Job/Unit: O43402
/KAP1
Date: 20-01-15 18:12:57
Pages: 9
H. S. P. Rao, N. Muthanna
FULL PAPER
δ = 188.9, 162.0, 143.1, 141.0, 133.1 (q, J = 33.1 Hz), 127.7, 127.1,
(Z)-3-Amino-3-(4-methoxyphenyl)-1-[4-(trifluoromethyl)phenyl]-
126.4, 126.3–126.3 (m), 125.6–125.3 (m), 125.2 (d, J = 27.7 Hz), prop-2-en-1-one (3n): Following the general procedure (Method A),
122.5 (d, J = 27.9 Hz), 92.6 ppm. HRMS (ESI): calcd. for
C17H11F6NOH [M + H] 360.0823; found 360.0821.
the reaction of Zn (488 mg, 7.52 mmol), 4-methoxybenzonitrile (1d;
501 mg, 3.76 mmol), 2-bromo-1-[4-(trifluoromethyl)phenyl]ethan-
one (2b; 1.004 g, 3.76 mmol), trimethylsilyl chloride (12 mg, 3 mol-
%), THF (15 mL), 4 h, and HCl (3 n, 0.5 mL) gave compound 3n
(Z)-3-Amino-1-(4-chlorophenyl)-3-[4-(trifluoromethyl)phenyl]prop-2-
en-1-one (3g): Following the general procedure (Method A), the
reaction of Zn (382 mg, 5.84 mmol), 4-(trifluoromethyl)benzoni-
trile (1b; 503 mg, 2.92 mmol), 2-bromo-1-(4-chlorophenyl)ethanone
(2c; 684 mg, 2.92 mmol), trimethylsilyl chloride (10 mg, 3 mol-%),
THF (15 mL), 3 h, and HCl (3 n, 0.5 mL) gave compound 3g
(84%) as a pale yellow solid, m.p. 115–117 °C. IR: ν = 3362, 3155,
˜
1618, 1600, 1537, 1323, 1014, 783 cm–1 1H NMR (400 MHz,
.
CDCl3 + CCl4, 1:1): δ = 10.55 (br. s, 1 H), 8.01 (d, J = 8.0 Hz, 2
H), 7.68 (d, J = 8.1 Hz, 2 H), 7.58 (d, J = 8.9 Hz, 2 H), 6.97 (d, J
= 8.9 Hz, 2 H), 6.07 (s, 1 H), 3.88 (br. s, 3 H) ppm. 13C NMR
(400 MHz, CDCl3 + CCl4, 1:1): δ = 188.1, 163.6, 162.1, 143.8,
135.4, 132.3 (q, J = 34.8 Hz), 129.5, 127.9, 127.6 (q, J = 7.7 Hz),
124.0 (d, J = 240.3 Hz), 114.6, 91.3, 55.5 ppm. HRMS (ESI): calcd.
for C17H14F3NO2Na [M + Na] 344.0874; found 344.0875.
(89%) as a pale yellow oil. IR: ν = 3308, 3158, 1614, 1601, 1534,
˜
1
1324, 1014, 783 cm–1. H NMR (400 MHz, CDCl3): δ = 10.31 (br.
s, 1 H), 7.86–7.77 (m, 2 H), 7.71 (d, J = 3.5 Hz, 4 H), 7.44–7.30
(m, 2 H), 6.02 (s, 1 H), 5.67 (br. s, 1 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 188.9, 161.6, 141.1, 138.3, 137.7, 132.8 (q, J =
32.8 Hz), 128.8, 128.7, 127.7, 126.2 (q, J = 3.7 Hz), 123.8 (d, J =
272.5 Hz), 92.2 ppm. HRMS (ESI): calcd. for C16H11ClF3NONa
[M + Na] 348.0379; found 348.0380.
(Z)-3-Amino-1-phenyl-3-(1-tosyl-1H-indol-3-yl)prop-2-en-1-one (3t):
Following the general procedure (Method A), the reaction of Zn
(219 mg, 3.36 mmol), 1-tosyl-1H-indole-3-carbonitrile (1h; 503 mg,
1.68 mmol), 2-bromo-1-phenylethanone (2a; 336 mg, 1.68 mmol),
trimethylsilyl chloride (6 mg, 3 mol-%), THF (15 mL), 3 h, and
HCl (3 n, 0.5 mL) gave compound 3t (80%) as a pale yellow solid,
(Z)-3-Amino-1-(4-methoxyphenyl)-3-[4-(trifluoromethyl)phenyl]-
prop-2-en-1-one (3h): Following the general procedure (Method A),
the reaction of Zn (379 mg, 5.84 mmol), 4-(trifluoromethyl)benzo-
nitrile (1b; 502 mg, 2.92 mmol), 2-bromo-1-(4-methoxyphenyl)eth-
anone (2d; 651 mg, 2.92 mmol), trimethylsilyl chloride (10 mg,
3 mol-%), THF (15 mL), 6 h, and HCl (3 n, 0.5 mL) gave com-
m.p. 160 °C. IR: ν = 3443, 3379, 3059, 2926, 1732, 1601, 1571,
˜
1516, 1446, 1373, 1173, 959, 744, 683, 664 cm–1 1H NMR
.
(400 MHz, CDCl3): δ = 10.34 (br. s, 1 H), 8.23–7.69 (m, 7 H), 7.53–
7.05 (m, 7 H), 6.21 (s, 1 H), 5.59 (br. s, 1 H), 2.33 (s, 3 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 190.3, 155.8, 145.7, 140.2, 135.3,
134.7, 131.2, 130.2, 128.4, 127.5, 127.2, 127.1, 125.7, 125.6, 124.2,
120.7, 120.2, 114.0, 92.7, 21.7 ppm. HRMS (ESI): calcd. for
C24H20N2O3SNa [M + Na] 439.1092; found 439.1094.
pound 3h (81%) as a pale yellow oil. IR: ν = 3308, 3155, 1597,
˜
1
1556, 1498, 1323, 1303, 1259, 1168, 1138, 848, 785 cm–1. H NMR
(400 MHz, CDCl3 + CCl4, 1:1): δ = 10.24 (br. s, 1 H), 7.88 (d, J =
8.9 Hz, 2 H), 7.70 (d, J = 5.6 Hz, 4 H), 6.90 (d, J = 8.9 Hz, 2 H),
6.05 (s, 1 H), 5.43 (br. s, 1 H), 3.85 (s, 3 H) ppm. 13C NMR
(400 MHz, CDCl3 + CCl4, 1:1): δ = 189.4, 162.4, 160.5, 141.6,
133.6 (q, J = 32.7 Hz), 129.4, 127.0, 126.1, 125.7 (q, J = 3.7 Hz),
123.9 (d, J = 272.5 Hz), 122.5, 113.7, 92.3, 55.4 ppm. HRMS (ESI):
calcd. for C17H14F3NO2Na [M + Na] 344.0874; found 344.0875.
(Z)-3-Amino-1-phenyl-3-(pyridin-3-yl)prop-2-en-1-one (3u): Follow-
ing the general procedure (Method A), the reaction of Zn (624 mg,
9.6 mmol), pyridine-3-carbonitrile (1i; 504 mg, 4.80 mmol), 2-
bromo-1-phenylethanone (2a; 956 mg, 4.80 mmol), trimethylsilyl
chloride (15 mg, 3 mol-%), THF (15 mL), 3 h, and HCl (3 n,
0.5 mL) gave compound 3u (78%) as a colourless solid, m.p. 76 °C.
(Z)-3-Amino-3-(4-chlorophenyl)-1-[4-(trifluoromethyl)phenyl]prop-2-
en-1-one (3j): Following the general procedure (Method A), the re-
action of Zn (474 mg, 7.29 mmol), 4-chlorobenzonitrile (1c;
502 mg, 3.62 mmol), 2-bromo-1-[4-(trifluoromethyl)phenyl]etha-
none (2b; 974 mg, 3.62 mmol), trimethylsilyl chloride (11 mg,
3 mol-%), THF (15 mL), 4 h, and HCl (3 n, 0.5 mL) gave com-
IR: ν = 3351, 3154, 3058, 1604, 1562, 1529, 1474, 1328, 1230, 1021,
˜
749, 693 cm–1. 1H NMR (400 MHz, CDCl3): δ = 10.28 (br. s, 1 H),
8.86 (d, J = 1.8 Hz, 1 H), 8.66 (dd, J = 4.9, 1.6 Hz, 1 H), 7.95–7.86
(m, 3 H), 7.50–7.35 (m, 4 H), 6.07 (s, 1 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 190.4, 159.8, 151.3, 147.5, 139.9, 134.3,
133.5, 131.4, 128.4, 127.2, 123.8, 92.5 ppm. HRMS (ESI): calcd.
for C14H12N2ONa [M + Na] 247.0847; found 247.0841.
pound 3j (82%) as a colourless solid, m.p. 145–147 °C. IR: ν =
˜
3302, 3155, 1618, 1600, 1537, 1323, 1014, 783 cm–1 1H NMR
.
(400 MHz, CDCl3): δ = 10.45 (br. s, 1 H), 8.01 (d, J = 8.1 Hz, 2
H), 7.69 (d, J = 8.2 Hz, 2 H), 7.63–7.52 (m, 2 H), 7.53–7.39 (m, 2
H), 6.07 (s, 1 H), 5.59 (br. s, 1 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 188.6, 162.4, 143.1, 137.1, 135.5, 132.5 (q, J =
32.4 Hz), 129.4, 127.9, 127.7, 127.5, 125.3 (q, J = 7.6 Hz), 123.9 (d,
J = 2 7 2 . 4 H z ) , 9 1 . 8 p p m . H R M S ( E S I ) : c a l c d . f o r
C16H11ClF3NONa [M + Na] 348.0379; found 348.0378.
(Z)-3-Amino-1,4-diphenylbut-2-en-1-one (3v): Following the general
procedure (Method A), the reaction of Zn (556 mg, 8.54 mmol), 2-
phenylacetonitrile (1j; 505 mg, 4.27 mmol), 2-bromo-1-phenyl-
ethanone (2a; 850 mg, 4.27 mmol), trimethylsilyl chloride (13 mg,
3 mol-%), THF (15 mL), 6 h, and HCl (3 n, 0.5 mL) gave com-
pound 3v (67%) as a colourless solid, m.p. 81 °C. IR: ν = 3165,
˜
1
3060, 2926, 1601, 1566, 1485, 1328, 1226, 742, 695 cm–1. H NMR
(400 MHz, CDCl3): δ = 10.19 (br. s, 1 H), 7.85 (dd, J = 8.0, 1.5 Hz,
2 H), 7.44–7.34 (m, 3 H), 7.33–7.28 (m, 2 H), 7.27–7.21 (m, 3 H),
5.80 (s, 1 H), 5.33 (br. s, 1 H), 3.56 (s, 2 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 189.7, 164.9, 140.2, 135.7, 130.9, 129.2,
128.9, 128.2, 127.4, 127.1, 92.5, 42.5 ppm. HRMS (ESI): calcd. for
C16H15NONa [M + Na] 260.1051; found 260.1054.
(Z)-3-Amino-1,3-bis(4-chlorophenyl)prop-2-en-1-one (3k): Following
the general procedure (Method A), the reaction of Zn (472 mg,
7.29 mmol), 4-chlorobenzonitrile (1c; 503 mg, 3.64 mmol), 4-chlo-
rophenacyl bromide (2c; 847 mg, 3.64 mmol), trimethylsilyl chlor-
ide (12 mg, 3 mol-%), THF (15 mL), 3 h, and HCl (3 n, 0.5 mL)
gave compound 3k (87%) as a colourless solid, m.p. 96 °C. IR: ν
˜
= 3479, 3358, 3170, 1595, 1556, 1530, 1479, 1325, 1092, 1012, 841,
(Z)-5-Amino-2,2-dimethyloct-4-en-3-one (3y): Following the general
procedure (Method A), the reaction of Zn (942 mg, 14.28 mmol),
777 cm–1. 1H NMR (400 MHz, CDCl3): δ = 10.36 (br. s, 1 H), 7.86
(d, J = 8.7 Hz, 2 H), 7.55 (d, J = 8.7 Hz, 2 H), 7.41 (dd, J = 17.5, butyronitrile (1k; 502 mg, 7.24 mmol), 1-bromo-3,3-dimethylbutan-
8.7 Hz, 4 H), 6.03 (s, 1 H), 5.52 (br. s, 1 H) ppm. 13C NMR 2-one (2e; 1278 mg, 7.24 mmol), trimethylsilyl chloride (24 mg,
(100 MHz, CDCl3): δ = 188.7, 161.9, 138.4, 137.3, 136.9, 135.8, 3 mol-%), THF (15 mL), 4 h, and HCl (3 n, 0.5 mL) gave com-
129.3, 128.6, 128.5, 127.7, 91.6 ppm. HRMS (ESI): calcd. for
C15H11Cl2NONa [M + Na] 314.0114; found 314.0115.
pound 3y (75%) as a colourless oil. IR: ν = 2962, 2866, 1618, 1525,
˜
1351, 1148 cm–1. 1H NMR (400 MHz, CDCl3 + CCl4, 1:1): δ =
6
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