Phthalocyanines and related compounds: XLI. Synthesis of 9,10-diphenylanthracene-2,3-dicarboxylic acid derivatives

Article abstract of DOI:10.1134/S107036320604027X

Derivatives of 9,10-diphenylanthracene-2,3-dicarboxylic acid were synthesized by the Diels-Alder reaction of 1,3-diphenylisobenzofuran with adducts of furan (or silvan) and the corresponding maleic (fumaric) acid derivative or with trans-cyclohex-4-ene-1,2-dicarbonitrile, followed by aromatization. Pleiades Publishing, Inc., 2006.

Full text of DOI:10.1134/S107036320604027X

ISSN 1070-3632, Russian Journal of General Chemistry, 2006, Vol. 76, No. 4, pp. 654 658.
Pleiades Publishing, Inc., 2006.
Original Russian Text
pp. 689 693.
V.F. Donyagina, E.I. Kovshev, E.A. Luk’’yanets, 2006, published in Zhurnal Obshchei Khimii, 2006, Vol. 76, No. 4,
Phthalocyanines and Related Compounds:
XLI.1 Synthesis of 9,10-Diphenylanthracene-2,3-dicarboxylic
Acid Derivatives
V. F. Donyagina, E. I. Kovshev, and E. A. Luk’’yanets
Research Institute of Organic Intermediate Products and Dyes,
ul. B. Sadovaya 1/4, Moscow, 101999 Russia
Received May 12, 2005
Abstract Derivatives of 9,10-diphenylanthracene-2,3-dicarboxylic acid were synthesized by the Diels
Alder reaction of 1,3-diphenylisobenzofuran with adducts of furan (or silvan) and the corresponding maleic
(fumaric) acid derivative or with trans-cyclohex-4-ene-1,2-dicarbonitrile, followed by aromatization.
DOI: 10.1134/S107036320604027X
In the preceding communication we described the
synthesis of 1-phenylnaphthalene-2,3-dicarboxylic
acid derivatives by the reaction of 2-bromomethyl-
benzophenones with derivatives of maleic acid,
which was accompanied by intermediate formation of
the corresponding Diels Alder adducts [1]. In the
present work we used the Diels Alder reaction to ob-
tain derivatives of 9,10-diphenylanthracene-2,3-di-
carboxylic acid which attract interest as, e.g., fluore-
scent labels for the determination of singlet oxygen in
aqueous medium [2]. Some of these compounds are
starting materials in the synthesis of tetra-2,3-(9,10-
diphenylanthraceno)porphyrazines (linearly fused
anthracene analogs of phthalocyanines) whose long-
wave absorption maximum in the electronic spectrum
is located in the near IR region; such substances may
be used in optical data storage devices [3 6].
methyl maleate adduct in boiling chloroform. It was
found that the initially formed diepoxy compound lost
two water molecules on treatment with dehydrating
agents to afford the corresponding anthracene [2, 9].
We believed that the above scheme may be con-
venient for the synthesis of various 9,10-diphenylan-
thracene-2,3-dicarboxylic acid derivatives, namely its
anhydride II, imide III, N-phenylimide IV, and dinit-
rile V, as well as of 1-methyl-9,10-diphenylanthracene-
2,3-dicarboximide (VI) and 1-methyl-9,10,N-triphenyl-
anthracene-2,3-dicarboximide (VII). As dienophiles
in the Diels Alder reaction with 1,3-diphenyl-2-ben-
zofuran we used cyclic adducts derived from furan
and maleic anhydride, maleimide, and Nphenylmale-
imide: 3,6-epoxy-1,2,3,4-tetrahydrophthalic anhydride
(VIII), 3,6-epoxy-1,2,3,4-tetrahydrophthalimide (IX),
and 3,6-epoxy-N-phenyl-1,2,3,4-tetrahydrophthal-
imide (X), respectively. Also, the adduct of furan with
fumaronitrile, 3,6-epoxy-1,2,3,4-tetrahydrophthaloni-
trile (XI) and analogous 2-methylfuran (silvan) ad-
ducts, 3,6-epoxy-1-methyl-1,2,3,4-tetrahydrophthal-
imide (XII), 3,6-epoxy-1-methyl-N-pheny-1,2,3,4-
tetrahydrophthalimide (XIII), and 3,6-epoxy-1-methyl-
1,2,3,4-tetrahydrophthalic anhydride (XIV), were used.
Taking into account that adducts VIII XIV are un-
stable (they are capable of undergoing thermal retro-
Diels Alder decomposition), the reactions with 1,3-di-
phenyl-2-benzofuran were carried out by keeping mix-
tures of the reactants in chloroform for several days
at room temperature. The reaction was assumed to be
complete when a yellow green luminescence intrinsic
to the initial diene disappeared and an abundant white
crystalline solid (adduct XV XXI) separated. The
products were then subjected to aromatization by
treatment with acid reagents. Adducts XV XVII re-
Rigaudy et al. [7, 8] reported on the synthesis of
9,10-diphenylanthracene-2,3-dicarboxylic acid ester
and 9,10-diphenylanthracene-2,3-dicarbonitrile in 5
35% yield via cycloaddition of dimethyl acetylenedi-
carboxylate and but-2-yne-1,4-dinitrile, respectively,
at the 1,4 positions of 9,10-diphenylanthracene.
However, the described procedures can hardly be
regarded as preparative because of difficult isolation
of the esters and low accessibility of dicyanoacetylene;
the synthesis of the latter is poorly reproducible but
highly explosive.
Dimethyl 9,10-diphenylanthracene-2,3-dicarboxy-
late was also synthesized by the Diels Alder reaction
of 1,3-diphenyl-2-benzofuran (I) with the furan di-
1
For communication XL, see [1].
654

PHTHALOCYANINES AND RELATED COMPOUNDS: XLI.
655
adily lost water on heating with BF3 Et2O in boiling
acetonitrile to give anthracenes II V in 47 79% yield.
Compounds II V were isolated as bright yellow sub-
stances showing luminescence in solution. The aro-
matization of compound XVIII was accompanied by
partial hydrolysis of dinitrile V to imide III. The latter
was the only isolated compound when a solution of
XVIII in methanol was heated under reflux while
bubbling dry hydrogen chloride therethrough.
nes, 1,4-diphenylnaphthalene-2,3-dicarboximide
(XXII) and 1,4,N-triphenylnaphthalene-2,3-dicarbox-
imide (XXIII). 1,4-Diphenylnaphthalene-2,3-dicar-
boxylic anhydride ( XXIV)was the only aromatization
product obtained from compound XXI. The electron-
impact mass spectrum of diepoxy derivative XXI
lacked molecular ion peak, and the base peak with m/z
270 belonged to 1,3-diphenyl-2-benzofuran. The mass
spectrum of the aromatization product contained a
strong peak with m/z 350 due to naphthalene deriva-
tive XXIV. Most probably, diepoxy compounds XIX
XXI under the aromatization conditions undergo par-
tial (compounds XIX and XX) or complete (XXI)
retro-Diels Alder decomposition into the initial com-
Analogous treatment of silvan adducts XIX and
XX resulted in formation of the corresponding anthra-
cenes VI and VII with a much lower yield (19 23%).
Apart from compounds VI and VII, we isolated crys-
talline products which were initially assigned the struc- ponents, and diene I thus formed reacted with maleic
ture of the corresponding monoepoxy derivatives,
1,4-epoxy-9,10-diphenyl-1,2,3,4-tetrahydroanthra-
cenes, which could be formed via elimination of one
water molecule from XIX and XX [2]. However, the
data of elemental analysis and the mass spectra indi-
cated that these compounds are substituted naphthale-
acid derivative. As a result, the yield of anthracene
derivative was considerably reduced or it was not
formed at all. Compounds XXIII and XXIV were
identical to those obtained by the direct reactions of
diene I with N-phenylmaleimide and maleic anhydride
[10, 11].
Ph
Ph
O
Ph
R1
R1
R1
R1
R1
R1
+
O
O
O
R2
Ph
R2
Ph
XV XXI
R2
Ph
Ph
I
VIII XIV
II VII
Ph
O
R1
R1
R1
R1
R1
R1
+
O
XIX XXI
I +
Ph
Me
Ph
XXII XXIV
II, VIII, XV, R2 = H, R1R1 = OCOCO; III, IX, XVI, R2 = H, R1R1 = OCNHCO; IV, X, XVII, R2 = H, R1R1 =
OCNPhCO; V, XI, XVIII, R1 = CN; VI, XII, XIX, XXII, R2 = Me, R1R1 = OCNHCO; VII, XIII, XX, XXIII, R2 = Me,
R1R1 = OCNPhCO; XIV, XXI, XXIV, R2 = Me, R1R1 = OCOCO.
These results indicate lower a stability of silvan
adducts XIX XXI, as compared to the corresponding
furan derivatives; a probable reason is peri arrange-
ment of the phenyl and methyl groups.
140 C, we isolated 9,10-epoxy-9,10-diphenyl-1,2,3,4,
4a,9,9a,10-octahydroanthracene-2,3-dicarbonitrile
(XXVI) which was treated with BF3 Et2O to obtain
tetrahydro derivative XXVII as a result of elimination
of water molecule. Aromatization of XXVII by treat-
ment with N-bromosuccinimide (NBS) under condi-
tions of radical initiation gave 9,10-diphenylanthra-
cene-2,3-dicarbonitrile (V). The mass spectrum of
XXVI, as well as of diepoxy compound XXI, con-
tained a strong peak with m/z 270, which belongs to
the molecular ion derived from diene I. Samples of
dinitrile V synthesized by the two methods were
We have developed an alternative procedure for
the synthesis of dinitrile V via Diels Alder reaction
of 1,3-diphenyl-2-benzofuran with excess trans-
cyclohex-4-ene-1,2-dicarbonitrile (XXV). Thermal
dehydration of primary adduct XXVI gave 9,10-di-
phenyl-1,2,3,4-tetrahydroanthracene-2,3-dicarbonitrile
(XXVII). When the reaction was carried out below
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 4 2006

656
DONYAGINA et al.
Ph
Ph
CN
CN
CN
>140 C
NBS
h
CN
Ph
Ph
XXVII
V
CN
CN
I +
BF3 Et2O
Ph
XXV
CN
>140 C
O
CN
Ph
XXVI
identical, and their characteristics coincided with
those reported in [8].
3,6-Epoxy-1,2,3,6-tetrahydrophthalonitrile (XI)
was synthesized from 3 g of fumaronitrile and 4 ml
of furan in 15 ml of dioxane. Yield 33%, mp 111 C;
published data [17]: mp 111 C.
The structure and purity of compounds II XXVII
were confirmed by elemental analysis, electronic spec-
troscopy, mass spectrometry, and thin-layer chroma-
tography.
3,6-Epoxy-3-methyl-1,2,3,6-tetrahydrophthal-
imide (XII) was synthesized as described above for
compound IX from silvan and maleimide. Yield 90%,
mp 163 165 C; published data [18]: mp 163 165 C.
EXPERIMENTAL
3,6-Epoxy-3-methyl-1,2,3,6-tetrahydrophthalic
anhydride (XIV) was synthesized by the procedure
described in [12]. Yield 93%, mp 74 75 C (decomp.).
The mass spectra were recorded on an LKB-2091
mass spectrometer (Sweden). Column chromato-
graphy was performed using silica gel L 40/100 m.
The purity of the products was checked by thin-layer
chromatography on Silufol UV-254 plates. Com-
mercial furan and 1,3-diphenyl-2-benzofuran (from
Aldrich) were used. 2-Methylfuran (bp 63 64 C) was
synthesized by the procedure described in [12].
9,10-Diphenylanthracene-2,3-dicarboxylic an-
hydride (II). A solution of 0.27 g of 1,3-diphenyl-2-
benzofuran and 0.17 g of adduct VIII in 5 ml of
chloroform was kept at room temperature until the re-
action was complete. The white solid was filtered off,
washed with chloroform, dried, and mixed with a solu-
tion of 1 ml of BF3 Et2O in 4 ml of acetonitrile, and
the mixture was heated for 4 h under reflux, cooled,
and poured into water. The precipitate was filtered off,
washed with water, dried, and recrystallized from
benzene. Yield 0.28 g (70%), mp >360 C; published
data [9]: mp 382 383 C; Rf 0.62 (chloroform). Mass
spectrum, m/z: 400 [M]+. Calculated: M 400.43.
trans-Cyclohex-4-en-1,2-dicarbonitrile (XXV)
was synthesized by reaction of fumaronitrile with 2,5-
dihydrothiophene-1,1-dioxide (butadiene adduct with
sulfur anhydride). Yield of 80%, mp 128 130 C;
published data [13]: mp 125 C.
3,6-Epoxy-1,2,3,6-tetrahydrophthalic anhydride
(VIII) was synthesized by mixing 2 g of maleic an-
hydride with 1.5 ml of furan in 5 ml of diethyl ether.
Yield quantitative, mp 125 C (decomp.) [14].
9,10-Diphenylanthracene-2,3-dicarboximide
(III). a. A solution of 0.54 g of 1,3-diphenyl-2-benzo-
furan and 0.32 g of adduct IX in 15 ml of chloroform
was kept at room temperature until the reaction was
complete. The precipitate was filtered off, washed
with chloroform, dried, and mixed with 15 ml of
methanol, and the mixture was heated for 4 h under
reflux while bubbling dry hydrogen chloride. The
mixture was cooled, poured into water, and neutra-
lized with sodium carbonate, and the yellow preci-
pitate was filtered off, washed with methanol, and re-
crystallized from benzene hexane. Yield 0.63 g (79%),
mp >360 C, Rf 0.77 (benzene ethyl acetate, 4:1).
3,6-Epoxy-1,2,3,6-tetrahydrophthalimide (IX)
was synthesized by reaction of 2 g of maleimide with
5 ml of furan in 25 ml of diethyl ether. Yield quanti-
tative, mp 131 C (decomp.); published data [15]: mp
130 132 C (decomp.).
3,6-Epoxy-N-phenyl-1,2,3,6-tetrahydrophthal-
imide (X) was synthesized by reaction of 5 ml of
furan with 8.7 g of N-phenylmaleimide in 50 ml of
chloroform. Yield 90%, mp 163 165 C; published
data [16]: mp 165.5 C.
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PHTHALOCYANINES AND RELATED COMPOUNDS: XLI.
657
Mass spectrum, m/z: 399 [M]+. Calculated: M 399.45.
Found, %: C 84.41; H 4.30; N 3.39. C28H17NO2.
Calculated, %: C 84.19; H 4.29; N 3.51.
off and recrystallized from acetonitrile. Yield 0.57 g
(83%), mp 277 279 C (decomp.). Mass spectrum,
m/z: 384 [M]+. Calculated: M 384.48.
b. Compound III was synthesized from 0.146 g of
1,3-diphenyl-2-benzofuran and 0.088 g of adduct IX
in 4 ml of dioxane; a solid separated and was dis-
solved in 4 ml of methanol, and the solution was
heated under reflux while bubbling dry hydrogen
chloride through the solution over a period of 2 h.
Yield 0.11 g (51%), mp >360 C (from benzene
hexane).
b. A mixture of 0.05 g of 1,3-diphenyl-2-benzo-
furan and 0.14 g of compound XXV in 0.5 ml of
xylene was heated for 5 h at 140 150 C. It was then
cooled, and the precipitate was filtered off. Yield
0.05 g (68%), mp 277 279 C (decomp.).
1-Methyl-9,10-diphenylanthracen-2,3-dicarb-
oximide (VI) was synthesized in 23% yield from
1,3-diphenyl-2-benzofuran and adduct XII following
the procedure described above for compound III. mp
310 312 C (from benzene hexane), Rf 0.81 (benzene
ethyl acetate, 4:1). Mass spectrum, m/z: 413 [M]+.
Calculated: M 413.48. Found, %: C 83.57; H 4.70; N
4.17. C29H19NO2. Calculated, %: C 84.24; H 4.63;
N 3.39.
9,10,N-Triphenylanthracene-2,3-dicarboximide
(IV) was synthesized as described above for com-
pound II from 0.27 g of 1,3-diphenyl-2-benzofuran
and 0.24 g of adduct X. Yield 73%, mp 344 345 C
(decomp.), Rf 0.54 (chloroform). Found, %: C 85.49;
H 4.49; N 2.97. C34H21NO2. Calculated, %: C 85.87;
H 4.45; N 2.95.
From the filtrate we isolated imide XXII. Yield
42%, mp 318 319 C, Rf 0.75 (benzene ethyl acetate,
4:1). Found, %: C 82.28; H 4.41; N 4.00. C24H15NO2.
Calculated, %: C 82.50; H 4.33; N 4.01.
9,10-Diphenylanthracene-2,3-dicarbonitrile (V).
a. Compound V was synthesized from 0.83 g of 1,3-
diphenyl-2-benzofuran and 0.45 g of adduct XI in
25 ml of dioxan. After treatment with BF3 Et2O, the
mixture was subjected to column chromatography on
silica gel. We isolated 0.55 g (47%) of compound V,
mp 351 353 C (from MeCN); published data [8]: mp
351 352 C; Rf 0.36 (chloroform), and 0.25 g (21%) of
imide III, mp >360 C (from benzene hexane), Rf 0.77
(benzene ethyl acetate, 4:1).
1-Methyl-9,10,N-triphenylanthracene-2,3-di-
carboximide (VII) was synthesized as described
above for compound IV from 1,3-diphenyl-2-benzo-
furan and adduct XIII. Yield 19%, mp 348 349 C
(decomp., from benzene hexane), Rf 0.42 (benzene).
Found, %: C 85.09; H 4.70; N 2.83. C35H23NO2.
Calculated, %: C 85.87; H 4.73; N 2.86. The mother
liquir was evaporated, and the residue was recrystal-
lized from benzene hexane to isolate imide XXIII.
Yield 40%, mp 295 296 C; published data [10]:
mp 297 298 C, Rf 0.39 (benzene). Mass spectrum,
m/z: 425 [M]+. Calculated M: 425.49.
b. A mixture of 0.3 g of compound XXVII and
0.4 g of N-bromosuccinimide in 10 ml of carbon
tetrachloride was heated for 4 h under reflux on ex-
posure light produced by a 60-W lamp. The mixture
was evaporated to dryness, and the solid residue was
washed with hot water and recrystallized from aceto-
nitrile. Yield 0.24 g (80%), mp 353 354 C; published
data [8]: mp 351 352 C; Rf 0.36 (chloroform).
1,4-Diphenylnaphthalene-2,3-dicarboxylic
anhydride (XXIV) was synthesized as described
above for compound II from 0.11 g of diene I and
0.08 g of adduct XIV. Yield 53%, mp 273 275 C
[11], Rf 0.62 (chloroform). Mass spectrum, m/z: 350
9,10-Epoxy-9,10-diphenyl-1,2,3,4,4a,9,9a,10-
octahydroanthracene-2,3-dicarbonitrile (XXVI). A
mixture of 0.54 g of diene I and 1.42 g of compound
XXV in 2 ml of xylene was heated for 5 h at 130
140 C. The solvent was evaporated to dryness, and
the residue was subjected to vacuum sublimation to
remove excess initial compound XXV. The residue
was recrystallized from hexane to isolate 0.72 g (90%)
of compound XXVI with mp 225 227 C (decomp.).
Found, %: C 83.89; H 5.17; N 7.23. C28H22N2O.
Calculated, %: C 83.56; H 5.51; N 6.96.
[M]+. Calculated: M 350.37.
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