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Organic & Biomolecular Chemistry
Bruker FT-IR Tensor 27 infrared spectrophotometer. 1H NMR (14), 105 (11), 77 (11). Anal. calcd for C20H14N4O4: C, 64.17; H,
spectra were recorded on a Bruker Avance III 400 MHz spectro- 3.77; N, 14.97%. Found: C, 63.98; H, 3.60; N, 14.79%.
meter. 13C NMR spectra were recorded on the same instrument
2,2′-(1,4-Phenylene)bis(3-benzoylindolizine-1-carbonitrile)
at 100 MHz using TMS as an internal standard. Mass spectra (7a). Orange powder, yield: 92%. m.p. 326–328 °C. IR (KBr,
were measured on a GCMS-QP1000 EX spectrometer at 70 eV. νmax/cm−1): 2192 (CN), 1654 (CvO), 1593, 1536 (CvC). 1H
Elemental analyses were performed using a Heracus CHN-O- NMR (400 MHz, DMSO-d6) δppm: 7.96–7.78 (m, 8H, CH–Ar),
3
3
Rapid analyzer. Ultrasonication was performed in a Bandelin- 7.72 (t, 2H, J = 8 Hz, CH–Ar), 7.60 (t, 4H, J = 8 Hz, CH–Ar),
3
Sonorex Ultrasonic Bath (Super RK) with a frequency of 7.34 (t, 2H, J = 8 Hz, CH–Ar), 7.28 (s, 4H, CH–Ar), 6.96 (t, 2H,
100 kHz. The internal dimensions of the ultrasonic tank were 3J = 8 Hz, CH–Ar).13C NMR (100 MHz, DMSO-d6) δppm: 189.7
240 × 140 × 100 mm with a liquid holding capacity of (CvO), 154.8, 143.5, 141.4, 140.5, 136.5, 135.4, 133.4, 132.7,
3 L. Pyridinium32 and 2-chloropyridinium bromides33 were 130.9, 130.7, 129.7, 128.6, 121.0, 117.9, 114.6 (CN). MS (m/z):
prepared according to literature procedures.
566 (M+) (3), 552 (9), 524 (8), 436 (6), 368 (19), 313 (35), 286
Typical procedure for the preparation of compounds (3, 7, (72), 236 (43), 205 (35), 155 (100), 105 (52), 77 (60). Anal. calcd
8a–c). A solution of 2-benzylidenemalononitrile (4) (2 mmol) for C38H22N4O2: C, 80.55; H, 3.91; N, 9.89%. Found: C, 80.36;
or 2,2′-(1,4-phenylenebis(methanylylidene))dimalononitrile (2) H, 3.75; N, 9.71%.
(1 mmol), pyridinium (1a–c) or 2-chloropyridinium bromide
2,2′-(1,4-Phenylene)bis(3-(4-bromobenzoyl)indolizine-1-
(6a–c) (2 mmol) and triethylamine (0.2 mL) in acetonitrile carbonitrile) (7b). Brown powder, yield: 91%. m.p. 269–270 °C.
(10 mL) were irradiated at room temperature for 20–35 min IR (KBr, νmax/cm−1): 2208 (CN), 1667 (CvO), 1625, 1580
(the progress of the reaction was monitored by TLC, with (CvC). 1H NMR (400 MHz, DMSO-d6) δppm: 7.97–6.93 (m, 20H,
hexane–ethyl acetate used as an eluent). The reaction mixture CH–Ar). 13C NMR (100 MHz, DMSO-d6) δppm: 189.1 (CvO),
was diluted with 50 mL of water and the resulting precipitate 154.8, 143.8, 141.4, 140.4, 136.3, 136.2, 134.4, 133.5, 131.7,
was collected by filtration. The crude product was recrystal- 130.9, 130.7, 126.7, 121.0, 117.9, 114.7 (CN). MS (m/z): 724
lized using dichloromethane–n-hexane (1 : 2) to give the pure (M + 2) (1), 722 (M+) (1), 648 (2), 578 (5), 478 (10), 436 (15), 340
solid sample for analysis.
(31), 286 (100), 253 (30), 200 (16), 183 (100), 155 (83), 123 (45),
3,3′-(1,4-Phenylene)bis(2-benzoylcyclopropane-1,1-dicarbo- 107 (25), 91 (46), 75 (35). Anal. calcd for C38H20Br2N4O2: C,
nitrile) (3a). Black powder, yield: 89%. m.p. 270 °C (dec.). IR 63.00; H, 2.78; N, 7.73%. Found: C, 62.81; H, 2.62; N, 7.58%.
(KBr, νmax/cm−1): 2208 (CN), 1655 (CvO), 1593, 1523 (CvC).
Dimethyl 2,2′-(1,4-phenylene)bis(1-cyanoindolizine-3-carb-
1H NMR (400 MHz, DMSO-d6) δppm: 7.95–7.19 (m, 14H, CH– oxylate) (7c). Yellow powder, yield: 90%. m.p. 290 °C (dec.). IR
Ar), 3.06 (d, 2H, 3J = 4 Hz, CH), 1.16 (d, 2H, 3J = 4 Hz, CH). 13 (KBr, νmax/cm−1): 2208 (CN), 1734 (CvO), 1614, 1539 (CvC).
NMR (100 MHz, DMSO-d6) δppm: 190.3 (CvO), 153.9, 130.6, 1H NMR (400 MHz, DMSO-d6) δppm: 8.12–6.87 (m, 12H, CH–
C
129.4, 128.7, 127.8, 126.8, 114.2 (CN), 45.6 (CH), 28.9 (CH), 8.6 Ar), 3.72 (s, 3H, OCH3). 13C NMR (100 MHz, DMSO-d6) δppm
:
(C). MS (m/z): 466 (M+) (1), 462 (6), 394 (3), 368 (18), 319 (16), 161.3 (CvO), 154.7, 142.1, 141.0, 131.3, 130.6, 130.0, 129.3,
273 (13), 218 (7), 174 (41), 121 (8), 105 (63), 77 (100). Anal. 120.8, 120.2, 114.6, 113.4 (CN), 53.6 (OCH3). MS (m/z): 474
calcd for C30H18N4O2: C, 77.24; H, 3.89; N, 12.01%. Found: C, (M+) (1), 406 (8), 331 (100), 286 (25), 246 (42), 202 (13), 176
77.07; H, 3.72; N, 11.84%.
(24), 155 (22), 119 (12), 101 (13), 83 (13). Anal. calcd for
3,3′-(1,4-Phenylene)bis(2-(4-bromobenzoyl)cyclopropane-1,1- C28H18N4O4: C, 70.88; H, 3.82; N, 11.81%. Found: C, 70.71; H,
dicarbonitrile) (3b). Black powder, yield: 88%. m.p. 300 °C 3.67; N, 11.66%.
(dec.). IR (KBr, νmax/cm−1): 2192 (CN), 1657 (CvO), 1625, 1577
3-Benzoyl-2-phenylindolizine-1-carbonitrile (8a). Yellow
(CvC). 1H NMR (400 MHz, DMSO-d6) δppm: 8.97–7.89 (m, 12H, powder, yield: 94%. m.p. 223–225 °C. IR (KBr, νmax/cm−1):
CH–Ar), 3.91 (d, 2H, 3J = 4 Hz, CH), 2.09 (d, 2H, 3J = 4 Hz, CH). 2208 (CN), 1648 (CvO), 1593, 1571 (CvC). 1H NMR (400 MHz,
13C NMR (100 MHz, DMSO-d6) δppm: 190.0 (CvO), 146.4, DMSO-d6) δppm: 7.99–7.90 (m, 3H, CH–Ar), 7.84 (t, 1H, 3J =
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146.2, 132.5, 132.2, 130.1, 127.8, 113.5 (CN), 37.2 (CH), 30.6 8 Hz, CH–Ar), 7.72 (t, 1H, J = 4 Hz, CH–Ar), 7.64–7.22 (m, 8H,
(CH), 14.7 (C). MS (m/z): 624 (M + 2) (1), 622 (M+) (1), 604 (12), CH–Ar), 6.98 (t, 1H, 3J = 8 Hz, CH–Ar). 13C NMR (100 MHz,
552 (9), 481 (2), 436 (4), 393 (6), 339 (28), 313(29), 286 (41), 236 DMSO-d6) δppm: 190.0 (CvO), 154.7, 147.8, 144.8, 141.7, 140.5,
(33), 183 (29), 127 (27), 97 (41), 79 (100). Anal. calcd for 135.7, 135.3, 132.5, 132.2, 130.5, 130.5, 129.6, 129.5, 128.6,
C30H16Br2N4O2: C, 57.72; H, 2.58; N, 8.97%. Found: C, 57.55; 120.9, 118.0, 114.7 (CN). MS (m/z): 322 (M+) (12), 304 (6), 266
H, 2.43; N, 8.80%.
(57), 244 (100), 207 (17), 161 (28), 129 (12), 105 (36), 77 (41).
Dimethyl 3,3′-(1,4-phenylene)bis(2,2-dicyanocyclopropane- Anal. calcd for C22H14N2O: C, 81.97; H, 4.38; N, 8.69%. Found:
carboxylate) (3c). Brown powder, yield: 89%. m.p. 119 °C C, 81.80; H, 4.22; N, 8.52%.
(dec.). IR (KBr, νmax/cm−1): 2258 (CN), 1737 (CvO), 1614, 1523
3-(4-Bromobenzoyl)-2-phenylindolizine-1-carbonitrile (8b).
(CvC). 1H NMR (400 MHz, DMSO-d6) δppm: 7.01 (s, 2H, Yellow powder, yield: 93%. m.p. 180 °C (dec.). IR (KBr, νmax
/
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CH–Ar), 6.71 (s, 2H, CH–Ar), 3.86 (d, 2H, J = 4 Hz, CH), 2.24 cm−1): 2192 (CN), 1648 (CvO), 1616, 1580 (CvC). 1H NMR
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(s, 3H, OCH3), 1.61 (d, 2H, J = 4 Hz, CH). 13C NMR (100 MHz, (400 MHz, CDCl3) δppm: 7.95 (t, 1H, 3J = 4 Hz, CH–Ar), 7.93
DMSO-d6) δppm: 166.1 (CvO), 131.1, 129.1, 112.3 (CN), 53.2 (t, 1H, 3J = 4 Hz, CH–Ar), 7.81 (s, 1H, CH–Ar), 7.72 (t, 1H, 3J = 4
(OCH3), 37.5 (CH), 32.1 (CH), 14.0 (C). MS (m/z): 374 (M+) (2), Hz, CH–Ar), 7.70 (t, 1H, J = 4 Hz, CH–Ar), 7.53–7.22 (m, 6H,
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330 (28), 285 (11), 271 (100), 230 (28), 202 (74), 165 (39), 127 CH–Ar), 7.95 (t, 1H, 3J = 4 Hz, CH–Ar), 6.64–6.60 (m, 1H,
7862 | Org. Biomol. Chem., 2014, 12, 7859–7863
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