610 N. Venkatesham et al.
mixture was treated with DCE and dried over anhydrous Na2SO4 and concentrated to obtain the
end product. The products were identified by IR, 1H NMR, and MS spectra. IR spectra showed
the characteristic peaks of the –SCN group between 2120 and 2150 cm−1 and the C–S stretching
between 650 and 750 cm−1. The regio-chemistry of substitution was deduced by interpretation of
1H NMR spectra and by their comparison with the spectral and physical data of those of authentic
samples.[4–18,29–34] Mass and 1H NMR data for typical examples are given below:
Spectroscopic data of representative compounds
(1) 2-Thiocyanato phenol: 1H NMR (CDCl3): δ 7.14 (d, J = 8.1 Hz, 1H), 6.73 (m, J = 7.9 Hz,
2H), 6.54 (d, J = 8.1 Hz, 1H), 4.83 (s, 1H), m/z = 151.
(2) 2-methyl-4-thiocyanato-phenol: 1H NMR (CDCl3): δ 6.63–7.24 (m, 3H), 6.13 (brs, 1H), 3.26
(s, 3H), m/z = 165 (mp 70–74◦C).
(3) 3-methyl-4-thiocyanato-phenol: 1H NMR (CDCl3): δ 7.13 (d, J = 7.9 Hz, 1H), 6.93 (m, 2H),
4.84 (s, 1H), 2.32 (s, 1H), m/z = 165.
(4) 4-bromo-2-thiocyanato-phenol: 1H NMR (CDCl3): δ 7.22 (s, 1H), 7.03 (d, J = 8.1 Hz, 1H),
6.53 (d, J = 8.1 Hz, 1H), 4.84 (s, 1H) m/z = 230.
1
(5) 4-Thiocyanatoaniline: H NMR (CDCl3): δ 7.38 (d, J = 8.7 Hz, 2H), 6.66 (d, J = 8.7 Hz,
2H), 3.94 (brd s, 2H), 13C NMR (75 Hz, CDCl3): δ 148.7, 134.3, 116.1, 112.3, 109.5, m/z = 150
(m.p.51–54◦C.)
1
(6) 2-Choloro-4-thiocyanatoaniline: H NMR (CDCl3): δ 7.52 (d, J = 8.2 Hz, 2H), 7.26 (dd,
J = 8.1 Hz, 1H), 6.76 (d, J = 8.2 Hz, 1H), 4.37 (brd s, 2H). m/z = 184 (m.p. 59–61◦C).
1
(7) 3-Methoxy-4-thiocyanatoaniline: H NMR (CDCl3): δ 7.29 (d, J = 8.3 Hz, 1H), 6.28 (dd,
J = 8.3 Hz, 1H), 6.24 (d, J = 8.2 Hz, 1H), 3.98 (s, 2H), 3.87 (s, 3H). m/z = 180 (m.p. 99–101◦C)
1
(8) 4-Thiocyanato-N-methylaniline: H NMR (CDCl3): δ 7.37 (d, J = 8.64 Hz, 2H), 6.59 (d,
J = 8.68 Hz, 2H), 4.11 (brd s, 1H), 2.85 (s, 3H). m/z = 164.
1
(9) 4-Thiocyanato-N, N-dimethylaniline: H NMR (CDCl3): δ 7.44 (d, J = 8.8 Hz, 2H), 6.66
(d, J = 8.8 Hz, 2H), 3.02 (s, 6H), 13C NMR (75 MHz, CDCl3): 151.5, 134.3, 113.2, 112.9, 106.4,
40.2. m/z = 178 (m.p. 72–74◦C).
(10) 4-Thiocyanato-N, N-diethylaniline: 1H NMR (CDCl3): δ 7.5–7.35 (m, 2H), 7.2–7.11 (m, 1H),
6.62–6.60 (m, 1H), 3.38 (q, J = 7.12 Hz, 4H), 1.16 (t, J = 5.4 Hz, 6H). 13C NMR(CDCl3): δ
149.2, 134.8, 125.3, 121.6, 112.8, 44.7, 12.3 (m/z) = 206 (M+) (mp 82–84◦C).
(11) 4-Thiocyanatodiphenylamine: 1H NMR (CDCl3): δ 7.43 (d, J = 8.1 Hz, 2H), 7.34 (t, J =
8.2 Hz, 2H), 7.14 (d, J = 8.1 Hz, 2H), 7.08 (t, J = 8.2 Hz, 1H), 7.03 (d, J = 8.2 Hz, 2H), 5.94
(brd s, 1H). m/z = 226 (m.p. 62–63◦C).
(12) Dithiocyanatodiphenylamine: 1H NMR (CDCl3): δ 7.49 (d, J = 8.4 Hz, 4H), 7.13 (d, J =
8.4 Hz, 4H), 6.09 (brd s, 1H). m/z = 283 (m.p. 110–111◦C).
(13) 3-thiocyanato-1H-indole: 1H NMR (CDCl3): δ 7.30 (m, 2H, J = 9.9 Hz, J = 6.9 Hz), 7.42
(m, 1H, J = 9.9 Hz, J = 7.2 Hz), 7.48 (d, 1H, J = 3 Hz), 7.09 (dd, 1H, J = 5.7 Hz, J = 3 Hz),
8.72 (br s, 1H), 13 C NMR (75 MHz, CDCl3): δ 135.9, 131.1, 127.4, 123.7, 121.8, 118.5, 112.3,
112.1, 91.53. m/z = 174 (mp 72–73◦C).
1
(14) 1-Methyl-3-thiocyanatoindole: H NMR (CDCl3): δ 7.83–7.36 (m, 5H), 3.74 (s, 3H).
13C NMR (CDCl3): δ 137.2, 135.2, 128.4, 123.4, 121.6, 118.8, 112.1, 110.3, 33.4 (m/z) = 188.
mp 79–81◦C.
1
(15) 5-Bromo-3-thiocyanatoindole: H NMR (CDCl3): δ 8.87 (br s, 1H), 7.92–7.15 (m, 5H).
13C NMR (CDCl3): δ 134.6, 132.2, 129.3, 123.1, 121.2, 115.4, 113.7, 111.9, 102.2 (m/z) =
251(M = 1), 253 (M + 2) (mp 126–127◦C).