Chao et al.
perature was set at 80 °C, and bromine (9.2 mL, 180 mmol)
was added dropwise over 2 h. The mixture was reacted further
at 80 °C for 16 h. The reaction mixture was cooled to room
temperature, and the excess Br2 was displaced by nitrogen.
The product was precipitated by addition of ice-water and
collected by suction filtration. The precipitate was washed with
water several times until the aqueous layer became neutral
to yield dibromo dianhydride as a crude product. The crude
product was then dried under reduced pressure at 120 °C and
used for the next step without further purification.
7.90 (m, 2H), 7.85 (d, J ) 8 Hz, 1H), 7.79 (d, J ) 8.0 Hz, 1H),
7.69-7.39 (m, 10H), 7.28 (d, J ) 7.6 Hz, 4H), 2.73-2.66 (m,
4H), 1.15-1.07 (m, 24H); 13C NMR (100 MHz, CDCl3) δ 163.2,
163.1, 145.5, 145.4, 140.1, 140.0, 139.4, 139.2, 136.7, 136.6,
135.3, 135.2, 134.4, 134.3, 134.1, 134.0, 130.7, 130.5, 130.4,
130.3, 130.2, 129.5, 129.4, 129.2, 129.04, 128.97, 128.9, 128.6,
128.5, 127.5, 127.3, 127.1, 126.8, 126.72, 126.67, 126.44,
126.37, 124.7, 124.6, 123.9, 122.2, 122.0, 29.24, 29.22, 24.15,
24.10; HRFAB m/z 963.4158, calcd for C68H54N2O4 m/z 962.4084.
Anal. Calcd for C68H54N2O4: C, 84.80; H, 5.65; N, 2.91.
Found: C, 85.05; H, 5.75; N, 2.76.
The crude 1,7-dibromoperylene-3,4,9,10-tetracarboxylic di-
anhydride (80 g, 14.5 mmol), excess 2,6-diisopropylaniline (88
mL, 46.7 mmol), and acetic acid (46 mL) were mixed and
heated at 120 °C in NMP (1 L) under a nitrogen atmosphere
for 120 h. The product was precipitated by the addition of
water and collected by suction filtration. The crude product
was washed with water until neutral and dried. The crude
product was first purified by column chromatography on silica
gel using CH2Cl2 as the eluent to obtain a mixture of the
isomeric diimides. The mixture was washed with EtOH (300
mL) and toluene (300 mL) and then heated at 80 °C in toluene
(300 mL) for 12 h. The pure diimide was recrystallized from
the hot toluene solution. The crystals were collected through
hot filtration to provide an essentially pure orange compound,
3 (46 g, 36% overall yield): 1H NMR (400 MHz, CDCl3) δ 9.56
(d, J ) 8.0 Hz, 2H), 9.01 (s, 2 H), 8.79 (d, J ) 8.0 Hz, 2H),
7.50 (t, J ) 8.0 Hz, 2H), 7.35 (d, J ) 8.0 Hz, 4H), 2.73 (septet,
J ) 6.8 Hz, 4H), 1.18 (d, J ) 6.8 Hz, 24H); 13C NMR (100 MHz,
CDCl3) δ 162.8, 162.3, 145.4, 138.3, 133.3, 133.1, 130.5, 129.96,
129.75, 129.48, 128.8, 127.5, 124.1, 123.1, 122.7, 120.9, 29.4,
24.1, 24.1; HRFAB m/z 869.1422, calcd for C48H40Br2N2O4 m/z
866.1355.
N,N′-Bis(2,6-diisopropylphenyl)-1,7-diphenylperylene-
3,4,9,10-tetracarboxydiimide (4c). The reaction of 3 (3.0 g,
3.5 mmol), phenylboronic acid22 (3.38 g, 27.7 mmol), Pd(PPh3)4
(100 mg, 2.5 mol %), and Na2CO3 (1.10 g, 10.4 mmol) in
degassed EtOH (3.5 mL), benzene (20 mL), and H2O (10 mL)
at 80 °C for 8 h followed by column chromatographic purifica-
tion on silica gel using toluene/CH2Cl2 (1:1) as the eluent
1
produced 4c as a red solid (2.7 g, 90%): mp > 390 °C dec; H
NMR (400 MHz, CDCl3) δ 8.71 (s, 2H), 8.20 (d, J ) 8.0 Hz,
2H), 7.92 (d, J ) 8.0 Hz, 2H), 7.62 (dd, J ) 8.0, 1.6 Hz, 4H),
7.53-7.45 (m, 8H), 7.32 (d, J ) 8.0 Hz, 4H), 2.74 (septet, J )
6.8 Hz, 4H), 1.15 (m, 24H); 13C NMR (100 MHz, CDCl3) δ
163.27, 163.24, 145.4, 141.9, 141.27, 135.7, 135.2, 132.9, 130.4,
130.3, 130.2, 129.9, 129.5, 129.5, 128.9, 128.7, 128.3, 124.0,
122.2, 121.8, 29.3, 24.2, 24.1; HRFAB m/z 863.3862, calcd for
m/z C60H50N2O4 862.3771. Anal. Calcd for C60H50N2O4: C,
83.50; H, 5.84; N, 3.25. Found: C, 83.54; H, 5.63; N, 3.17.
N,N′-Bis(2,6-diisopropylphenyl)-1,7-bis(biphenyl-4-yl)-
perylene-3,4,9,10-tetracarboxydiimide (4d). The reaction
of 3 (3.0 g, 3.5 mmol), biphenyl-4-boronic acid23 (5.48 g, 27.7
mmol), Pd(PPh3)4 (100 mg, 2.5 mol %), and Na2CO3 (1.10 g,
10.4 mmol) in degassed EtOH (3.5 mL), benzene (20 mL), and
H2O (10 mL) under nitrogen at 80 °C for 12 h followed by
column chromatographic purification on silica gel using toluene/
CH2Cl2 (1:1) as the eluent produced 4d as a red solid (91%,
A General Procedure for the Preparation of 1,7-
Ar2PDI. N,N′-Bis(2,6-diisopropylphenyl)-1,7-bis(2,4,6-tri-
methylphenyl)perylene-3,4,9,10-tetracarboxydiimide (4a).
A deaerated mixture of EtOH (8.2 mL), benzene (47 mL), and
H2O (23 mL) was added to a solid mixture of 3 (7.0 g, 8.1
mmol), 2,4,6-trimethylphenylboronic acid20 (10.6 g, 64.6 mmol),
Pd(PPh3)4 (466 mg, 5.0 mol %), and Na2CO3 (2.56 g, 24.2 mmol)
under nitrogen. The mixture was reacted at 80 °C for 120 h.
The reaction was quenched by the addition of water. The
mixture was extracted with CH2Cl2 several times. The com-
bined organic layer was dried over anhydrous MgSO4 and
concentrated under reduced pressure to provide a crude solid.
The crude solid was further purified by column chromatogra-
phy on silica gel using toluene/CH2Cl2 (1:1) as the eluent to
obtain 4a as an orange red solid (5.5 g, 72%): mp > 380 °C
dec; 1H NMR (400 MHz, CDCl3) δ 8.44 (s, 2H), 8.30 (d, J ) 8.0
Hz, 2H), 8.12 (d, J ) 8.0 Hz, 2H), 7.47 (t, J ) 7.6 Hz, 2H),
7.32 (d, J ) 7.6 Hz, 4H), 7.09 (s, 4H), 2.74 (septet, J ) 6.4 Hz,
1
3.2 g): mp > 390 °C dec; H NMR (400 MHz, CDCl3) δ 8.76
(s, 2H), 8.24 (d, J ) 8.0 Hz, 2H), 8.09 (d, J ) 8.0 Hz, 2H),
7.79-7.70 (m, 12H), 7.51-7.45 (m, 6H), 7.40 (t, J ) 8.0 Hz,
2H), 7.33 (d, J ) 8.0 Hz, 4H), 2.76 (septet, J ) 6.8 Hz, 4H),
1.81-1.15 (m, 24H); 13C NMR (100 MHz, CDCl3) δ 163.3, 163.2,
145.4, 141.5, 140.9, 140.8, 139.8, 135.8, 135.3, 132.9, 130.4,
130.3, 123.0, 129.6, 129.54, 129.47, 128.9, 128.8, 128.3, 127.8,
127.0, 124.0, 122.3, 121.9, 29.3, 24.2, 24.1; HRFAB m/z
1015.4472, calcd for C72H58N2O4 m/z 1014.4397. Anal. Calcd
for C60H50N2O4: C, 85.18; H, 5.78; N, 2.76. Found: C, 85.04;
H, 5.78; N, 2.89.
N,N′-Bis(2,6-diisopropylphenyl)-1,7-di(4-formylphenyl)-
perylene-3,4,9,10-tetracarboxydiimide (4e). The reaction
of 3 (3.0 g, 3.5 mmol), 4-formylphenylboronic acid24 (4.15 g,
27.7 mmol), Pd(PPh3)4 (100 mg, 2.5 mol %), and Na2CO3 (1.10
g, 10.4 mmol) in degassed EtOH (3.5 mL), benzene (20 mL)
and, H2O (10 mL) under nitrogen at 80 °C for 96 h followed
by column chromatographic purification on silica gel using
CH2Cl2 as the eluent produced 4e as a red solid (2.3 g, 72%):
mp > 380 °C dec; 1H NMR (400 MHz, CDCl3) δ 10.14 (s, 2H),
8.72 (s, 2H), 8.24 (d, J ) 8.4 Hz, 2H), 8.07 (d, J ) 8.4 Hz, 4H),
7.85 (t, J ) 8.4 Hz, 6H), 7.48 (t, J ) 7.6 Hz, 2H), 7.34 (d, J )
7.6 Hz, 4H), 2.73 (septet, J ) 6.8 Hz, 4H), 1.20-1.15 (m, 24H);
13C NMR (100 MHz, CDCl3) δ 191.1, 163.0, 162.9, 147.8, 145.4,
139.9, 136.0, 135.2, 134.6, 132.9, 131.4, 130.8, 130.2, 130.1,
129.9, 129.7, 129.3, 128.5, 124.0, 122.6, 122.3, 29.3, 24.2, 24.1;
HRFAB m/z 919.3757, calcd for m/z C62H50N2O6 918.3669.
Anal. Calcd for C62H50N2O6: C, 81.02; H, 5.48; N, 3.05.
Found: C, 80.80; H, 5.56; N, 2.85.
4H), 2.42 (s, 6H), 2.03 (s, 12H), 1.15 (d, J ) 6.4 Hz, 24H); 13
C
NMR (100 MHz, CDCl3) δ 163.4, 163.1, 145.5, 139.6, 138.8,
138.23, 136.1, 135.9, 134.0, 133.2, 130.9, 130.3, 130.0, 129.6,
128.5, 128.5, 127.0, 124.0, 122.6, 122.2, 29.3, 24.2, 21.4, 20.9;
HRFAB m/z 947.4796, calcd for C66H62N2O4 m/z 946.4710.
Anal. Calcd for C66H62N2O4: C, 83.69; H, 6.60; N, 2.96.
Found: C, 83.79; H, 6.42; N, 2.89.
syn- and anti-N,N′-Bis(2,6-diisopropylphenyl)-1,7-di-
naphth-1-ylperylene-3,4,9,10-tetracarboxydiimide (4b).
The reaction of 3 (3.0 g, 3.5 mmol), 1-naphthaleneboronic acid21
(4.76 g, 27.7 mmol), Pd(PPh3)4 (100 mg, 2.5 mol %), and
Na2CO3 (1.10 g, 10.4 mmol) in degassed EtOH (3.5 mL),
benzene (20 mL), and H2O (10 mL) under nitrogen at 80 °C
for 12 h followed by column chromatography purification on
silica gel using toluene/CH2Cl2 (1:1) as the eluent produced
4b (two conformational isomers, 1:1 ratio) as a red solid (2.7
g, 84%): mp > 390 °C dec; 1H NMR (400 MHz, CDCl3) δ 8.69,
8.67 (two conformers (1:1), s, 2H), 8.06-8.00 (m, 6H), 7.93-
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723.
(19) Hofkens, J.; Vosch, T.; Maus, M.; Kohn, F.; Cotlet, M.; Weil,
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