K. Mꢁllen et al.
7 Hz, 4H), 6.87 (m, 8H), 6.34 (d, J=7 Hz, 4H), 1.51 ppm (s, 9H);
13C NMR (62.5 MHz, CD2Cl2, 300 K): d=153.84, 144.68, 142.94, 139.06,
131.25, 129.65, 127.48, 127.28, 123.24, 121.26, 117.00, 82.22, 28.46 ppm;
FD mass spectrum (8 kV): m/z (%): calcd for: 663.87; found: 664.4
(100%) [M]+; elemental analysis calcd (%) for C41H33N3O2S2: C 74.18, H
5.01, N 6.33, S 9.66; found: C 74.16, H 5.11, N 6.18, S 9.68.
Experimental Section
General methods: 1H and 13C NMR spectra were recorded on Bruker
AMX250, Bruker AC300, AMX500 NMR and AMX700 NMR spectrom-
eters using the residual proton or the carbon signal of the deuterated sol-
vent as an internal standard. Chemical shifts are reported in parts per
million. FD mass spectra were performed with a VG-Instrument ZAB 2-
SE-FDP. UV/Vis absorption spectra were recorded on a Perkin Elmer
Lambda 40 spectrophotometer. The elemental analyses were carried out
by the Microanalytical Laboratory of Johannes Gutenberg University.
Di(phenothiazinylphenyl) amine (9): Compound 8 (2.6 g, 3.92 mmol) was
dissolved in acetic acid (60 mL) and the solution was refluxed overnight.
After cooling to room temperature, the mixture was filtered to get white
crystal. After washed by acetic acid once and dried, a white solid was ob-
tained (1.8 g, 82%). 1H NMR (250 MHz, THF, 300 K): d=7.99 (s, 1H),
7.42 (d, J=8 Hz, 4H), 7.31 (d, J=8 Hz, 4H), 6.93 (d, J=8 Hz, 4H), 6.75
(m, 8H), 6.32 ppm (d, J=8 Hz, 4H); 13C NMR (62.5 MHz, THF, 300 K):
d=145.93, 144.56, 134.13, 133.00, 127.71, 127.39, 123.13, 120.93, 120.01,
116.77 ppm; FD mass spectrum (8 kV): m/z (%): 563.75; found. 564.2
(100) [M+]; elemental analysis calcd (%) for C36H25N3S2: C 76.70, H 4.47,
N 7.45, S 11.38; found: C 76.72, H 4.56, N 7.36, S 11.36.
Materials: Tetrahydrofuran (Fluka) and toluene (Fluka) were distilled
over sodium/benzophenone. Tris(dibenzylideneacetone)dipalladium(0)
[Pd2ACHTUNGTRENNUNG
(dba)3] were purchased from Aldrich. N1-(4-(Dimethylamino)-
phenyl)-N4,N4-dimethylbenzene-1,4-diamine, benzoyl leuco methylene
blue and phenothiazine were purchased from ABCR GmbH. Column
chromatography was performed with dichloromethane (chromasolv,
Riedel), methanol, pentane or toluene on silica gel (Geduran Si60,
Merck). N-(2,6-Diisopropylphenyl)-perylene-3,4-dicarboximide and N-
(2,6-diisopropylphenyl)-9-bromo-perylene-3,4-dicarboximide were sup-
plied from BASF-AG (Ludwigshafen). N-(2,6-Diisopropylphenyl)-1,6,9-
tribromo-perylene-3,4-dicarboximide was synthesized as described be-
N-(2,6-Diisopropylphenyl)-9-di(phenothiazinylphenyl)amino-perylene-
3,4-dicarboximide (2): Compound 2 was obtained by general Buchwald–
Hartwig reaction condition (800 mg of N-(2,6-diisopropylphenyl)-9-bro-
moperylene-3,4-dicarboximide). Columnchromatography using dichloro-
methane on silica gave
2 as a
violet solid (1.2 g, 81%). 1H NMR
ACHTUNGTRENNUNG
fore.[13a] All reported yields are isolated yields.
(250 MHz, THF, 300 K): d=8.67–8.50 (m, 4H), 8.19 (d, J=8 Hz, 1H),
7.67 (d, J=8 Hz, 1H), 7.54–7.14 (m, 14H), 7.03–6.80 (m, 12H), 6.38 (d,
J=8 Hz, 4H), 2.77 (m, 2H), 1.16 ppm (d, J=7 Hz, 12H); 13C NMR
(62.5 MHz, CD2Cl2, 300 K): d=164.59, 147.99, 146.71, 146.46, 144.97,
138.53, 137.97, 137.76, 136.02, 132.51, 132.47, 132.35, 132.16, 131.19,
130.60, 129.53, 128.72, 128.29, 128.07, 127.45, 127.23, 125.79, 124.93,
123.10, 121.79, 121.46, 120.86, 116.66, 29.63, 24.28 ppm; FD mass spec-
trum (8 kV): m/z (%): calcd for 1043.33; found: 1045.3 (100) [M]+; ele-
mental analysis calcd (%) for C70H50N4O2S2: C 80.59, H 4.83, N 5.37, S
6.15; found: C 80.76, H 5.05, N 5.23, S 6.19.
General procedure: Buchwald–Hartwig cross-coupling reactions: A mix-
ture of 9-bromoperylene dicarboximide (1 equiv), amine (1. equiv), tris-
ACHTUNGTRENNUNG(dibenzylideneacetone) dipalladium(0) (5% equiv), tri-tert-butylphos-
phine (10%equiv), sodium-tert-butyl alcohol (1.5 equiv) and dry toluene
was stirred at 808C in an argon atmosphere overnight. The solvent was
removed under reduced pressure. The crude product was purified by
column chromatography on silica gel.
N-(2,6-Diisopropylphenyl)-9-di(p-dimethylamino-phenyl)aminoperylene-
3,4-dicarboximide (1): Compound 1 was obtained by general Buchwald–
Hartwig reaction conditions (250 mg of N-(2,6-diisopropylphenyl)-9-bro-
moperylene-3,4-dicarboximide). Column chromatography using dichloro-
methane/methanol 20:1 on silica gave 1 as a blue solid (200 mg, 60%).
1H NMR (250 MHz, CD2Cl2, 300 K): d=8.58 (t, 2H), 8.45 (d, J=8 Hz,
2H), 8.34 (t, 2H), 8.14 (d, J=8 Hz, 1H), 7.47 (m, 2H), 7.36 (d, J=8 Hz,
2H), 7.22 (d, J=8 Hz, 1H), 6.93 (d, J=9 Hz, 4H), 6.68 (d, J=9 Hz, 4H),
2.91 (s, 12H), 2.76 (m, 2H), 1.15 ppm (d, J=7 Hz, 12H); 13C NMR
(62.5 MHz, CD2Cl2, 300 K) d=164.73, 147.73, 146.75, 138.60, 132.52,
132.43, 132.27, 129.99, 129.72, 129.12, 127.21, 126.58, 125.52, 124.50,
121.16, 120.38, 119.95, 119.62, 114.07, 41.27, 29.40, 24.28 ppm; FD mass
spectrum (8 kV): m/z (%): calcd for 734.95; found: 735.0 (100) [M]+; ele-
mental analysis calcd (%) for C50H46N4O2: C 81.71, H 6.31, N 7.62;
found: C 80.95, H 6.32, N 6.92.
N-(2,6-Diisopropylphenyl)-9-(3,7-dimethylamino-phenothiazine-10-yl)-
perylene-3,4-dicarboximide (3):
A mixture of benzoylleucomethylene
blue (1.5 g, 3.8 mmol), NaOH (310 mg, 3.8 mmol), THF (5 mL) and
MeOH (15 mL) was stirred and refluxed in a 250 mL mono-necked
round flask for 12 h. After the temperature of the mixture was cooled
down to room temperature, the solvent was removed by bubbling with
argon. Then N-(2,6-diisopropylphenyl)-9-bromoperylene-3,4-dicarbox-
ACHUTNRGENiNUG mide (1.5 g, 3.1 mmol), [Pd2ACHTUGNTREN(NUGN dba)3] (123 mg, 0.13 mmol), tri-tert-butyl-
phosphine (27 mg, 0.13 mmol) and sodium tert-butoxide (12 mg,
0.13 mmol) and 100 mL of anhydrous toluene were added into the reac-
tion mixture under argon atmosphere. The suspension was refluxed for
1 h. The mixture was concentrated under reduced pressure. The crude
product was purified by silica column chromatography eluted with di-
chloromethane/MeOH 20:1 to give 3 as a brown powder (500 mg, 17%).
1H NMR (250 MHz, DMF, 300 K): d=9.07 (d, J=8 Hz, 1H), 8.98 (d, J=
8 Hz, 1H), 8.91 (d, J=8 Hz, 1H), 8.88 (d, J=8 Hz, 1H), 8.68 (d, J=8 Hz,
1H), 8.64 (d, J=8 Hz, 1H), 8.31 (d, J=8 Hz, 1H), 8.03 (d, J=8 Hz, 1H),
7.79 (t, 1H), 7.50 (t, 1H), 7.41 (d, J=8 Hz, 2H), 6.61 (d, J=4 Hz, 2H),
6.35 (d, J=9 Hz, 2H), 6.25 (d, J=8 Hz, 2H), 2.85 (m, 2H), 2.82 (s, 12H),
1.15 ppm (d, J=7 Hz, 12H); 13C NMR (62.5 MHz, CD2Cl2, 300 K): d=
164.61, 147.38, 146.74, 137.92, 137.61, 132.51, 132.46, 132.16, 131.15,
129.88, 128.58, 127.47, 125.12, 124.59, 121.91, 121.81, 121.47, 121.26, 41.83,
29.67, 24.30 ppm; FD mass spectrum (8 kV): m/z (%): calcd for: 765.00;
found: 765.3 (100) [M]+; elemental analysis calcd (%) for C50H44N4O2S:
C 78.50, H 5.80, N 7.32, S 4.19; found: C 78.50, H 5.76, N 7.31, S 4.22.
N-Boc-di(4-bromophenyl) amine (7): A mixture of di(4-bromophenyl)-
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
(20 mL) was refluxed for 24 h under argon. After cooling to room tem-
perature, the mixture was filtered to get white solid. After washed by
THF once and dried, white crystals were obtained (5 g, 96%). 1H NMR
(250 MHz, CD2Cl2, 300 K): d=7.44 (d, J=8 Hz, 4H), 7.11 (d, J=8 Hz,
4H), 1.44 ppm (s, 9H); 13C NMR (62.5 MHz, CD2Cl2, 300 K): d=153.21,
142.30, 132.18, 128.97, 119.39, 82.05, 28.25 ppm; FD mass spectrum
(8 kV): m/z (%): calcd for: 427.14; found: 427.8 (100) [M]+; elemental
analysis calcd (%) for C17H17Br2NO2: C 47.80, H 4.01, N 3.28; found: C
47.82, H 4.02, N 3.24.
N-Boc-di(phenothiazinylphenyl) amine (8): To a 100 mL Schlenk flask
containing 2a (5.0 g, 11.7 mmol), phenothiazine (2.7 g, 23.4 mmol), [Pd2-
N-(2,6-Diisopropylphenyl)-1,6-diphenylthio-9-bromoperylene-3,4-dicar-
boximide (15): N-(2,6-Diisopropylphenyl)-1,6,9-tribromoperylene-3,4-di-
carboximide (1 g, 1.39 mmol), thiophenol (153 mg, 1.39 mmol) and potas-
sium carbonate (128 mg, 1.39 mmol) were stirred in NMP (80 mL) at
room temperature. After 1.5 h, additional thiophenol (76 mg, 0.6 mmol)
and potassium hydrate (128 mg, 1.39 mmol) were added into the reaction
mixture. The mixture was stirred at the same temperature for another
1.5 h. After cooling down to room temperature, the reaction mixture was
poured into a mixture of water and HCl 4:1. The resulting precipitate
was washed by water and dried. The product was purified by column
chromatography on silica gel using dichloromethane/pentane 1:4 to give
A
(500 mg,
0.585 mmol),
tri-tert-butylphosphine
(118 mg,
0.585 mmol), sodium-tert-butoxide (3.9 g, 40.3 mmol) and anhydrous tolu-
ene (50 mL) were added under argon atmosphere. The mixture was re-
fluxed for 90 min. The hot reaction mixture was filtered in order to
remove insoluble solids. The filtrate was concentrated under reduced
pressure to give a white powder. The crude product was purified by silica
column chromatography eluted with dichloromethane/pentane 2:1 to
yield 8 as a white powder (6.4 g, 82%). 1H NMR (250 MHz, CD2Cl2,
300 K): d=7.53 (d, J=8 Hz, 4H), 7.40 (d, J=8 Hz, 4H), 7.02 (d, J=
882
ꢂ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2009, 15, 878 – 884