PAPER
Synthesis of Isothiocyanates
1671
O-Phenyl (3,5-Dimethylphenyl)carbamothioate (3f)
1H NMR (300 MHz, DMSO-d6): δ = 7.75 (d, J = 8.1 Hz, 2 H), 7.64
(d, J = 8.4 Hz, 1 H), 7.44 (t, J = 7.8 Hz, 2 H), 7.31–7.26 (m, 2 H),
7.17 (d, J = 7.8 Hz, 2 H).
13C NMR (75 MHz, DMSO-d6): δ = 186.9, 153.0, 138.7, 137.8,
129.8, 126.4, 124.9, 123.5, 90.4.
White solid; yield: 239 mg (0.93 mmol, 93%); mp 126–128 °C.
1H NMR (300 MHz, CDCl3): δ = 7.43 (t, J = 7.8 Hz, 2 H), 7.30 (t,
J = 7.5 Hz, 2 H), 7.15 (d, J = 7.8 Hz, 2 H), 6.98 (s, 1 H), 6.87 (s, 1
H), 2.33 (s, 6 H).
13C NMR (75 MHz, CDCl3): δ = 186.9, 152.5, 137.9, 135.6, 128.3,
126.7, 125.4, 121.9, 121.5, 120.1, 118.8, 20.3.
MS (ESI): m/z = 258 (M + H+, 100).
MS (ESI): m/z = 356 (M + H+, 100).
Anal. Calcd for C13H10INOS: C, 43.96; H, 2.84; N, 3.94; S, 9.03.
Found: C, 43.85; H, 2.91; N, 3.88; S, 9.10.
Anal. Calcd for C15H15NOS: C, 70.01; H, 5.87; N, 5.44; S, 12.46.
Found: C, 69.89; H, 5.96; N, 5.38; S, 12.39.
O-Phenyl (2-Chlorophenyl)carbamothioate (3o)
White solid; yield: 171 mg (0.65 mmol, 65%); mp 122–123 °C
(Lit.13 119–121 °C).
1H NMR (300 MHz, CDCl3): δ = 7.48–7.41 (m, 3 H), 7.36–7.28 (m,
O-Phenyl [4-(Dimethylamino)phenyl]carbamothioate (3g)
Yellow solid; yield: 231 mg (0.85 mmol, 85%); mp 148–149 °C
(Lit.10 130–132 °C).
3 H), 7.21–7.14 (m, 3 H).
1H NMR (300 MHz, CDCl3): δ = 7.47–7.39 (m, 3 H), 7.30–7.23 (m,
2 H), 7.17–7.12 (m, 2 H), 6.79–6.71 (m, 2 H), 2.96 (s, 6 H).
O-Phenyl (3-Bromophenyl)carbamothioate (3p)11
White solid; yield: 258 mg (0.84 mmol, 84%); mp 122–124 °C.
O-Phenyl (4-Nitrophenyl)carbamothioate (3h)11
The reaction was performed in refluxing THF; yellow solid; yield:
233 mg (0.85 mmol, 85%); mp 135–136 °C.
1H NMR (400 MHz, CDCl3): δ = 8.36 (t, J = 8.8 Hz, 2 H), 7.72 (d,
J = 8.8 Hz, 2 H), 7.44 (t, J = 8.0 Hz, 2 H), 7.32 (t, J = 7.2 Hz, 1 H),
7.18 (d, J = 8.0 Hz, 2 H).
1H NMR (300 MHz, CDCl3): δ = 7.51 (s, 1 H), 7.37 (t, J = 7.8 Hz,
2 H), 7.29–7.14 (m, 4 H), 7.07 (d, J = 7.8 Hz, 2 H).
O-Phenyl (2,4-Dichlorophenyl)carbamothioate (3q)
The reaction was performed in refluxing THF; white solid; yield:
184 mg (0.62 mmol, 62%); mp 102–103 °C.
1H NMR (300 MHz, CDCl3): δ = 8.55 (br s, 1 H), 7.48–7.41 (m, 3
H), 7.34–7.28 (m, 2 H), 7.17–7.12 (m, 2 H).
13C NMR (75 MHz, CDCl3): δ = 186.2, 151.7, 131.8, 130.5, 128.4,
13C NMR (125 MHz, CDCl3): δ = 189.7, 153.6, 148.7, 147.4, 129.8,
129.4, 127.0, 125.1, 121.6.
O-Phenyl (2-Nitrophenyl)carbamothioate (3i)
The reaction was performed in refluxing THF; yellow solid; yield:
225 mg (0.82 mmol, 82%); mp 95–97 °C.
1H NMR (300 MHz, CDCl3): δ = 11.03 (br s, 1 H), 8.82–8.80 (m, 1
H), 8.24 (dd, J1 = 8.4 Hz, J2 = 1.8 Hz, 1 H), 7.73–7.68 (m, 1 H),
7.49–7.43 (m, 2 H), 7.35–7.29 (m, 2 H), 7.17–7.14 (m, 2 H).
13C NMR (75 MHz, CDCl3): δ = 187.2, 152.7, 138.5, 135.2, 133.4,
129.5, 126.7, 125.9, 125.1, 124.0, 122.6.
MS (ESI): m/z = 275 (M + H+, 100).
128.3, 127.9, 126.7, 125.6, 124.1, 121.5.
MS (ESI): m/z = 298 (M + H+, 100).
Anal. Calcd for C13H9Cl2NOS: C, 52.36; H, 3.04; N, 4.70; S, 10.75.
Found: C, 52.21; H, 3.16; N, 4.61; S, 10.83.
O-Phenyl Naphthalen-1-ylcarbamothioate (3r)7
Reddish solid; yield: 260 mg (0.93 mmol, 93%); mp 143–145 °C.
1H NMR (300 MHz, CDCl3): δ = 8.14–7.78 (m, 3 H), 7.63–7.05 (m,
9 H).
Anal. Calcd for C13H10N2O3S: C, 56.92; H, 3.67; N, 10.21; S, 11.69.
Found: C, 56.79; H, 3.76; N, 10.11; S, 11.62.
O-Phenyl Benzylcarbamothioate (3s)
White solid; yield: 241 mg (0.99 mmol, 99%); mp 76–77 °C (Lit.12
75–77 °C).
1H NMR (300 MHz, CDCl3): δ = 7.43–7.27 (m, 8 H), 7.13–7.06 (m,
2 H), 4.83 (d, J = 5.4 Hz, 1 H), 4.68 (d, J = 5.4 Hz, 1 H).
O-Phenyl (3-Nitrophenyl)carbamothioate (3j)11
Yellow solid; yield: 244 mg (0.89 mmol, 89%); mp 114–115 °C.
1H NMR (300 MHz, CDCl3): δ = 8.08 (dd, J = 8.1, 1.2 Hz, 1 H),
7.58–7.21 (m, 6 H), 7.16 (d, J = 7.8 Hz, 2 H).
O-Phenyl (Furan-2-ylmethyl)carbamothioate (3t)
White oil; yield: 231 mg (0.99 mmol, 99%).
1H NMR (300 MHz, CDCl3): δ = 7.43–7.38 (m, 3 H), 7.32–7.27 (m,
1 H), 7.11–7.08 (m, 2 H), 6.93 (br s, 1 H), 6.39–6.33 (m, 2 H), 4.82
(d, J = 5.4 Hz, 1 H), 4.67 (d, J = 5.7 Hz, 1 H).
13C NMR (75 MHz, CDCl3): δ = 188.4, 152.1, 148.2, 141.7, 128.2,
125.2, 121.7, 109.6, 107.8, 41.6, 39.8.
O-Phenyl (4-Fluorophenyl)carbamothioate (3k)
White solid; yield: 215 mg (0.87 mmol, 87%); mp 138–140 °C
(Lit.10 136–138 °C).
1H NMR (300 MHz, CDCl3): δ = 7.64–7.61 (m, 1 H), 7.46–7.30 (m,
4 H), 7.15–7.09 (m, 4 H).
O-Phenyl (4-Chlorophenyl)carbamothioate (3l)
White solid; yield: 247 mg (0.94 mmol, 94%); mp 128–129 °C
(Lit.10 128–129 °C).
1H NMR (400 MHz, CDCl3): δ = 7.68–7.64 (m, 1 H), 7.43 (d, J =
8.0 Hz, 2 H), 7.37–7.29 (m, 4 H), 7.14 (d, J = 8.4 Hz, 2 H).
MS (ESI): m/z = 234 (M + H+, 100).
Anal. Calcd for C12H11NO2S: C, 61.78; H, 4.75; N, 6.00; S, 13.74.
Found: C, 61.62; H, 4.86; N, 5.93; S, 13.69.
O-Phenyl (Thiophen-2-ylmethyl)carbamothioate (3u)
White oil; yield: 239 mg (0.96 mmol, 96%).
1H NMR (300 MHz, CDCl3): δ = 7.43–7.38 (m, 2 H), 7.32–7.28 (m,
2 H), 7.15–7.06 (m, 3 H), 7.03–7.00 (m, 1 H), 6.91 (br s, 1 H), 4.99
(d, J = 5.1 Hz, 1 H), 4.84 (d, J = 5.7 Hz, 1 H).
13C NMR (75 MHz, CDCl3): δ = 188.3, 152.1, 137.3, 128.2, 126.2,
126.0, 125.2, 124.9, 121.7, 43.3, 41.5.
O-Phenyl (4-Bromophenyl)carbamothioate (3m)
White solid; yield: 289 mg (0.94 mmol, 94%); mp 124–125 °C
(Lit.10 125–126 °C).
1H NMR (300 MHz, CDCl3): δ = 7.62–7.59 (m, 1 H), 7.52 (d, J =
8.4 Hz, 2 H), 7.44 (t, J = 7.5 Hz, 2 H), 7.31 (t, J = 7.5 Hz, 2 H), 7.15
(d, J = 6.9 Hz, 2 H).
MS (ESI): m/z = 250 (M + H+, 100).
O-Phenyl (4-Iodophenyl)carbamothioate (3n)
White solid; yield: 319 mg (0.90 mmol, 90%); mp 164–166 °C.
Anal. Calcd for C12H11NOS2: C, 57.80; H, 4.45; N, 5.62; S, 25.72.
Found: C, 57.66; H, 4.58; N, 5.55; S, 25.79.
© Georg Thieme Verlag Stuttgart · New York
Synthesis 2013, 45, 1667–1674