H
M. C. Mollo et al.
Paper
Synthesis
2-(4-Nitrophenylthioamido)ethyl Acetate (3d)
HRMS (ESI): m/z [M + H]+ calcd for C13H16NO2S: 250.0896; found:
250.0893.
Yellow solid; yield: 413 mg (77%); mp 77–79 °C; Rf = 0.54 (hexane/
EtOAc, 3:2).
2-(2-Phenylethanethioamido)ethyl Acetate (3i)
1H NMR (600 MHz, CDCl3): = 2.13 (s, 3 H, CH3CO), 4.07 (q, J = 4.9 Hz,
2 H, N-CH2), 4.47 (t, J = 4.9 Hz, 2 H, O-CH2), 7.90 (d, J = 8.8 Hz, 2 H,
arom), 8.23 (d, J = 8.8 Hz, 2 H, arom), 8.45 (br s, 1 H, NH).
13C NMR (151 MHz, CDCl3): = 20.9, 47.3, 62.2, 123.7, 127.7, 146.1,
149.0, 172.5, 196.7.
Yellow oil; yield: 427 mg (90%); Rf = 0.57 (hexane/EtOAc, 3:2).
1H NMR (600 MHz, CDCl3): = 1.95 (s, 3 H, CH3CO), 3.88 (q, J = 5.2 Hz,
2 H, N-CH2), 4.14 (s, 2 H, -CH2-), 4.22 (t, J = 5.3 Hz, 2 H, O-CH2), 7.27–
7.40 (m, 5 H, arom).
13C NMR (151 MHz, CDCl3): = 20.6, 45.3, 53.2, 61.5, 127.9, 129.2,
HRMS (ESI): m/z [M + H]+ calcd for C11H13N2O4S: 269.0591; found:
129.6, 134.8, 171.1, 203.0.
269.0587.
HRMS (ESI): m/z [M + H]+ calcd for C12H16NO2S: 238.0896; found:
2-(2-Methylphenylthioamido)ethyl Acetate (3e)
238.0900.
Yellow oil; yield: 337 mg (71%); Rf = 0.50 (hexane/EtOAc, 3:2).
2-(2-Methylpropanethioamido)ethyl Acetate (3j)
1H NMR (600 MHz, CDCl3): = 1.97 (s, 3 H, -CH3), 2.27 (s, 3 H, CH3CO),
3.90–3.93 (m, 2 H, N-CH2), 4.22–4.24 (m, 2 H, O-CH2), 7.11–7.20 (m, 4
H, arom), 8.01 (br s, 1 H, NH).
13C NMR (151 MHz, CDCl3): = 18.9, 20.5, 44.6, 61.4, 125.6, 126.4,
128.7, 130.4, 132.5, 143.4, 171.0, 201.9.
Yellow oil; yield: 303 mg (80%); Rf = 0.55 (hexane/EtOAc, 3:2).
1H NMR (600 MHz, CDCl3): = 1.27 (d, J = 6.7 Hz, 6 H,-CH3), 2.11 (s, 3
H, CH3CO), 2.80–2.85 (m, 1 H, -CH-), 3.94 (q, J = 5.1 Hz, 2 H, N-CH2),
4.35 (t, J = 5.1 Hz, 2 H, O-CH2), 7.70 (br s,1 H, NH).
13C NMR (151 MHz, CDCl3): = 20.9, 22.5, 44.6, 45.6, 62.1, 171.9,
HRMS (ESI): m/z [M + H]+ calcd for C12H16NO2S: 238.0896; found:
212.4.
238.0892.
HRMS (ESI): m/z [M + H]+ calcd for C8H16NO2S: 190.0896; found:
(S)-2-Phenylthioamidopropyl Acetate (3f)
190.0898.
Yellow oil; yield: 394 mg (83%); []D25 –44.6 (c 2.00, CHCl3); Rf = 0.56
(hexane/EtOAc, 3:2).
3-Phenylthioamidopropyl Acetate (4a)
1H NMR (600 MHz, CDCl3): = 1.38 (d, J = 6.8 Hz, 3 H, -CH3), 2.11 (s, 3
H, CH3CO), 4.27 (dd, J = 11.7, 5.9 Hz, 1 H, -NCH), 4.38 (dd, J = 11.7, 5.9
Hz, 1 H, CHHCO), 5.03–5.09 (m, 1 H, CHHCO), 7.39 (t, J = 7.5 Hz, 2 H,
H-3′), 7.46 (t, J = 7.5 Hz, 1 H, H-4′), 7.74 (d, J = 7.5 Hz, 2 H, H-2′), 7.87
(br s, 1 H, NH).
13C NMR (151 MHz, CDCl3): = 15.8, 20.8, 51.2, 66.3, 126.6, 128.5,
131.1, 141.7, 171.6, 198.8.
Yellow oil; yield: 403 mg (85%); Rf = 0.50 (hexane/EtOAc, 3:2).
1H NMR (600 MHz, CDCl3): = 2.07–2.10 (m, 5 H, -CH2-, -CH3)*, 3.87–
3.90 (m, 2 H, N-CH2), 4.20–4.22 (m, 2 H, O-CH2), 7.38 (t, J = 8.0 Hz, 2
H, arom), 7.45 (t, J = 8.0 Hz, 1 H, arom), 7.76 (d, J = 8.0 Hz, 2 H, arom),
8.16 (br s, 1 H, NH); * overlapping signals.
13C NMR (151 MHz, CDCl3): = 20.9, 27.0, 43.4, 62.2, 126.6, 128.4,
131.1, 141.6, 171.5, 199.2.
HRMS (ESI): m/z [M + H]+ calcd for C12H16NO2S+: 238.0896; found:
238.0901.
HRMS (ESI): m/z [M + H]+ calcd for C12H16NO2S: 238.0896; found:
238.0891.
(R)-1-Phenylthioamidopropan-2-yl Acetate (3g)
Yellow oil; yield: 408 mg (86%); []D25 +16.3 (c 1.00, CHCl3); Rf = 0.56
(hexane/EtOAc, 3:2).
1H NMR (600 MHz, CDCl3): = 1.39 (d, J = 6.5 Hz, 3 H, -CH3), 2.10 (s, 3
H, CH3CO), 3.90 (ddd, J = 13.5, 8.5, 5.0 Hz, 1 H, -NCHH), 4.03 (ddd,
J = 15.0, 5.0, 2.5 Hz, 1 H, -NCHH), 5.24–5.29 (m, 1 H, -OCH), 7.39 (t,
J = 8.0 Hz, 2 H, H-3′), 7.46 (t, J = 8.0 Hz, 1 H, H-4′), 7.77 (d, J = 8.0 Hz, 2
H, H-2′), 8.30 (br s, 1 H, NH).
13C NMR (151 MHz, CDCl3): = 18.2, 21.2, 52.3, 69.6, 126.6, 128.5,
131.2, 141.2, 172.0, 199.3.
3-(4-Chlorophenylthioamido)propyl Acetate (4b)
Yellow oil; yield: 489 mg (90%); Rf = 0.60 (hexane/EtOAc, 3:2).
1H NMR (600 MHz, CDCl3): = 2.06–2.11 (m, 5 H, -CH2-, CH3CO)*, 3.89
(q, J = 6.2 Hz, 2 H, N-CH2), 4.22 (t, J = 5.9 Hz, 2 H, O-CH2), 7.35 (d,
J = 8.6 Hz, 2 H, H-3′), 7.73 (d, J = 8.6 Hz, 2 H, H-2′), 8.17 (br s, 1 H, NH);
* overlapping signals.
13C NMR (151 MHz, CDCl3): = 20.9, 27.1, 43.3, 62.1, 128.0, 128.6,
137.4, 139.8, 171.7, 197.6.
HRMS (ESI): m/z [M + H]+ calcd for C12H15ClNO2S: 272.0507; found:
272.0512.
HRMS (ESI): m/z [M + H]+ calcd for C12H16NO2S: 238.0896; found:
238.0900.
3-(4-Methoxyphenylthioamido)propyl Acetate (4c)
Yellow oil; yield: 454 mg (85%); Rf = 0.56 (hexane/EtOAc, 3:2).
(E)-2-(3-Phenylprop-2-enethioamido)ethyl Acetate (3h)
1H NMR (600 MHz, CDCl3): = 2.06–2.10 (m, 5 H, -CH2-, CH3CO)*, 3.83
(s, 3 H, OCH3), 3.90 (q, J = 6.2 Hz, 2 H, N-CH2), 4.22 (t, J = 5.9 Hz, 2 H,
O-CH2), 6.87 (d, J = 8.8 Hz, 2 H, H-3′), 7.80 (d, J = 8.8 Hz, 2 H, H-2′),
8.07 (br s, 1 H, NH); * overlapping signals.
13C NMR (151 MHz, CDCl3): = 20.9, 27.2, 43.2, 55.4, 62.2, 113.6,
128.4, 133.8, 162.2, 171.6, 197.9.
Yellow solid; yield: 344 mg (69%); mp 94–96 °C; Rf = 0.50 (hexane/
EtOAc, 3:2).
1H NMR (600 MHz, CDCl3): = 2.12 (s, 3 H, CH3CO), 4.08 (q, J = 5.1 Hz,
2 H, N-CH2), 4.40 (t, J = 5.1 Hz, 2 H, O-CH2), 6.84 (d, J = 15.4 Hz, 1 H,
=CHCS), 7.34–7.38 (m, 3 H, arom), 7.53–7.54 (m, 2 H, arom), 7.80 (d,
J = 15.4 Hz, 1 H, ArHC=), 7.84 (br s, 1 H, NH).
HRMS (ESI): m/z [M + H]+ calcd for C13H18NO3S: 268.1002; found:
268.0996.
13C NMR (151 MHz, CDCl3): = 20.9, 45.7, 62.2, 127.4, 128.0, 128.9,
129.9, 134.8, 141.9, 171.8, 195.3.
© 2020. Thieme. All rights reserved. Synthesis 2020, 52, A–N