The Journal of Organic Chemistry
Article
= 0.65 (SiO2, CH2Cl2). Mp: 319−321 °C (AcOEt). Spectral and
physical properties concurred with published data.31
1,2,4,5-Tetra(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole
(23). White solid. Yield: 158 mg (34%). Rf = 0.71 (SiO2, AcOEt/
hexanes, 1/4). Mp: 261−262 °C (AcOH). Spectral and physical
properties concurred with published data.31
3/1). Yield: 71 mg (48%). Rf = 0.41 (SiO2, AcOEt/hexanes, 1/4). Mp:
325−326 °C (toluene). 1H NMR (500 MHz, CDCl3): δ 7.43 (d, J 8.2
Hz, 2H), 7.38 (d, J 8.2 Hz, 2H), 7.24−7.16 (m, 6H), 7.07 (d, J 8.1 Hz,
2H), 7.00 (d, J 8.2 Hz, 2H), 6.94 (d, J 7.9 Hz, 2H), 6.82−6.77 (m, 4H),
6.50 (s, 1H), 2.39 (s, 3H), 2.36 (s, 3H). 13C NMR (125 MHz, CDCl3): δ
138.3, 137.8, 137.4, 136.8, 136.3, 136.10, 136.08, 135.9, 131.9, 131.79,
131.75, 131.19, 131.18, 131.1, 130.7, 130.1, 129.5, 128.0, 127.4, 125.4,
118.96, 118.95, 118.7, 110.1, 109.5, 109.4, 109.3, 94.5, 21.08, 21.04.
HRMS (EI): calcd for C41H27N5 589.2266 [M+], found 589.2259. Anal.
Calcd for C41H27N5: C, 83.51; H, 4.62; N, 11.88. Found: C, 83.47; H,
4.63; N, 11.72. λabs (CH2Cl2, ε × 10−3): 400 (43) nm.
General Procedure for the Synthesis of Pentaaryl- and
Hexaaryl-1,4-dihydropyrrolo[3,2-b]pyrroles 25, 26, and 34−
44. The parent 1,4-dihydropyrrolo[3,2-b]pyrrole (0.25 mmol), aryl
bromide (or iodide) (1 mmol), KOAc (1 mmol), and PdCl(C3H5)-
(dppb) (0.01 mmol) were placed in a 25 mL Schlenk flask, which was
flushed with argon prior to use. Then 8 mL of dry DMA was added and
the resulting mixture was stirred at 150 °C for 3 days. The product was
purified by means of flash column chromatography and then
recrystallized from toluene or ethyl acetate. The obtained crystals
were dried under reduced pressure.
3-(9,9-Dioctyl-9H-fluoren-2-yl)- 2,5-diphenyl-1,4-bis(4-methyl-
phenyl)dihydropyrrolo[3,2-b]pyrrole (25). Yellow solid. The product
was purified by means of flash column chromatography (SiO2, CH2Cl2/
hexanes 1/1). Yield: 140 mg (28%). Rf = 0.73 (SiO2, AcOEt/hexanes,
1:2). Mp: 67−68 °C (toluene). 1H NMR (500 MHz, CDCl3): δ 7.58 (d,
J 7.5 Hz, 1H), 7.31−7.26 (m, 1H), 7.26−7.22 (m, 2H), 7.19−7.10 (m,
10H), 7.05−6.97 (m, 5H), 6.86 (d, J 0.9 Hz, 1H), 6.83−6.79 (AA′XX′,
2H), 6.73 (d, J 8.2 Hz, 1H), 6.63 (dd, J 7.8 Hz, J 1.4 Hz, 1H), 6.46 (s,
1H), 2.35 (s, 3H), 2.21 (s, 3H), 1.75 (dt, J 12.7 Hz, J 4.8 Hz, 2H), 1.59
(dt, J 12.7 Hz, J 4.8 Hz, 2H), 1.25−1.17 (m, 4H), 1.17−1.07 (m, 8H),
1.06−0.98 (m, 4H), 0.97−0.90 (m, 4H), 0.82 (t, J 7.0 Hz, 6H), 0.53−
0.39 (m, 4H). 13C NMR (125 MHz, CDCl3): δ 150.8, 149.7, 141.4,
138.5, 137.5, 136.5, 136.3, 135.8, 135.0, 133.8, 133.1, 132.6, 132.3, 131.0,
130.0, 129.9, 129.55, 129.49, 128.7, 128.4, 128.0, 127.6, 127.2, 126.50,
126.46, 126.04, 125.97, 125.3, 125.1, 122.7, 119.2, 118.1, 110.8, 93.3,
54.6, 40.4, 31.8, 30.1, 29.42, 29.39, 23.6, 22.6, 21.0, 14.1. HRMS (ESI)
calcd for C61H66N2 826.5226 [M+], found 826.5225. Anal. Calcd for
C61H66N2: C, 88.57; H, 8.04; N, 3.39. Found: C, 88.36; H, 8.14; N, 3.24.
λabs (CH2Cl2, ε × 10−3): 331 (40) nm.
2,5-Bis(4-cyanophenyl)-3-(9,9-dioctyl-9H-fluoren-3-yl)-1,4-bis(4-
methylphenyl)dihydropyrrolo[3,2-b]pyrrole (26). Yellow solid. The
product was purified by means of flash column chromatography (SiO2,
CH2Cl2/hexanes 1/1). Yield: 66 mg (30%). Rf = 0.66 (SiO2, AcOEt/
hexanes, 1/4). Mp: 229−231 °C (toluene). 1H NMR (500 MHz,
CDCl3): δ 7.62 (d, J 7.2 Hz, 1H), 7.42 (AA′XX′, 2H), 7.35−7.31 (m,
1H), 7.30−7.27 (m, 3H), 7.27−7.25(m, 1H), 7.22−7.17 (m, 5H), 7.11
(AA′XX′, 2H), 7.07 (AA′XX′, 2H), 6.85 (s, 1H), 6.78 (s, 4H), 6.64 (dd,
J 7.7 Hz, J 1.3 Hz, 1H), 6.54 (s, 1H), 2.40 (s, 3H), 2.25 (s, 3H), 1.84−
1.76 (m, 2H), 1.66−1.60 (m, 2H), 1.24−1.18 (m, 4H), 1.18−1.12 (m,
8H), 1.08−1.01 (m, 4H1.01−0.93 (m, 4H), 0.82 (t, J 7.0 Hz, 6H), 0.49
(quint, J 7.8 Hz, 4H). 13C NMR (125 MHz, CDCl3): δ 150.7, 150.2,
140.9, 139.4, 137.8, 137.0, 136.9, 136.7, 136.2, 135.6, 131.9, 131.72,
131.69, 131.5, 131.4, 131.3, 130.8, 130.0, 129.7, 129.2, 127.9, 127.1,
127.0, 126.7, 125.3, 125.0, 122.8, 119.4, 119.1, 118.8, 118.6, 112.3, 109.1,
109.0, 94.7, 54.8, 40.3, 31.8, 30.0, 29.5, 29.3, 23.7, 22.6, 21.0, 14.1.
HRMS (ESI) calcd for C63H64N4 876.5131 [M+], found 876.5124. Anal.
Calcd for C63H64N4: C, 86.26; H, 7.35; N, 6.39. Found: C, 86.02; H,
7.38; N, 6.30. λabs (CH2Cl2, ε × 10−3): 404 (40) nm.
2,5-Bis(4-cyanophenyl)-1,4-bis(4-methylphenyl)-3-(4-nitro-
phenyl)dihydropyrrolo[3,2-b]pyrrole (34). Orange solid. The product
was purified by means of flash column chromatography (SiO2, CH2Cl2/
hexanes 1/1). Yield: 36 mg (24%). Rf = 0.51 (SiO2, AcOEt/hexanes, 1/
4). Mp: 344−346 °C (toluene). 1H NMR (500 MHz, CDCl3): δ 7.80
(AA′XX′, 2H), 7.44 (AA′XX′, 2H), 7.39 (AA′XX′, 2H), 7.20 (t, J 8.5 Hz,
4H), 7.08 (AA′XX′, 2H), 7.03 (AA′XX′, 2H), 6.95 (d, J 8.0 Hz, 2H),
6.84−6.81 (m, 2H), 6.51 (s, 1H), 2.40 (s, 3H), 2.34 (s, 3H). 13C NMR
(125 MHz, CDCl3): δ 145.9, 140.4, 138.0, 137.4, 136.9, 136.22, 136.19,
136.1, 135.9, 131.9, 131.8, 131.1,, 130.1, 129.6, 128.0, 127.5, 125.5,
122.7, 119.0, 118.6, 110.3, 109.4, 94.5, 21.1. HRMS (EI): calcd for
C40H27N5O2 609.2165 [M+], found 609.2184. λabs (CH2Cl2, ε × 10−3):
393 (40) nm.
2,5-Bis(4-cyanophenyl)-1,4-bis(4-methylphenyl)-3-(pyridin-3-yl)-
1,4-dihydropyrrolo[3,2-b]pyrrole (36). Yellow solid. The product was
purified by means of flash column chromatography (SiO2, CH2Cl2/
MeOH 95/5). Yield: 30 mg (21%). Rf = 0.71 (SiO2, CH2Cl2/MeOH,
95/5). Mp: 319−320 °C (toluene, dec). 1H NMR (500 MHz, CDCl3): δ
8.34 (d, J 2.0 Hz, 1H), 8.02 (s, 1H), 7.43 (d, J 7.8 Hz, 2H), 7.36 (d, J 7.8
Hz, 2H) 7.23−7.17 (m, 4H), 7.09 (d, J 7.6 Hz, 2H), 7.04−6.98 (m, 3H),
6.95−6.88 (m, 3H), 6.80 (d, J 7.5 Hz, 2H), 6.52 (s, 1H), 2.39 (s, 3H),
2.32 (s, 3H). 13C NMR (125 MHz, CDCl3): δ 151.1, 147.0, 137.9, 137.6,
137.5, 136.6, 136.3, 136.2, 136.0, 135.6, 132.1, 131.9, 131.8, 131.7, 131.3,
131.0, 130.1, 129.6, 129.3, 127.9, 127.3, 125.4, 122.4, 119.0, 118.8, 109.9,
109.2, 107.2, 94.5, 21.09, 21.04. HRMS (EI): calcd for C39H27N5
565.2266 [M+], found 565.2280. λabs (CH2Cl2, ε × 10−3): 395 (33) nm.
2,5-Bis(4-cyanophenyl)-3-(4-methoxyphenyl)-1,4-bis(4-methyl-
phenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (37). Yellow solid. The
product was purified by means of flash column chromatography
(SiO2, AcOEt/hexanes 1/4). Yield: 50 mg (34%). Rf = 0.45 (SiO2,
1
AcOEt/hexanes, 1/4). Mp: 298−300 °C (toluene). H NMR (500
MHz, CDCl3): δ 7.42 (d, J 8.3 Hz, 2H), 7.33 (d, J 8.3 Hz, 2H), 7.20 (d, J
8.3 Hz, 2H), 7.17 (d, J 8.3 Hz, 2H), 7.08 (d, J 8.1 Hz, 2H), 7.03 (d, J 8.2
Hz, 2H), 6.89 (d, J 8.0 Hz, 2H), 6.78 (d, J 8.1 Hz, 2H), 6.62 (d, J 8.5 Hz,
2H), 6.52 (d, J 6.8 Hz, 2H), 6.51 (s, 1H), 3.75 (s, 3H), 2.39 (s, 3H), 2.32
(s, 3H). 13C NMR (125 MHz, CDCl3): δ 158.1, 137.8, 137.1, 136.8,
136.7, 136.1, 135.8, 135.6, 131.9, 131.7, 131.7, 131.6, 131.4, 130.9, 130.0,
129.2, 129.0, 128.2, 127.9, 127.2, 125.3, 125.0, 113.1, 111.3, 109.1, 108.9,
94.6, 55.2, 21.04, 21.02. HRMS (EI): calcd for C41H30N4O 594.2420
[M+], found 594.2430. λabs (CH2Cl2, ε × 10−3): 406 (43) nm.
2,5-Bis(4-cyanophenyl)-3-(3,5-dimethoxyphenyl)-1,4-bis(4-meth-
ylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (38). Yellow solid. The
product was purified by means of flash column chromatography (SiO2,
AcOEt/hexanes 1/4). Yield: 45 mg (29%). Rf = 0.43 (SiO2, AcOEt/
hexanes, 1/4). Mp: 340−342 °C (toluene). 1H NMR (500 MHz,
CDCl3): δ 7.43 (AA′XX′, 2H), 7.35 (AA′XX′, 2H), 7.21 (AA′XX′, 2H),
7.17 (d, J 8.0 Hz, 2H), 7.08 (m, 4H), 6.92 (AA′XX′, 2H), 6.80 (AA′XX′,
2H), 6.51 (s, 1H), 6.23 (t, J 2.2 Hz, 1H), 5.89 (d, J 2.2 Hz, 2H), 3.43 (s,
6H), 2.39 (s, 3H), 2.32 (s, 3H). 13C NMR (125 MHz, CDCl3): δ 160.0,
137.8, 137.0, 136.6, 136.3, 135.9, 135.6, 134.6, 131.9, 131.7, 131.5, 131.4,
131.0, 130.9, 130.0, 129.2, 128.0, 127.3, 125.4, 119.08, 119.05, 111.6,
109.3, 109.2, 108.8, 99.3, 94.8, 54.8 21.02, 20.93. HRMS (EI): calcd for
C42H32N4O2 624.2525 [M+], found 624.2542. λabs (CH2Cl2, ε × 10−3):
401 (43) nm.
2,5-Bis(4-cyanophenyl)-1,4-bis(4-methylphenyl)-3,6-bis(4-(penta-
fluoro-λ6-sulfanyl)phenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (39).
Yellow-greenish solid. The product was purified by means of flash
column chromatography (SiO2, CH2Cl2/hexanes 1/1−3/1). Yield: 78
mg (35%). Rf = 0.56 (SiO2, AcOEt/hexanes, 1/4). Mp: 330−331 °C
1
(toluene). H NMR (500 MHz, CDCl3): δ 7.36 (AA′XX′, 4H), 7.30
(AA′XX′, 4H), 7.01 (AA′XX′, 4H), 6.86 (d, J 8.0 Hz, 4H), 6.78 (d, J 8.5
Hz, 4H), 6.70 (AA′XX′, 4H), 2.29 (s, 6H). 13C NMR (125 MHz,
CDCl3): δ 151.6 (m), 137.8, 136.8, 135.9, 135.2, 132.3, 131.8, 131.1,
130.4, 129.5, 129.4, 127.4, 125.2 (m), 125.1, 118.7, 110.2, 108.0, 20.8.
HRMS (EI): calcd for C46H30N4F10S2 892.1752 [M+], found 892.1734.
λabs (CH2Cl2, ε × 10−3): 395 (33) nm.
2,5-Bis(4-cyanophenyl)-1,4-bis(4-methylphenyl)-3,6-bis(4-nitro-
phenyl)dihydropyrrolo[3,2-b]pyrrole (40). Orange solid. The product
was purified by means of flash column chromatography (SiO2, CH2Cl2/
hexanes 2/1) Yield: 97 mg (53%). Rf = 0.42 (SiO2, AcOEt/hexanes, 1/
4). Mp: 354−356 °C (toluene). 1H NMR (500 MHz, CDCl3): δ 7.79
(AA′XX′, 4H), 7.35 (AA′XX′, 4H), 6.98 (AA′XX′, 4H), 6.91 (d, J 8.0
2,3,5-Tris(4-cyanophenyl)-1,4-bis(4-methylphenyl)-1,4-dihydro-
pyrrolo[3,2-b]pyrrole (35). Yellow solid. The product was purified by
means of flash column chromatography (SiO2, CH2Cl2/hexanes 1/1−
3126
dx.doi.org/10.1021/jo5002643 | J. Org. Chem. 2014, 79, 3119−3128