15.
Gaussian 09, Revision C.01, Frisch M. J.; Trucks G. W.; Schlegel H. B.; Scuseria G.
E.; Robb M. A.; Cheeseman J. R.; Scalmani G.; Barone V.; Mennucci B.; Petersson
G.A.; Nakatsuji H.; Caricato M.; Li X.; Hratchian H. P.; Izmaylov A. F.; J. Bloino G.
A.; Zheng G.; Sonnenberg J. L.; Hada M.; Ehara M.; Toyota K.; Fukuda R.; Hasegawa
J.; Ishida M.; Nakajima T.; Honda Y.; Kitao O.; Nakai H.; Vreven T.; Montgomery, Jr.
J. A.; Peralta J. E.; Ogliaro F.; Bearpark M.; Heyd J. J.; Brothers E.; Kudin K. N.;
Staroverov V. N.; Keith T.; Kobayashi R.; Normand J; Raghavachari K.; Rendell A.;
Burant J. C.; Iyengar S. S.; Tomasi J.; Cossi M.; Rega N.; Millam J. M.; Klene M.;
Knox J. E.; Cross J. B.; Bakken V.; Adamo C.; Jaramillo J.; Gomperts R.; Stratmann
R. E.; Yazyev O.; Austin A. J.; Cammi R.; Pomelli C.; Ochterski J. W.; Martin R. L.;
Morokuma K.; Zakrzewski V. G.; Voth G. A.; Salvador P.; Dannenberg J. J.; Dapprich
S.; Daniels A. D.; Farkas O.; Foresman J. B.; Ortiz J. V.; Cioslowski J.; Fox D. J.
Gaussian, Inc., Wallingford CT, 2010.
16.
3,6-Bis(4'-diphenylaminostilben-4-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione
(1)
(3.00 g, 3.633 mmol) was suspended in NMP (70 ml). The mixture was heated and the
temperature maintained at 120 ˚C during the reaction. K2CO3 (2.01 g, 14.511 mmol)
was added and the mixture became darker and lost its fluorescence. The 2-ethylhexyl
ester of bromoacetic acid (3.64 g, 14.511 mmol) was added slowly over 1 h and the
mixture was heated for another 2 h. After cooling to room temperature, the mixture
was poured into demineralized H2O (150 ml) to form a stable emulsion. The emulsion
was extracted with CHCl3 (3x100 mL). Separation of the phases was possible only
after addition of NaCl to the H2O phase. The organic solution was dried over MgSO4
and the solvent removed by distillation. The liquid residue was recrystallized from
cyclohexane and gave 1.03 g of dark-brown crystals of E-bis(2-ethylhexyl) 2,2′-(3,6-
bis{4-[4-(diphenylamino)styryl]phenyl}-1,4-dioxopyrrolo[3,4-c]pyrrole-2,5-(1H,4H)-
diyl diacetate (1a) (yield 24%).
m. p. 168 – 170 ˚C. Anal. Calcd. for C78H78N4O6: C 80.24; H 6.73; N 4.80. Found: C
79.72; H 6.71; N, 4.65.
17.
3-Phenyl-6-(4'-diphenylaminostilben-4-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (2)
(1.00 g, 1.793 mmol) was suspended in DMF (70 ml), together with K2CO3 (1.00 g,
7.173 mmol) and the temperature of the mixture was increased to 120 ˚C. Over the
next 60 min, the 2-ethylhexyl ester of bromoacetic acid (1.75 g, 7.173 mol) was added
dropwise. After an additional 1 h, the reaction was cooled to room temperature and
poured into brine (700 ml). The product, E-bis(2-ethylhexyl) 2,2′-(3-{4-[4-
(diphenylamino)styryl]phenyl}-1,4-dioxo-6-phenylpyrrolo[3,4-c]pyrrole-2,5-(1H,4H)-
diyl diacetate (2a) was precipitated and isolated by filtration. Chromatographic
purification gave 0.90 g of a red microcrystalline solid (yield 55%).
m. p. 70-74 ˚C. Anal. Calcd. for C58H63N3O6: C 77.56; H 7.07; N 4.68. Found: C
76.18; H 6.98; N 4.51.
1
18.
NMR spectra were recorded on a Bruker Avance II spectrometer (400.13 MHz for H
and 100.62 MHz for 13C) in CDCl3. The 1H and 13C NMR chemical shifts are given on
the δ scale (ppm) and are referenced to internal TMS. All 2D experiments (gradient-
selected (gs)-COSY, (gs)-NOESY, gs-HMQC, gs-HMBC) were performed using the
manufacturer’s software (TOPSPIN 2.1).
12