E
X. Chen et al.
Paper
Synthesis
13C NMR (100 MHz, CDCl3): δ = 181.09, 168.48, 143.67, 138.62,
133.77, 130.38, 130.02, 128.72, 127.14, 126.36, 109.94, 52.45, 29.60,
21.30, 13.91.
HRMS (ESI): m/z calcd for C15H21N2O2S+ (M + H)+: 293.1318; found:
293.1318.
Methyl 3-Phenyl-2-[(3-propylthioureido)methyl]acrylate (7m)
Colorless oil; yield: 496 mg (85%); Rf = 0.18 (PE/EtOAc 4:1).
IR (KBr): 3100, 3041, 1688, 1611, 1499, 1453, 1033 cm–1
1H NMR (400 MHz, CDCl3): δ = 7.88 (s, 1 H, =CH), 7.43 (br s, 5 H, ArH),
6.41 (s, 2 H, NH), 4.49 (s, 2 H, CH2), 3.86 (s, 3 H, CH3), 3.32 (s, 2 H, CH2),
1.59–1.50 (m, 2 H, CH2), 0.92 (t, J = 7.4 Hz, 3 H).
.
Methyl 2-[(3-Propylthioureido)methyl]-3-(m-tolyl)acrylate (7i)
Colorless oil; yield: 508 mg (83%); Rf = 0.25 (PE/EtOAc 4:1).
13C NMR (100 MHz, CDCl3): δ = 181.24, 168.48, 143.55, 133.82,
129.57, 129.34, 128.84, 127.33, 109.94, 52.51, 22.01, 11.32.
IR (KBr): 3100, 3041, 1693, 1608, 1504, 1457, 1034 cm–1
.
1H NMR (400 MHz, CDCl3): δ = 7.85 (s, 1 H, =CH), 7.36–7.11 (m, 4 H,
ArH), 6.39 (s, 1 H, NH), 6.29 (s, 1 H, NH), 4.48 (s, 2 H, CH2), 3.85 (s, 3 H,
CH3), 3.32 (s, 2 H, CH2), 2.39 (s, 3 H, CH3), 1.56–1.51 (m, 2 H, CH2), 0.92
(t, J = 7.4 Hz, 3 H, CH3).
13C NMR (100 MHz, CDCl3): δ = 181.22, 168.51, 143.68, 138.64,
133.74, 130.40, 130.01, 128.73, 127.14, 126.36, 109.94, 52.48, 22.01,
21.32, 11.31.
HRMS (ESI): m/z calcd for C15H21N2O2S+ (M + H)+: 293.1318; found:
293.1320.
Methyl 3-(4-Fluorophenyl)-2-[(3-propylthioureido)methyl]acry-
late (7n)
Colorless oil; yield: 515 mg (83%); Rf = 0.20 (PE/EtOAc 4:1).
IR (KBr): 3097, 3039, 1685, 1608, 1499, 1457, 1037 cm–1
.
1H NMR (400 MHz, CDCl3): δ = 7.81 (s, 1 H, CH3), 7.47 (s, 2 H, ArH),
7.13 (t, J = 8.6 Hz, 2 H, ArH), 6.43 (s, 1 H, NH), 6.36 (s, 1 H, NH), 4.54 (s,
2 H, CH2), 3.85 (s, 3 H, CH3), 3.31 (s, 2 H, CH2), 1.61–1.54 (m, 2 H, CH2),
0.95 (t, J = 7.2 Hz, 3 H, CH3).
13C NMR (100 MHz, CDCl3): δ = 181.36, 168.52, 164.50, 162.01,
142.32, 131.65 (d, J = 8.0 Hz), 129.97 (d, J = 3.0 Hz), 127.08, 116.10,
115.89, 109.97, 52.50, 29.63, 22.03, 11.34.
HRMS (ESI): m/z calcd for C16H23N2O2S+ (M + H)+: 307.1475; found:
307.1475.
Methyl 2-[(3-Butylthioureido)methyl]-3-(m-tolyl)acrylate (7j)
Colorless oil; yield: 550 mg (86%); Rf = 0.25 (PE/EtOAc 4:1).
IR (KBr): 3095, 3034, 1688, 1608, 1499, 1457, 1035 cm–1
.
1H NMR (400 MHz, CDCl3): δ = 7.83 (s, 1 H, =CH), 7.33–7.29 (m, 1 H,
ArH), 7.24–7.18 (m, 3 H, ArH), 6.49 (s, 1 H, NH), 6.36 (s, 1 H, NH), 4.49
(s, 2 H, CH2), 3.83 (s, 3 H, CH3), 3.35 (s, 2 H, CH2), 2.38 (s, 3 H, CH3),
1.49–1.46 (m, 2 H, CH2), 1.34–1.30 (m, 2 H, CH2), 0.90 (t, J = 7.2 Hz, 3
H, CH3).
13C NMR (100 MHz, CDCl3): δ = 181.09, 169.36, 144.51, 139.46,
134.65, 131.27, 130.99, 129.59, 128.04, 127.33, 53.33, 31.69, 22.19,
20.85, 14.58.
HRMS (ESI): m/z calcd for C15H20FN2O2S+ (M + H)+: 311.1224; found:
311.1220.
Methyl 2-[(3-Isopropylthioureido)methyl]-3-phenylacrylate (7o)
Colorless oil; yield: 484 mg (83%); Rf = 0.16 (PE/EtOAc 4:1).
IR (KBr): 3097, 3035, 1690, 1605, 1499, 1457, 1033 cm–1
.
1H NMR (400 MHz, CDCl3): δ = 7.88 (s, 1 H, =CH), 7.46–7.43 (m, 5 H,
ArH), 6.40 (s, 1 H, NH), 6.20 (s, 1 H, NH), 4.46 (s, 2 H, CH2), 4.18–4.11
(m, 1 H, CH), 3.85 (s, 3 H, CH3), 1.15 (d, J = 6.4 Hz, 6 H, 2 × CH3).
13C NMR (100 MHz, CDCl3): δ = 180.07, 168.41, 143.42, 133.80,
129.57, 129.36, 128.86, 127.33, 109.92, 52.50, 46.29, 22.27.
HRMS (ESI): m/z calcd for C17H25N2O2S+ (M + H)+: 321.1631; found:
321.1630.
Methyl 2-[(3-Phenylthioureido)methyl]-3-(m-tolyl)acrylate (7k)
Colorless oil; yield: 510 mg (75%); Rf = 0.20 (PE/EtOAc 4:1).
HRMS (ESI): m/z calcd for C15H21N2O2S+ (M + H)+: 293.1318; found:
293.1318.
IR (KBr): 3097, 3038, 1686, 1608, 1499, 1459, 1030 cm–1
.
1H NMR (400 MHz, CDCl3): δ = 7.84 (s, 2 H, =CH, NH), 7.46–7.41 (m, 5
H, ArH), 7.18 (d, J = 8.0 Hz, 2 H, ArH), 7.00 (d, J = 7.2 Hz, 2 H, ArH), 6.59
(s, 1 H, NH), 4.74 (s, 2 H, CH2), 3.77 (s, 3 H, CH3), 2.35 (s, 3 H, CH3).
13C NMR (100 MHz, CDCl3): δ = 180.22, 168.73, 143.40, 138.42,
133.66, 130.28, 130.26, 128.53, 126.71, 126.62, 52.63, 52.32, 42.82,
29.22, 21.25.
Methyl 2-[(3-Cyclohexylthioureido)methyl]-3-phenylacrylate (7p)
Colorless oil; yield: 530 mg (80%); Rf = 0.20 (PE/EtOAc 4:1).
IR (KBr): 3094, 3038, 1673, 1602, 1499, 1457, 1034 cm–1
.
1H NMR (400 MHz, CDCl3): δ = 7.87 (s, 1 H, =CH), 7.43 (br s, 5 H, ArH),
6.36 (s, 1 H, NH), 6.25 (s, 1 H, NH), 4.46 (s, 2 H, CH2), 3.85 (s, 3 H, CH3),
1.96 (d, J = 11.6 Hz, 2 H, CH2), 1.71–1.58 (m, 3 H, CH2), 1.45–1.21 (m, 3
H, CH2), 1.20–1.03 (m, 3 H, CH2).
13C NMR (100 MHz, CDCl3): δ = 179.96, 168.42, 143.39, 133.81,
129.56, 129.36, 128.85, 127.36, 52.52, 32.53, 25.30, 24.61.
HRMS (ESI): m/z calcd for C19H21N2O2S+ (M + H)+: 341.1318; found:
341.1318.
Methyl 3-(m-Tolyl)-2-{[3-(p-tolyl)thioureido]methyl}acrylate (7l)
Light yellow solid; yield: 531 mg (75%); mp 139–141 °C; Rf = 0.22
(PE/EtOAc 4:1).
HRMS (ESI): m/z calcd for C18H25N2O2S+ (M + H)+: 333.1631; found:
333.1631.
IR (KBr): 3100, 3041, 1681, 1608, 1500, 1457, 1034 cm–1
.
Methyl
3-(3-Chlorophenyl)-2-[(3-isopropylthioureido)methyl]-
1H NMR (400 MHz, CDCl3): δ = 7.80 (s, 2 H, =CH, NH), 7.34–7.29 (m, 2
H, ArH), 7.25–7.16 (m, 4 H, ArH), 7.00 (d, J = 7.6 Hz, 2 H, ArH), 6.59 (s,
1 H, NH), 4.74 (s, 2 H, CH2), 3.76 (s, 3 H, CH3), 2.39 (s, 3 H, CH3), 2.34 (s,
3 H, CH3).
acrylate (7q)
Colorless oil; yield: 560 mg (86%); Rf = 0.16 (PE/EtOAc 4:1).
IR (KBr): 3097, 3055, 1691, 1611, 1499, 1454, 1034 cm–1
.
1H NMR (400 MHz, CDCl3): δ = 7.79 (s, 1 H, =CH), 7.41–7.38 (m, 4 H,
ArH), 6.31 (s, 1 H, NH), 6.10 (s, 1 H, NH), 4.50 (s, 2 H, CH2), 4.10 (s, 1 H,
CH), 3.87 (s, 3 H, CH3), 1.19 (d, J = 6.4 Hz, 6 H, 2 × CH3).
13C NMR (100 MHz, CDCl3): δ = 180.09, 168.13, 143.75, 138.47,
133.81, 130.52, 130.34, 130.30, 128.58, 126.75, 124.95, 52.24, 42.61,
29.65, 21.33, 20.99.
13C NMR (100 MHz, CDCl3): δ = 168.22, 141.69, 135.66, 130.17,
HRMS (ESI): m/z calcd for C20H23N2O2S+ (M + H)+: 355.1475; found:
129.52, 129.29, 127.33, 109.98, 52.65, 22.37.
355.1476.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–I