References and Notes
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General Procedure
for the Synthesis of Thioamide
To a mixture of aryl
nitrile (1 equiv) and CaH2 (1 equiv) was taken in a two-necked
50 mL round-bottomed flask, and the content was cooled to 0 ˚C
and added thioacetic acid (1.5 equiv). After stirring for 15 min
the reaction mixture was heated in an oil bath at 80 ˚C
for the given period of time (Table
[¹]
).
After the completion of the reaction, the contents were cooled to
r.t., 50% aq EtOAc (2 × 10 mL)
was added and stirred for some time till the layers separated. Extraction was
done once again with EtOAc, and the combined organic layer was filtered
through Celite pad, and concentrated under reduced pressure to get
the crude product. It was then purified by crystallization using
PE and EtOAc (9:1). All the novel products were characterized by
NMR and MS analysis.
4-Bromo-2-chlorobenzenecarbothioamide
(2b)
¹H NMR (400 MHz, DMSO-d
6): δ = 7.31
(d, 1 H), 7.50 (q, 1 H), 7.75 (s, 1 H), 9.73 (br s, 1 H), 10.23
(br s, 1 H) ppm. ¹³C NMR (100 MHz,
DMSO-d
6): δ = 126.5,
129.1, 129.7, 133.3, 136.6, 141.3, 188.5 ppm. Anal. Calcd (%)
for C7H5BrClNS: C, 33.56; H, 2.01; N, 5.59.
Found: C, 33.54; H, 2.22; N, 5.55. MS: m/z = 251.0 [M+].
4-Chloro-3-nitrobenzenecarbothioamide (2d)
¹H
NMR (400 MHz, DMSO-d
6): δ = 7.8
(d, 1 H), 8.1 (d, 1 H), 8.5 (s, 1 H), 9.8 (br s, 1 H), 10.2 (br
s, 1 H) ppm.
¹³C NMR (100
MHz, DMSO-d
6): δ = 124.7,
128.0, 131.8, 132.4, 139.6, 147.2, 196.5 ppm. Anal. Calcd (%)
for C7H5ClN2O2S: C,
33.81; H, 2.33; N, 12.93. Found: C, 33.76; H, 2.38; N, 12.96. MS: m/z = 214.9 [M+].
2-(3,4-Dichlorophenyl)ethanethioamide (2f)
¹H
NMR (400 MHz, DMSO-d
6): δ = 3.8
(s, 2 H), 7.2 (d, 1 H), 7.5 (s, 1 H), 7.6 (d, 1 H), 9.4 (s, 1 H),
9.5 (s, 1 H) ppm. ¹³C NMR (100 MHz,
DMSO-d
6): δ = 50.5,
129.6, 129.8, 130.6, 131.1, 131.2, 138.8, 204.9 ppm. Anal. Calcd
(%) for C8H7Cl2NS: C,
43.65, H, 3.21, N, 6.36. Found: C, 43.76, H, 3.28, N, 6.34; MS: m/z = 219.9 [M+].
3-(4-Iodophenyl)propanethioamide (2g)
¹H
NMR (400 MHz, DMSO-d
6): δ = 3.7
(s, 2 H), 7.1 (d, 2 H), 7.6 (d, 2 H), 9.3 (br s, 1 H), 9.4 (br s,
1 H) ppm. ¹³C NMR: (100 MHz, DMSO-d
6): δ = 50.7,
93.0, 131.6, 137.3, 137.6, 205.4 ppm. Anal. Calcd (%) for
C8H8INS: C, 34.67; H, 2.91; N, 5.05. Found:
C, 34.65; H, 2.98; N, 5.11. MS:
m/z = 277.8 [M+].
2-[4-(Trifluoromethoxy)phenyl]ethanethioamide
(2i)
¹H NMR (400 MHz, DMSO-d
6): δ = 3.8
(s, 2 H), 7.2 (d, 2 H), 7.4 (d, 2 H), 9.4 (br s, 1 H), 9.5 (br s,
1 H) ppm. ¹³C NMR (100 MHz, DMSO-d
6): δ = 50.5,
116.7, 131.0, 131.3, 136.8, 137.3, 147.6, 147.7, 205.4 ppm. Anal.
Calcd (%) for C9H8F3NOS:
C, 45.95; H, 3.43; N, 5.95. Found: C, 45.98; H, 3.48; N, 5.98. MS: m/z = 235.8 [M+].
Propanethioamide (2t)
¹H
NMR (400 MHz, DMSO-d
6): δ = 1.2
(t, 3 H) 2.6 (q, 2 H), 7.2 (s, 1 H), 8.0 (s, 1 H) ppm. ¹³C
NMR (100 MHz, DMSO-d
6): δ = 15.0,
42.1, 208.6 ppm. Anal. Calcd (%) for C3H7NS: C,
40.41; H, 7.91; N, 15.71. Found: C, 40.45; H, 7.98; N, 15.78. GC-MS: m/z = 89.1 [M+].
2,2-Dimethylpropanethioamide (2v)
¹H
NMR (400 MHz, DMSO-d
6): δ = 1.3
(s, 9 H) 7.0 (br s, 1 H), 7.7 (br s, 1 H) ppm. ¹³C
NMR: (100 MHz, DMSO-d
6): δ = 32.5,
48.8, 221.8 ppm. Anal. Calcd (%) for C5H11NS:
C, 51.23; H, 9.46; N, 11.95. Found: C, 51.31; H, 9.48; N, 11.98. MS: m/z = 118.0 [M+].
21
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