Job/Unit: O50206
/KAP1
Date: 08-04-15 12:05:22
Pages: 8
J. Ma, L. Yin, G. Zou, Q. Zhang
FULL PAPER
1
,7-Dibromo-N,NЈ-Bis[2-(dimethylamino)ethyl]-3,4,9,10-perylene-
tetracarboxylic Diimides (7a): Compound 2 (950 mg, 1.73 mmol),
-(dimethylamino)ethylamine (0.50 mL, 5.3 mmol), and acetic acid
500 mg, 8.33 mmol) in H O/2-propanol (2:1, v/v, 20 mL) were
for 18 h. After cooling the mixture to
Cl
30 cm long and 4 cm diameter) with CHCl
v/v, R = 0.48) as eluent. The green fraction was collected and after
evaporation of the solvent, 9 was collected as a green powder
3
/petroleum ether (40:1,
f
2
(
1
2
(67.0 mg, 67%). H NMR (400 MHz, CDCl
3
): δ = 9.60 (d, 2 H),
stirred at 80 °C under N
room temperature and evaporation of the solvent, CH
was added. The brownish red solution was washed with a saturated
aqueous NaCl solution (30 mL ϫ3) and water (30 mL ϫ 3) and
then dried with anhydrous sodium sulfate. The crude product was
purified by silica gel column chromatography (200–300 mesh,
2
8.45–8.41 (m, 4 H), 4.24–4.19 (t, 4 H), 3.49 (m, 4 H), 2.97–2.86 (m,
2
2
(60 mL) 4 H), 1.81–1.70 (m, 16 H), 1.48 (m, 4 H), 1.00 (t, 6 H) ppm. Good
agreement was found with the literature.[
17]
3
=
0 cm long and 4 cm diameter) with CH
0.37) as eluent and 7a was obtained after evaporation of the
2
Cl
2
/MeOH (10:1, v/v, R
f
Acknowledgments
1
solvent as a red powder (0.72 g, 60 %). H NMR (400 MHz,
CDCl ): δ = 9.37 (d, 2 H), 8.82 (s, 2 H), 8.60 (d, 2 H), 4.32 (t, 4
H), 2.70 (t, 4 H), 2.35 (s, 12 H) ppm. HRMS: calcd. for
This work was supported by the National Natural Science Founda-
tion of China (NSFC) (grant numbers 21074123, 91027024,
3
51173176, and 51273186).
+
C
32
H
27Br
2
N
2
O
4
[M + H] 691.0300; found 961.0356.
,7-Dibromoperylene-3,4,9,10-tetracarboxylic Dianhydride (2a):
KOH (4.0 g, 70 mmol) was dissolved in 2-propanol (80 mL) at
1
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6
0
0 °C. After cooling the solution to room temperature, 7a (0.60 g,
.87 mmol) was added under N and then the mixture was stirred
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2
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at 80 °C for 12 h. The obtained solution changed from brownish
red to green after cooling to room temperature. Acetic acid
(100 mL) was poured slowly into the above solution and stirred at
room temperature for 8 h. The red precipitate was separated by
centrifugation (4000 rpm, 3 min), washed with n-hexane, and then
dried under vacuum. The red solid was finally dissolved in concen-
[
[
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0911–10921; b) R. Marty, R. Nigon, D. Leite, H. Frauenrath,
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trated sulfuric acid (20 mL) and then dipped carefully into H
100 mL) at 0 °C. After separation by centrifugation (4000 rpm,
min), the solid was washed with H O and then dried under vac-
2
O
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2012, 48, 3644–3646; b) J. t. Schiphorst, A. M. Kendhale,
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illy III, B. A. Gregg, ACS Appl. Mater. Interfaces 2011, 3,
uum to give 2a (0.45 g, 94%), which could not be purified owing
to its insolubility in organic solvents.
1
,7-Dibromo-N,NЈ-dibutyl-3,4,9,10-perylenetetracarboxylic Di-
imides (4a): A suspension of 2a (0.17 g, 0.31 mmol) obtained from
the above reaction, n-butylamine (0.10 mL, 1.0 mmol), and acetic
acid (100 mg, 1.67 mmol) in N-methyl-2-pyrrolidinone (NMP; [4] D. Ke, A. Tang, C. Zhan, J. Yao, Chem. Commun. 2013, 49,
4
381–4387; e) J. Zhang, S. Singh, D. K. Hwang, S. Barlow, B.
Kippelen, S. R. Marder, J. Mater. Chem. C 2013, 1, 5093–5100.
5
mL) was stirred at 85 °C under N
2
for 12 h. After purification
4914–4916.
[
[
[
[
5] a) D. Ley, C. X. Guzman, K. H. Adolfsson, A. M. Scott, A. B.
Braunschweig, J. Am. Chem. Soc. 2014, 136, 7809–7812; b) F.
Schlosser, J. Sung, P. Kim, D. Kim, F. Würthner, Chem. Sci.
following the same method as that used for the synthesis of 4, 4a
was obtained as a brown powder (0.18 g, 88 %). 1H NMR
(
4
400 MHz, CDCl
.18–4.12 (t, 4 H), 1.72–1.64 (m, 4 H), 1.40 (m, 4 H), 0.93 (t, 6
H) ppm.
3
): δ = 9.42 (d, 2 H), 8.86 (s, 2 H), 8.64 (d, 2 H),
2
012, 3, 2778–2785.
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2
1
,7-Bis(n-butylthio)-N,NЈ-dibutyl-3,4,9,10-perylenetetracarboxylic
2
Diimides (8): A mixture of 4a (132 g, 0.2 mmol), o-xylene (5 mL),
anhydrous potassium carbonate (304 mg, 2.2 mmol), CTAB (7 mg,
7] a) X. Zhang, S. Pang, Z. Zhang, X. Ding, S. Zhang, S. He, C.
Zhan, Tetrahedron Lett. 2012, 53, 1094–1097; b) P. Rajasingh,
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Chem. 2007, 72, 5973–5979.
0
8
.02 mmol), and n-butanethiol (0.17 mL, 1.6 mmol) was heated to
0 °C under N . The reaction mixture was kept at this temperature
2
for about 12 h and then the solvents were evaporated under reduced
pressure. The residue was purified by column chromatography on
silica gel (200–300 mesh, 30 cm long and 4 cm diameter) with
8] a) M. J. Ahrens, M. J. Tauber, M. R. Wasielewski, J. Org.
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Chem. 2014, 79, 6655–6662.
2 2 f
CH Cl /n-hexane (10:1, v/v, R = 0.37) as eluent. The red fraction
[
[
was collected and after evaporation of the solvent, 8 was collected
1
as an dark purple powder (52.5 mg, 77%). H NMR (400 MHz,
CDCl
3
): δ = 8.86 (d, 2 H), 8.79 (s, 2 H), 8.69 (d, 2 H), 4.27–4.22
(t, 4 H), 3.22 (m, 4 H), 1.77 (m, 4 H), 1.71–1.64 (m, 4 H), 1.48 (m,
8
C
H), 1.01 (t, 6 H), 0.91 (t, 6 H) ppm. HRMS: calcd. for
[
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anco, Bioconjugate Chem. 2011, 22, 1309–1319.
+
40
43 2 4 2
H N O S [M + H] 679.2586; found 679.2659.
[
1
,7-Dipiperidinyl-N,NЈ-dibutyl-3,4,9,10-perylenetetracarboxylic Di-
imides (9): A mixture of 4a (99 mg, 0.15 mmol) and piperidine
5.9 mL, 60 mmol) was heated to 55 °C under N . The reaction
(
2
[13] S. Dey, A. Efimov, H. Lemmetyinen, Eur. J. Org. Chem. 2012,
mixture was kept at this temperature for about 24 h and then the
solvents were evaporated under reduced pressure. The residue was
purified by column chromatography on silica gel (200–300 mesh,
2367–2374.
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6
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