Synthesis and properties of dicarboximide derivatives of perylene and azaperylene

Article abstract of DOI:10.3987/COM-09-S(S)104

The N-alkyl dicarboximide derivatives of naphthylisoquinoline and binaphthalene were prepared by the hetero coupling reaction of the corresponding N-alkyl dicarboximide derivatives of stannylnaphthalene with bromodimethyisoquinoline and bromodimethylnaphthalene, respectively. The ring closing of the N-hexyl derivatives of naphthylisoquinoline and binaphthalene produced the N-hexyldicarboximide derivatives of azaperylene and perylene having the same substituents, respectively. The absorption spectra and fluorescence spectra of the azaperylene and perylene derivatives were investigated.

Full text of DOI:10.3987/COM-09-S(S)104

HETEROCYCLES, Vol. 80, No. 2, 2010
1197
HETEROCYCLES, Vol. 80, No. 2, 2010, pp. 1197 - 1213. © The Japan Institute of Heterocyclic Chemistry
Received, 3rd August, 2009, Accepted, 4th September, 2009, Published online, 15th September, 2009
DOI: 10.3987/COM-09-S(S)104
SYNTHESIS AND PROPERTIES OF DICARBOXIMIDE DERIVATIVES
OF PERYLENE AND AZAPERYLENE
Yukinori Nagao,* Tatsurou Yoshida, Koji Arimitsu, and Kozo Kozawa
Department of Pure and Applied Chemistry, Faculty of Science and Technology,
Tokyo University of Science, Noda, Chiba 278-8510, Japan
Abstract – The N-alkyl dicarboximide derivatives of naphthylisoquinoline and
binaphthalene were prepared by the hetero coupling reaction of the
corresponding N-alkyl dicarboximide derivatives of stannylnaphthalene with
bromodimethyisoquinoline and bromodimethylnaphthalene, respectively. The
ring closing of the N-hexyl derivatives of naphthylisoquinoline and
binaphthalene produced the N-hexyldicarboximide derivatives of azaperylene
and perylene having the same substituents, respectively. The absorption spectra
and fluorescence spectra of the azaperylene and perylene derivatives were
investigated.
INTRODUCTION
Perylene dyes have a high fastness to light and a high stability to heat. Moreover, perylene dyes have
absorption in the visible light range in the solid form and an n-type semiconductorcharacter. Recently,
some of them are being used not only as pigments, but also as functional dyes for organic
photoconductors in electrophotography, organic EL devices, and organic solar cells (photovoltaic cells).
Paying attention to the usefulness of perylene dyes, the synthesis of the azaperylene derivative having an
N atom in its skeleton is useful because it is assumed that the azaperylene derivatives have analogous
properties to the perylene derivatives, and the difference in the perylene properties is very interesting.
≠ Dedicated to Professor Emeritus Akira Suzuki on the occasion of his 80th birthday.

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HETEROCYCLES, Vol. 80, No. 2, 2010
Furthermore, it is expected that replacement of the C-atom in the perylene skeleton by the N atom
produces an increasing absorption intensity. Previously, azaperylene derivatives having the N-pentyl
group were prepared1, but these derivatives had no adequate solubility. In this study, the synthesis of
an azaperylene derivative containing the N-hexyl group was investigated and then the synthesis of the
corresponding perylene derivatives with the same groups was investigated.
1, 4, 5
The stannyl substituted naphthalenedicarboximides 3a,b2, 3 and isoquinoline bromides 7
were
prepared from naphthalic anhydride 1 and acetophenone 4, respectively (Schemes 1 and 2). The
naphthylisoquinoline derivatives 8a,b 3 that were obtained via the heterocoupling reaction of 3a,b and 7
in the presence of Pd(PPh3)4, were cyclized using t-BuOK/DBN to synthsize the azaperylene derivative
9a (Schemes 3 and 4). In addition, naphthylbromide 12 7, 8, 9 was prepared from naphthalic anhydride 15
(Scheme 2). The binaphthalene derivatives 13a,b 3 that were obtained via the heterocoupling reaction of
3a,b and 12 in the presence of Pd(PPh3)4 , was cyclized using t-BuOK/DBN to synthesize the perylene
derivative 14a (Scheme 4). The optical properties of the prepared azaperylene derivative 9a and
perylene derivative 14a were compared.
RESULTS AND DISCUSSION
Preparation of stannylnaphthalenedicarboximide 3a,b
The bromo naphthalenedicarboximides 2a,b and stannylnaphthalenedicarboximides 3a,b (a: alkyl =
n-hexyl, b: alkyl = cyclohexyl) were prepared according to Scheme 1. Compounds 2a,b (a: 90%, b:
80%) were synthesized by imidization of the anhydride 1 with n-hexylamine and cyclohexylamine,
respectively. 3a,b (a:82%, b:71%) were then synthesized by the substitution of 2a,b with SnBu3.
O
O
O
N
O
N
Br
Br
SnBu3
n-RNH2
Sn2Bu6
R
R
EtOH
Pd(PPh3)4 (cat.)
O
O
O
toluene
1
2a,b
3a,b
R= a: n-Hex
b: c-Hex
Scheme 1

HETEROCYCLES, Vol. 80, No. 2, 2010
1199
Preparation of bromoisoquinoline 7 and bromonaphthalene 12
Bromoisoquinoline 7 and bromonaphthalene 12 were prepared according to Scheme 2. The imine 5
(90%) was prepared from O-methyl acetophenone (4), and isoquinoline 6 (35%) was prepared from 5
using sulfuric acid . The bromoisoquinoline 7 (86%) was then prepared by the bromination of 6 with
NBS.
Hydroxymethylbromonaphthalene 10 was prepared from the anhydride 1 in a 64% yield, then the
bromomethybromonaphthalene 11 was prepared in a 70% yield by the bromine substitution of the
hydroxyl group using PBr3. After reduction of 11 by LiAlH4, the bromonaphthalene 12 was
produced, but a side reaction occurred and purification was very difficult. The starting material was then
changed from the anhydride 1 to 15, and methylnaphthalene 18 was prepared in a 92％ yield in 3 steps
reaction from 15. The bromonaphthalene 12 (63%) was then prepared by the bromination of 18 with
NBS.
Me
Me
Me
Me
Br
Me
Me
Me
CH(OMe)2CH2NH2
toluene
NBS
conc.H2SO4
MeO
MeO
COMe
conc.H2SO4
N
N
6
N
4
5
7
O
Br
CH2OH
CH2OH
Br
CH2Br
CH2Br
Br
Br
Me
Me
LiAlH4
PBr3
O
CH2Cl2
Et2O
O
10
1
11
12
O
O
CH2Br
Me
CH2OH
CH2OH
PBr3
NaBH4
Br
Me
Me
LiAlH4
Et2O
NBS
DMF
CH2Br
Me
CH2Cl2
O
DMSO
12
15
16
18
17
Scheme 2
Palladium-catalyzed coupling reaction of stannylnaphthalenedicarboximide 3a,b with
bromoisoquinoline7 and bromonaphthalene 12
The naphthylisoquinolines 8a,b and binaphthalenes 13a,b (a: alkyl = n-hexyl, b: alkyl = cyclohexyl)

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HETEROCYCLES, Vol. 80, No. 2, 2010
were prepared according to Scheme 3. 8a,b and 13a,b were prepared by the palladium-catalyzed hetero
coupling reaction of stannylnaphthalenedicarboximide 3a,b with bromoisoquinoline 7 and
bromonaphthalene 12, respectively.
O
O
SnBu3
Br
Me
Me
Me
Me
R
N
Pd(PPh3)4 (cat.)
mesitylene
R
N
+
O
N
O
N
7
8a,b
3a,b
3a,b
O
O
N
Br
Me
Me
SnBu3
Pd(PPh3)4 (cat.)
mesitylene
Me
Me
R
N
+
R
O
O
12
13a,b
R= a: n-Hex b: c-Hex
Scheme 3
Preparation of azaperylene derivative 9a and perylene derivative 14a
The azaperylene derivative 9a and perylene derivative 14a were prepared according to Scheme 4. The
ring-closing reactions of the naphthylisoquinolines and binaphthalenes with a complex base reagent
(t-BuOK/DBN) were investigated. The reaction mechanism of this method is not clear, but an alkyl
chain participated in the reaction progress. 9a (12%) and 14a (10%) containing a hexyl group were
obtained, but 8b and 13b containing a cyclohexyl group did not give the corresponding ring-closing
products (Table 1). Neither using other ring-closing reaction conditions or bases were reaction
successful.
O
O
Me
Me
Me
Me
t-BuOK/ DBN
R
N
R
N
O
O
N
N
9a
8a,b
O
O
Me
Me
Me
Me
t-BuOK/ DBN
R
N
R
N
O
O
a
b
: c-Hex
R= : n-Hex
14a
13a,b
Scheme 4

HETEROCYCLES, Vol. 80, No. 2, 2010
1201
Table 1. Yields and mp of azaperylene and perylene derivatives
for the ring-closing reaction with t-BuOK/DBU
Alkyl chain
Products
Yield (%)
mp (℃)
n-C6H13
c-Hex
9a
9b
12
236.1~236.4
no reaction
10
--
254.1~254.4
--
n-C6H13
c-Hex
14a
14b
no reaction
Photophysical Properties
Absorption spectra in CHCl3 and thin film
The absorption spectra of azaperylene 9a and perylene 14a in CHCl3 are presented in Figure 1 and Table
2. The changes in λmax were significantly red shifted due to the change in the absorption spectrum by
the ring-closing reaction of naphthylisoquinoline 8a and binaphthalene 13a. Because forming the
perylene or azaperylene skeleton by a ring-closure reaction extended the π- conjugate system, 9a from
8a had about a 150 nm (Figure 1 a) red shift and 14a from 13a had about 160 nm (Figure 1 b) red shift.
In addition, compared to before the ring-closure, the ε rise was about 2.5 times and 2.0 times,
respectively.
1.6
1.6
O
O
Me
Me
1.4
C6H13
N
O
1.4
1.2
1
C6H13
N
O
Me
Me
O
N
O
N
1.2
1
14a
Me
Me
O
N
O
9a
C6H13
Me
Me
C6H13
N
13a
0.8
0.6
0.4
0.2
0
0.8
0.6
0.4
0.2
0
8a
300
350
400
450
500
550
600
650
300
350
400
450
500
550
600
650
Wavelength/nm
Wavelength/nm
Figure 1. (a) UV/Vis spectra of 8a
and 9a *Solv.: CHCl3(C=5.0×10-5 mol/l)
Figure 1. ( b) UV/Vis spectra of 13a
and 14a *Solv.: CHCl3(C=5.0×10-5 mol/l)
Table 2. Absorption spectra of 8a and azaperylenes 9a, and 13a and perylene 14a in CHCl3
8a
9a
13a
14a
Compound
λmax/nm [ε]/ l/mol・cm
336 [1.2×104]
489 [3.3×104]
345 [1.4×104]
510 [3.0×104]

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HETEROCYCLES, Vol. 80, No. 2, 2010
As for λmax, 9a has a shorter wavelength than 14a in CHCl3 (Table 2). Maybe the lone pair electron of
the N atom had no influence on the π conjugated system. However, introducing the N atom in the
perylene skeleton decreased the π-electron density of the perylene skeleton by the electron withdrawing
nature of the N atom which lead to the blue shift. According to the molecular orbital calculation, the
stabilization of the HOMO is a slightly higher and gave a calculated short wavelength shift. On the other
hand, the absorption strength increases by the N atom introduction, deflection occurs in the electronic
density of the perylene skeleton and a change occurs in the transition moment. The absorption spectrum
in the film state is shown in Figure 2.
In the solid state, the visible absorption spectrum of the thin film is broad compared to the visible
absorption spectrum in solution (Figure 2 b). The distance between molecules becomes short in the solid
state, a deviation occurs in the electric charge of the molecule by the interaction between molecules, and
it is thought that it becomes a broad absorption by affecting the electronic change energy. Maybe two
perylene derivatives form H-aggregate, and λmax in the solid showed blue shifts: 9a (490→458 nm),
14a (510→446 nm) compared to the values in solution. Different from that in CHCl3, the λmax of 9a
showed a longer wavelength than 14a in the solid state. Maybe by introducing the N atom, itproduces a
deflection in the electronic density of the perylene skeleton, and a change in the aspect or interval of the
intermolecular packing compared to perylene.
O
Me
C6H13
N
O
Me
N
9a
O
N
O
Me
Me
C6H13
14a
Wavelength/nm
Figure 2. UV/Vis spectra of 9a and 14a of thin film (500Å)

HETEROCYCLES, Vol. 80, No. 2, 2010
1203
Table 3. The absorption spectrum of 9a and 14a in the film state
thin film (500Å)
λmax/nm
9a
14a
446
458
Fluorescence spectra
The fluorescence spectra of azaperylene 9a and perylene 14a in CHCl3 are presented in Figure 3. It is
generally reported that the fluorescence intensities remarkably decrease by introducing an N atom, such
as pyridine or quinoline, for the N-hetero compound compared with benzene and naphthalene. Normally
the singlet excitation electron which is in a state returns to the ground state while producing the
fluorescence. However, because of the triplet excitation state by the n-π* transition of the lone pair
electron, radiationless transition and electron withdrawing of the N atom remarkably decrease the
fluorescence intensities. However, 14a showed a equally strong fluorescence intensity compared to 9a
and it is shown that azaperylene had a sufficient fluorescence intensity equal to perylene. Maybe the
dimethyl, which was substituted at the 1,8- position, play a role in preventing the remarkable decrease in
fluorescence. Corresponding N-pentylazaperylene derivative1 previously obtained had poor solubility in
CHCl3 and gave no clear 1H-NMR. But this derivative show similar absorption and fluorescence spectra
with those of 9a. The relative quantum yield of the N-pentyl derivative was 0.89 and 9a have almost
equal fluorescence intensity with that.
140
O
Me
C6H13
N
O
120
100
80
60
40
20
0
Me
O
N
O
N
Me
Me
C6H13
9a
14a
450
500
550
600
650
700
750
800
Wavelength/nm
Figure 3. Fluorescence spectra of 9a (green) and 14a (red) *Solv.: CHCl3 (C=2.0×10-5mol/l)

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HETEROCYCLES, Vol. 80, No. 2, 2010
Table 4. Fluorescence spectra of azaperylene 9a and perylene 14a
Compound
9a
14a
573
Emission λmax/nm
550
Fluorescence ( relative intensity)
116.3
120.9
CONCLUSION
N-Hexyl-1,8-dimethylazaperylene-8,9-dicarboximide (9a) and N-hexyl-1,8-dimethylperylene- 8,9-
dicarboximide (14a) were synthesized via the hetero coupling reaction of the corresponding
stannylnaphthalenedicarboximide 3a with isoquinoline bromide 7 and naphthyl bromide 12 in the
presence of Pd(PPh3)4, and ring-cyclization of these coupling products using t-BuOK/DBN, respectively.
The absorption strength increases by the N atom introduction into the perylene skeleton for deflection to
the electronic density in azaperylene skeleton. The azaperylene indicate sufficient intensity of
fluorescence equal to perylene.
EXPERIMENTAL
Instrument Melting points were determined using an MRK MP-MG. The IR spectra were recorded by a
JASCO FT/IR-410 using a potassium bromide pellet. The 1H-NMR and 13C-NMR spectra were acquired
1
by a JEOL JNM-ECP300 at 300 and 75 MHz in CDCl3. The H-NMR coupling constants are given in
Hz and all chemical shifts are relative to the internal standard of tetramethylsilane. Low-resolution
electron impact mass spectra were obtained using a JEOL MS station.
Manufacture of thin film
The Manufacturing of the thin films were performed by a vacuum deposition method using a high
vacuum vapor deposition device, EBH-6 (Ulvac Co., Ltd.). The film thickness was measured using an
Alpha-Step500 (Tencor Company) surface shape measuring instrument and CRT -5000 (Ulvc Co., Ltd.)
film thickness counter . The vacuum degree was measured by a GI-TL2 ionization gauge.
A sample first put it in the vacuum bottom of 10-5 Torr, and heated and after vapor deposition speed
became constant, objective thickness of film was obtained by vapor deposition.

HETEROCYCLES, Vol. 80, No. 2, 2010
1205
Synthesis of materials
1,8-N-Alkyl-4-bromonaphthalenedicarboximide (2a,b) (a: alkyl = n-hexyl, b: alkyl = cyclohexyl)
A solution of compound 1 (5.0 g , 1.8×10-2 mol), n-hexylamine (10.0 mL , 7.0×10-2 mol) in EtOH (300
mL) were heated to 78 °C for 5 h with stirring. After the reaction, the mixture was cooled to rt and
removed 1 by filtration. After evaporation of the filtrate, the solid was washed with water and dried.
Recrystallization from EtOH yielded 2a (6.0 g, 90%) as yellow needles. Similarly, cyclohexylamine
produced 2b (5.2 g, 80%)
(2a): mp 65.0~65.4 °C (lit.,2 65.3~65.7 °C), IR (KBr) νC=O imide/cm-1 : 1662, 1701 MS(FAB) (m/z):
360｛M+H｝+,362｛M+H+2｝+ 1H-NMR (300 MHz, Solv.:CDCl3, Ref.:TMS) δ: 8.65 (d, J=7.5 Hz, 1H,
arom.H), 8.56 (d, J=7.5 Hz, 1H, arom.H), 8.43 (d, J=8.0 Hz, 1H, arom.H), 8.05 (d, J=8.0 Hz, 1H,
arom.H), 7.85 (t, J=7.5 Hz, 1H, arom.H), 4.16 (t, J=8.0 Hz, 2H, -NCH2), 1.74 (d, J=7.5 Hz, 2H, -CH2-),
13
1.43 (d, J=7.5 Hz, 2H, -CH2-), 1.33~1.35 (m, 4H, -CH2CH2-), 0.89 （t, J=7.5 Hz, 3H, CH3）. C-NMR
(75 MHz, Solv.:CDCl3, Ref.:TMS) δ14.27, 22.53, 26.75, 27.99, 31.51, 40.59, 122.24, 123.09, 128.01,
128.91, 130.01, 130.53, 131.02, 131.12, 131.92, 133.10, 163.50, 163.52
(2b) mp 265.7~266.1 °C (lit.,10 265.0 °C) IR (KBr) νC=O imide/cm-1 : 1663, 1703 MS(FAB) (m/z): 358
｛M+H｝+, 360｛M+H+2｝+ 1H-NMR (300 MHZ, Solv.: CDCl3, Ref.:TMS) δ: 8.58 (d, J=6.9Hz,
1H,arom.H), 8.47 (d, J=6.9Hz, 1H, arom.H), 8.08 (d, J=7.5Hz, 1H, arom.H), 7.88 (d, J=7.5Hz, 1H,
arom.H), 7.34 (t, J=7.5Hz, 1H, arom.H), 4.95~4.99 (m, 1H, -NCH-), 1.87~1.92 (m, 2H), 1.74~1.71 (m,
13
3H), 1.25~1.30 (m, 18H), 0.84~0.94 (m, 12H) ppm. C-NMR (75 MHz, Solv.:CDCl3, Ref.:TMS) δ:
25.40, 26.50, 29.05, 53.92, 122.81, 123.66,128.02, 128.96, 129.72, 130.41, 131.01, 131.07, 131.83,
132.79, 163.97, 163.99
1,8-N-Alkyl-4-tributylstannylnaphthalene-dicarboximide (3a,b)(a: alkyl = n-hexyl, b: alkyl =
cyclohexyl)
Each compound 2a,b (2.5 g, 6.94~6.98×10-3 mol), hexabutylditin (7.5 g, 1.3×10-3 mol), and Pd(PPh3)4
(0.050 g (4.3×10-5 mol) in toluene (150 mL) was refluxed for 48 h under a nitrogen atmosphere. After
the reaction, the solvent was removed by evaporation and the residue was purified by column

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HETEROCYCLES, Vol. 80, No. 2, 2010
chromatography on silica gel using toluene as the eluent, affording the product as a yellow viscous
liquid 3a (3.1 g, 82%) and yellowish-green viscous liquid 3b (2.8 g, 71%)
(3a): IR (KBr) νC=O imide/cm-1 : 1694 MS(FAB) (m/z): 568｛M-2｝+, 570｛M｝+, 572｛M+2｝+1H-NMR
(300 MHz, Solv.:CDCl3, Ref.:TMS) δ: 8.65 (d, J=7.5 Hz, 1H, arom.H), 8.56 (d, J=7.5 Hz, 1H, arom.H),
8.43 (d, J=8.0 Hz, 1H, arom.H), 8.05 (d, J=8.0 Hz, 1H, arom.H), 7.85 (t, J=7.5 Hz, 1H, arom.H), 4.16 (t,
13
J=8.0Hz, 2H, -NCH2), 1.25~1.34 (m, 9H), 1.33~1.35 (m, 15H), 0.89 （m, 14H）. C-NMR (75 MHz,
Solv.:CDCl3, Ref.:TMS) δ10.57, 13.39, 22.38, 26.66, 27.06, 28.76, 28.89, 29.02, 31.37, 40.12, 122.43,
123.31, 126.23, 127.85, 129.22, 130.41,135.62, 135.76, 137.27, 153.84,163.70, 164.20
(3b): IR (KBr) νC=O imide/cm-1 : 1694 MS(FAB) (m/z): 566｛M-2｝+, 568｛M｝+, 570｛M+2｝+ 1H-NMR
(300 MHZ, Solv.: CDCl3, Ref.:TMS) δ: 8.58 (d, J=6.9 Hz, 1H, arom.H), 8.47 (d, J=6.9 Hz, 1H, arom.H),
8.08 (d, J=7.5 Hz, 1H, arom.H), 7.88 (d, J=7.5 Hz, 1H, arom.H), 7.34 (t, J=7.5 Hz, 1H, arom.H),
4.95~4.99 (m, 1H, -NCH-), 1.87~1.92 (m, 2H), 1.74~1.71 (m, 3H), 1.25~1.30 (m, 20H), 0.84~0.94 (m,
13
12H). C-NMR (75 MHz, Solv.:CDCl3, Ref.:TMS) δ10.75, 13.36, 17.25, 26.73, 27.22, 28.24, 29.04,
53.62, 124.04, 126.47, 128.09, 128.17, 129.37, 130.55, 135.67, 135.87, 137.31, 153.67, 164.53, 165.03
N-Acetaldehyde dimethyl acetal-α-(o-toluyl)ethane imine (5)
Compound 4 (30 g, 2.2×10-3 mol), 2,2-dimethoxyethylamine (30 g, 2.3×10-1 mol), and p-toluene
sulfonic acid monohydrate (0.2 g, 1.2×10-3 mol) in toluene (150 mL) were refluxed for 48 h using a
Dean-Stark. trap. After the reaction, the solvent was removed by evaporation and purified by distillation
under reduced pressure affording the product as a colorless liquid 5 (45 g, 89%)
(5): bp 94.1 °C/ 1.5 mmHg, MS (FAB) (m/z): 222｛M+1｝+ 1H-NMR (300 MHz, Solv.:CDCl3,
Ref.:TMS) δ: 7.11~7.21 (m, 3H, arom.H), 6.87 (d, J=7.5 Hz, 1H, arom.H), 4.56 (t, J=4.0 Hz, 1H, CH),
3.30 (s, 6H, OCH3), 3.10 (d, J=6.0 Hz, 2H, N-CH2-), 2.26 (s, 3H, CH3), 2.20 (s, 3H, CH3).
1,8-Dimethylisoquinoline (6)
To a 500 mL, 4-necked flask equipped with a condenser was charged 95% conc.H2SO4 (250 mL). After
heating at 130 °C, compound 5 (50 g, 2.2×10-1 mol) was added portionwise over 30 min and stirred for
1 h. After the reaction, the solution was neutralized with 50% aq.KOH. The solution was filtered off
under reduced pressure. The salt after was washing with Et2O, the water layer was abstracted with Et2O.

HETEROCYCLES, Vol. 80, No. 2, 2010
1207
The organic liquid was dried (KOH) for 24 h.
The dried solution was evaporated under reduced pressure. The residual solid was purified by distillation
under reduced pressure to give a white solid 6 (12 g, 35%)
(6): mp 48.5~49.0 °C (48.5~50.0 °C)5 IR (KBr) νC=N /cm-1 : 1429, 1462, 1492 MS(FAB) (m/z): 158
｛M+1｝+ 1H-NMR (300 MHz, Solv.:CDCl3, Ref.:TMS) δ: 8.36 (d, J=6.0Hz, 1H, arom.H), 7.90 (d,
J=6.0Hz, 1H, arom.H), 7.65 (t, J=7.5Hz, 1H, arom.H), 7.20 (d, J=7.5Hz, 1H, arom.H), 3.12 (s, 3H,
-CH3), 2.84 (s, 3H, -CH3), 13C-NMR (75 MHz, Solv.:CDCl3, Ref.:TMS) δ22.44, 25.98, 115.51, 117.01,
126.20, 127.33, 129.78, 132.82, 133.09, 138.88, 155.62
5-Bromo-1,8-dimethylisoquinoline (7)
Compound 6 (8.0 g, 3.4×10-2 mol), NBS (9.4 g, 5.3×10-2 mol) 95% conc.H2SO4 (80 mL) were added
under a nitrogen atmosphere, and heated to 65 °C with stirring for 6 h. After the reaction, the reacted
solution was mixed with 10% aq.NaNO2 (100 mL) and neutralized with 50% aq.KOH. The solution was
filtered off under reduced pressure. The salt was washed with CHCl3 and the water layer was extracted
with CHCl3. The organic liquid was dried (KOH) for 24 h. The dried solution was evaporated under
reduced pressure to remove the solvent. The residual solid was purified by distillation under reduced
pressure to give a white powder 7 (10 g, 81%)
(7) : mp 89.1~89.6 °C (lit.,1 89.2~91.0 °C), IR (KBr) νC=N /cm-1 : 1428, 1482 MS(FAB) (m/z): 236
｛M-1｝+,238｛M+1｝+ 1H-NMR (300 MHz, Solv.:CDCl3, Ref.:TMS) δ: 8.25 (d, J=6.0 Hz, 1H, arom.H),
7.57 (d, J=7.5 Hz, 1H, arom.H), 7.43 (d, J=7.5 Hz, 1H, arom.H), 7.31 (d, J=6.0 Hz, 1H, arom.H), 7.29
13
(d, J=7.5 Hz, 1H, arom.H), 3.08 (s, 3H, -CH3), 2.88(s, 3H, -CH3). C-NMR (75 MHz, Solv.:CDCl3,
Ref.:TMS) δ22.61, 26.92, 117.05, 122.98, 126.03, 127.29, 129.98, 131.69, 132.97, 134.81, 137.73
5-(1,8-N-Alkyl-dicarboximidenaphthyl)-1,8-dimethylisoquinoline (8a,b)(a: alkyl = n-hexyl, b: alkyl
= cyclohexyl)
Each compound 3a,b (3.3 g, 5.8×10-3 mol), 7 (2.0 g, 8.4×10-3 mol), and Pd(PPh3)4 (0.050 g, 4.3×10-5
mol) in mesitylene (50 mL) were refluxed for 72 h under a nitrogen atmosphere．After the reaction, the
solvent was removed by evaporation and the residue was purified by column chromatography on silica
gel using AcOEt as the eluent. The crude solid was recrystallized from methanol affording the product

1208
HETEROCYCLES, Vol. 80, No. 2, 2010
as a white powder 8a (0.89 g, 35%) and light brown powder 8b (0.95 g, 39%)
(8a): mp 158.0~158.4 °C IR (KBr) νC=N /cm-1 : 1655 νC=O /cm-1 : 1694 MS(FAB) (m/z): 437｛M+1｝+
1H-NMR (300 MHz, Solv.:CDCl3, Ref.:TMS) δ: 8.71 (d, J=7.0 Hz, 1H, arom.H), 8.60 (d, J=7.0 Hz, 1H,
arom.H), 8.08 (d, J=6.0 Hz, 1H, arom.H), 7.59~7.69 (m, 5H, arom.H), 6.94 (d, J=6.0 Hz 1H, arom.H),
4.17(t, J=7.5 Hz, 2H, -CH2), 3.17 (s, 3H, -CH3), 3.01 (s, 3H, -CH3), 1.72 (m, 2H, -CH2-), 1.10~1.19 (m,
6H, -CH2CH2CH2-), 0.89 (m, 3H, -CH3) . 13C-NMR (75 MHz, Solv.:CDCl3, Ref.:TMS) δ14.01, 22.60,
26.23, 26.83, 28.10, 29.82, 31.58, 40.56, 117.91, 122.54, 127.05, 128.38, 128.96, 129.99, 130.71, 131.00,
131.14, 131.32, 132.49, 134.38, 136.84, 137.26, 141.53, 144.53, 159.16, 164.02, 164.17 HRMS [m/z]
Found:437.2235 Calcd.:437.2229｛M+1｝+
(8b) mp 265.1~265.4 °C IR (KBr) νC=N /cm-1 : 1654 νC=O /cm-1 : 1694 MS(FAB) (m/z): 435｛M+1｝+
1H-NMR (300 MHZ , solv.: CDCl3, Ref.:TMS) δ: 8.69 (d, J=7.5 Hz, 1H, arom.H), 8.59 (d, J=8.4 Hz,
1H, arom.H), 8.16 (d, J=7.5 Hz, 1H, arom.H), 7.65~7.71 (m, 5H, arom.H), 7.27 (d, J=7.5 Hz, 1H,
arom.H), 4.95~4.99 (m, 1H, -NCH-), 3.23 (s, 3H, -CH3), 3.07 (s, 3H, -CH3), 2.55~2.60 (m, 2H),
1.87~1.92 (m, 2H), 1.75~1.80 (m, 3H), 1.28~1.31 (m, 3H) . 13C-NMR (75 MHz, Solv.:CDCl3,
Ref.:TMS) δ14.21, 21.08, 25.47, 26.23, 26.56, 29.13, 29.85, 58.82, 117.89, 123.07, 123.53, 127.06,
128.39, 128.94, 129.96, 130.60, 130.74, 130.95, 131.00, 131.19, 132.15, 134.42, 136.83, 137.19, 141.57,
144.18, 159.15, 164.45, 164.61 . HRMS [m/z] Found:435.2075 Calcd.:435.2073｛M+1｝+
N-Hexyl-1,8-dimethylazaperylene-8,9-dicarboximide (9a)
To a 100 mL, 4-necked flask equipped with a condenser was charged with t-BuOK (1.0 g, 8.9×10-3
mol) and DBN (2.0 g, 1.6×10-2 mol) that was heated to 140 ℃ for 1 h with stirring. Each compound
8a,b (0.50 g, 1.2×10-3 mol) was added and stirred for 7 h. After the reaction, 100 mL of water was
added and the solution was filtered off under reduced pressure. The solid was washed with
MeOHmethanol and purified by column chromatography on silica gel using AcOEt as the eluent. The
crude solid was recrystallized from MeOH affording the product as a red solid 9a (0.051 g, 12%). 8b did
not give the corresponding product.
(9a): mp 236.1~236.4 °C IR (KBr) νC=N /cm-1 : 1655 νC=O /cm-1 : 1693 MS(FAB) (m/z): 435｛M+1｝+
1H-NMR (300 MHz,Solv.:CDCl3, Ref.:TMS) δ: 8.84 (s, 1H, arom.H), 7.80~8.26 (m, 6H, arom.H), 4.16

HETEROCYCLES, Vol. 80, No. 2, 2010
1209
(t, J=7.5 Hz, 2H, -CH2), 3.03 (s, 3H, -CH3), 2.75 (s, 3H, -CH3), 1.78~1.74 (m, 2H, -CH2-), 1.65~1.71 (m,
6H, -CH2CH2CH2-), 1.39 (t, 3H, -CH2CH3). 13C-NMR (75 MHz, Solv.:CDCl3, Ref.:TMS) δ14.09,
22.61, 26.25, 26.87, 28.04, 29.90, 31.58, 40.47, 118.87, 119.26, 120.45, 120.91, 125.26, 125.74,
126.47, 127.76, 130.66, 130.92, 131.25, 131.33, 134.35, 134.89, 135.74, 138.23, 139.12, 139.45, 160.60,
163.36, 163.39 . HRMS [m/z] Found:435.2073 Calcd.:435.2072｛M+1｝+
4-Bromo-1,8-bis(hydroxymethyl)naphthalene (10)
To a 500 mL, 4-necked flask equipped with a condenser was charged Et2O (100 mL) and lithium
aluminum hydride (5.0 g, 1.3×10-1 mol) Compound 1 (5.0 g, 1.8×10-2 mol) was slowly added and
stirred 48 h. After the reaction, AcOEt (200 mL) was added portionwise over 30 min and stirred 1 h.The
solution was neutralized with 10% aq.HCl. The organic layer was evaporated and purified by
recrystallization from acetone to yield white needles 10 (3.1 g, 64%).
Analysis data: (10): mp 161.7~162.2 °C (lit.,8 162.0~163.0 °C) IR (KBr) νOH: 3233, 3346 MS(FAB)
(m/z): 265｛M｝+, 267{M+2}+ 1H-NMR (300 MHz, Solv.:CDCl3, Ref.:TMS) δ: 8.14 (d, J=7.5 Hz, 1H,
arom.H), 8.04 (d, J=8.5 Hz, 1H, arom.H), 7.89 (d, J=8.0 Hz, 1H, arom.H), 7.52 (t, J=8.0 Hz, 1H,
13
arom.H), 7.39 (d, J=7.5 Hz, 1H, arom.H), 5.76 (s, 2H, -OH), 5.01 (s, 4H, -CH2-). C-NMR (75 MHz,
Solv.:CDCl3, Ref.:TMS) δ63.12, 63.48, 122.41, 126.79, 127.36, 128.17, 129.20, 129.52, 131.53,
132.42, 139.41, 139.56
4-Bromo-1,8-bis(bromomethyl)naphthalene (11)
To a 500 mL 4-necked flask equipped with a condenser was charged Et2O (200 mL) CH2Cl2 and
compound 10 (5.0 g, 1.8×10-2 mol) and stirred . PBr3 was added slowly and stirred 12 h. After the
reaction, the reacted solution was filled with 10% aq.NaNO2 (100 mL) and organic liquid was dried
(MgSO4) 12 h. The dried solution was evaporated under reduced pressure. Crude solid was
recrystallized from ethanol affording the product as pink solid 11 (5.2 g, 70%)
1
Analysis data: (11): mp 123.1~123.4 °C (lit.,8 122.0~123.6 °C) IR (KBr) νC-Br: 1200 H-NMR (300
MHz, Solv.:CDCl3, Ref.:TMS) δ: 8.41 (d, J=7.2 Hz, 1H, arom.H), 7.72 (d, J=7.8 Hz, 1H, arom.H),
7.45~7.55 (m, 2H, arom.H), 7.38 (d, J=7.8 Hz, 1H, arom.H), 5.27 (s, 2H, -CH2-), 5.27 (s, 2H, -CH2-) .
13C-NMR (75 MHz, Solv.:CDCl3, Ref.:TMS) δ36.50, 36.52, 125.68, 126.44, 127.06, 130.27, 130.32,

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HETEROCYCLES, Vol. 80, No. 2, 2010
130.97, 132.78, 133.54, 133.87, 133.98
1,8-Bis(hydroxymethyl)naphthalene (16)
To a 500 mL 4-necked flask equipped with a condenser was charged Et2O (100 mL) and lithium
aluminum hydride (5.0 g, 1.3×10-1 mol). Compound 15 (5.0 g, 1.8×10-2 mol) was added slowly and
stirred 48 h. After the reaction, AcOEt (200 mL) was added portionwise over 30 min and stirred 1 h. The
solution was neutralized with 10% aq.HCl. The organic layer was evaporated and purified by
recrystallization from acetone yielded white needle 16 (3.4 g, 70%).
(16): mp 159.6~160.2 °C (lit.,8 160.0~161.0 °C) IR (KBr) νOH: 3230, 3346 MS(FAB) (m/z): 188｛M｝+
1H-NMR (300 MHz, Solv.:CDCl3, Ref.:TMS) δ: 7.81 (d, J=8.1Hz, 1H, arom.H), 7.50 (d, J=8.1 Hz, 1H,
13
arom.H), 7.40 (t, J=8.1 Hz, 1H, arom.H), 5.23 (s, 2H, -CH2-), 2.94 (s, 1H, -OH). C-NMR (75 MHz,
Solv.:CDCl3, Ref.:TMS) δ63.65, 124.89, 128.08, 129.00, 130.03, 135.07, 138.50
1,8-Bis(bromomethyl)naphthalene (17)
To a 500 mL 4-necked flask equipped with a condenser was charged Et2O (200 mL), CH2Cl2 and
Compound 16 (4.0 g, 1.5×10-2 mol) then stirred. PBr3 was slowly added and stirred for 12 h. After the
reaction, to the reacted solution was added 10% aq.NaNO2 (100 mL) and the organic liquid was dried
(MgSO4) for 12 h. The dried solution was evaporated under reduced pressure. The crude solid was
recrystallized from EtOH affording the product as a pink solid 17 (7.1 g, 85%)
(17): mp 130.6~131.0 °C (lit.,8 130.0~131.5 °C) IR (KBr) νC-Br: 1202 1H-NMR (300 MHz, Solv.:CDCl3,
Ref.:TMS) δ: 8.14 (d, J=8.1 Hz, 1H, arom.H), 7.89 (d, J=8.1 Hz, 1H, arom.H), 7.52 (t, J=8.1 Hz, 1H,
arom.H), 5.30 (s, 2H, -CH2-) 13C-NMR(75 MHz, Solv.:CDCl3, Ref.:TMS) δ37.14, 119.96, 121.51,
125.68, 126.56, 131.90, 133.38
1,8-Dimethylnaphthalene (18)
Compound 17 (3.0 g, 7.5×10-3 mol), NaBH4 (2.4 g, 9.0×10-2 mol) , and DMSO (40 mL) were heated
to 80 °C for 48 h with stirring. After the reaction, the mixture was cooled to rt and abstracted with water
and CHCl3. The organic liquid was evaporated under reduced pressure. The crude solid was purified by
column chromatography on silica gel using hexane as the eluent, affording the product as a white
powder 18 (1.5 g, 94%)

HETEROCYCLES, Vol. 80, No. 2, 2010
1211
(18): mp 79.9~80.4 °C (lit.,9 80.0~81.0 °C) MS(FAB) (m/z): 156 ｛M｝+ 1H-NMR (300 MHz,
Solv.:CDCl3, Ref.:TMS) δ: 7.56 (d, J=6.9 Hz, 1H, arom.H), 7.32 (d, J=6.9 Hz, 1H, arom.H),
7.19 (t, J=6.9 Hz, 1H, arom.H), 2.81 (s, 3H, -CH3) . 13C-NMR (75 MHz, Solv.:CDCl3, Ref.:TMS)
δ22.58, 124.95, 127.18, 129.51, 133.03, 135.36, 135.54
4-Bromo-1,8-dimethylnaphthalene (12)
Compound 18 (5.0 g, 1.8×10-2 mol), NBS (0.75 g, 3.3×10-3 mol) , and DMF (30 mL) were stirred at
rt for 30 h. After the reaction ended, the mixture was washed with water and extracted with CHCl3. The
organic liquid was evaporated under reduced pressure to remove the solvent. The crude solid was
purified by column chromatography on silica gel using hexane as the eluent, affording the product as a
white solid 12 (0.53 g, 70%)
(12): mp 29.7~30.1 °C (lit.,9 29.8~30.0 °C) MS(FAB) (m/z): 233｛M-1｝+,235｛M+1｝+ 1H-NMR (300
MHz, Solv.:CDCl3, Ref.:TMS) δ: 7.53 (d, J=7.7 Hz, 1H, arom.H), 7.33 (t, J=8.3 Hz, 1H, arom.H), 7.23 (d,
J=8.3 Hz, 1H, arom.H), 7.00 (d, J=7.7 Hz, 1H, arom.H), 2.86 (s, 3H, -CH3), 2.84 (s, 3H, -CH3). 13C-NMR
(75 MHz, Solv.:CDCl3, Ref.:TMS) δ21.38, 21.43, 117.31, 121.77, 122.29, 124.78, 124.91, 125.80,
128.64, 129.80, 131.11, 131.38
5-(1,8-N-Alkyldicarboximidenaphthyl)-1,8-dimethylnaphthalene (13a,b)(a: alkyl = n-hexyl, b:
alkyl = cyclohexyl)
Each compound 3a,b (3.3 g, 5.8×10-3 mol), and 12 (2.0 g, 8.4×10-3 mol), and Pd(PPh3)4 (0.050 g, 4.3
×10-5 mol) in mesitylene (50 mL) were refluxed for 72 h under nitrogen atmosphere． After the
reaction, the solvent was evaporated and the residue purified by column chromatography on silica gel
using toluene as the eluent, affording the product as a yellowish white powder 13a (0.65 g, 26%) and
white powder 13b (0.83 g, 33%)
(13a): mp 171.0~171.3 °C IR (KBr) νC=O imide/cm-1 : 1698 MS(FAB) (m/z): 436｛M+1｝+ 1H-NMR
(300 MHz, Solv.:CDCl3, Ref.:TMS) δ: 8.69 (d, J=7.2 Hz, 1H, arom.H), 8.68 (d, J=7.2 Hz, 1H, arom.H),
7.70~7.73 (m, 2H, arom.H), 7.52 (t, J=8.2 Hz, 1H, arom.H), 7.38 (t, J=7.2 Hz, 1H, arom.H), 7.29 (d,
J=7.2 Hz, 1H, arom.H), 7.26 (d, J=7.2 Hz, 1H, arom.H), 7.12 (d, J=8.2 Hz, 1H, arom.H), 7.08 (d, J=8.2
Hz, 1H, arom.H), 4.22 (t, J=7.5 Hz, 2H, -NCH2), 3.05 (s, 3H, -CH3), 3.02 (s, 3H, -CH3), 1.72~1.79 (m,
2H, -CH2-), 1.34~1.41 (m, 6H, -CH2CH2CH2-), 0.92 (t, 3H, -CH3) . 13C-NMR (75 MHz, Solv.:CDCl3,

1212
HETEROCYCLES, Vol. 80, No. 2, 2010
Ref.:TMS) δ14.07, 22.56, 26.28, 26.36, 26.80, 28.08, 31.36, 40.47, 122.04, 122.81, 125.54, 125.66,
126.71, 127.11, 128.75, 129.75, 130.74, 131.12, 131.36, 132.98, 133.17, 134.08, 135.42, 135.97, 136.60,
146.51, 164.12, 164.28. HRMS [m/z] Found:436.2280 Calcd.:436.2276 ｛M+1｝+
(13b) mp 255.0~255.3 °C IR (KBr) νC=O imide/cm-1 : 1695 MS(FAB) (m/z): 433｛M+1｝+ 1H-NMR
(300 MHZ, solv.: CDCl3, Ref.:TMS) δ: 8.67 (d, J=7.5 Hz, 1H, arom.H), 8.57 (d, J=6.6 Hz, 1H, arom.H),
7.68~7.73 (m, 2H, arom.H), 7.53 (d, J=7.5 Hz, 1H, arom.H), 7.41 (d, J=7.5 Hz, 1H, arom.H), 7.26~7.29
(m, 2H, arom.H), 7.14~7.19 (m, 2H, arom.H), 5.12 (m, 1H, -NCH), 3.05 (s, 3H, -CH3), 3.02 (s, 3H,
13
-CH3), 2.54~2.62 (m, 2H), 1.89~1.94 (m, 2H), 1.76~1.80 (m, 3H), 1.37~1.46 (m, 3H). C-NMR (75
MHz, Solv.:CDCl3, Ref.:TMS) δ25.45, 26.27, 26.35, 26.55, 29.10, 53.72, 122.59, 123.36, 125.51,
125.67, 126.73, 127.08, 128.32, 128.78, 129.74, 130.62, 131.00, 131.22, 132.63, 133.17, 134.09, 135.47,
135.95, 136.55, 146.16, 164.56, 164.72 . HRMS [m/z] Found:434.2123 Calcd.:434.2120｛M+1｝+
N-Hexyl-1,8-dimethylperylene-8,9-dicarboximide (14a)
To a 100 mL, 4-necked flask equipped with a condenser was charged with t-BuOK (1.0g, 8.9×10-3 mol),
and DBN (2.0g, 1.6×10-2 mol) then heated to 140 °C for 1 h and stirred. Each compound 13a,b (0.50 g,
1.2×10-3 mol) was added and stirred for 7 h. After the reaction ended, 100 mL of water was added
and the solution was filtered off under reduced pressure.The solid was washed with methanol and
purified by column chromatography on silica gel using CHCl3 as the eluent. The crude solid was
recrystallized from methanol affording the product as a red solid 14a (0.050 g, 10%). 13b did not give
the corresponding product.
(14a): mp 254.1~254.4 °C IR (KBr) νC=O imide/cm-1 : 1688 MS(FAB) (m/z): 434｛M+1｝+ 1H-NMR
(300 MHz, Solv.:CDCl3, Ref.:TMS) δ: 8.41 (d, J=8.0 Hz, 2H, arom.H), 8.11~8.16 (m, 4H, arom.H),
7.54 (d, J=7.7 Hz, 2H, arom.H), 4.16 (t, J=7.3Hz, 2H, -NCH2), 2.87 (s, 3H, -CH3-CH3), 1.61~1.65 (m,
2H, -CH2-), 1.25~1.29 (m, 6H, -CH2CH2, CH2-), 0.89 (t, 3H, -CH3) . 13C-NMR (75 MHz,
Solv.:CDCl3, Ref.:TMS) δ14.11, 22.61, 26.88, 28.09, 29.69, 31.61, 40.39, 119.22, 119.84, 123.62,
125.70, 127.54, 128.82, 129.27, 130.71, 131.13, 137.49, 139.61, 149.63, 163.93 HRMS [m/z]
Found.:433.2036 Calcd.:433.2042｛M｝+

HETEROCYCLES, Vol. 80, No. 2, 2010
1213
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