10.1002/ejoc.201900634
European Journal of Organic Chemistry
FULL PAPER
7.8 Hz, 1H), 7.09 (dd, J = 4.8, 3.6 Hz, 1H), 5.83 (s, 1H), 2.95 (q, J = 7.4
Hz, 2H), 1.37 (t, J = 7.2 Hz, 3H). 13C NMR (151 MHz, CDCl3) δ 179.0,
166.0, 146.6, 138.1, 130.3, 129.0 (2C), 127.8, 127.7, 126.3, 125.1(2C),
89.2, 26.1, 13.3.
S-ethyl 3-oxo-3-phenylpropanethioate (2a) [keto/enol = 1.3:1]: yield: 61
mg (98%); slight yellow oil; 1H NMR (600 MHz, CDCl3) δ for keto-2a: 7.96
(d, J = 7.8 Hz, 2H), 7.59 (t, J = 7.2 Hz, 1H), 7.48 (t, J = 7.8 Hz, 2H), 4.21(s,
2H), 2.93 (q, J = 7.2 Hz, 2H), 1.26 (t, J = 7.2 Hz,3H); δ for enol-2a: 13.2
(br, 1H), 7.78 (d, J = 8.4 Hz, 2H), 7.48 (t, J = 7.8 Hz,1H), 7.42 (t, J = 7.2
Hz, 2H), 6.08 (s, 1H), 3.00 (q, J = 7.2 Hz, 2H), 1.33 (t, J = 7.2 Hz, 3H). 13
C
NMR (151 MHz, CDCl3) δ for keto-2a: 192.2, 192.0, 133.8, 131.6, 128.8
(2C), 128.7 (2C), 54.0, 24.0, 14.4; δ for enol-2a: 195.0, 168.8, 136.1, 133.0,
128.6 (2C), 126.4 (2C), 97.2, 22.9, 14.9. HR-MS (ESI): m/z = 231.0454,
calcd. for C11H12O2S (M+Na)+ 231.0450.
(E)-3-(ethylthio)-1-(furan-2-yl)-3-(phenylamino)prop-2-en-1-one (1m):
yield: 0.43 g (78%); yellow solid, mp 61−63 °C; 1H NMR (600 MHz, CDCl3)
δ 13.23 (s, 1H), 7.49 (d, J =1.2 Hz, 1H), 7.36 (t, J = 7.8 Hz, 2H), 7.30 (d, J
= 7.2 Hz, 2H), 7.23 (t, J = 7.2 Hz, 1H), 7.07 (d, J = 3.6 Hz, 1H), 6.49 (dd, J
= 3.6, 1.8 Hz, 1H), 5.92 (s, 1H), 2.96 (q, J = 7.2 Hz, 2H), 1.36 (t, J = 7.2
Hz, 3H). 13C NMR (151 MHz, CDCl3) δ 175.3, 166.7, 154.0, 144.1, 138.1,
128.9 (2C), 126.2, 125.1(2C), 113.0, 112.0, 88.6, 26.0, 13.2.
S-ethyl 3-oxo-3-(p-tolyl)propanethioate (2b) [keto/enol = 1.8:1]: yield:
1
63 mg (95%); slight yellow oil; H NMR (600 MHz, CDCl3) δ for keto-2b:
7.86 (d, J = 7.8 Hz, 2H), 7.27 (d, J = 8.4 Hz, 2H), 4.17 (s, 2H), 2.92 (q, J =
7.2 Hz, 2H), 2.41 (s, 3H), 1.26 (t, J = 7.4 Hz, 3H); δ for enol-2b: 13.2 (br,
1H), 7.68 (d, J = 8.4 Hz, 2H), 7.21 (d, J = 8.4 Hz, 2H), 6.05 (s, 1H), 2.96
(q, J = 7.2 Hz, 2H), 2.39 (s, 3H), 1.33 (t, J = 7.8 Hz,3H).13C NMR (151 MHz,
CDCl3) δ for keto-2b: 192.3, 191.5, 144.7, 133.6, 129.4 (2C), 128.9 (2C),
53.9, 23.9, 21.6, 14.4; δ for enol-2b: 194.8, 169.0, 142.2, 130.0, 129.3 (2C),
126.3 (2C), 96.6, 22.8, 21.5, 14.9. HR-MS (ESI): m/z = 245.0610, calcd.
for C12H14O2S (M+Na)+ 245.0607.
(E)-3-((4-chlorophenyl)amino)-3-(ethylthio)-1-phenylprop-2-en-1-one
1
(1o): yield: 0.39 g (62%); yellow solid, mp 65−67 °C; H NMR (600 MHz,
CDCl3) δ 13.54 (s, 1H), 7.89 (d, J = 7.2 Hz, 2H), 7.50–7.41 (m, 3H), 7.33
(d, J = 8.4 Hz, 2H), 7.26 (d, J = 9.0 Hz, 2H), 5.95 (s, 1H), 2.96 (q, J = 7.2
Hz, 2H), 1.37 (t, J = 7.2 Hz, 3H). 13C NMR (151 MHz, CDCl3) δ 186.2,
166.1, 139.9, 136.8, 131.7, 131.0, 129.1 (2C), 128.3 (2C), 127.0 (2C),
126.4 (2C), 89.9, 26.1, 13.3.
S-ethyl 3-(4-methoxyphenyl)-3-oxopropanethioate (2c) [keto/enol =
2:1]: yield: 56 mg (78%); slight yellow oil; 1H NMR (600 MHz, CDCl3) δ for
keto-2c: 7.95 (d, J = 9.0 Hz, 2H), 6.94 (d, J = 9.0 Hz, 2H), 4.16 (s, 2H),
3.87 (s, 3H), 2.92 (q, J = 7.2 Hz, 2H), 1.26 (t, J = 7.8 Hz, 3H); δ for enol-
2c: 13.33 (br, 1H), 7.75 (d, J = 8.4 Hz, 2H), 6.92(d, J = 9.0 Hz, 2H), 6.01(s,
1H), 3.85 (s, 3H), 2.99 (q, J = 7.8 Hz, 2H), 1.33 (t, J = 7.8 Hz, 3H). 13C
NMR (151 MHz, CDCl3) δ for keto-2c: 192.4, 190.3, 164.0, 131.2 (2C),
129.0, 113.9 (2C), 53.9, 23.9, 14.4; δ for enol-2c: 194.5, 168.8, 162.4,
128.1 (2C), 125.0, 113.9 (2C), 95.8, 22.8, 15.0.
(E)-3-(ethylthio)-3-((4-methoxyphenyl)amino)-1-phenylprop-2-en-1-
one (1p): yield: 0.42 g (67%); yellow solid, mp 60−62 °C; 1H NMR (600
MHz, CDCl3) δ 13.32 (s, 1H), 7.89 (d, J = 7.8 Hz, 2H), 7.48 – 7.40 (m, 3H),
7.23 (d, J = 9.0 Hz, 2H), 6.89 (d, J = 9.0 Hz, 2H), 5.90 (s, 1H), 3.80 (s, 3H),
2.93 (q, J = 7.2 Hz, 2H), 1.40–1.32 (m, 3H). 13C NMR (151 MHz, CDCl3)
δ 185.8, 167.6, 158.2, 140.3, 130.8, 130.7, 128.2 (2C), 127.2(2C),
126.9(2C), 114.1(2C), 88.6, 55.3, 25.9, 13.3.
(E)-3-(ethylthio)-3-(methylamino)-1-phenylprop-2-en-1-one (1q): yield:
0.31 g (71%); yellow solid, mp 52−54 °C; 1H NMR (600 MHz, CDCl3) δ
11.80 (s, 1H), 7.82 (dd, J = 7.8, 1.2 Hz, 2H), 7.43–7.38 (m, 3H), 5.70 (s,
1H), 3.06 (d, J = 4.2 Hz, 3H), 3.00 (q, J = 7.2 Hz, 2H), 1.43 (t, J = 7.8 Hz,
3H). 13C NMR (151 MHz, CDCl3) δ 185.1, 169.8, 140.8, 130.3, 128.2 (2C),
126.8 (2C), 86.9, 30.3, 25.5, 13.6.
S-ethyl 3-(3-methoxyphenyl)-3-oxopropanethioate (2d) [keto/enol =
1
1.3:1]: yield: 54 mg (75%); slight yellow oil; H NMR (600 MHz, CDCl3) δ
for keto-2d: 7.53 (d, J = 7.2 Hz,1H), 7.39 (t, J = 7.8 Hz, 1H), 7.32 (t, J =
7.8 Hz, 1H), 7.14 (dd, J = 8.4, 2.4Hz, 1H), 4.20 (s, 2H), 3.85 (s, 3H), 2.94
(q, J = 7.8 Hz, 2H), 1.27 (t, J = 7.8 Hz, 3H); δ for enol-2d: 13.23 (br, 1H),
7.50 (s, 1H), 7.36 (d, J = 7.8 Hz, 1H), 7.32 (t, J = 7.8 Hz,1H), 7.02 (dd, J =
8.4Hz, 3.0 Hz, 1H), 6.07 (s, 1H), 3.85 (s, 3H), 3.00 (q, J = 7.2 Hz, 2H), 1.34
(t, J = 7.2 Hz, 3H). 13C NMR (151 MHz, CDCl3) δ for keto-2d: 192.2, 191.8,
159.9, 137.3, 129.7, 121.5, 118.7, 112.7, 55.4, 54.1, 24.0, 14.4; δ for enol-
2d: 195.1, 168.5, 159.7, 134.3, 129.6, 120.5, 117.6, 111.4, 97.4, 55.4, 23.0,
14.9. HR-MS (ESI): m/z=261.0546, calcd. for C12H14O3S (M+Na)+
261.0556.
(E)-3-(methylthio)-1-phenyl-3-(phenylamino)prop-2-en-1-one
(1r):
yield: 0.50 g (92%); yellow solid, mp 57−59 °C; 1H NMR (600 MHz, CDCl3)
δ 13.52 (s, 1H), 7.91 (d, J = 7.2 Hz, 2H), 7.48–7.41 (m, 3H), 7.36 (t, J =
7.2 Hz, 2H), 7.32 (d, J = 7.2 Hz, 2H), 7.24 (t, J = 7.2 Hz, 1H), 5.88 (s, 1H),
2.41 (s, 3H). 13C NMR (151 MHz, CDCl3) δ 186.0, 167.5, 140.2, 138.1,
130.8, 129.0 (2C), 128.3 (2C), 127.0(2C), 126.3, 125.2(2C), 88.6, 14.7.
S-ethyl 3-(4-chlorophenyl)-3-oxopropanethioate (2e) [keto/enol = 1:1]:
yield: 55 mg (76%); slight yellow oil; 1H NMR (600 MHz, CDCl3) δ for keto-
2e: 7.72 (d, J = 8.4 Hz, 2H), 7.39 (d, J = 8.4 Hz, 2H), 4.18 (s, 2H), 3.00 (q,
J = 7.2 Hz, 2H), 1.26 (t, J = 7.2 Hz, 3H); δ for enol-2e: 13.22 (br, 1H), 7.90
(d, J = 8.4 Hz, 2H), 7.45 (d, J = 8.4 Hz, 2H), 6.04 (s,1H), 2.93 (q, J = 7.2
Hz, 2H), 1.33 (t, J = 7.8 Hz, 3H). 13C NMR (151 MHz, CDCl3) δ for keto-
2e: 191.9, 190.6, 137.7, 131.4, 129.1 (2C), 128.9 (2C), 54.0, 23.0, 14.4; δ
for enol-2e: 195.1, 167.4, 140.4, 134.3, 130.2 (2C), 127.6 (2C), 97.3, 24.0,
(E)-3-(benzylthio)-1-phenyl-3-(phenylamino)prop-2-en-1-one
(1s):
yield: 0.58 g (84%); yellow solid, mp 135−137 °C; 1H NMR (600 MHz,
CDCl3) δ 13.41 (s, 1H), 7.82 (d, J = 7.2 Hz, 2H), 7.48–7.45 (m,1H), 7.42 (t,
J = 7.2 Hz, 2H), 7.36 (t, J = 7.8 Hz, 2H), 7.31 (d, J = 7.8 Hz, 2H), 7.29 (d,
J = 2.4Hz, 3H), 7.26–7.21 (m, 2H), 5.95 (s, 1H), 4.10 (s, 2H). 13C NMR
(151 MHz, CDCl3) δ 186.5, 165.0, 139.9, 138.1, 133.9, 133.3, 131.1, 130.3
(2C), 129.1 (2C), 129.0 (2C), 128.4 (2C), 127.0 (2C), 126.4, 125.1 (2C),
90.8, 36.1.
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