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ethyl acetate 20:1) yielded the product as a mixture of regioisom-
ers in 60% (23.2 mg, 0.18 mmol) combined yield as a colorless oil.
The regioisomers were separated by using semi-preparative HPLC
(petroleum ether/ethyl acetate 20:1). Spectroscopic data were
identical to those described in the literature.[36] Rf =0.38 (petroleum
ether/ethyl acetate 20:1); 1H NMR (300 MHz, CDCl3): d=7.53–7.35
(m, 6H), 5.88 ppm (d, J=16.8 Hz, 1H); 13C NMR (75 MHz, CDCl3):
d=150.7, 133.6, 131.2, 129.1, 127.4, 118.2, 96.4 ppm; IR (film) n˜ =
3054 (w), 2216 (s), 1617 (s), 1576 (m), 1494 (m), 1448 (m), 1338 (w),
1300 (w), 1271 (w), 1180 (m), 1159 (w), 1159 (w), 1075 (w), 1029
(w), 965 (s), 920 (w), 844 (w), 827 (w), 778 (m, 746 (s), 687 (s), 623
(m), 579 (m), 533 (m), 503 (m), 436 cmÀ1 (m); GC–MS (ESI): m/z (%):
129 (100) [M+], 102 (19), 76 (5), 63 (4), 51 (7).
(%): 207 (100) [M+], 128 (73), 101 (21), 77 (10), 564 (10), 50 (9);
HRMS (ESI): m/z: calcd for C9H6BrN+Na+: 229.9576: found:
229.9583. Z isomer: Rf =0.35 (petroleum ether/ethyl acetate 10:1);
1H NMR (300 MHz, CDCl3): d=7.82 (d, J=9.4 Hz, 2H), 7.58 (d, J=
7.7 Hz, 1H), 7.33 (t, J=7.7 Hz, 1H), 7.06 (d, J=12.0 Hz, 1H),
5.52 ppm (d, J=12.0 Hz, 1H); 13C NMR (75 MHz, CDCl3): d=147.0,
135.4, 133.8, 132.1, 130.5, 127.1, 123.0, 116.8, 96.8 ppm; IR (film)
n˜ =3064 (w), 2968 (w), 2922 (w), 2851 (w), 2214 (m), 1708 (w), 1611
(w), 1557 (s), 1473 (m), 1424 (m), 1387 (w), 1297 (w), 1284 (w),
1230 (w), 1180 (m), 1093 (w), 1073 (m), 997 (m), 970 (w), 951 (w),
907 (w), 882 (m), 791 (s), 752 (m), 727 (m), 678 (s), 664 (m), 656 (w),
593 (m), 513 cmÀ1 (m); GC–MS (EI, 70 eV): m/z (%): 207 (100) [M+],
128 (92), 101 (24), 75 (13), 50 (11); HRMS (ESI): m/z: calcd for
C9H6BrN+: 209.9756; found: 209.9769.
(E)-3-(3-Chlorophenyl)acrylonitrile 8m: The product was obtained
according to GP-III starting from 3-chlorobenzaldehyde (34 mL,
0.3 mmol) and chloroacetonitrile (25 mL, 0.39 mmol) as a mixture of
regioisomers (E/Z=76:24). Purification by using silica gel chroma-
tography (petroleum ether/ethyl acetate 10:1) yielded the product
as a mixture of regioisomers in 82% (40.4 mg, 0.25 mmol) com-
bined yield as a colorless oil. The regioisomers were separated by
using semi-preparative HPLC (petroleum ether/ethyl acetate 10:1).
Spectroscopic data were identical to those described in the litera-
ture.[37] E isomer: Rf =0.36 (petroleum ether/ethyl acetate 10:1);
1H NMR (300 MHz, CDCl3): d=7.46–7.30 (m, 5H), 5.90 ppm (d, J=
16.5 Hz, 1H); 13C NMR (75 MHz, CDCl3): d=149.0, 135.3, 135.2,
131.1, 130.4, 127.1, 125.6, 117.6, 98.0 ppm; IR (film) n˜ =3064 (w),
2926 (w), 2854 (w), 2218 (s), 1620 (m), 1593 (m), 1565 (s), 1474 (m),
1428 (m), 1416 (m), 1308 (w), 1285 (w), 1259 (w), 1204 (m), 1066
(w), 1133 (w), 1095 (m), 1077 (m), 997 (w), 962 (s), 905 (s), 888 (m),
745 (s), 776 (w), 730 (s), 706 (s), 698 (s), 678 (s), 649 (m), 623 (w),
568 (w), 509 (w), 439 (w), 419 cmÀ1 (m); GC–MS (EI, 70 eV): m/z (%):
163 (100) [M+], 136 (8), 128 (49), 101 (7); HRMS (ESI): m/z: calcd for
C9H6ClN +: 163.0189; found: 166.0185. Z isomer: Rf =0.36 (petrole-
um ether/ethyl acetate 10:1); 1H NMR (300 MHz, CDCl3): d=7.76
(dt, J1 =6.7 Hz, J2 =1.8 Hz, 1H), 7.71 (t, J=1.8 Hz, 1H), 7.45–7.35
(m, 2H), 7.08 (d, J=12.1 Hz, 1H), 5.52 ppm (d, J=12.1 Hz, 1H);
13C NMR (75 MHz, CDCl3): d=147.1, 135.1, 134.0, 131.0, 130.2,
129.1, 126.7, 116.8, 96.8 ppm; IR (film) n˜ =3066 (w), 2969 (w), 2926
(w), 2854 (w), 2214 (s), 1709 (w), 1612 (m), 1592 (w), 1562 (s), 1478
(m), 1389 (w), 1300 (w), 1283 (w), 1227 (w), 1181 (m), 1001 (m),
1081 (m), 999 (w), 956 (w), 882 (m), 854 (w), 833 (m), 794 (s), 757
(m), 732 (w), 679 (s), 649 (m), 579 (w), 485 (w), 425 cmÀ1 (w); GC–
MS (EI, 70 eV): m/z (%): 163 (100) [M+], 136 (8), 128 (48), 101 (8);
HRMS (ESI): m/z: calcd for C9H6ClN +: 163.0189: found: 163.0187.
(E)-3-(4-Methoxyphenyl)acrylonitrile 8o: The product was ob-
tained according to GP-III starting from anisaldehyde (41 mL,
0.3 mmol) and chloroacetonitrile (25 mL, 0.39 mmol) as a mixture of
regioisomers (E/Z=67:33). Purification by using silica gel chroma-
tography (petroleum ether/ethyl acetate 10:1) yielded the product
as a mixture of regioisomers in 69% (26.6 mg, 0.21 mmol) com-
bined yield as a colorless oil. The regioisomers were separated by
using semi-preparative HPLC (petroleum ether/ethyl acetate 10:1).
Spectroscopic data were identical to those described in the litera-
ture.[37] E isomer: Rf =0.29 (petroleum ether/ethyl acetate 10:1);
1H NMR (300 MHz, CDCl3): d=7.40 (d, J=8.7 Hz, 2H), 7.33 (d, J=
16.7 Hz, 1H), 6.91 (d, J=8.8 Hz, 2H), 5.71 (d, J=16.7 Hz, 1H),
3.85 ppm (s, 3H); 13C NMR (75 MHz, CDCl3): d=162.1, 150.0, 132.0,
129.1, 126.4, 118.7, 114.5, 99.4, 55.5 ppm; IR (film) n˜ =2936 (w),
2840 (w), 2212 (s), 1682 (m), 1598 (s), 1574 (m), 1510 (s), 1460 (m),
1442 (w), 1423 (m), 1311 (m), 1249 (s), 1215 (m), 1174 (s), 1158 (s),
1111 (w), 1024 (s), 967 (m), 834 (s), 802 (s), 768 (m), 717 (w), 641
(w), 607 (m), 599 (m), 543 (m), 516 (m), 496 (m), 480 cmÀ1 (m); GC–
MS (ESI): m/z (%): 159 (100) [M+], 144 (17), 135 (30), 116 (27), 89
(18). Z isomer: Rf =0.29 (petroleum ether/ethyl acetate 10:1);
1H NMR (300 MHz, CDCl3): d=7.80 (d, J=8.8 Hz, 2H), 7.03 (d, J=
12.0 Hz, 1H), 6.95 (d, J=8.8 Hz, 2H), 5.29 (d, J=12.0 Hz, 1H),
3.86 ppm (s, 3H); 13C NMR (75 MHz, CDCl3): d=161.7, 148.0, 131.0,
126.6, 114.3, 91.9, 55.4 ppm; IR (film) n˜ =3065 (w), 2962 (w), 2839
(w), 2209 (s), 1599 (s), 1569 (m), 1509 (s), 1460 (m), 1442 (w), 1424
(w), 1403 (w), 1327 (w), 1307 (m), 1257 (s), 1172 (s), 1117 (w), 1027
(s), 971 (w), 835 (s), 751 (m), 709 (m), 690 (m), 629 (w), 578 (s), 516
(m), 496 (m), 454 (w), 416 cmÀ1 (w); GC–MS (ESI): m/z (%): 159
(100) [M+], 144 (16), 116 (24), 89 (15), 63 (6).
(E)-3-(2-Nitrophenyl)acrylonitrile 8p: The product was obtained
according to GP-III starting from 2-nitrobenzaldehyde (45.3 mg,
0.3 mmol) and chloroacetonitrile (25 mL, 0.39 mmol) as a mixture of
regioisomers (E/Z=65:25). Purification by using silica gel chroma-
tography (petroleum ether/ethyl acetate=5:1) yielded the product
as a mixture of regioisomers in 22% (11.4 mg, 0.07 mmol) com-
bined yield as a colorless oil. The regioisomers were separated by
using semi-preparative HPLC (petroleum ether/ethyl acetate 5:1).
Spectroscopic data were identical to those described in the litera-
ture.[39] Rf =0.36 (petroleum ether/ethyl acetate 5:1); 1H NMR
(300 MHz, CDCl3): d=8.22 (d, J=8.4 Hz, 1H), 7.87 (d, J=7.6 Hz,
1H), 7.77 (t, J=7.6 Hz, 1H), 7.73 (d, J=11.7 Hz, 1H), 7.65 (d, J=
7.8 Hz, 1H), 5.72 ppm (d, J=11.7 Hz, 1H); 13C NMR (75 MHz, CDCl3):
d=146.6, 134.3, 131.0, 130.7, 129.6, 125.3, 115.9, 100.2 ppm; IR
(film) n˜ =3111 (w), 3063 (m), 2918 (m), 2849 (w), 2217 (m), 1602
(w), 1567 (m), 1514 (s), 1437 (m), 1382 (m), 1342 (s), 1305 (m), 1291
(m), 1218 (m), 1178 (w), 1161 (w), 1140 (w), 1076 (w), 997 (m), 945
(w), 884 (m), 856 (m), 809 (s), 787 (s), 763 (s), 742 (m), 710 (s), 687
(m), 662 (m), 587 (w), 550 (w), 523 cmÀ1 (w); GC–MS (EI, 70 eV): m/z
(E)-3-(3-Bromophenyl)acrylonitrile 8n: The product was obtained
according to GP-III starting from 3-bromobenzaldehyde (35 mL,
0.3 mmol) and chloroacetonitrile (25 mL, 0.39 mmol) as a mixture of
regioisomers (E/Z=75:25). Purification by using silica gel chroma-
tography (petroleum ether/ethyl acetate 10:1) yielded the product
as a mixture of regioisomers in 79% (49.2 mg, 0.24 mmol) com-
bined yield as a colorless oil. The regioisomers were separated by
using semi-preparative HPLC (petroleum ether/ethyl acetate 10:1).
Spectroscopic data were identical to those described in the litera-
ture.[38] E isomer: Rf =0.35 (petroleum ether/ethyl acetate 10:1);
1H NMR (300 MHz, CDCl3): d=7.62–7.53 (m, 2H), 7.40–7.35 (m, 1H),
7.31 (d, J=4.3 Hz, 1H), 7.28 (d, J=8.7 Hz, 1H), 5.90 ppm (d, J=
16.6 Hz, 1H); 13C NMR (75 MHz, CDCl3): d=148.9, 135.5, 134.0,
130.6, 130.1, 126.0, 123.3, 117.5, 98.1 ppm; IR (film) n˜ =3060 (w),
2218 (s), 1620 (m), 1590 (w), 1562 (m), 1472 (m), 1424 (m), 1415
(m), 1283 (w), 1259 (w), 1202 (m), 1170 (w), 1090 (w), 1071 (m),
1032 (w), 994 (m), 961 (s), 887 (m), 873 (m), 826 (w), 775 (s), 732
(w), 680 (s), 623 (w), 561 (w), 508 cmÀ1 (w); GC–MS (EI, 70 eV): m/z
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