S. Raouafi et al. / C. R. Chimie xxx (2017) 1e7
5
7.66 (d, J ¼ 7.2 Hz, 2H); 7.74 (d, J ¼ 8.1 Hz, 2H); 13C NMR
108.42 (C); 113.89 (2CeH); 117.98 (CN); 125.17 (2CeH);
126.26 (C); 129.14 (2CeH); 130.50 (2CeH); 131.65 (C);
138.33 (C); 140.31 (CeH); 160.82 (CeO).
(75 MHz, CDCl3):
d (ppm): 112.14 (C); 117.08 (CN); 124.31
(CeBr); 125.52 (2CeH); 128.60 (2CeH); 128.91 (CeH);
130.08 (2CeH); 131.71 (2CeH); 132.15 (C); 133.75 (C);
140.10 (CeH).
4.2.8. (Z)-3-(p-Cyanophenyl)-2-(p-tolyl)acrylonitrile (8h)
White solid, 78%, mp ¼ 190e192 ꢂC; 1H NMR (300 MHz,
4.2.2. (Z)-3-(p-Methoxyphenyl)-2-phenylacrylonitrile (8b)
White solid, 76%, mp ¼ 93e95 ꢂC; 1H NMR (300 MHz,
CDCl3):
d
(ppm): 2.37 (s, 3H, CH3); 7.30 (d, J ¼ 8.7 Hz, 2H);
7.50 (s, 1H, Hvinyl); 7.61 (d, J ¼ 8.1 Hz, 2H); 7.76 (d, J ¼ 8.4 Hz,
CDCl3):
d
(ppm): 3.89 (s, 3H, OCH3); 6.99 (d, J ¼ 8.7 Hz, 2H);
2H); 7.97 (d, J ¼ 8.1 Hz, 2H); 13C NMR (75 MHz, CDCl3):
7.38e7.48 (m, 4H); 7.66 (d, J ¼ 8.7 Hz, 2H); 7.89 (d,
d (ppm): 21.17 (CH3); 113.41 (C); 115.48 (C); 117.13 (CN);
J ¼ 8.7 Hz, 2H); 13C NMR (75 MHz, CDCl3):
d
(ppm): 54.88
118.12 (CN); 126.11 (2CeH); 129.46 (2CeH); 129.91
(2CeH); 130.88 (C); 132.53 (2CeH); 138.05 (CeH); 138.17
(C); 140.51 (C).
(OCH3); 108.41 (C); 113.93 (2CeH); 117.89 (CN); 125.29
(2CeH); 126.11(C); 128.19 (CeH); 128.45 (2CeH); 130.63
(2CeH); 134.47 (C); 141.29 (CeH); 160.99 (C).
4.2.9. (Z)-3-(30,40-Dimethoxyphenyl)-2-(p-tolyl)acrylonitrile
(8i)
4.2.3. (Z)-3-(p-Cyanophenyl)-2-phenyl)acrylonitrile (8c)
White solid, 82%, mp ¼ 66e68 ꢂC; 1H NMR (300 MHz,
Yellow solid, 74%, mp ¼ 95e97 ꢂC; 1H NMR (300 MHz,
CDCl3):
d
(ppm): 7.46e7.50 (m, 3H); 7.53 (s, 1H, Hvinyl); 7.69
CDCl3): d (ppm): 2.41 (s, 3H, CH3); 3.96 (s, 3H, OCH3); 3.99
e7.76 (m, 4H); 7.95 (d, J ¼ 8.1 Hz, 2H); 13C NMR (75 MHz;
(s, 3H, OCH3); 6.94 (d, J ¼ 8.1 Hz, 1H); 7.26 (d, J ¼ 7.8 Hz,
2H); 7.37 (d, J ¼ 8.4 Hz, 1H); 7.42 (s, 1H, Hvinyl); 7.57 (d,
J ¼ 7.8 Hz, 2H); 7.72 (s, 1H); 13C NMR (75 MHz, CDCl3):
CDCl3):
d (ppm): 113.14 (C); 115.04 (C); 116.53 (CN); 117.57
(CN) 125.73 (2CeH); 128.74 (2CeH); 129.05 (2CeH);
129.56 (CeH); 132.08 (2CeH); 133.16 (C); 137.37 (C); 138.78
(CeH).
d
(ppm): 21.05 (CH3); 55.97 (OCH3); 56.05 (OCH3); 108.94
(C); 111.21 (CeH); 111.24 (CeH); 118.60 (CN); 124.11 (CeH);
125.67 (2CeH); 127.03 (C); 129.65 (2CeH); 132.11 (C);
138.88 (C); 141.03 (CeH); 149.27 (C); 151.19 (C).
4.2.4. (Z)-3-(30,40-Dimethoxyphenyl)-2-phenylacrylonitrile
(8d)
Yellow solid, 75%, mp ¼ 91e93 ꢂC; 1H NMR (300 MHz,
4.2.10. (Z)-3-(Thiophen-2-yl)-2-(p-tolyl)acrylonitrile (8j)
Orange solid, 71%, mp ¼ 125e127 ꢂC; 1H NMR (300 MHz,
CDCl3): d (ppm): 3.97 (s, 3H, OCH3); 4.00 (s, 3H, OCH3); 6.94
(d, J ¼ 8.4 Hz, 1H); 7.36e7.48 (m, 5H); 7.66 (d, J ¼ 7.2 Hz,
CDCl3): d (ppm): 2.39 (s, 3H, CH3); 7.12e7.15 (m, 1H); 7.22 (d,
2H); 7.74 (d, J ¼ 1.8 Hz, 1H); 13C NMR (75 MHz, CDCl3):
J ¼ 8.1 Hz, 2H); 7.51e7.55 (m, 3H); 7.60 (s,1H, Hvinyl); 7.65 (d,
d
(ppm): 55.52 (2 OCH3); 108.02 (C); 110.26 (CeH); 110.45
J ¼ 3.6 Hz, 1H); 13C NMR (75 MHz; CDCl3):
d (ppm): 20.60
(CeH); 118.19 (CN); 123.92 (CeH); 125.30 (2CeH); 126.26
(C); 128.29 (CeH); 128.53 (2CeH); 134.33 (C); 141.64
(CeH); 148.57 (CeO); 150.67 (CeO).
(CH3); 108.08 (C); 117.62 (CN); 125.10 (2CeH); 127.63 (CeH);
129.01 (CeH); 129.25 (2CeH); 130.71 (C); 131.21 (CeH);
132.59 (CeH); 137.65 (C); 138.65 (C).
4.2.5. (Z)-3-(30-Methoxyphenyl)-2-phenylacrylonitrile (8e)
Yellow solid, 73%, mp ¼ 40e42 ꢂC; 1H NMR (300 MHz,
4.3. General procedure for the photocyclization of
insaturated nitriles into phenanthrenes
a,b-
CDCl3):
d
(ppm): 3.88 (s, 3H, OCH3); 7.00 (dd, J1 ¼ 2.1 Hz,
J2 ¼ 7.8 Hz, 1H); 7.36 (d, J ¼ 7.8 Hz, 1H); 7.40e7.51 (m, 6H);
To a solution of olefin 8 (2 mmol) in toluene (1.2 L) was
added iodine (558 mg, 1.1 equiv). The solution was
degassed for 15e30 min and then propylene oxide
(50 equiv) was added. Irradiation was performed using a
falling-film photoreactor and a high-pressure Hg-vapor
lamp (500 W, Hanovia). A flow of argon was maintained
throughout the irradiation. The reaction was monitored by
thin-layer chromatography. After completion, the solvent
was removed under reduced pressure and the crude res-
idue was purified by silica gel column chromatography
with cyclohexane/EtOAc (80:20) as the eluent. Spectro-
scopic data for the phenanthrene derivatives are given
subsequently.
7.68 (d, J ¼ 7.8 Hz, 1H); 7.69 (d, J ¼ 8.4 Hz, 1H); 13C NMR
(75 MHz, CDCl3):
d (ppm): 54.91 (OCH3); 111.37 (C); 113.00
(CeH); 116.52 (CeH); 117.56 (CN); 121.71 (CeH); 125.54
(2CeH); 128.57 (2CeH); 128.74 (CeH); 129.44 (CeH);
133.98 (C); 134.47 (C); 141.69 (CeH); 159.37 (CeO).
4.2.6. (Z)-3-(p-Bromophenyl)-2-(p-methylphenyl)acrylonitrile
(8f)
White solid, 71%, mp ¼ 107e109 ꢂC; 1H NMR (300 MHz,
CDCl3):
d
(ppm): 2.40 (s, 3H, CH3); 7.23 (d, J ¼ 8.1 Hz, 2H);
7.41 (s, 1H, Hvinyl); 7.54e7.60 (m, 4H); 7.72 (d, J ¼ 8.7 Hz,
2H); 13C NMR (75 MHz, CDCl3):
d
(ppm): 20.61 (CH3); 112.11
(C); 117.17 (CN); 124.04 (C); 125.39 (2CeH); 129.28 (2CeH);
130.00 (2CeH); 130.96 (C); 131.65 (2CeH); 132.32 (C);
139.02 (CeH); 139.19 (C).
4.3.1. 3-Bromophenanthrene-9-carbonitrile (P1)
Yellow solid, 70%, mp ¼ 176e178 ꢂC; 13C NMR (300 MHz,
CDCl3):d(ppm):7.73e7.79(m,4H);8.14(s,1H,H10);8.25e8.28
4.2.7. (Z)-3-(p-Methoxyphenyl)-2-(p-tolyl)acrylonitrile (8g)
Yellow solid, 75%, mp ¼ 95e97 ꢂC; 1H NMR (300 MHz,
(m,1H); 8.54e8.57 (m,1H); 8.74 (s,1H, H5); 13C NMR(75 MHz,
CDCl3): (ppm): 109.44 (C); 117.04 (CN); 122.60(CeH); 124.15
d
CDCl3):
d
(ppm): 2.39 (s, 3H, CH3); 3.87 (s, 3H, OCH3); 6.97
(C); 125.36 (CeH); 125.68 (CeH); 127.78 (C); 128.04 (CeH);
128.28 (CeH); 128.38 (C); 128.62 (C); 130.25 (CeH); 130.45
(CeH); 132.49 (C); 134.26 (CeH); HRMS (MALDI-TOF) Calcd
for C15H8BrN [M]þ, 280.9840; found, 280.9836.
(d, J ¼ 8.7 Hz, 2H); 7.23 (d, J ¼ 8.1 Hz, 2H); 7.42 (s,1H, Hvinyl);
7.54 (d, J ¼ 8.1 Hz, 2H); 7.86 (d, J ¼ 8.7 Hz, 2H); 13C NMR
(75 MHz, CDCl3):
d (ppm): 20.56 (CH3); 54.86 (OCH3);
Please cite this article in press as: S. Raouafi, et al., Synthesis and characterization of phenanthrene derivatives for optoelectronic