI; one of
them, compound Va, was also prepared by us earlier
[31]. It should be noted that all the final products
contain more sulfanyl groups (three or four) than might
be expected at the 1:2 stoichiometric reagent ratio we
used. This result can be explained by initial
substitution of the pyridyloxy group in dinitrile I. The
intermediate dinitrile formed by sulfanyl substitution
for the pyridyloxy group should be more susceptible to
further nucleophilic attack than parent dinitrile I in
view of the fact that the sulfanyl group is a weaker π-
donor compared to the aryloxy group; as a result, tri-
and tetrasulfanyl-substituted dinitriles (V, VI, and VII,
respectively) are formed.
Such a preferable substitution of the pyridyloxy
group in the 4 position compared with the chlorine
atom in the 3 position is consistent with the data of
Wang et al. [22] who described the substitution of the
aryloxy group in preference to fluorine in 3,4,5-tris-
(aryloxy)-6-fluorophthalonitrile under the action of
alkoxide ion (Scheme 2).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 9 2008

1796
VOLKOV et al.
Scheme 2.
F
C8H
O
F
17O
O
CN
CN
O
O
CN
CN
CN
CN
C8H17
octan-1-ol
K2CO3, 85оС, 72 h
octan-1-ol
K2CO3, DMF,
100оС, 30 h
C8H17O
HO
O
O
O
O
Under more rigid conditions (reagent ratio 1:4,
temperature 70°C ), both the pyridyloxy groups and
chlorine atoms in phthalonitrile I can be replaced by
sulfanyl groups to prepare tetrasulfanyl-substituted
phthalonitriles VII in high yields (70–75%).
quantitative yield [31]. We expected to obtain
symmetrical tetrasubstituted phthalonitrile VIII with
two different sulfanyl groups by reacting dinitrile II
with another thiol Actually, the reaction of
phthalonitrile II with decanethiol in a 1:2 ratio at room
temperature in the presence of triethylamine afforded
expected compound VIII (Scheme 3, Tables 2 and 3)
but in a low yield (17%). Along with this compound,
we isolated from the resulting reaction mixture four
other phthalonitriles. Two of them, IX and X, like
dinitriles V and VI in the preceding experiment, are
formed by substitution of three of the four existing
groups and were isolated in a total yield of 15%.
Therewith, one or both phenylsulfanyl groups of the
parent compound were substituted, and this is the first
example for phthalonitriles, when sulfanyl is a leaving
group.
As a result, the aryloxy groups introduced in the
first step in the 4 and 5 positions of tetrachloro-
phthalonitrile to form 4,5-bis(aryloxy)-3,6-dichloro-
phthalonitriles were substituted in the second step by a
stronger nucleophile (thiolate anion). Hence,
consecutive action on tetrachlorophthalonitrile of O-
and then S-nucleophiles holds little promise in terms
of selective synthesis of polysubstituted phthalo-
nitriles.
Dinitrile II is formed at a 1:2 tetrachlorophthalo-
nitrile:thiophenol under mild conditions with nearly
Two other additional products, phthalonitriles XI
and VIIa, isolated with yields of 5.5 and 12.3%,
respectively, contain more phenylsulfanyl groups than
parent phthalonitrile II (three and four, respectively).
This can be explained by the fact that the phenyl-
thiolate anion generated in the course of formation of
compounds IX and X compares in nucleophilicity with
the decyl analog and takes part in further nucleophilic
attack; as a result, more diverse substitution products
are formed.
Table 1. Reaction of thiols with phthalonitrile I
Yield, %a
Dinitrile I : RSH
RSH
T, °C
molar ratio
V
VI
VII
Ph (a)
1:2
1:4
20
20
70
20
20
70
2.0
14.1 13.7
26.7 24.6
1.3 74.7
31.6 16.0
31.5 16.9
0.6 72.2
17.7
1.7
It becomes obvious that using S-nucleophiles in the
second step of chlorine substitution in tetrachloro–
phthalonitrile after using either O- or another S-
nucleophile in the first step does not lead to selective
synthesis of polysubstituted phthalonitriles.
Bu (b)
1:2
1:4
2.3
12.3
1.5
a
In a further experiment we assumed that the 4- and
5-phenylsulfanyl groups in dinitrile II would resist to
Yield after column chromatography (sorbent silica gel, eluent
benzene).
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PHTHALOCYANINES AND RELATED COMPOUNDS: XLVIII.
Table 2. Melting points, elemental analyses, and IR and mass spectra of the obtained phthalonitriles
Elemental analysis data
1797
Comp. Yield,
mp,c
νCN
,
Found, %
Cl
Calculated, %
M+
b
no.а
%
°С
cm–1
Formula
C
H
N
S
C
H
Cl
N
S
d
12.3
56.16 6.37 8.21 6.43 22.42 С20H27ClN2S3 56.25 6.37
8.30
6.56 22.52 2233 426
7.70 17.63 2232 545
8.65 19.80 2230 485
4.07 18.61 2236 688
4.12 14.15 2241 678
3.72 17.02 2239 752
4.48 20.52 2238 624
5.30 12.13 2242 530
Vb
56.33 6.43 8.37 6.61 22.62
26.7 122–123 68.12 3.47
–
–
–
7.62 17.55 С31H19N3OS3 68.23 3.51
–
–
VIa
VIb
VIII
IX
68.34 3.55
7.78 17.71
d
31.6
17.0
6.3
61.74 6.36
61.90 6.44
8.60 19.72 С25H31N3OS3 61.82 6.43
8.75 19.87
d
d
d
69.62 7.53
69.79 7.58
3.88 18.47 C40H52N2S4
3.94 18.56
69.72 7.61
–
67.04 9.37 5.09 4.10 14.07 C38H63ClN2S3 67.16 9.34
67.20 9.40 5.18 4.26 14.27
5.22
–
8.8
69.98 9.04
70.21 9.11
–
–
–
3.62 16.93 С44H68N2S4
70.16 9.10
X
3.79 17.14
5.5
99–102 69.06 5.75
69.25 5.78
4.40 20.41 C36H36N2S4
4.62 20.58
69.19 5.81
–
XI
22.3 163–165 72.62 3.85
72.75 3.88
5.18 11.97 C30H18N4O2S2 72.70 3.81
5.35 12.22
–
XII
6.1
2.4
2240 471
2237 545
XIII
XIV
XVа
61.7 212–214 60.50 2.74 17.76 10.48 7.96 С20H11Cl2N3S 60.62 2.80 17.89 10.60
8.09 2235 395
60.65 2.80 17.97 10.62 8.18
63.3
85–87
57.33 3.97 18.72 11.09 8.43 С18H15Cl2N3S 57.45 4.03 18.84 11.17
8.52 2236 375
XVb
57.52 4.06 18.93 11.24 8.65
68.9 187–189 66.27 3.40 7.43 8.79 13.53 С26H16ClN3S2 66.44 3.43
7.54
8.24
–
8.94 13.64 2232 469
9.77 14.91 2232 429
7.73 17.69 2233 543
8.69 19.88 2236 483
10.89 12.46 2230 514
XVIа
XVIb
XVIIа
XVIIb
XVIIIa
66.41 3.47 7.60 8.88 13.75
d
64.6
61.33 5.61 8.11 9.65 14.83 С22H24ClN3S2 61.45 5.63
61.54 5.66 8.30 9.87 15.02
68.3 163–165 70.57 3.81
–
–
–
7.78 17.54 С32H21N3S3
70.69 3.89
64.56 6.88
70.74 3.87
7.86 17.76
d
65.7
64.45 6.81
64.62 6.85
8.54 19.73 С26H33N3S3
–
8.77 19.91
74.2 202–205 65.26 5.00
65.42 5.06
10.76 12.31 C28H26N4O2S2 65.35 5.09
10.98 12.54
–
75.0 211–213 70.44 5.94
70.62 5.99
–
10.88 12.37 C30H30N4S2
11.07 12.60
70.55 5.92
–
10.97 12.55 2228 510
XVIIIb
XIX
72.4 270–272 55.52 1.61 23.37 13.81
55.73 1.64 23.55 13.95
–
C14H5Cl2N3O 55.66 1.67 23.47 13.91
–
2231 301
a
Compounds Va, VIIa and VIIb have been characterized in [31]. b Yields of products after separation of mixtures by preparative column
c
chromatography [sorbent silica gel; eluents: benzene (V–XIV), toluene (XV–XVII), or ethyl acetate (XVIII, XIX)]. From
ethanol. d Yellow oil crystallizing on storage.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 9 2008

1798
VOLKOV et al.
Scheme 3.
Cl
Cl
SDec
Cl
PhS
PhS
CN
CN
PhS
PhS
CN DecS
+
CN
CN
2 DecSH
Et3N,
DMF, 20оС
CN DecS
SDec
SDec
IX
II
VIII
SDec
SDec
PhS
CN PhS
+
CN
CN
+
+ VIIа
DecS
CN PhS
SDec
SPh
XI
X
Dec = n-C10H21.
substitution by a weaker nucleophile (pyridinolate
anion). As would be expected [32], the reaction of
dinitrile II with lithium pyridin-3-olate in a 1:2 ratio
proceeds at an elevated temperature, but even within 6
h at 150°C only half of the substrate is involved in
substitution. The expected symmetrical 4,5-bis-
(phenylsulfanyl)-3,6-bis(pyridin-3-yloxy)phthalonitrile
(XII) was obtained (accounting for the conversion of
the parent dinitrile) in a fairly good yield of 43% and
could be easily isolated from the reaction mixture by
chromatography. We also isolated trace amounts of
two others phthalonitriles (Scheme 4, Tables 1, 2). One
of them, compound XIII, results from phenoxy
substitution for one chlorine atom only. The formation
of the other product, tris(phenylsulfanyl)-substituted
dinitrile XIV, provides evidence showing that the
pyridin-3-olate still attacks the 4 and 5 positions to
substitute the phenylsulfanyl groups. Such substitution
is also confirmed by the appearance of a typical
thiophenol odor upon acidification of the reaction
mixture.
This, the of an S-nucleophile in the first step and of
an O-nucleophile in the second step can lead to selec-
tive formation of symmetrical aryloxy(sulfanyl)-substi-
tuted phthalonitriles from tetrachlorophthalonitrile.
Table 3. 13C NMR spectra of certain obtained phthalonitriles (DMSO-d6)
Product
δC, ppm
147.9 (CAr–S), 137.8 (CAr–S'), 134.5 (CAr'–S), 129.8 (CAr'–H), 129.6 (CAr'–H), 127.7 (CAr'–H), 124.7 (CAr–CN), 114.8
(CN), 37.0 (CH2–S'), 32.0, 29.8, 29.6, 29.4, 29.2, 28.7, 28.5, 22.8 (CH2), 14.7 (CH3)
VIII
154.7 (CAr–O), 153.6 (CAr'–O), 145.6 (CAr'''–H), 142.2 (CAr''–H), 138.6 (CAr–S), 134.0 (CAr'–H), 130.2 (CAr'–S), 129.7
(CAr'–H), 128.5 (CAr''–H), 125.2 (CAr'–H), 123.5 (CAr''–H), 113.2 (CAr–CN), 112.7 (CN)
XII
155.9 (CAr–N), 148.2 (CAr–S), 135.7 (CAr'–S), 129.5 (CAr'–H), 127.3 (CAr'–H), 125.7 (CAr'–H), 114.1 (CAr–CN), 112.4
(CN), 67.6 (CH2–O), 51.0 (CH2–N)
XVIIIа
ХVIIIb
XIX
156.8 (CAr–N), 148.3 (CAr–S), 135.7 (CAr'–S), 129.3 (CAr'–H), 127.2 (CAr'–H), 125.9 (CAr'–H), 114.0 (CAr–CN), 112.1 (CN)
52.4 (CH2–N), 25.7(CH2), 23.5 (CH2)
146.4 (CAr'–O), 141.3 (CAr–O), 136.7 (CAr–N), 133.9 (CAr–Cl), 132.1 (CAr–Cl), 127.6 (CAr'–N), 125.6 (CAr'–H), 123.9
(CAr'–H), 116.0 (CAr'–H), 115.3 (CAr'–H), 113. 8 (CAr–CN), 111.9 (CAr–CN), 109.7 (CN), 108.0 (CN)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 9 2008

PHTHALOCYANINES AND RELATED COMPOUNDS: XLVIII.
1799
Scheme 4.
Cl
OPy
OPy
OPy
PhS
PhS
CN
CN
PhS
PhS
CN PhS
+
CN PhS
+
CN
CN
2 PyOLi
DMF,
150оС, 6 h
CN PhS
CN PhS
Cl
OPy
SPh
Cl
II
XII
XIII
XIV
Py = pyridine-3-yl.
Amino-substituted phthalonitriles obtained from
tetrachlorophthalonitrile by substitution in the first step
[1] proved to be ever more attractive substrates for the
synthesis of variously substituted phthalonitriles. The
model 3,4,6-trichlorо-5-(phenylamino)phthalonitrile (III)
did not enter into further nucleophilic substitution with
aryloxides even at an elevated temperature (100°C) but
reacted with thiols already at room temperature. In this
case, by contrast with the three preceding ones, we
observed exclusive substitution of one (XV), two
(XVI), or three (XVII) chlorine atoms
by
phenylsulfanyl groups, depending on the
stoichiometric ratio of the substarte and nucleophile
(Scheme 5, Table 2).
Scheme 5.
Cl
RS
CN
CN
n = 1
PhHN
Cl
XV
SR
Cl
RS
CN
CN
Cl
CN
CN
n = 2
n RSH
Et3N, DMF, 20оС
PhHN
PhHN
Cl
XVI
Cl
III
SR
RS
CN
CN
n = 3
PhHN
SR
XVII
R = Ph (XVa–XVIIa), Bu (XVb–XVIIb).
The same reaction but at an elevated temperature
(80°C) proceeds smoothly with diaminodichloro-
substituted phthalonitriles IV and leads to symmetrical
4,5-diamino-3,6-disulfanyl-substituted phthalonitriles
XVIII in ~75% yield (Scheme 6, Tables 2 and 3).
tetrachlorophthalonitrile is suitable not only for
synthesis of aminochloro-substituted-phthalonitriles
[1], but also for further synthesis from them of amino
(sulfanyl)- substituted phthalonitriles.
We also attempted to prepare polyfunctional phthalo-
nitriles directly from tetrachlorophthalonitriles in one
The last two experiments show that the use of
amines in the first step of nucleophilic substitution in
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 9 2008

1800
VOLKOV et al.
Scheme 6.
Cl
Cl
S
X
X
X
X
CN
CN
CN
CN
N
N
N
N
2 PhSH
Et3N, DMF, 80оС
S
IV
XVIII
X = O (IVa, XVIIIa), CH2 (IVb, XVIIIb).
Scheme 7.
ONa
Cl
Cl
O
CN
CN
Cl
Cl
CN
CN
NH2
DMF, 80оС, 5 h
N
H
Cl
XIX
Cl
step, using a bifunctional nucleophile (Scheme 7,
Tables 2, 3). The use of such nucleophile as о-amino-
Bruker AM-300 instrument from solutions in DMSO-
d6, internal reference TMS. The composition of the
reaction mixtures and the individuality of the obtained
substances were monitored by TLC on Silufol UV-254
plates.
phenoxide anion in
a
1:1 molar ratio with
tetrachlorophthalonitrile at 80°C for 5 h allows to
synthesize in one step in high yield (~72%)
tetrasubstituted
phthalonitrile
ХIХ
containing
substituents of three different types.
Reaction of phthalonitriles I–IV with thiols
(general procedure). To a solution of 5.0 mmol of
phthalonitrile I–IV and corresponding amount of a
thiol (10.0 and 20.0 mmol with I, 10.0 mmol with II;
5.0, 10.0, and 15.0 mmol with III; and 10.0 mmol with
IV) in 20 ml of DMF we added dropwise at 20°C
under stirring an equimolar amount of triethylamine.
The reaction mixture was kept at room temperature (I–
III) or at 70 (I) or 80°C (IV) for 45 min and then
poured to a saturated solution of NaCl and extracted
with ethyl acetate. The organic layer was washed with
two portions of water, dried over anhydrous Na2SO4,
and the solvent was removed under a vacuum. The
residue was subjected to chromatography on silica gel
(eluent benzene, toluene, and ethyl acetate for the
reactions with I and II, III, and IV, respectively). The
resulting crystalline substances were recrystallized
from ethanol.
Thus, by consecutive action of different
nucleophiles on tetrachlorophthalonitrile we syn-
thesized a wide series of tetrasubstituted phthalonitriles
and showed that the nature and sequence of
introducing nucleophiles into such stepwise
nucleophilic substitution are of key importance for
selective synthesis of phthalonitriles with substituents
of different types.
EXPERIMENTAL
Elemental analyses were carried out on a Hewlett-
Packard HP 185B C,H,N-analyzer. The IR spectra
were taken from KBr pellets on a FSM 1201 FT–IR
spectrometer. The mass spectra were measured on an
MKh-1321 instrument (ionizing electron energy
70 eV). The 13C NMR spectra were obtained on a
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 9 2008

PHTHALOCYANINES AND RELATED COMPOUNDS: XLVIII.
1801
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Reaction of phthalonitrile II with lithium
pyridin-3-olate. A solution of 0.50 g of phthalonitrile
II and 0.245 g of lithium pyridine-3-olate in 20 ml of
DMF was heated at 150°C for 6 h, cooled to room
temperature, poured to a saturated solution of NaCl,
and extracted with ethyl acetate. The organic layer was
then washed with two portions of water, dried over
anhydrous Na2SO4, the solvent was evaporated under a
vacuum, and the residue was subjected to chroma-
tography on silica gel (eluent benzene) to isolate 0.28 g
of parent dinitrile II, 0.22 g (22.3 or 43.1% with
account for conversion) of dinitrile XII, 0.035 g
(6.1%) of dinitrile XIII, and 0.016 g (2.4%) of dinitrile
XIV. Dinitrile XII was recrystallized from ethanol.
Reaction of tetrachlorophthalonitrile with ortho-
aminophenol. A solution of 1.33 g of tetrachloro-
phthalonitrile and 0.65 g of ortho-aminophenol sodium
salt in 20 ml of DMF was heated to 80°C and kept at
that temperature for 5 h. Then the reaction mixture was
cooled to room temperature, and 120 ml of water was
added to it. The precipitate formed was filtered off,
washed on the filter with hot water, dried, dissolved in
ethyl acetate, and subjected to chromatography on
silica gel (eluent ethyl acetate). Recrystallization from
ethanol gave 1.09 g (72.4%) of compound XIX.
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ACKNOWLEDGMENTS
This work was financially supported by the
Moscow Government.
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