Synthesis and optical properties of novel compounds containing carbazole and 1,8-naphthalimide groups

Article abstract of DOI:10.3184/030823408X304041

A series of novel carbazole-naphthalimide compounds with moieties capable of carrier-balance and electroluminescence were synthesised and characterised, and theirs luminescent properties had been studied.

Full text of DOI:10.3184/030823408X304041

JOURNAL OF CHEMICAL RESEARCH 2008
MARCH, 137–140
RESEARCH PAPER 137
Synthesis and optical properties of novel compounds containing
carbazole and 1, 8-naphthalimide groups
Guo-Liang Fenga,b*, Shun-Jun Jib*, Li-Jun Genga, Bing Bianb and Yu Liub
aSchool of Science, Hebei University of Science and Technology, Shijiazhuang 050018, P. R.China.
bKey Laboratory of Organic Synthesis of Jiangsu Province, School of Chemistry and Chemical Engineering Suzhou(Soochow)
University, Renai Road, Suzhou Industrial Park, Suzhou 215123, P. R.China.
A
series of novel carbazole-naphthalimide compounds with moieties capable of carrier-balance and
electroluminescence were synthesised and characterised, and theirs luminescent properties had been studied.
Keywords: carbazole, naphthalimide, fluorescence, Suzuki cross-coupling
Since Tang and Vanslyke first reported the use of multi-layer
organic thin films for light-emitting devices (LEDs),1 organic
light-emitting devices (OLEDs) have gained great interest
all over the world. OLEDs have received more attention
because of their potential applications in various displays.2-7
The organic electroluminescent devices have shown several
advantages over inorganic ones, such as low cost, high
luminous efficiency, wide selection of emission colours via
molecular design of organic materials, and easy processing.
As an important part of luminescent and fluorescent materials,
some two and three chromophores light emitting compounds
were synthesised.8
During the past several years, the synthesis and application
of carbazole derivatives have been of great interest for the
chemists and material scientists because these compounds
are quite interesting due to their intrinsic photophysical and
redox properties: they exhibit relatively intense luminescence
and undergo reversible oxidation processes which make them
suitable as hole carriers.9,10 Moreover, carbazole can be easily
functionalised at its 3-, 6-, or 9-position and the carbazole
moiety is beneficial for raising the glass-transition temperature
and thermal stability. So carbazole derivatives are widely used
as building blocks for potential organic semiconductors,11-14
organic light-emitting devices.15-17 It is also well known that
the 1,8-naphthalimide usually exhibits strong fluorescent
emission on irradiation, which usually acts as supermolecular
moieties for the study of photo-induced electron transfer,18,19
fluorescence switcher20 or liquid crystal displays.21 Recently,
1,8-naphthalimide derivatives utilised as electroluminescent
materials have been reported,22 whose fluorescence emission
can be widely tuned (from blue to yellow, green and even
red) with amino- and alkoxy-groups at the 4-position of 1,8-
naphthalimide. Many multichromophore compounds have
been synthesised.23,24 Our group has previously reported the
synthesis of several 1,8-naphthalimide derivatives containing
pyrazoline,25 which have good green fluorescence.
As a continuation of our works, we synthesised a series of
novel two chromophores compounds containing carbazole
and 1, 8-naphthalimide groups using carbazolboronic acids
and 4-bromo-1,8-naphthalimides in this paper (Scheme 1),
which had good green light fluorescence. At the same time
some three chromophores compounds were obtained by the
same method (Scheme 2). These compounds have not been
reported previously.
To synthesise the targeting two chromophores compounds,
our design is to attach carbazole directly to the 1,8-
naphthalimide via Suzuki cross-coupling. First, the 1,8-
naphthalimide compounds 1a–f were prepared according
to the literature (Scheme 1).26 Second, the boronic acid
of carbazole 2a–c) as the key intermediate for the whole
procedure was synthesised smoothly via
a three-step
Ar(R)
N
1a:
1b:
methyl
butyl
R=
O
O
O
O
O
R=
R=
Ar=
Ar=
1c:
1d:
1e:
1f:
benzyl
phenyl
4-methoxyphenyl
a
H2N-Ar(R)
Br
Br
1 (a-f)
Ar= 1-naphthyl
Ar1(R1)
N
H
N
Ar1(R1)
N
Ar1(R1)
N
d
c
b1,b2
B(OH)2
2a-2c
Br
phenyl
butyl 2c:
2a:
hexyl 2b:
Ar1=
R1=
R1=
e
Ar1(R1)
N
O
N
O
O
N
O
Br
(R)Ar
(R)Ar
N
Ar1(R1)
(HO)2B
3 (a-h)
1 (a-f)
2(a-c)
Scheme 1 a, Ar(R)NH2, CH3COOH(CH3CH2OH), reflux; b1, carbazole: 1-bromohexane = 1: 1.1, KOH, tetrabutyl ammonim
bromide, DMSO, 100°C; b2, carbazole:1-iodobenzene = 1:1, CuI, K3PO4, L-proline, DMSO; c, 9-hexyl-9H-carbazole: NBS = 1: 1,
CHCl3, DMF, dark, 0°C; d, n-BuLi (1.2 eq), THF, –78°C, (CH3O)3B(2.4eq), H2O/HCl; e, Pd(PPh3)4, K2CO3, toluene, 80°C.
* Correspondent. E-mail: fengguoliang@hebust.edu.cn
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138 JOURNAL OF CHEMICAL RESEARCH 2008
Ar1(R1)
N
Ar1(R1)
N
Ar1(R1)
N
2d:
R1 = hexyl
b
a
2e:
Ar1 = phenyl
(HO)2B
B(OH)2
Br
Br
Ar1(R1)
Ar(R)
N
N
Ar1(R1)
N
O
O
c
O
N
O
(HO)2B
B(OH)2
N
O
Ar(R)
(R)Ar
Br
3 (i-l)
O
,
2d 2e
1b
, 1e
Scheme 2 a, 9-hexyl-9H-carbazole: NBS = 1: 2, CHCl3, DMF, Dark, 0°C; b, n-BuLi (3.0 eq), THF, –78°C, (CH3O)3B(5.0eq), H2O/HCl;
c, Pd(PPh3)4, K2CO3, T = toluene, 80°C.
reaction.27,28 9-Alkylcarbazole was obtained by the reaction of
carbazole with 1-bromohexane or 1-bromobutane in DMSO
catalysed by KOH and 9-arylcarbazole were synthesised in
the presence of L-proline in DMSO, then 9-alkylcarbazole and
9-arylcarbazole with NBS translated into 3-bromocarbazole
in CHCl3, the boronic acid of carbazole was obtained via
lithiathion with n-BuLi, followed by quenching with trimethyl
borate and hydrolysis under acidic conditions. The final step to
3a–h was also outlined in Scheme 1. As shown in Scheme 1,
the carbazole moiety was introduced by C–C bond connection
at its 3 position through a Suzuki cross-coupling of 1a–f with
the boronic acid of carbazole (2a–c) catalysed by Pd(PPh3)4.
As we anticipated the products bearing carbazole-3-yl onto
the 1,8-naphthalimide were all efficiently achieved with the
excellent yields.
In order to synthesise the three chromophores compounds
3i–l, firstly we obtained 3,6-disbromo-9-hexylcarbazole and
3,6-disbromo-9-phenyllcarbazole as shown in Scheme 2.
Following, 3,6-disbromo-9-hexyl carbazole and 3,6-disbromo-
9-phenyllcarbazole synthesised the bisboronic acid of
carbazole via lithiathion with n-BuLi, followed by quenching
with trimethyl borate and hydrolysis under acidic conditions.
The final step to the three chromophores compounds (3i–l)
was also outlined in Scheme 2.
it can be found that the maximum fluorescence emission
wavelengths of 4-(9-phenyl-carbazol-3-yl)-1,8-naphthalimide
(3h) shows a small blue-shift compared with that of 4-(9-
alkyl-carbazol-3-yl)-1,8-naphthalimide (3a–g). The same
phenomenon was found in three chromophores compounds
(3k, 3l) compared with (3i, 3j). Mention must be made here
that the maximum fluorescence emission wavelengths of three
chromophores compounds (3i, 3j, 3k) has a small blue-shift
compared with that of two chromophores compounds (3b, 3e,
3h), respectively.
Figure 1 presented the emission spectrums of 3b at
different excitation wavelengths 280, 345 and 401 nm in
CH2Cl2 solution (1 × 10-5 M). We can find their intensity
of fluorescence all at 534 nm. It indicated that excitation
wavelengths do not affect the emission wavelengths. The
maximum fluorescence emission wavelengths of 3b in
different solvent were presented in Fig. 2. As shown in Fig. 2,
the emission band strongly occurs blue-shift on decreasing the
polar nature the solvent, reaching a maximum at 476 nm in
toluene.
In conclusion, a series of novel two chromophores and
three chromophores compounds containing carbazolyl and
3000
2800
2600
2400
2200
Optical properties
The photophysical properties of all compounds 3a–l were
examined in dilute CH2Cl2 solution (ca 10-5 M). Photophysical
data are summarised in Table 1.
2000
3b 401nm
1800
1600
1400
1200
1000
800
600
400
200
0
3b 345nm
3b 280nm
The UV-Vis spectrums of 3a–l were shown in Table 1. As
shown in Table 1, the absorption spectra of the molecules 3a–l
exhibited the characteristic absorption peaks of carbazole unit
between 280 and 345 nm and that of the 1,8-naphthalimide at
400 nm. It should be noted that not only does the absorption
maximum of N-aryl-1,8-naphthalimide (3d–f) shows a small
red-shift compared with that of N-alkyl-1,8-naphthalimide
(3a–c), but also the absorption maximum of 4-(9-phenyl-
carbazol -3-yl)-1,8-naphthalimide (3h, 3k, 3l) shows a small
blue-shift compared with that of 4-(9-hexyl-carbazol-3-yl)-
1,8-naphthalimide (3g, 3i, 3j).
500
600
Wavelength (nm)
The emission spectrums of 3a–l were also presented in
Table 1. For two chromophores compounds (3a and 3h),
Fig. 1 The fluorescence emission spectra of 3b at different
excitation wavelengths in CH2Cl2 (1 × 10-5 M).
Table 1 Absorption and fluorescence spectra of 3a–l in CH2Cl2 solution
Compound
abs (nm)
3a
3b
3c
3d
3e
3f
3g
3h
3i
3j
3k
3l
l
280
345
401
536
280
345
401
534
282
345
401
539
285
344
407
539
281
344
406
539
282
344
408
542
280
345
401
534
286
345
395
522
284
345
401
522
282
343
401
527
285
345
394
514
282
344
396
516
lemmax (nm)
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JOURNAL OF CHEMICAL RESEARCH 2008 139
3500
3000
2500
2000
1500
1000
500
4-(9-hexyl-carbazol-3-yl)-N-benzyl-1,8-naphthalimide (3c): Green
powder (yield: 82%). M.p. 174–175°C. 1H NMR (CDCl3, 400 MHz)
δ: 0.90 (t, J = 7.4 Hz, 3H), 1.35–1.95 (m, 8H), 4.39 (t, J = 7.0 Hz,
2H), 5.44 (s, 2H), 7.32 (d, J = 8.0 Hz, 2H), 7.50–7.59 (m, 8H), 7.70
(t, J = 8.0 Hz, 1H), 7.82 (d, J = 7.6 Hz, 1H), 8.12 (d, J = 7.2 Hz, 1H),
8.23 (s, 1H), 8.42 (d, J = 7.6 Hz, 1H), 8.65–8.71 (m, 2H). IR (KBr,
cm-1): 3064, 2956, 2933, 2856, 1690, 1659, 1590, 1520, 1466, 1381,
1343, 1235, 1150, 1026, 965, 810, 779, 746, 695. Anal. Calcd. for
C37H32N2O2: C, 82.81; H, 6.01; N, 5.22; Found: C, 82.93; H, 5.95;
N, 5.04.
4-(9-hexyl-carbazol-3-yl)-N-phenyl-1,8-naphthalimide (3d): Green
powder(yield:83.4%).M.p.196.5-198°C.1HNMR(CDCl3,400MHz)
δ: 0.90 (t, J = 7.4 Hz, 3H), 1.25–2.17 (m, 8H), 4.40 (t, J = 7.0 Hz,
2H), 7.37 (d, J = 6.8 Hz, 2H), 7.50–7.62 (m, 8H), 7.74 (t, J = 7.8 Hz,
1H), 7.87 (d, J = 7.6 Hz, 1H), 8.14 (d, J = 7.2 Hz, 1H), 8.26 (s, 1H),
8.48 (d, J = 7.6 Hz, 1H), 8.68–8.74 (m, 2H). IR (KBr, cm-1): 3056,
2956, 2933, 2856, 1706, 1667, 1590, 1489, 1466, 1366, 1243, 1188,
1026, 810, 790, 756. Anal. Calcd. for C36H30N2O2: C, 82.73; H, 5.79;
N, 5.36; Found; C, 82.86; H, 5.90; N, 5.47.
3b Toluene
3b CH2Cl2
3b Acetone
3b DMF
0
400
450
500
550
600
650
Wavelength (nm)
4-(9-hexyl-carbazol-3-yl)-N-(4-methoxyphenyl)-1,8-naphtha-
1
limide (3e): Green powder (yield: 87%). M.p. 248–249°C. H NMR
Fig. 2 The fluorescence emission spectra of 3b in solvents of
(CDCl3, 400 MHz) δ: 0.90 (t, J = 7.4 Hz, 3H), 1.32–1.97 (m, 8H),
3.89 (s, 3H), 4.40 (t, J = 7.0 Hz, 2H), 7.09 (d, J = 8.0 Hz, 2H), 7.26–
7.29 (m, 3H), 7.48–7.64 (m, 4H), 7.73 (t, J = 8.0 Hz, 1H), 7.85 (d,
J = 7.2 Hz, 1H), 8.14 (d, J = 7.6 Hz, 1H), 8.26 (s, 1H), 8.47 (d,
J = 8.0 Hz, 1H), 8.68-8.73 (m, 2H). IR (KBr, cm-1): 3064, 2956,
2933, 2863, 1706, 1659, 1590, 1513, 1466, 1366, 1297, 1250, 1188,
1027, 810, 787, 741. Anal. Calcd. for C37H32N2O3: C, 80.41; H, 5.84;
N, 5.07; Found; C, 80.53; H, 5.81; N, 5.23.
different polarities.
1,8-naphthalimide groups were synthesised via Suzuki
cross-coupling. Their absorption and photoluminescence in
dicholomethane solution were studied. They have different
emitting fluorescence wavelengths ranging from 514 to
542 nm that may be served as good green light emitting
materials. The application of novel compounds is under way
in our laboratory.
4-(9-hexyl-carbazol-3-yl)-N-[1]naphthyl-1,8-naphthalimide (3f):
Green powder (yield: 85.5%). M.p. 214.5–216°C. H NMR (CDCl3,
1
400 MHz) δ: 0.91 (t, J = 7.4 Hz, 3H), 1.36–1.56 (m, 8H), 4.41
(t, J = 6.4 Hz, 2H), 7.29 (d, J = 7.0 Hz, 1H), 7.45–7.78 (m, 9H), 7.76
(t, J = 7.8 Hz, 1H), 7.90 (d, J = 7.2 Hz, 1H), 7.96–8.03 (m, 2H), 8.16 (d,
J = 7.6 Hz, 1H), 8.29 (s, 1H), 8.53 (d, J = 8.4 Hz, 1H), 8.71–8.76 (m,
2H). IR (KBr, cm-1): 3056, 2956, 2933, 2856, 1705, 1667, 1590, 1466,
1358, 1243, 1196, 1026, 872, 787, 749. Anal. Calcd. for C40H32N2O2:
C, 83.89; H, 5.63; N, 4.89; Found: C, 84.03; H, 5.51; N, 4.72.
Experimental
All chemicals were obtained commercially and used without
further purification unless otherwise noted. THF was distilled over
sodium and diphenylketone before use. Carbazole was purchased
from Aldrich. Melting points were determined by an XT-5A micro-
Experimental procedure (3g–h): To a degassed (N2) solution of
the 4-bromo-1,8-naphthalimide 1b (2 mmol) and Pd(PPh3)4 catalyst
(115 mg, 0.1 mmol, 5 mol.% per C–Br bond) in toluene (30 ml),
a solution of carbazole-boronic acid 2b–c (2.3 mmol) in toluene
(10 ml) and 2M aqueous K2CO3 solution (4 ml) was added via syringe.
The reaction mixture was stirred at 80°C for 10 h. After cooling, the
product was extracted with DCM, washed with water and dried over
MgSO4. The solvent was evaporated to afford the crude mixture.
After column chromatography on silica gel eluting with petroleum
ester:ethyl acetate (8:1), pure compounds 3g–h were obtained.
4-(9-butyl-carbazol-3-yl)-N-butyl-1,8-naphthalimide (3g): Green
powder (yield: 85%). M.p. 167–168.5°C. 1H NMR (400 MHz, CDCl3)
δ: 1.00 (t, J = 7.2 Hz, 6H), 1.45–1.50 (m, 4H), 1.77 (t, J = 7.6 Hz,
2H), 1.94 (t, J = 7.2 Hz, 2H), 4.24 (t, J = 7.6 Hz, 2H), 4.40 (t, J = 7.2 Hz,
2H), 7.26–7.27 (m, 2H), 7.48–7.62 (m, 3H), 7.71 (t, J = 8 Hz, 1H),
7.83 (d, J = 7.6 Hz, 1H), 8.12 (d, J = 8 Hz, 1H), 8.24 (s, 1H), 8.42
(d, J = 8.4 Hz, 1H), 8.64–8.69 (m, 2H). IR (KBr, cm-1): 3056, 2948,
2870, 1697, 1659, 1589, 1466, 1381, 1358, 1234, 1149, 1072, 949,
872, 810, 802, 748. Anal. Calcd. for C32H30N2O2: C, 80.98; H, 6.37;
N, 5.90; Found: C, 80.79; H, 6.32; N, 5.97.
4-(9-phenyl-carbazol-3-yl)-N-butyl-1,8-naphthalimide (3h): Green
powder (yield: 82%). M.p. 169–170°C. 1H NMR (400 MHz, CDCl3)
δ: 1.01 (t, J = 7.2 Hz, 3H), 1.45–1.52 (m, 2H), 1.75–1.77 (m, 2H),
4.24 (t, J = 7.2 Hz, 2H), 7.26 (s, 1H), 7.30–7.40 (m, 1H), 7.47–7.49
(m, 2H), 7.53–7.56 (m, 3H), 7.65–7.76 (m, 4H), 7.84 (d, J = 7.6 Hz,
1H), 8.18 (d, J = 7.6 Hz, 1H), 8.29 (s, 1H), 8.41 (d, J = 8.4 Hz, 1H),
8.65-8.70 (m, 2H). IR (KBr, cm-1): 3056, 2955, 2871, 1697, 1589,
1651, 1505, 1458, 1358, 1234, 1188, 1072, 1026, 995, 941, 846, 810,
756, 694. Anal. Calcd. for C34H26N2O2: C, 82.57; H, 5.30; N, 5.66;
Found: C, 82.49; H, 5.32; N, 5.77.
1
melting point apparatus and are uncorrected. H NMR spectra were
determined on a Varian VXP-400s spectrometer using CDCl3 as
solvent and tetramethylsilane (TMS) as internal reference. IR Spectra
was obtained on a Nicolet FT-IR500 spectrophotometer using
KBr pellets. Elementary analyses were performed by a Carlo-Erba
EA1110 CNNO–S analyser. Absorption spectra were determined on
a Shimadzu UV-240 Spectrometer. Photoluminescence(PL) spectra
were measured using a Shimadzu RF-5301PC spectrofluorometer at
a concentration of 1.0 × 10-5 M in dichloromethane.
Experimental procedure (3a–f)
To a degassed (N2) solution of the 4-bromo-1, 8-naphthalimide 1a–f
(2 mmol) and Pd(PPh3)4 catalyst (115 mg, 0.1 mmol, 5 mol.% per
C–Br bond) in toluene (30 ml), a solution of carbazole-boronic acid
(2.3 mmol) in toluene (10 ml) and 2M aqueous K2CO3 solution
(4 ml) was added via syringe. The reaction mixture was stirred at 80°C
for 10 h. After cooling, the product was extracted with DCM, washed
with water and dried over MgSO4. The solvent was evaporated to
afford the crude mixture. After column chromatography on silica gel
eluting with petroleum ester:ethyl acetate(8:1), pure compounds 3a–f
were obtained.
4-(9-hexyl-carbazol-3-yl)-N-methyl-1,8-naphthalimide (3a): Green
powder(yield:87.6%).M.p.167.5–168.5°C.1HNMR(CDCl3,400MHz)
δ: 0.90 (t, J = 7.4 Hz, 3H), 1.35–1.96 (m, 8H), 4.39 (t, J = 7.8 Hz,
2H), 3.63 (s, 2H), 7.51–7.62 (m, 5H), 7.72 (t, J = 8.0 Hz, 1H), 7.84
(d, J = 7.6 Hz, 1H), 8.14 (d, J = 7.6 Hz, 1H), 8.26 (s, 1H), 8.44 (d,
J = 8.0 Hz, 1H), 8.66–8.71 (m, 2H). IR (KBr, cm-1): 3056, 2956,
2933, 2856, 1698, 1659, 1590, 1490, 1466, 1405, 1366, 1289, 1235,
1158, 1042, 926, 818, 799, 749. Anal. Calcd. for C31H28N2O2: C,
80.84; H, 6.13; N, 6.08; Found: C, 80.93; H, 6.01; N, 5.89.
4-(9-hexyl-carbazol-3-yl)-N-butyl-1,8-naphthalimide (3b): Green
powder (yield: 89%). M.p. 127–128°C. 1H NMR (CDCl3, 400 MHz)
δ: 0.90 (t, J = 7.4 Hz, 3H), 1.01 (t, J = 7.4 Hz, 3H), 1.35–1.97 (m,
12H), 4.24 (t, J = 7.2 Hz, 2H), 4.40 (t, J = 7.8 Hz, 2H), 7.47–7.62 (m,
5H), 7.70 (t, J = 7.8 Hz, 1H), 7.82 (d, J = 7.6 Hz, 1H), 8.13 (d, J = 7.6
Hz, 1H), 8.24 (s, 1H), 8.41 (d, J = 8.4 Hz, 1H), 8.64–8.69 (m, 2H).
IR (KBr, cm-1): 3064, 2956, 2933, 2863, 1698, 1659, 1590, 1490,
1466, 1389, 1358, 1266, 1235, 1150, 1073, 949, 810, 780, 741, Anal.
Calcd. for C34H34N2O2: C, 81.24; H, 6.82; N, 5.57; Found: C, 81.30;
H, 6.75; N, 5.64.
Experimental procedure (3i–l): To a degassed (N2) solution of
the 4-bromo-1, 8-naphthalimide 1b or 1e (2 mmol) and Pd(PPh3)4
catalyst (115 mg, 0.1 mmol, 5 mol.% per C–Br bond) in toluene
(30 ml), a solution of carbazole–boronic acid 2d or 2e (0.67 mmol)
in toluene (10 ml) and 2M aqueous K2CO3 solution (4 ml) was added
via syringe. The reaction mixture was stirred at 80°C for 24 h. After
cooling, the product was extracted with DCM, washed with water
and dried over MgSO4. The solvent was evaporated to afford the
crude mixture. After column chromatography on silica gel eluting
with petroleum ester:dichloromethane (1:1), pure compounds
were obtained.
3i–l
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140 JOURNAL OF CHEMICAL RESEARCH 2008
4,4'-(9-hexyl-carbazol-3,6-yl)-N-butyl-1,8-naphthalimide
(3i):
References
Green powder (yield: 69%). M.p. 226–227.5°C. 1H NMR (400 MHz,
CDCl3) δ: 0.90–1.02 (m, 9H), 1.35–1.57 (m, 10H), 1.70–1.78 (m,
4H), 2.01–2.05 (m, 2H), 4.24 (t, J = 9.6 Hz, 4H), 4.49 (t, J = 9.2 Hz,
2H), 7.63–7.72 (m, 6H), 7.82 (d, J = 10.4 Hz, 2H), 8.27 ((s, 2H), 8.40
(d, J = 11.2 Hz, 2H), 8.62–8.68 (m, 4H); IR (KBr, cm-1): 3072, 2956,
2863, 1697, 1659, 1589, 1481, 1466, 1358, 1281, 1234, 1188, 1149,
1072, 1026, 957, 864, 810, 756, 617. Anal. Calcd. for C50H47N3O4:
C, 79.65; H, 6.28; N, 5.57; Found: C, 79.56; H, 6.23; N, 5.64.
4,4'-(9-hexyl-carbazol-3,6-yl)-N-(4-methoxyphenyl)-1,8-naphtha-
limide (3j): Green powder (yield: 65%). M.p. >300°C. 1H NMR
(CDCl3, 400 MHz) δ: 0.92 (t, J = 6.8 Hz, 3H), 1.34–1.44 (m, 6H),
2.01–2.05 (m, 2H), 3.89 (s, 6H), 4.49 (t, J = 9.2 Hz, 2H), 7.06–7.08
(m, 4H), 7.24–7.26 (m, 4H), 7.65–7.76 (m, 6H), 7.85 (d, J = 7.2 Hz,
2H), 8.31 (s, 2H), 8.45–8.47 (m, 2H), 8.68 (d, J = 7.2 Hz, 2H), 8.71
(d, J = 7.6 Hz, 2H). IR (KBr, cm-1): 3072, 2933, 2863, 1706, 1667,
1590, 1513, 1466, 1366, 1281, 1242, 1188, 1134, 1034, 864, 818,
779, 756. Anal. Calcd. for C56H43N3O6: C, 78.76; H, 5.08; N, 4.92;
Found: C, 79.02; H, 5.21; N, 5.04.
4,4'-(9-phenyl-carbazol-3,6-yl)-N-butyl-1,8-naphthalimide (3k):
Green powder (yield: 66%). M.p. 281–283°C. 1H NMR (CDCl3,
400 MHz) δ: 0.97 (t, J = 7.2 Hz, 6H), 1.14–1.49 (m, 4H), 1.69–1.76
(m, 4H), 4.22 (t, J = 9.6 Hz, 4H), 7.60–7.70 (m, 12H), 7.81 (d,
J = 7.6 Hz, 2H), 8.30 (s, 1H), 8.38 (d, J = 8.4 Hz, 2H), 8.62 (d,
J = 7.2 Hz, 2H), 8.66 (d, J = 7.6 Hz, 2H). IR (KBr, cm-1): 3064, 2955,
2871, 1698, 1659, 1590, 1497, 1458, 1358, 1281, 1234, 1188, 1072,
949, 872, 818, 787, 756, 702. Anal. Calcd. for C50H39N3O4: C, 80.52;
H, 5.27; N, 5.63; Found: C, 80.40; H, 5.21; N, 5.74.
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4,4'-(9-phenyl-carbazol-3,6-yl)-N-(4-methoxyphenyl)-1,8-naphtha-
limide (3l): Green powder (yield: 63%). M.p. >300°C.
1H NMR (CDCl3, 400 MHz) δ: 3.89 (s, 6H), 7.07–7.09 (m, 4H),
7.27–7.29 (m, 2H), 7.60–7.77 (m, 14H), 7.87 (d, J = 8.0 Hz, 2H),
8.36 (s, 1H), 8.46 (d, J = 8.4 Hz, 2H), 8.69 (d, J = 7.6 Hz, 2H), 8.73
(d, J = 7.6 Hz, 2H). IR (KBr, cm-1): 3056, 2932, 2840, 1706, 1667,
1590, 1512, 1488, 1366, 1242, 1188, 1134, 1034, 818, 779, 756, 702.
Anal. Calcd. for C56H35N3O6: C, 79.51; H, 4.17; N, 4.97; Found: C,
79.43; H, 4.28; N, 5.14.
This work was supported by the Key Laboratory of Organic
Synthesis of Jiangsu Province (No S8109108), the Natural
Science Foundation of Jiangsu Province (No BK2004038,
2006048).
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Received 22 January 2008; accepted 4 March 2008
Paper 08/5057 doi: 10.3184/030823408X304041
PAPER: 08/5057