Reactions of Perylene with Aryne Intermediates

Article abstract of DOI:10.1134/S1070428019030278

The Diels-Alder reactions of perylene (diene) with 1,2-didehydrobenzene and 4,5-dimethoxy-1,2-didehydrobenzene (dienophiles) generated in situ by two methods were studied. According to the first method, diazonium salts derived from anthranilic acids and stabilized by 4-dodecylbenzenesulfonic acid were treated with potassium fluoride in toluene in the presence of 18-crown-6 on heating. The second method involved generation of arynes directly from substituted anthranilic acids by the action of isoamyl nitrite in toluene on heating. The corresponding Diels-Alder adducts, naphtho[1,2,3,4-ghi]perylene and 10,11-dimethoxynaphtho-[1,2,3,4-ghi]perylene, were isolated in up to 77% yield. The yield was higher when the aryne intermediate was generated from the stabilized diazonium salts. 4,5-Difluoro-1,2-dehydrobenzene and 2,3-dehydronaphthalene generated by both methods failed to react with perylene.

Full text of DOI:10.1134/S1070428019030278

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2019, Vol. 55, No. 3, pp. 409–411. © Pleiades Publishing, Ltd., 2019.
Russian Text © The Author(s), 2019, published in Zhurnal Organicheskoi Khimii, 2019, Vol. 55, No. 3, pp. 477–480.
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COMMUNICATIONS
Reactions of Perylene with Aryne Intermediates
D. E. Pavlyuka, S. Gundalaa, I. S. Kovaleva, D. S. Kopchuka, b,
A. P. Krinochkina, b, A. V. Budeeva, G. V. Zyryanova, b,* P. Venkatapuramc,
V. L. Rusinova, b, and O. N. Chupakhina, b
a Yeltsin Ural Federal University, ul. Mira 19, Yekaterinburg, 620002 Russia
*e-mail: gvzyryanov@gmail.com
b Postovskii Institute of Organic Synthesis, Ural Branch, Russian Academy of Sciences,
ul. S. Kovalevskoi/Akademicheskaya 22/20, Yekaterinburg, 620137 Russia
c Sri Venkateswara University, Tirupati, Andhra Pradesh, 517502 India
Received March 14, 2018; revised December 28, 2018; accepted January 18, 2019
Abstract—The Diels–Alder reactions of perylene (diene) with 1,2-didehydrobenzene and 4,5-dimethoxy-1,2-
didehydrobenzene (dienophiles) generated in situ by two methods were studied. According to the first method,
diazonium salts derived from anthranilic acids and stabilized by 4-dodecylbenzenesulfonic acid were treated
with potassium fluoride in toluene in the presence of 18-crown-6 on heating. The second method involved
generation of arynes directly from substituted anthranilic acids by the action of isoamyl nitrite in toluene on
heating. The corresponding Diels–Alder adducts, naphtho[1,2,3,4-ghi]perylene and 10,11-dimethoxynaphtho-
[1,2,3,4-ghi]perylene, were isolated in up to 77% yield. The yield was higher when the aryne intermediate was
generated from the stabilized diazonium salts. 4,5-Difluoro-1,2-dehydrobenzene and 2,3-dehydronaphthalene
generated by both methods failed to react with perylene.
Keywords: perylene, 1,2-didehydrobenzene, arynes, cycloaddition, naphtho[1,2,3,4-ghi]perylenes.
DOI: 10.1134/S1070428019030278
Perylene derivatives attract interest as components
of molecular electronic and nonlinear optical devices
emitting in the near-IR region [1, 2]. Perylenes are
often used in organic synthesis as dienes in reverse-
electron-demand Diels–Alder reactions with some
dienophiles, e.g., with maleic anhydride [3], 1,2-dide-
hydrobenzene [4, 5], etc. In most cases, readily acces-
sible 1,2-didehydrobenzene was used as aryne interme-
diate. Nevertheless, Diels–Alder reactions and related
transformations involving both simple arynes or their
hetero analogs and their functionalized or fused deriva-
tives seem to be promising ways of functionalization
of poly(hetero)aromatics, since these reactions make it
possible to synthesize (formally in one step) various
chemosensors [6–9], fluorophores [10], and biologi-
cally active compounds [11] that are often inaccessible
by conventional methods [12, 13].
derivatives generated in situ by different methods.
Among numerous procedures for the generation of
arynes [12, 13], we tried two methods, namely a mod-
ified procedure with the use of stabilized diazonium
salts [14] (method a) and generation of arynes directly
from anthranilic acids (method b). The latter method
was traditionally used in our studies.
The reactions of perylene with 1,2-didehydroben-
zene generated from stabilized 2-carboxybenzene-
diazonium salt [14] by the action of KF in the presence
of 18-crown-6 (method a), as well as directly from
anthranilic acid by the action of isoamyl nitrite
(method b), on heating afforded naphtho[1,2,3,4-ghi]-
perylene (2) in 77 and 45% yield, respectively. 4,5-Di-
methoxy-1,2-didehydrobenzene generated by the two
methods reacted with perylene to give previously
unknown 10,11-dimethoxynaphtho[1,2,3,4-ghi]pery-
lene (3) in 41 (a) and 32% yield (b). Thus, method a
seems more favorable from the viewpoint of the
product yield but less efficient from the viewpoint of
Herein we report the results of our study of the
reactivity of perylene in Diels–Alder reactions with
1,2-didehydrobenzene and its substituted and fused
409

PAVLYUK et al.
410
X
X
X
X
a or b
1
2, 3
2, X = H; 3, X = OMe.
a: (1) i-C5H13ONO, X2C6H2NH2CO2H, C12H25C6H4SO3H, EtOAc, 25°C, 1 h; (2) KF, 18-crown-6, toluene, reflux, 1 h.
b: i-C5H13ONO, X2C6H2NH2CO2H, toluene–1,4-dioxane, reflux, 1 h.
atom economy. Other arynes, in particular 4,5-di-
fluoro-1,2-didehydrobenzene [18–20] and 2,3-didehy-
dronaphthalene [10] generated by both methods, failed
to react with perylene, and the latter was recovered
from the reaction mixtures.
stirring, and a solution of 1.2 mmol of anthranilic or
2-amino-4,5-dimethoxybenzoic acid in 2 mL of anhy-
drous 1,4-dioxane was added dropwise over a period
of 30 min. The mixture was then stirred under reflux
for an additional 1 h, cooled to room temperature, and
washed with 3 M aqueous sodium hydroxide (3×
7.5 mL). The organic phase was dried over Na2SO4
and evaporated under reduced pressure, and the prod-
uct was isolated by silica gel column chromatography
using methylene chloride–ethyl acetate (1:1) as eluent.
The structure of compounds 2 and 3 was confirmed
1
by H NMR and mass spectra and elemental analyses.
1
Their H NMR spectra contained signals from protons
of the perylene and fused arene fragments as charac-
teristic multiplets in the aromatic region, and the
spectrum of 3 also displayed a signal of two methoxy
groups.
Naphtho[1,2,3,4-ghi]perylene (2). Yield 103 mg
(0.32 mmol, 77%, a), 60 mg (0.18 mmol, 45%, b);
mp 266°C (from CH2Cl2); published data [21]:
Method a. Anthranilic or 2-amino-4,5-dimethoxy-
benzoic acid, (18.2 mmol), was dissolved in 50 mL of
ethyl acetate, a solution of 6 g (18.2 mmol) of
4-dodecylbenzenesulfonic acid was added with vigor-
ous stirring, 2.57 mL (19.1 mmol) of isoamyl nitrite
was added to the resulting suspension, and the mixture
was stirred for 1 h. The precipitate of diazonium salt
was filtered off, washed with 20 mL of ethyl acetate,
and dried in a vacuum desiccator for 3 h at room
temperature. Yield 8 g (92%).
1
mp 268–270°C. H NMR spectrum (CDCl3), δ, ppm:
3
7.92–8.01 m (4H), 8.21 d (2H, J = 7.6 Hz), 8.28 m
3
3
(2H, J = 9.0 Hz), 8.98 m (2H, J = 7.6 Hz), 9.08 m
3
(2H, J = 9.0 Hz), 9.15–9.21 m (2H). Mass spectrum
(EI): m/z 326 (Irel 100%). Found, %: C 95.81; H 4.21.
C26H14. Calculated, %: C 95.68; H 4.32. M 326.
10,11-Dimethoxynaphtho[1,2,3,4-ghi]perylene
(3). Yield 65 mg (0.17 mmol, 41%, a), 51 mg
1
(0.13 mmol, 32%, b). H NMR spectrum (CDCl3), δ,
3
ppm: 4.21 s (6H, OMe), 7.90 d.d (1H, 5-H, J = 7.7,
Perylene, 0.1 g (0.41 mmol), was dissolved in
25 mL of toluene, and 0.24 g (4.2 mmol) of freshly
calcined potassium fluoride and 27 mg (0.1 mmol) of
18-crown-6 were added. The mixture was heated to
100°C, and the corresponding freshly prepared diazo-
nium salt, 0.8 g (1.68 mmol), was added in small
portions over a period of 1 h under continuous stirring.
The mixture was stirred for 1 h more and evaporated
under reduced pressure, and the oily residue was
subjected to alumina column chromatography using
toluene–methylene chloride (1:1) as eluent to isolate
compound 2 or 3.
8.0 Hz), 8.05–8.12 m (4H), 8.18 s (2H, 9-H, 12-H),
3
3
8.64 d (2H, J = 9.3 Hz), 8.84 d (2H, J = 7.5 Hz).
Mass spectrum (ESI): m/z 387.14 (Irel 100%) [M + H]+.
Found, %: C 86.87; H 4.51. C28H18O2. Calculated, %:
C 87.02; H 4.69. M + H 387.14.
1
The H NMR spectra were recorded on a Bruker
Avance-400 spectrometer at 400 MHz relative to
tetramethylsilane as internal standard. The melting
points were measured on a Boetius melting point
apparatus. The mass spectra were recorded on Bruker
Daltonics MicrOTOF-Q II (electrospray ionization)
and Shimadzu GCMS-QP2010Ultra instruments (elec-
tron impact). The elemental compositions were
determined with a Perkin Elmer 2400 Series II CHN
analyzer.
Method b. Perylene, 0.1 g (0.41 mmol), was
dissolved in 50 mL of anhydrous toluene, 1.3 mL
(1.2 mmol) of isoamyl nitrite was added, the mixture
was heated to the boiling point under argon with
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 3 2019

REACTIONS OF PERYLENE WITH ARYNE INTERMEDIATES
411
10. Kopchuk, D.S., Chepchugov, N.V., Taniya, O.S.,
Khasanov, A.F., Giri, K., Kovalev, I.S., Santra, S.,
Zyryanov, G.V., Majee, A., Rusinov, V.L., and Chupa-
khin, O.N., Tetrahedron Lett., 2016, vol. 57, p. 5639.
doi 10.1016/j.tetlet.2016.11.008
ACKNOWLEDGMENTS
The analytical studies were carried out using the
facilities of the “Spectroscopy and Analysis of Organic
Compounds” Joint Center at the Postovskii Institute of
Organic Synthesis (Ural Branch, Russian Academy of
Sciences).
11. Tadross, P.M. and Stoltz, B.M., Chem. Rev., 2012,
vol. 112, p. 3550. doi 10.1021/cr200478h
12. Kovalev, I.S., Kopchuk, D.S., Zyryanov, G.V., Slepu-
khin, P.A., Rusinov, V.L., and Chupakhin, O.N., Chem.
Heterocycl. Compd., 2012, vol. 48, p. 536. doi 10.1007/
s10593-012-1028-9
FUNDING
This study was performed under financial support
by the Russian Science Foundation (project no. 18-13-
00365).
13. Pérez, D., Peña, D., and Guitian, E., Eur. J. Org. Chem.,
2013, p. 5981. doi 10.1002/ejoc.201300470
14. Gusel’nikova, O.A., Kutonova, K.V., Trusova, M.E.,
Postnikov, P.S., and Filimonov, V.D., Russ. Chem. Bull.,
Int. Ed., 2014, vol. 63, p. 289. doi 10.1007/s11172-014-
0427-8
CONFLICT OF INTERESTS
The authors declare the absence of conflict of
interests.
15. Kopchuk, D.S., Chepchugov, N.V., Gorbunov, E.B.,
Zyryanov, G.V., Kovalev, I.S., Nosova, E.V., Slepu-
khin, P.A., Rusinov, V.L., and Chupakhin, O.N., J. Iran.
Chem. Soc., 2017, vol. 14, p. 1507. doi 10.1007/s13738-
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