E
S. Redon et al.
Paper
Synthesis
1H NMR (400 MHz, CDCl3): = 7.31 (dd, J = 7.8, 1.4 Hz, 1 H), 7.16 (m, 2
H), 6.94 (dd, J = 8.3, 2.4 Hz, 1 H), 3.83 (s, 3 H).
1H NMR (400 MHz, CDCl3): = 7.63 (d, J = 8.2 Hz, 2 H), 7.41 (d, J = 8.1
Hz, 2 H), 4.73 (s, 2 H), 1.78 (s, 1 H).
13C NMR (62.9 MHz, CDCl3): = 160.5 (C), 131.1 (CH), 124.6 (CH),
13C NMR (62.9 MHz, CDCl3): = 143.2 (C), 133.1 (2 × CH), 128.6
122.4 (C), 117.8 (CH), 115.7 (CH), 101.5 (CN), 55.5 (OCH3).
(2 × CH), 120.3 (C), 101.9 (CN), 64.1 (CH2).
HRMS (ESI+): m/z calcd for [C8H7NOSe + Na]+: 235.9585; found:
HRMS (ESI+): m/z calcd for [C8H7NOSe + NH4]+: 231.0031; found:
235.9583.
231.0030.
1-Methoxy-2-selenocyanatobenzene (2o)
1-Selenocyanato-3-(trifluoromethyl)benzene (2u)
Colorless oil; yield: 187 mg (88%).
White solid; yield: 170 mg (68%); mp 28–29 °C.
1H NMR (400 MHz, CDCl3): = 7.64 (dd, J = 7.8, 1.4 Hz, 1 H), 7.35 (dd,
J = 8.2, 1.5 Hz, 1 H), 7.03 (dd, J = 7.7, 1.1 Hz, 1 H), 6.90 (d, J = 8.2 Hz, 1
H), 3.90 (s, 3 H).
13C NMR (62.9 MHz, CDCl3): = 155.9 (C), 130.2 (CH), 130.0 (CH),
122.9 (CH), 112.7 (C), 111.1 (CH), 101.4 (CN), 56.3 (OCH3).
1H NMR (400 MHz, CDCl3): = 7.89 (s, 1 H), 7.85 (d, J = 7.9 Hz, 2 H),
7.70 (d, J = 7.8 Hz, 1 H), 7.57 (dd, J = 7.8, 7.9 Hz, 1 H).
13C NMR (62.9 MHz, CDCl3): = 135.9 (CH), 132.7 (q, 2JC,F = 33.3 Hz, C),
3
3
131.0 (CH), 129.2 (q, JC,F = 3.8 Hz, CH), 126.7 (q, JC,F = 3.6 Hz, CH),
123.1 (q, 1JC,F = 272.9 Hz, C), 123.0 (C), 100.6 (CN).
HRMS (ESI+): m/z calcd for [C8H7NOSe + Na]+: 235.9585; found:
19F NMR (376 MHz, CDCl3): = –62.91 (s, 3 F).
235.9584.
HRMS (ESI+): m/z calcd for [C8H4F3NSe + Ag]+: 357.8509; found:
357.8510.
1,2,3-Trimethoxy-5-selenocyanatobenzene (2p)
Yellow oil; yield: 229 mg (84%).
1-Nitro-3-selenocyanatobenzene (2v)
1H NMR (400 MHz, CDCl3): = 6.85 (s, 2 H), 3.9 (s, 6 H), 3.8 (s, 3 H).
Orange solid; yield: 66 mg (29%); mp 58–59 °C.
13C NMR (62.9 MHz, CDCl3): = 154.2 (CH), 139.7 (C), 115.0 (C), 110.9
(2 × CH), 101.7 (C), 61.0 (CH3), 56.5 (2 × CH3).
HRMS (ESI+): m/z calcd for [C10H12NO3Se + H]+: 273.9977; found:
273.9978.
1H NMR (400 MHz, CDCl3): = 8.50 (dd, J = 1.8, 1.8 Hz, 1 H), 8.30 (dd,
J = 8.3, 0.9 Hz, 1 H), 8.00 (dd, J = 7.8, 0.9 Hz, 1 H), 7.65 (dd, J = 8.1, 8.0
Hz, 1 H).
13C NMR (62.9 MHz, CDCl3): = 148.9 (C), 138.1 (CH), 131.4 (CH),
127.1 (CH), 124.7 (CH), 123.8 (C), 100.1 (CN).
HRMS (ESI+): m/z calcd for [C7H4N2O2Se + Ag]+: 334.8485; found:
2-Selenocyanatothiophene (2q)
334.8489.
Yellow oil; yield: 141 mg (74%).
1H NMR (400 MHz, CDCl3): = 7.58 (dd, J = 5.5, 1.25 Hz, 1 H), 7.46 (dd,
J = 3.5, 1.0 Hz, 1 H), 7.08 (dd, J = 5.2, 3.5 Hz, 1 H).
(E)-1-Methyl-4-(2-selenocyanatovinyl)benzene (2w)3b
White solid; yield: 140 mg (63%); mp 65 °C.
1H NMR (300 MHz, CDCl3): = 7.27 (d, J = 8.1 Hz, 2 H), 7.10–7.19 (m, 3
H), 6.79 (d, J = 15.3 Hz, 1 H), 2.36 (s, CH3, 3 H).
13C NMR (62.9 MHz, CDCl3): = 139.1 (CH), 134.7 (CH), 128.8 (CH),
112.5 (C), 101.1 (CN).
HRMS (ESI+): m/z calcd for [C5H3NSSe + Na]+: 211.9044; found:
211.90421.
13C NMR (62.9 MHz, CDCl3): = 142.1 (CH), 139.8 (C), 132.5 (C), 129.8
(2 × CH), 126.9 (2 × CH), 105.9 (CH), 100.6 (CN), 21.5 (CH3).
3-Selenocyanatothiophene (2r)
1,2-Diselanes 3a–c,e–g,j,l–o,q; General Procedure
Yellow oil; yield: 139 mg (74%).
To a solution of SeO2 (333 mg, 3 mmol, 3 equiv) in wet DMSO (1 mL)
was added malononitrile (66 mg, 1 mmol, 1 equiv). The solution was
stirred at rt for 30 min, then arylboronic acid 1 (1 mmol, 1 equiv) was
added. The mixture was heated at 60 °C for 10 h, then KOH (110 mg, 2
equiv) was added. The mixture was heated at 110 °C for 12 h. After
cooling to rt, H2O (10 mL) was added, and the resulting mixture was
extracted with DCM (3 × 10 mL). The combined organic layers were
dried (Na2SO4), filtered, and reduced under vacuum. The crude prod-
uct was purified by column chromatography (PE/DCM 90:10) to af-
ford the desired pure diselane compound 3.
1H NMR (400 MHz, CDCl3): = 7.66 (dd, J = 3.0, 1.2 Hz, 1 H), 7.45 (d,
J = 5.2, 3.0 Hz, 1 H), 7.75 (dd, J = 5.0, 1.2 Hz, 1 H).
13C NMR (62.9 MHz, CDCl3): = 131.6 (CH), 131.5 (CH), 128.3 (CH),
112.1 (C), 101.1 (CN).
HRMS (ESI+): m/z calcd for [C5H3NSSe + Na]+: 211.9044; found:
211.9041.
1-Selenocyanato-4-(trifluoromethoxy)benzene (2s)
Yellow solid; yield: 173 mg (65%); mp 43–44 °C.
1H NMR (400 MHz, CDCl3): = 8.46 (d, J = 8.9 Hz, 1 H), 7.97 (d, J = 8.9
Hz, 2 H).
1,2-Bisphenyldiselane (3a)15b
Yellow solid; yield: 111 mg (71%); mp 62–63 °C.
1H NMR (400 MHz, CDCl3): = 7.65–7.60 (m, 1 H), 7.30–7.20 (m, 4 H).
13C NMR (62.9 MHz, CDCl3): = 131.6 (2 × CH), 131.0 (C), 129.3
13C NMR (62.9 MHz, CDCl3): = 150.4 (C), 134.7 (2 × CH), 122.7
(2 × CH), 120.3 (q, 1JC,F = 258.7 Hz, CF3), 119.8 (C), 101.0 (CN).
19F NMR (376 MHz, CDCl3): = –57.91 (s, 3 F).
(2 × CH), 127.9 (CH).
HRMS (ESI+): m/z calcd for [C8H4F3NOSe + Na]+: 289.9303; found:
289.9299.
1,2-Bis(4-fluorophenyl)diselane (3b)15b
Yellow oil; yield: 127 mg (73%).
1H NMR (400 MHz, CDCl3): = 7.53–7.57 (m, 2 H), 6.95–7.00 (m, 2 H).
(4-Selenocyanatophenyl)methanol (2t)
White solid; yield: 200 mg (94%); mp 52–53 °C.
© 2019. Thieme. All rights reserved. — Synthesis 2019, 51, A–G