S2
An Approach to Synthesis of Thioesters and Selenoesters Promoted by Rongalite®
J. Braz. Chem. Soc.
S-Phenyl thiopropionate (3j)9
d 3.24 (d, J 7.5 Hz, 2H) , 4.69 (t, J 7.6 Hz, 1H), 7.19-7.43
(m, 13H); C NMR (125 MHz, CDCl3): d 49.22, 49.43,
123.9, 125.6, 1207.7, 128.6, 129.4, 130.9, 131.8, 134.2,
135.5, 135.8, 139.5, 141.9, 193.9. ESI-MS: m/z (%): 422
([M+4]+, 10), 420([M+2]+, 36), 418(M+, 100).Anal. calc. for
C21H16Cl2OS2: C, 60.14; H, 3.85; Found: C, 60.08; H, 3.94.
Oil; 1H NMR (300 MHz, CDCl3): d 1.24 (t, J 7.50 Hz,
3H), 2.70 (q, J 7.49 Hz, 2H), 7.42-7.43 (m, 5H); 13C NMR
(125 MHz, CDCl3): d 8.75, 36.09, 126.91, 128.12, 128.26,
133.50, 197.13.
13
S-4-Tolyl thiopropionate (3k)3
Oil; 1H NMR (300 MHz, CDCl3): d 1.21 (t, J 7.47 Hz,
3H), 2.36 (s, 3H), 2.67 (q, J 7.50 Hz, 2H), 7.19 -7.30 (m,
4H); 13C NMR (125 MHz, CDCl3): d 9.53, 21.20, 36.90,
124.30, 129.89, 134.39, 139.43, 198.57.
Se-Phenyl selenobenzoate (5a)
Yellow solid; mp 40-41 °C (Lit.12 mp 37-38 °C);
1H NMR (300 MHz, CDCl3): d 7.43-7.52 (m, 5H), 7.60-
7.63 (m, 3H), 7.93-7.96 (m, 2H); 13C NMR (125 MHz,
CDCl3): d 125.78, 127.30, 128.91, 129.02, 129.33, 133.84,
136.29, 138.52, 192.30.
S-4-Chlorophenyl thiopropionate (3l)3
Oil; 1H NMR (300 MHz, CDCl3): d 1.23 (t, J 7.48 Hz,
3H), 2.69 (q, J 7.48 Hz, 2H), 7.32 -7.41 (m, 4H); 13C NMR
(125 MHz, CDCl3): d 8.43, 36.09, 126.87, 128.12, 128.26,
133.50, 197.16.
Se-phenyl 4-methoxyselenobenzoate (5b)
White solid; mp 56-58 °C (Lit.13 mp 61-62 °C); 1H NMR
(300 MHz, CDCl3): d 6.96 (d, J 6.9Hz, 2H), 7.42-7.44 (m,
3H), 7.59-7.63 (m, 2H), 7.92 (d, J 6.9Hz, 2H); 13C NMR
(125 MHz, CDCl3): d 55.52, 114.05, 125.97, 128.84,
129.22, 129.61, 131.25, 136.35, 164.14, 191.20.
S-Phenyl 2-Furancarbothioate (3m)
White solid; mp 51-52 °C (Lit.10 mp 51-52 °C); 1H NMR
(300 MHz, CDCl3): d 6.58-6.60 (m, 1H), 7.27 (d, J 3.6 Hz,
1H), 7.46-7.63 (m, 5H), 7.64 (s, 1H); 13C NMR (125 MHz,
CDCl3): d 111.39, 115.21, 125.23, 128.23, 128.55, 134.12,
145.45, 149.39, 177.59.
Se-Phenyl 2-iodoselenobenzoate (5c)
Yellow solid; mp 59-60 °C (Lit.14 mp 76 °C);1H NMR
(300 MHz, CDCl3): d 7.18-7.18 (m, 1H), 7.43-7.7.45 (m,
4H), 7.63-7.69 (m, 3H), 7.96 (d, J 7.9Hz, 1H); 13C NMR
(125 MHz, CDCl3): d 90.20, 126.65, 128.01, 128.39,
129.17, 129.45, 132.53, 135.75, 140.97, 143.76, 195.61.
S-4-Tolyl 2-Furancarbothioate (3n)
White solid; mp 63-65°C; 1H NMR (300 MHz, CDCl3):
d 2.41 (s, 3H), 6.57-6.59 (m, 1H), 7.25-7.41 (m, 5H), 7.63
13
(m, 1H); C NMR (125 MHz, CDCl3): d 21.34, 112.35,
Se-Phenyl 2-Furancarboselenoate (5d)15
116.09, 122.64, 130.10, 135.06, 139.95, 146.37, 150.49,
179.06. ESI-MS: m/z (%): 218 (M+, 100). Anal. calc. for
C12H10O2S: C, 66.03; H, 4.62; Found: C, 60.10; H, 4.59.
Oil; 1H NMR (300 MHz, CDCl3): d 6.59-6.60 (m, 1H),
7.21-7.23 (m, 1H), 7.41-7.44 (m, 3H), 7.58-7.63 (m, 3H);
13C NMR (125 MHz, CDCl3): d 112.77, 115.18, 124.74,
129.10, 129.32, 136.30, 146.57, 151.74, 180.72.
S-Phenyl 3-phenyl-3-(phenylthio)propanethioate (4a)11
White solid; mp 74-76°C; 1H NMR (300 MHz, CDCl3):
d 3.27 (d, J 6 Hz, 2H), 4.75 (t, J 6 Hz, 1H), 7.23-7.43 (m,
15H); 13C NMR (125 MHz, CDCl3): d 49.28, 49.42, 127.37,
127.70, 127.82, 128.54, 128.94, 129.18, 129.48, 133.67,
134.39, 139.97, 194.59.
References
1. Katritzky,A. R.; Shestopalov,A.A.; Suzuki, K.; Synthesis 2004,
1806.
2. Movassagh, B.; Zakinezhad, Y.; J. Chem. Res. 2006, 369.
3. Barbero, M.; Degani, I.; Dughera, S.; Fochi, R.; Synthesis 2003,
1225.
S-4-Tolyl 3-phenyl-3-(phenylthio)propanethioate (4b)12
White solid; mp 82-83 °C; 1H NMR (300 MHz, CDCl3):
d 2.34 (s, 3H), 2.38 (s, 3H), 3.26 (d, J 7.6 Hz, 2H), 4.70 (t,
J 7.6 Hz, 1H), 7.07-7.32 (m, 13H); 13C NMR (125 MHz,
CDCl3): d 21.10, 21.26, 49.08, 49.44, 127.50, 127.74,
128.38, 128.91, 129.63, 129.68, 129.99, 133.70, 134.26,
138.23, 139.66, 139.96, 194.59.
4. Os’kina, I. A.; Vlasov, V. M.; Russian J. Org. Chem. 2008, 44,
561.
5. Kingsbury, C.A.; Phosphorus, Sulfur Silicon Relat. Elem.1981,
9, 315.
6. Brindaban, C. R.; Tanmay, M.; J. Org. Chem. 2004, 69, 5793.
7. Nyquist, R. A.; Potts, W. J.; Spectrochim. Acta 1959, 514.
8. Buchholz, G.; Martens, J.; Praefcke, K.; Synthesis 1974, 9, 666.
9. Danheiser, R. L.; Nowick, J. S.; J. Org. Chem. 1991, 56, 1176.
10. Katritzky, A. R.; Shestopalov , A. A.; Suzuki, K.; Synthesis
2004, 1806.
S-4-Chlorophenyl 3-(4-chlorophenylthio)-3-
phenylpropanethioate (4c)
White solid; mp 63-65 °C; 1H NMR (300 MHz, CDCl3):