Phthalocyanines and related compounds: XXXIX. Synthesis of derivatives of some substituted 1-phenylnaphthalene-2,3-dicarboxylic acids

Article abstract of DOI:10.1007/s11176-005-0320-0

Derivatives (dinitriles, anhydrides, imides, N-phenylimides) of substituted 1-phenylnaphthalene-2,3-dicarboxylic and 1-phenylphenanthrene-2,3-dicarboxylic acids were prepared by the reactions of 2-bromomethylbenzophenones with various dienophiles. Starting from these derivatives, gallium complexes of substituted tetra-1-phenyl-2,3-naphthalocyanines and tetra(1-phenyl-2,3-phenanthro) porphyrazine were synthesized. 2005 Pleiades Publishing, Inc.

Full text of DOI:10.1007/s11176-005-0320-0

Russian Journal of General Chemistry, Vol. 75, No. 5, 2005, pp. 795 799. Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 5, 2005,
pp. 841 846.
Original Russian Text Copyright
2005 by Donyagina, Luk’’yanets.
Phthalocyanines and Related Compounds:
XXXIX.1 Synthesis of Derivatives
of Some Substituted 1-Phenylnaphthalene-2,3-dicarboxylic Acids
V. F. Donyagina and E. A. Luk’’yanets
Institute of Organic Intermediates and Dyes, Moscow, Russia
Received July 15, 2003
Abstract Derivatives (dinitriles, anhydrides, imides, N-phenylimides) of substituted 1-phenylnaphthalene-
2,3-dicarboxylic and 1-phenylphenanthrene-2,3-dicarboxylic acids were prepared by the reactions of 2-bro-
momethylbenzophenones with various dienophiles. Starting from these derivatives, gallium complexes of
substituted tetra-1-phenyl-2,3-naphthalocyanines and tetra(1-phenyl-2,3-phenanthro)porphyrazine were
synthesized.
Annelated analogs of phthalocyanines, primarily
isomeric 1,2- and 2,3-naphthalocyanines, are being
extensively studied as compounds exhibiting strong
absorption in the near IR range [2]. Metal complexes
of tetra-1-phenyl-2,3-naphthalocyanines, showing
increased solubility in organic solvents owing to the
steric effect of the phenyl groups, are less studied.
However, these compounds have already found appli-
cations, in particular, in photoconducting materials for
information recording and in optical recording devices
using semiconductor lasers [3].
ducts undergo dehydration catalyzed by the eliminated
HBr and transform into 1-phenyl-2,3-disubstituted
naphthalenes.
In this study we applied this method to preparing
a series of 1-phenyl-substituted naphthalene-2,3-dicar-
boxylic acids and their annelated analogs, namely,
dinitrile I, anhydride II, and imide III of 1-phenyl-
naphthalene-2,3-dicarboxylic acid; dinitrile IV, anhy-
dride V, and imide VI of 7-tert-butyl-1-(p-tert-butyl-
phenyl)naphthalene-2,3-dicarboxylic acid; dinitrile
VII, anhydride VIII, imide IX, and N-phenylimide X
of 1-(p-tert-butylphenyl)naphthalene-2,3-dicarboxylic
acid; anhydride XI and imide XII of 7-tert-butyl-1-
phenylnaphthalene-2,3-dicarboxylic acid; anhydride
XIII and imide XIV of 1-(p-biphenylyl)naphthalene-
2,3-dicarboxylic acid XIV; anhydride XV and imide
XVI of 1-phenylphenanthrene-2,3-dicarboxylic acid.
These compounds are of interest, in particular, as
intermediates for preparing the corresponding substi-
tuted 2,3-naphthalocyanines.
These compounds were prepared from anhydrides
of substituted 1-phenylnaphthalene-2,3-dicarboxylic
acids, which, in turn, were synthesized by intermolec-
ular condensation of phenylpropiolic acids in acetic
anhydride, and also from the corresponding imides
and dinitriles [2, 4, 5]. This route, however, allowed
only preparation of compounds with the same sub-
stituents in the naphthalene core and phenyl group.
Among other known routes to 1-phenylnaphthalene-
2,3-dicarboxylic acid derivatives based on the Diels
Alder reaction of the intermediate 1-phenylisobenzo-
furans [6 12], the most attractive are the reactions
of 2-(bromomethyl)benzophenones with esters and
N-phenylimide of maleic acid, because of the avail-
ability of the starting chemicals and simple implemen-
tation [6]. It is suggested that 2-(bromomethyl)benzo-
phenones A, being unstable, readily cyclize under the
conditions of the Diels Alder reaction to form the
corresponding 1-phenylisobenzofurans B, which form
with dienophiles adducts C. When heated, these ad-
The starting 2-methylbenzophenones, 2-methylben-
zophenone XVII, 4,4 -di(tert-butyl)-2-methylbenzo-
phenone XVIII, 4 -tert-butyl-2-methylbenzophenone
XIX, 5-tert-butyl-2-methylbenzophenone XX, 4 -(p-
biphenylyl)-2-methylbenzophenone XXI, and 1-ben-
zoyl-2-methylnaphthalene XXII, were prepared by the
Friedel Crafts condensation in the presence of anhy-
drous aluminum chloride in benzene (for XVII) or in
CS2 (for XVIII XXII) in 62 83% yields. Compounds
XVII, XXI, and XXII were prepared by published
procedures [13 15]. Methylbenzophenones XVIII and
XX were prepared by the reactions of 4-tert-butyltolu-
ene with 4-tert-butylbenzoyl chloride and benzoyl
1
For communication XXXVIII, see [1].
1070-3632/05/7505-0795 2005 Pleiades Publishing, Inc.

796
DONYAGINA, LUK’’YANETS
chloride, respectively, and methylbenzophenone XIX,
by the reaction of tert-butylbenzene with 2-toluyl
chloride; the products were purified by vacuum distil-
lation.
C(CH3)3
(CH3)3C
(CH3)3C
CO
CO
CO
CH3
CH3
CH3
XVII
XVIII
XIX
COC6H5
CH3
C(CH3)3
CH3
CO
CO
XX
CH3
XXI
XXII
Methylbenzophenones XVII XXII were converted
into the corresponding bromomethyl derivatives A,
which were cyclized into isobenzofurans B, converted
into Diels Alder adducts C, and dehydrated to obtain
the final products. The whole sequence of reactions
was performed as one-pot synthesis without isolation
of the intermediates. Methylbenzophenones XVII XX
were brominated with bromine and N-bromosuccin-
imide in CCl4. To avoid bromination of the benzene
ring, compound XXI was converted to benzyl bromide
A with N-bromosuccinimide. Successful bromination
of 1-benzoyl-2-methylnaphthalene XXII was possible
only with bromine.
CH2Br
CH3
CO
Br2 or bromosuccinimide
R1
R3
R1
R3
CO
CCl4, h
R2
R2
XVII XXII
A
X
X
X
X
H+
H2O
O
O
CHX=CHX
R1
R1
R1
HBr
R2
R2
R2
R3
R3
R3
I XVI
B
C
R1 = R2 = R3 = H, X = CN (I), X, X = COOCO (II), CONHCO (III); R1 = R3 = t-Bu, R2 = H, X = CN (IV), X, X =
COOCO (V), CONHCO (VI); R1 = R2 = H, R3 = t-Bu, X = CN (VII), X, X = COOCO (VIII), CONHCO (IX),
CONPhCO (X); R2 = R3 = H, R1 = t-Bu, X, X = COOCO (XI), CONHCO (XII); R1 = R2 = H, R3 = Ph, X, X = COOCO
(XIII), CONHCO (XIV); R1, R2 = CH=CHCH=CH, R3 = H, X, X = COOCO (XV), CONHCO (XVI).
As dienophiles we used fumarodinitrile, maleic
anhydride, maleimide, and N-phenylmaleimide. With
fumarodinitrile, the reaction was complicated by par-
tial hydrolysis of the dinitriles formed; along with
these products, we isolated the corresponding imides
in up to 8% yields. The final products I XVI are
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 5 2005

PHTHALOCYANINES AND RELATED COMPOUNDS: XXXIX.
Yields, constants, elemental analyses, and mass spectra of I XVI
797
Found, %
Calculated, %
M
mp,
C
Refer-
ences
Formula
(solvent for crystallization)
m/z
C
H
N
C
H
N
[M+]
I
II
III
IV
V
53 213 214 (benzene heptane)
61 246 247 (benzene)
66 254 255 (chloroform)
49 215 216 (heptane)
60 190 191 (heptane)
64 295 296 (benzene)
[5]
[2, 4]
[2, 3]
[2]
[2]
[2]
C26H26N2
366 366.51
VI
VII 46 232 233 (benzene heptane) 85.03 5.89 8.87 C22H18N2 85.13 5.84 9.02 310 310.39
VIII 64 260 262 (benzene) 79.82 5.21 C22H18O3 79.98 5.49
IX
X
XI
97 291 293 (benzene)
65 199 201 (chloroform)
72 200 201 (benzene)
79.91 5.67 3.78 C22H19NO2 80.22 5.81 4.25
82.67 5.47 3.19 C28H23NO2 82.94 5.72 3.45
79.52 5.27
79.83 5.73 3.84 C22H19NO2 80.22 5.81 4.25
81.84 3.90 C24H14O3 82.27 4.03
82.13 4.10 3.70 C24H15NO2 82.50 4.33 4.01 349 349.38
81.16 3.34 C22H12O3 81.47 3.73
81.60 3.71 3.98 C22H13NO2 81.72 4.05 4.33 323 323.34
C22H18O3 79.98 5.49
XII 94 255 257 (benzene)
XIII 71 293 294 (heptane)
XIV 78 304 305 (benzene)
XV 63 245 246 (benzene)
XVI 96 304 306 (benzene)
crystalline substances. After recrystallization from
appropriate solvent, we obtained their analytically
pure samples in 46 78% yield. The physical proper-
ties, yields, mass spectra, and elemental analyses of
I XVI are listed in the table.
R1
R2
R3
R3
By the reactions of these anhydrides, imides, and
dinitriles with GaBr3 in a urea melt or in refluxing
sulfolane, we prepared the gallium complexes of tetra-
1-phenyl-2,3-naphthalocyanines (XXIII XXVII) and
tetra-1-phenyl-2,3-phenanthroporphyrazine (XXVIII);
with the anhydrides and imides, the yields were high-
er. All the complexes are well soluble in organic sol-
vents, which allowed their isolation in the analytically
pure form by column chromatography on alumina,
with benzene or chloroform as eluent. The complexes
prepared from anhydrides and imides were mixtures
of isomers differing in the relative position of phenyl
groups. For complex XXIII prepared from dinitrile I
by refluxing in sulfolane, the isomers were not de-
tected chromatographically, which may be due to dif-
ferent orientation of the phthalogen molecules under
the conditions of the template synthesis.
R2
N
N
N
Ga
N
R1
Br
N
N
R1
N
R2
N
R3
R3
R2
R1
XXII XXVIII
R1 = R2 = R3 = H (XXIII); R1 = R3 = t-Bu, R2 = H
(XXIV); R1 = R2 = H, R3 = t-Bu (XXV); R1 = t-Bu, R2 =
R3 = H (XXVI); R1 = R2 = H, R3 = Ph (XXVII); R1,
R2 = CH=CHCH=CH, R3 = H (XXVIII).
Solutions of XXIII XXVII in chloroform have an
absorption spectrum typical of 2,3-naphthalocyanines.
The spectra contain a strong long-wave band with a
maximum at 820 826 nm (Q band), two well-resolved
vibronic satellites at 700 780 nm, a weak broad band
in the form of a shoulder at 406 435 nm, and a strong
band in the UV range at 338 344 nm, related to the
Soret band in porphyrazines. All the bands show a
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 5 2005

798
DONYAGINA, LUK’’YANETS
10 15-nm bathochromic shifty relative to the corre-
sponding bands in the spectrum of gallium tetra-5-
tert-butyl-2,3-naphthalocyanine [16]. The low range in
which the band positions vary in the series XXIII
XXVII indicates that the tert-butyl and phenyl groups
in the positions remote from the macroring affect the
chromophoric system insignificantly. On the other
hand, these peripheral groups considerably increase
the solubility of the complexes in organic solvents.
4 -(p-Biphenylyl)-1-methylbenzophenone XXI:
yield 77%, mp 103 104 C (from hexane) [14].
1-Benzoyl-2-methylnaphthalene XXII: yield 82%,
mp 74 75 C (from hexane) [15].
1-Phenyl-2,3-dicyanonaphthalene I. To a reflux-
ing solution of 4.3 g of 2-methylbenzophenone XVII
in 20 ml of CCl4, illuminated with a 300-W lamp, we
added dropwise a solution of 3.7 g of Br2 in 20 ml of
CCl4. After the reaction completion, the lamp was
switched off, and a solution of 1.7 g of fumarodinitrile
in 10 ml of CHCl3 was added. The mixture was re-
fluxed for 20 h, after which imide III was filtered off;
yield 0.5 g (8%), mp 238 C. The solvents were re-
moved in a vacuum, and the residue was recrystallized
from benzene hexane. Yield of the dinitrile 2.6 g
(53%), mp 213 214 C [5].
In the spectrum of XXVIII, the long-wave bands
are somewhat shifted hypsochromically relative to the
corresponding bands in the spectrum of gallium tetra-
6-tert-butyl-2,3-naphthalocyanine, which is consistent
with the previously published data for the related
porphyrin systems [17, 18].
EXPERIMENTAL
Dinitriles IV and VII were prepared similarly from
benzophenones XVIII and XIX. Anhydrides II, V,
VIII, XI, and XV, imides III, VI, and XIV, and
N-phenylimide X were also prepared similarly starting
from approprite maleic acid derivative (anhydride,
The electronic absorption spectra of solutions of
gallium complexes XXIII XXVIII were recorded on
a Hewlett Packard HP-8453 spectrophotometer in
plane-parallel cells, layer thickness 1 cm. The mass
spectra of XXIII and XXIV were taken on a Finnigan- imide, N-phenylimide).
LCQ mass spectrometer, and those of the other com-
pounds, on an LKB-2091 mass spectrometer.
1-( p-Biphenylyl)naphthalene-2,3-dicarboxylic
anhydride XIII. A mixture of 2.7 g of methylbenzo-
phenone XXI and 1.6 g of N-bromosuccinimide in
20 ml of CCl4 was refluxed for 30 min under illumi-
nation with a 300-W lamp, after which a solution
of 1 g of maleic anhydride in 30 ml of CHCl3 was
added. The mixture was refluxed for 20 h and cooled,
the solvents were removed in a vacuum, and the
residue was recrystallized from heptane; yield 2.48 g
2-Methylbenzophenones XVI XXII. A 0.01-mol
portion of appropriate hydrocarbon was added to a
solution of 0.012 mol of anhydrous AlCl3 in 20 ml of
CS2. The mixture was allowed to stand at room tem-
perature for 20 min, after which a solution of 0.01 mol
of appropriate acid chloride in 10 mol of CS2 was
added dropwise over a period of 10 min. The mixture
was refluxed until the HCl evolution ceased, after (71%), mp 293 294 C.
which it was poured onto a mixture of ice and hydro-
Imide XIV was prepared similarly starting from
maleimide and was recrystallized from benzene.
chloric acid. The organic layer was extracted with
diethyl ether; the ether extracts were washed with
dilute NaOH and water. The solvent was distilled off,
and the residue was distilled in a vacuum.
1-(4-tert-Butylphenyl)naphthalene-2,3-dicarb-
oxylic acid imide IX was prepared in 97% yield by
fusion of anhydride X with urea.
2-Methylbenzophenone XVII: yield 67%, bp
122 123 C (2 mm Hg) [13].
7-tert-Butyl-1-phenylnaphthalene-2,3-dicarboxylic
acid imide XII (yield 94%) and 1-phenylphenanthre-
ne-2,3-dicarboxylic acid imide XVI (yield 96%) were
prepared similarly, starting from anhydrides XI and
XV, respectively.
4,4 -Di(tert-butyl)-2-methylbenzophenone XVIII:
yield 83%, bp 190 195 C (1 mm Hg). Mass spec-
trum, m/z: 308 [M+]. Found, %: C 85.19; H 8.77.
C22H28O. Calculated, %: C 85.66; H 9.15.
(Tetra-1-phenyl-2,3-naphthalocyaninato)bromo-
gallium XXIII. A mixture of 1.1 g of imide III,
0.31 g of GaBr3, 3 g of urea, and a catalytic amount
of ammonium molybdate was heated for 2 h at 270
290 C. After cooling, the fusion cake was treated with
hot water, 5% HCl, again hot water, and diluted
ethanol. The residue was treated with chloroform and
chromatographed on alumina (eluent chloroform) to
obtain the spectrally pure complex (0.58 g, 53%).
4 -tert-Butyl-2-methylbenzophenone XIX: yield
62%, bp 157 161 C (1 mm Hg). Mass spectrum, m/z:
252 [M+]. Found, %: C 85.53; H 7.64. C18H20O.
Calculated, %: C 85.67; H 7.99.
5-tert-Butyl-2-methylbenzophenone XX: yield
65%, bp 158 162 C (2 mm Hg). Mass spectrum, m/z:
252 [M+]. Found, %: C 85.38; H 7.82. C18H20O.
Calculated, %: C 85.67; H 7.99.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 5 2005

PHTHALOCYANINES AND RELATED COMPOUNDS: XXXIX.
Electronic absorption spectrum in chloroform, , nm
799
REFERENCES
(log ): 820 (5.30), 776 (4.52), 726 (4.57), 421 sh
(4.44), 338 (4.87). Mass spectrum, m/z: 1167.5 [M+].
Found, %: C 74.60; H 3.74; N 8.98. C72H40BrGaN8.
Calculated, %: C 74.17; H 3.46; N 9.61. Compound
XXIII was also obtained in 17% yield by refluxing
for 3 h a mixture of 0.1 g of dinitrile I and 0.03 g of
GaBr3 in 1 ml of sulfolane in the presence of a
catalytic amount of ammonium molybdate.
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3. US Patent 5053323, 1991, Ref. Zh. Khim., 1993,
[Tetra-7-tert-butyltetra-1-(4-tert-butylphenyl)-
2,3-naphthalocyaninato]bromogallium XXIV was
prepared from imide VI, GaBr3, and a catalytic amount
of ammonium molybdate by heating in a urea melt for
2 h at 270 290 C. The complex was purified by
chromatography on alumina; eluent chloroform, yield
37%. Electronic absorption spectrum in chloroform, ,
nm (log ): 826 (5.38), 782 (4.54), 732 (4.61), 434 sh
(4.42), 340 (4.87). Mass spectrum, m/z: 1614 [M+].
Found, %: C 77.81; H 6.83; N 6.41. C104H104BrGaN8.
Calculated, %: C 77.32; H 6.44; N 6.94.
4N173.
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[Tetra-1-(4-tert-butylphenyl)-2,3-naphthalocya-
ninato]bromogallium XXV was prepared similarly to
XXIII from imide IX in 33% yield. Electronic absorp-
tion spectrum in chloroform, , nm (log ): 825 (5.31),
779 (4.36), 731 (4.36), 433 sh (3.78), 342 (4.74).
Found, %: C 75.44; H 5.17; N 7.62. C88H72BrGaN8.
Calculated, %: C 75.97; H 5.22; N 8.05.
8. Meyers, A.I., Roth, G.P., Hoyer, D., Barner, B.A.,
and Laucher, D., J. Am. Chem. Soc., 1988, vol. 110,
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J. Chem. Soc., Perkin Trans. 1, 1988, no. 6, p. 1603.
(Tetra-7-tert-butyltetra-1-phenyl-2,3-naphthalo-
cyaninato)bromogallium XXVI was prepared simi-
larly to XXIII from imide IX in 40% yield. Electronic
absorption spectrum in chloroform, , nm (log ):
825 (5.31), 782 (4.40), 730 (4.46), 435 sh (3.95), 339
(4.04). Found, %: C 75.27; H 5.10; N 7.81. C88H72
BrGaN8. Calculated, %: C 75.97; H 5.22; N 8.05.
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[Tetra(p-biphenylyl)-2,3-naphthalocyaninato]-
bromogallium XXVII. A mixture of 0.16 g of an-
hydride XIII, 1 g of urea, 0.5 g of ammonium sulfate,
and a catalytic amount of ammonium molybdate was
heated for 3 h at 280 300 C. After the standard work-
up and chromatography of the residue on alumina,
0.065 g (40%) of XXVII was obtained. Electronic
absorption spectrum in chloroform, , nm (log ): 826
(5.30), 780 (4.58), 731 (4.56), 435 sh (4.28), 336
(4.89). Found, %: C 78.63; H 3.57; N 7.23. C96H56
BrGaN8. Calculated, %: C 78.38; H 3.84; N 7.62.
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konferentsiya po khimii i biokhimii porfirinov (III All-
Union Conf. on Chemistry and Biochemistry of
Porphyrins), Samarkand, 1982, p. 25.
(Tetra-1-phenyl-2,3-phenanthroporphyrazina-
to)bromogallium XXVIII was prepared in 39% yield
similarly to XXIII. Electronic absorption spectrum in
chloroform, , nm (log ): 795 (5.29), 756 (4.54), 707
(4.43), 406 sh (4.56), 344 (4.84). Found, %: C 77.89;
H 3.90; N 7.72. C88H48BrGaN8. Calculated, %: C
77.32; H 3.54; N 8.19.
18. Kuznetsova, N.A., Gretsova, N.S., Kalmykova, E.A.,
Makarova, E.A., Dashkevich, S.N., Kaliya, O.L., and
Luk’’yanets, E.A., Zh. Obshch. Khim., 2000, vol. 70,
no. 1, p. 140.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 5 2005